Nanoscience & Technology Aliofkhazraei

Ali
Milne

GRAPHENE SCIENCE HANDBOOK Ozkan

Mitura

GRAPHENE
Gervasoni
Applications and Industrialization

SCIENCE

GRAPHENE SCIENCE HANDBOOK

Applications and Industrialization
“This is a very good and excellent book on graphene material which is not only useful for researchers but also for students...
This hand book is devoted to different applications of graphene materials in different fields...”
—Dr. Noorunnisa Khanam Patan, Center for Advanced Materials, Qatar University

HANDBOOK
“Graphene Science Handbook: Applications and Industrialization is a comprehensive collection of the most recent
advances on diverse areas of graphene science and development. The book has recognized editors and as such attracted high
quality authors for chapters. The chapters have their own independent structures that allow the readers to read and use
them as separate reference entities. … Most of the chapters have been well written and are easy to read and understand. I
recommend this book as a good reference that covers both basic and advanced topics regarding graphene.”
—Professor Kourosh Kalantar-Zadeh, Royal Melbourne Institute of Technology (RMIT), Australia

Applications and
“Many practical applications utilize not only graphene’s electronic properties and optical transparency but also its extremely
high thermal conductivity, mechanical strength and flexibility, tunable electron density, excellent current-carrying capacity,
and ultimate surface-to-volume ratio. The present volume provides a scope of applications in sensors and nanodevices that
use one or several unique material characteristics of graphene.”
—Dr. Alexander A. Balandin, University of California Presidential Chair Professor

“I am confident in the materials … The wide scope of information covered, and the qualifications of the contributors
projects a positive image of the potential quality of the publication.”
Industrialization
—Albert V. Tamashausky, Asbury Carbons Inc.

“This book is a result of an impressive project to collect views from experts in every aspect of graphene science. All popular
topics in the research of this impressive material are covered. This is the best and most complete presentation that has been
published so far for the hottest material of our times. A must-have reference.”
—Ioannis Remediakis, Department of Materials Science and Technology, University of Crete, Greece

“…this set of volumes represents a complete handbook showing the state of the art of science and technology related with
graphene. This set of books is written by great specialists and competent experts. For someone who works in this field, this
set of volumes is an essential reference for the characterization and application of graphene.” EDITED BY
—Dr. Alex Axelevitch, Holon Institute of Technology (HIT)
Mahmood Aliofkhazraei • Nasar Ali
William I. Milne • Cengiz S. Ozkan
Stanislaw Mitura • Juana L. Gervasoni
K20508
ISBN: 978-1-4665-9133-2
90000

9 781466 591332

K20508_COVER_Final.indd 1 3/17/16 5:04 PM

GRAPHENE
SCIENCE
HANDBOOK
Applications and
Industrialization
 GRAPHENE
SCIENCE
HANDBOOK
Applications and
Industrialization

EDITED BY
Mahmood Aliofkhazraei • Nasar Ali
William I. Milne • Cengiz S. Ozkan
Stanislaw Mitura • Juana L. Gervasoni
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2016 by Taylor & Francis Group, LLC
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Version Date: 20160330

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Contents
Preface.......................................................................................................................................................................................... ix
Editors........................................................................................................................................................................................... xi
Contributors ...............................................................................................................................................................................xiii

Section I  Biomaterial

Chapter 1 Design and Applications of Graphene- and Biomolecule-Based Nanosensors and Nanodevices........................... 3
Ke Xu, Preeti Pratap, Mitra Dutta, and Michael Stroscio

Chapter 2 Graphene-Based DNA Sensors.............................................................................................................................. 13

Hatef Sadeghi

Chapter 3 Antimicrobial Perspectives for Graphene-Based Nanomaterials.......................................................................... 27

Archana Ramchandra Deokar, Madhulika Sinha, Ganesh Gollavelli, and Yong-Chien Ling

Chapter 4 Biomedical Applications of Graphene................................................................................................................... 41

Maria Caffo, Lucia Merlo, Daniele Marino, and Gerardo Caruso

Chapter 5 Graphene Biodevices.............................................................................................................................................. 57

Xiaochen Dong, Beibei Zhan, and Wei Huang

Chapter 6 Antibacterial and Antifungal Activities of Graphene Nanosheets......................................................................... 71

Montree Sawangphruk

Chapter 7 Applications of Graphene in Biosensing................................................................................................................ 81

D. P. Nikolelis, Z. H. Ibupoto, G.-P. Nikoleli, and M. Willander

Chapter 8 Graphene-Based Biosensor Technologies.............................................................................................................. 91

Arzum Erdem, Ece Eksin, and Mihrican Muti

Chapter 9 Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications................... 105
Suresh Kumar Kailasa, Hui-Fen Wu, and Jigneshkumar V. Rohit

Chapter 10 Richness of Graphene-Based Materials in Biomimetic Applications.................................................................. 125

Bhaskar Garg and Yong-Chien Ling

Section II  Nanocomposites

Chapter 11 Graphene-Based Polymer Nanocomposites......................................................................................................... 145

S. Chatterjee and B. T. T. Chu

v
vi Contents

Chapter 12 Preparation of Cellulose/Graphene Nanocomposites............................................................................................161

Nguyen Dang Luong and Jukka Seppälä

Chapter 13 Straightforward Routes for the Preparation of Graphene-Based Polymer Nanocomposites................................175

Giulio Malucelli and Alberto Mariani

Chapter 14 Polymer Devices with Graphene: Solar Cells and Ultracapacitors.......................................................................191

Agnieszka Iwan, Bronislaw Szubzda, and Andrzej Sikora

Section III  Electrical/Sensor Devices

Chapter 15 Graphene-Based Sensors: Current Status and Future Trends...............................................................................211

Goutam Koley, Amol Singh, and Ahsan Uddin

Chapter 16 Effect of External Electric Fields on the Multifunctional Applications of Graphene......................................... 235
Zhimin Ao, Qing Jiang, Sean Li, Shixue Dou, and Guoxiu Wang

Chapter 17 Impact of the Structural Properties of Graphene on SiC Surfaces on Their Electronic Applications:
An Assessment..................................................................................................................................................... 255
Jolanta Borysiuk and Jakub Sołtys

Chapter 18 Resistive Nonvolatile Memories Based on Graphene-Related Materials: State of the Art.................................. 269
P. Bondavalli, D. Ihnatov, D. Pribat, and P. Legagneux

Chapter 19 Applications of Graphene-Based Materials in Electronic Devices...................................................................... 279

Gaurav Gupta, Minggang Zeng, Argo Nurbawono, Wen Huang, and Gengchiau Liang

Chapter 20 Graphene- and Graphene-Oxide-Based Gas Sensors.......................................................................................... 299

Vladimir Aroutiounian

Section IV  New Applications

Chapter 21 Graphene-Based Materials for Fuel Cells: Approaches and Applications............................................................313

Junrui Li and Haolin Tang

Chapter 22 Chemistry and Applications of Supramolecular Graphene Derivatives.............................................................. 337

Hugo Bares, Jean-Baptiste Verlhac, and Dario M. Bassani

Chapter 23 Applications of Graphene in Tissue Engineering................................................................................................ 353

Eoin Murray, Brianna C. Thompson, and Gordon G. Wallace

Chapter 24 Graphene in Space................................................................................................................................................ 365

Domingo Aníbal García-Hernández and Franco Cataldo
Contents vii

Chapter 25 Graphene Materials in Energy Storage Applications........................................................................................... 377

Grzegorz Lota, Krzysztof Fic, Ilona Acznik, and Katarzyna Lota

Chapter 26 Applications of Graphene in Fuel/Propellant Combustion.................................................................................. 391

Bruce Chehroudi

Chapter 27 Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields.................. 399
Zhu-Yin Sui, Ding Zhou, and Bao-Hang Han

Chapter 28 New Energy Material: Graphene..........................................................................................................................419

Hongying Hou, Xianxi Liu, and Jinhui Peng

Chapter 29 Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell.............................................. 439
Avijit Ghosh and Anil Verma

Index.......................................................................................................................................................................................... 463
Preface
The theory behind “graphene” was first explored by the
physicist Philip Wallace in 1947. However, the name “gra-
phene” was not actually coined until 40 years later, where
it was used to describe single sheets of graphite. Ultimately,
Professor Geim’s group in Manchester (UK) was able to
manufacture and see individual atomic layers of graphene in
2004. Since then, much more research has been carried out
on the material, and scientists have found that graphene has
unique and extraordinary properties. Some say that it will
literally change our lives in the twenty-first century. Not only
is graphene the thinnest possible material, but it is also about
200 times stronger than steel and conducts electricity bet-
ter than any other material at room temperature. This mate-
rial has created huge interest in the electronics industry, and
Konstantin Novoselov and Andre Geim were awarded the
2010 Nobel Prize in Physics for their groundbreaking experi-
ments on graphene.
Graphene and its derivatives (such as graphene oxide) have
the potential to be produced and used on a commercial scale,
and research has shown that corporate interest in the discov-
ery and exploitation of graphene has grown dramatically in
the leading countries in recent decades. In order to understand
how this activity is unfolding in the graphene domain, publi-
cation counts have been plotted in Figure P.1. Research and
commercialization of graphene are both still at early stages,
but policy in the United States as well as in other key coun-
tries is trying to foster the concurrent processes of research
and commercialization in the nanotechnology domain.
Graphene can be produced in a multitude of ways. Initially,
Novoselov and Geim employed mechanical exfoliation by
using a Scotch tape technique to produce monolayers of the
material. Liquid-phase exfoliation has also been utilized.
Several bottom-up or synthesis techniques developed for gra-
phene include chemical vapor deposition, molecular beam
epitaxy, arc discharge, sublimation of silicon carbide, and epi-
taxy on silicon carbide.
The first volume of this handbook concerns the fabrica-
tion methods of graphene. It is divided into four sections: (1)
fabrication methods and strategies, (2) chemical-based meth-
ods, (3) nonchemical methods, and (4) advances of fabrication
methods.
Carbon is the sixth most abundant element in nature and
is an essential element of human life. It has different struc-
tures called carbon allotropes. The most common crystal-
line forms of carbon are graphite and diamond. Graphite is
a three-dimensional allotrope of carbon with a layered struc-
ture in which tetravalent atoms of carbon are connected to
three other carbon atoms by three covalent bonds and form
a hexagonal network structure. Each one of these aforemen-
tioned layers is called a graphene layer or sheet. Each sheet is
placed in parallel on other sheets. Hence, the fourth valence
electron connects the sheets to each other via van der Waals
bonding. The covalent bond length is 0.142 nm. The bonds
that are formed by carbon atoms between layers are weak;
therefore, the sheets can slide easily over each other. The dis-
tance between layers is 0.335 nm. Due to its unique structure
and geometry, graphene possesses remarkable physical–­
chemical properties, including a high Young’s modulus, high
fracture strength, excellent electrical and thermal conductiv-
ity, high charge carrier mobility, large specific surface area,
and biocompatibility.
These properties enable graphene to be considered as an
ideal material for a broad range of applications, ranging from
quantum physics, nanoelectronics, energy research, catalysis,
and engineering of nanocomposites and biomaterials. In this
context, graphene and its composites have emerged as a new
biomaterial, which provides exciting opportunities for the
development of a broad range of applications, such as nano-
carriers for drug delivery. The building block of graphene
is completely different from other graphite materials and
three-dimensional geometric shapes of carbon, such as zero-
dimensional spherical fullerenes and one-dimensional carbon
nanotubes.
The second volume of this handbook is predominantly
about the nanostructure and atomic arrangement of graphene.
The chapters in this volume focus on atomic arrangement
and defects, modified graphene, characterization of graphene
and its nanostructure, and also recent advances in graphene
nanostructures. The planar structure of graphene provides an
excellent opportunity to immobilize a large number of sub-
stances, including biomolecules and metals. Therefore, it is
not surprising that graphene has generated great interest for
its nanosheets, which nowadays can serve as an excellent plat-
form for antibacterial applications, cell culture, tissue engi-
neering, and drug delivery.
It is possible to produce composites reinforced with gra-
phene on a commercial scale and low cost. In these composites,
the existence of graphene leads to an increase in conductivity
and strength of various three-dimensional materials. In addi-
tion, it is possible to use cheaply manufactured graphene in
these composites. For example, exfoliation of graphite is one
of the cheapest graphene production techniques. The behavior
of many two-dimensional materials and their equivalent three-
dimensional forms are completely different. The origin of the
aforementioned differences in the behavior of these materials
is associated with the weak forces that hold a large number of
single layers together to create a bulk material. Graphene can
be used in nanocomposites. Currently, researchers have been
able to produce several tough and light materials by adding
small amounts of graphene to metals, polymers, and ceram-
ics. The composite materials usually show better electrical
conductivity characteristics compared with pure bulk materi-
als, and they are also more resistant against heat.
The third volume describes graphene’s electrical and opti-
cal properties and also focuses on nanocomposites and their
applications. The fourth volume relates to the mechanical
ix
x Preface
16,000
14,000
12,000
Number of documents
10,000
8000
6000
4000
2000
0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014
FIGURE P.1  Number of documents published around graphene during recent years, extracted from Scopus search engine by searching
“graphene” in title + keywords + abstract.
and chemical properties of graphene and cites recent devel-
opments. The fifth volume presents other topics, such as size
effects in graphene, characterization, and applications based
on size-affected properties. In recent years, scientists have
produced advanced composites using graphene, which are
excellent from the point of view of mechanical and ther-
mal properties. However, in some of these composites, high
electrical conductivity only is desirable. For example, the
Institute of Metal Research, Chinese Academy of Sciences
(IMR, CAS) has created a polymer matrix composite rein-
forced with graphene, which has a high electrical conduc-
tivity. In this composite, a flexible network of graphene has
been added to a polydimethylsiloxane matrix (of the silicon
family).
Investigation of early corporate trajectories for graphene
has led to three major observations. First, the discovery-to-
application cycle for graphene seems to be accelerated, for
example, compared to fullerene. Even though the discovery
of graphene is relatively new, large and small firms have con-
tributed to an upsurge in early corporate activities. Second, a
rapid globalization has occurred by companies in the United
States, Europe, Japan, South Korea, and other developed
economies, which were involved in early graphene activities.
Chinese companies are currently starting to enter the gra-
phene domain, resulting in the expansion of research capabil-
ity of nanotechnology. Nevertheless, science alone does not
guarantee commercial exploitation. To clarify the issue, the
level of corporate patenting in the United Kingdom, which is a
pioneer in graphene research, is slightly ahead of Canada and
Germany; however, it is dramatically lower than in the United
States, Japan, and South Korea. Third, the potential applica-
tions of graphene are rapidly expanding. Corporate patent-
ing trends are indicative of their enthusiasm to utilize the
features of graphene in various areas, including transistors,
Year
electronic memory and circuits, capacitors, displays, solar
cells, batteries, coatings, advanced materials, sensors, and
biomedical devices. Although graphene was initially pro-
posed as an alternative to silicon, its initial applications have
been in electronic inks and additives to resins and coatings.
We have identified six areas of emerging applications for gra-
phene, including displays/screens, memory chips, biomedical
devices, batteries/fuel cells, coatings, inks, and materials. In
the investigation of the corporate engagement in graphene, we
sought to understand early corporate activity patterns related
to broader research and invention trends. In traditional inno-
vation models, a lag between research publication and patent-
ing is consistent with the linear model. However, more recent
innovation models are stressing concurrent launch, open inno-
vation, and strategic property management.
The sixth volume of this handbook is about the applica-
tion and industrialization of graphene, starting with chapters
about biomaterials and continues onto nanocomposites, elec-
trical/sensor devices, and also new and novel applications.
The editorial team would like to thank all contributors
for their excellent chapters contributed to the creation of this
handbook and for their hard work and patience during its
preparation and production. We sincerely hope that the pub-
lication of this handbook will help people, especially those
working with graphene, and benefit them from the knowledge
contained in the published chapters.
Summer 2015
Mahmood Aliofkhazraei
Nasar Ali
William I. Milne
Cengiz S. Ozkan
Stanislaw Mitura
Juana L. Gervasoni
Editors
Mahmood Aliofkhazraei is an assistant professor in the
Materials Engineering Department at Tarbiat Modares
University. Dr. Aliofkhazraei’s research interests include nan-
otechnology and its use in surface and corrosion science. One
of his main interests is plasma electrolysis, and he has pub-
lished more than 40 papers and a book in this area. Overall
he has published more than 12 books and 90 journal articles.
He has delivered invited talks, including keynote addresses
in several countries. Aliofkhazraei has received numerous
awards, including the Khwarizmi award, IMES medal, INIC
award, best-thesis award (multiple times), best-book award
(multiple times), and the best young nanotechnologist award
of Iran (twice). He is on the advisory editorial board of several
materials science and nanotechnology journals.
Nasar Ali is a visiting professor at Meliksah University in
Turkey. Earlier he held the post of chief scientific officer at
CNC Coatings Company based in Rochdale, UK. Prior to
this Dr. Ali was a faculty member (assistant professor) at the
University of Aveiro in Portugal where he founded and led
the Surface Engineering and Nanotechnology group. Dr. Ali
has extensive research experience in hard carbon-coating
materials, including nanosized diamond coatings and CNTs
deposited using CVD methods. He has over 120 interna-
tional refereed research publications, including a number of
book chapters. Dr. Ali serves on a number of committees for
international conferences based on nanomaterials, thin films,
and emerging technologies (nanotechnology), and he chairs
the highly successful NANOSMAT congress. He served as
the fellow of the Institute of Nanotechnology for 2 years on
invitation. Dr. Ali has authored and edited several books on
surface coatings, thin films, and nanotechnology for lead-
ing publishers, and he was also the founder of the Journal
of Nano Research. Dr. Ali was the recipient of the Bunshah
prize for presenting his work on time-modulated CVD at the
ICMCTF-2002 Conference in San Diego, California.
William I. Milne, FREng, FIET, FIMMM, was head of elec-
trical engineering at the Cambridge University from 1999
until 2014 and has been director of the Centre for Advanced
Photonics and Electronics (CAPE) since 2004. He earned a
BSc at St. Andrews University in Scotland in 1970 and later
earned a PhD in electronic materials at the Imperial College
London. In 2003 he was awarded a DEng (honoris causa) by the
University of Waterloo, Canada, and he was elected as Fellow
of the Royal Academy of Engineering in 2006. He received
the JJ Thomson medal from the Institution of Engineering
and Technology in 2008 for achievement in electronics and
the NANOSMAT prize in 2010. He is a distinguished visit-
ing professor at Tokyo Institute of Technology, Japan, and a
distinguished visiting professor at Southeast University in
Nanjing, China, and at Shizuoka University, Japan. He is also
a distinguished visiting scholar at KyungHee University, Seoul
and a high-end foreign expert for the Changchun University
of Science and Technology in China. In 2015, he was elected
to an Erskine Fellowship to visit the University of Canterbury,
New Zealand. His research interests include large area silicon-
and carbon-based electronics, thin film materials, and, most
recently, MEMS and carbon nanotubes, graphene, and other
1-D and 2-D structures for electronic applications, especially
for field emission. He has published/presented approximately
800 papers, of which around 200 were invited/keynote/­plenary
talks—his “h” index is currently 57 (Web of Science).
Cengiz S. Ozkan has been a professor of mechanical engi-
neering and materials science at the University of California,
Riverside, since 2009. He was an associate professor from
2006 to 2009 and an assistant professor from 2001 to 2006.
Between 2000 and 2001 he was a consulting professor at
Stanford University. He earned a PhD in materials science
and engineering at Stanford University in 1997. Dr. Ozkan’s
areas of expertise include nanomaterials for energy storage;
synthesis/­processing including graphene, III–V, and II–VI
materials; novel battery and supercapacitor architectures;
nanoelectronics; biochemical sensors; and nanopatterning
for beyond CMOS (complementary metal-oxide semiconduc-
tor). He organized and chaired 20 scientific and international
conferences. He has written more than 200 technical publica-
tions, including journal papers, conference proceedings, and
book chapters. He holds over 50 patent disclosures, has given
more than 100 presentations worldwide, and is the recipient of
more than 30 honors and awards. His important contributions
include growth of hierarchical three-dimensional graphene
nanostructures; development of a unique high-throughput
metrology method for large-area CVD-grown graphene
sheets; doping and functionalization of CVD-grown and
pristine graphene layers; study of digital data transmission
in graphene and InSb materials; memory devices based on
inorganic/organic nanocomposites, novel lithium-ion batter-
ies based on nano-silicon from beach sand and silicon dioxide
nanotubes; fast-charging lithium-ion batteries based on silicon-
decorated three-dimensional nano-carbon architectures; and
high-performance supercapacitors based on three-dimen-
sional graphene foam architectures.
Stanislaw Mitura has been a professor in biomedical engi-
neering at Koszalin University of Technology from 2011. He
is a visiting professor at the Technical University (TU) of
Liberec and was awarded a doctor honoris causa from TU
Liberec. He was a professor of materials science at Lodz
University of Technology from 2001 to 2014. He earned
an MSc in physics at the University of Lodz in 1974, a
PhD in mechanical engineering at the Lodz University
of Technology  (1985), and a DSc in materials science at
the Warsaw University of Technology in 1993. Professor
Mitura’s most prominent cognitive achievements comprise
xi
xii
the following: from the concept of nucleation of diamond
powder particles to the synthesis of nanocrystalline diamond
coatings (NDC); discovery of ­diamond bioactivity; a concept
of the gradient transition from carbide forming metal to dia-
mond film; and technology development of nanocrystalline
diamond coatings for medical purposes. Professor Mitura
has published over 200 peer-reviewed articles, communica-
tions, and proceedings, over 50 invited talks, and contributed
to 7 books and ­proceedings, including Nanotechnology for
Materials Science (Pergamon, Elsevier, 2000) and Nanodiam
(PWN, 2006). He organized and co-organized several con-
ferences focused on materials science and engineering, espe-
cially diamond synthesis under reduced pressure. He is an
elected member of the Academy of Engineering in Poland,
guest editor in few international j­ournals, including Journal
of Nanoscience and Nanotechnology, Journal of Superhards
Materials and also a member of the editorial boards of sev-
eral journals and an elected Fellow of various foreign scien-
tific societies.
Juana L. Gervasoni earned her doctorate in physics at the
Instituto Balseiro, Bariloche, Argentina, in 1992. She has been
head of the Department of Metal Materials and Nanostructures,
Applied Research of Centro Atomico Bariloche (CAB),
National Atomic Energy Commission (CNEA), since 2012.
She has been member of the Coordinating Committee of the
CNEA Controlled Fusion Program since 2013. Her area of
Editors
scientific research involves the interactions of atomic particles
of matter, electronic excitations in solids, surfaces, and nano-
systems, the absorption of hydrogen in metals, and study of
new materials under irradiation. Gervasoni is a researcher at
the National Atomic Energy Commission of Argentina and
the National Council of Scientific and Technological Research
(CONICET, Argentina). She teaches at the Instituto Balseiro
and is involved in directing graduate students and postdoc-
torates. She has published over 100 articles in international
journals, some of which have a high impact factor, and she
has attended many international conferences. Gervasoni is a
member of the Executive Committee and/or the International
Scientific Advisory Board of the International Conference on
Surfaces Coatings and Nanostructured Materials (Nanosmat)
since 2010, Latin American Conference on Hydrogen and
Sustainable Energy Sources (Hyfusen), and the International
Conference on Clean Energy (International Conference on
Clean Energy, ICCE-2010) and guest editor of the International
Journal of Hydrogen Energy (Elsevier). Recently she has
focused her research on the study of hydrogen storage in car-
bon nanotubes. Along with her academic and research work,
Gervasoni is heavily involved in gender issues in the scien-
tific community, especially in Argentina and Latin America.
She is a member of the Third World Organization for Women
in Science (TWOWS), branch of the Third World Academy
of Science (TWAS), Trieste, Italy, since 2010, as well as of
Women in Nuclear (WiN) since 2013.
Contributors
Ilona Acznik Franco Cataldo
Central Laboratory of Batteries and Cells Istituto Nazionale di Astrofisica—Osservatorio
Institute of Non-Ferrous Metals Division Astrofisica di Catania
in Poznan Catania, Italy
Poznan, Poland
and
Zhimin Ao Actinium Chemical Research
Centre for Clean Energy Technology Rome, Italy
School of Chemistry and Forensic Science
University of Technology S. Chatterjee
Sydney, New South Wales, Australia Laboratory for Functional Polymers
Swiss Federal Laboratories for Materials Science
Vladimir Aroutiounian and Technology (EMPA)
Yerevan State University Dübendorf, Switzerland
Yerevan, Armenia
Bruce Chehroudi
Hugo Bares Advanced Technology Consultants
Institut des Sciences Moléculaires Laguna Niguel, California
CNRS UMR 5255
University of Bordeaux B. T. T. Chu
Talence, France Laboratory for Functional Polymers
Swiss Federal Laboratories for Materials Science
Dario M. Bassani and Technology (EMPA)
Institut des Sciences Moléculaires Dübendorf, Switzerland
CNRS UMR 5255
University of Bordeaux Archana Ramchandra Deokar
Talence, France Department of Chemistry
National Tsing Hua University
P. Bondavalli Hsinchu, Taiwan
Thales Research and Technology
Palaiseau, France Xiaochen Dong
Institute of Advanced Materials (IAM)
Jolanta Borysiuk Jiangsu National Synergistic Innovation Center for
Institute of Physics Advanced Materials (SICAM)
Polish Academy of Sciences Nanjing University of Technology (NanjingTech)
and Nanjing, China
Faculty of Physics
University of Warsaw Shixue Dou
Warsaw, Poland Institute for Superconducting and Electronic
Materials
Maria Caffo Australian Institute of Innovative Materials
Department of Neurosciences University of Wollongong
University of Messina School of Medicine North Wollongong, New South Wales, Australia
Messina, Italy
Mitra Dutta
Gerardo Caruso Department of Electrical and Computer
Department of Neurosciences Engineering
University of Messina School of Medicine University of Illinois at Chicago
Messina, Italy Chicago, Illinois

xiii
xiv Contributors

Ece Eksin Wei Huang

Analytical Chemistry Department Institute of Advanced Materials (IAM)
Faculty of Pharmacy Jiangsu National Synergistic Innovation Center for
Ege University Advanced Materials (SICAM)
and Nanjing University of Technology (NanjingTech)
Biotechnology Department Nanjing, China
Institute of Natural and Applied Sciences
Bornova, Izmir, Turkey Wen Huang
Department of Electrical and Computer
Arzum Erdem Engineering
Analytical Chemistry Department National University of Singapore
Faculty of Pharmacy Singapore
Ege University
and Z. H. Ibupoto
Biotechnology Department Department of Science and Technology
Institute of Natural and Applied Sciences Linköping University
Bornova, Izmir, Turkey Norrköping, Sweden

Krzysztof Fic D. Ihnatov

Institute of Chemistry and Technical Thales Research and Technology
Electrochemistry Palaiseau, France
Poznan University of Technology
Poznan, Poland Agnieszka Iwan
Electrotechnical Institute
Domingo Aníbal García-Hernández Division of Electrotechnology and
Institute of Astrophysics of the Canary Islands Materials Science
and Wroclaw, Poland
Department of Astrophysics
University of La Laguna Qing Jiang
Tenerife, Spain Key Laboratory of Automobile Materials
Jilin University
Bhaskar Garg Changchun, China
Department of Chemistry
National Tsing Hua University Suresh Kumar Kailasa
Hsinchu, Taiwan Department of Chemistry
S. V. National Institute of Technology
Avijit Ghosh
Surat, Gujarat, India
Department of Chemical Engineering
Haldia Institute of Technology Goutam Koley
Haldia, West Bengal, India Department of Electrical Engineering
Ganesh Gollavelli University of South Carolina
Department of Chemistry Columbia, South Carolina
National Tsing Hua University
P. Legagneux
Hsinchu, Taiwan
Thales Research and Technology
Gaurav Gupta Palaiseau, France
Department of Electrical and Computer
Junrui Li
Engineering
State Key Laboratory of Advanced Technology for
National University of Singapore
Materials Synthesis and Processing
Singapore
and
Bao-Hang Han Department of Chemistry
National Center for Nanoscience and Technology Wuhan University of Technology
Beijing, China Wuhan, China

Hongying Hou Sean Li

Faculty of Materials and Engineering School of Materials Science and Engineering
Kunming University of Science and Technology University of New South Wales
Kunming, China Sydney, New South Wales, Australia
Contributors xv

Gengchiau Liang Eoin Murray

Department of Electrical and Computer Institute for Sports Research
Engineering Nanyang Technological University
National University of Singapore Singapore
Singapore
and
Intelligent Polymer Research Institute
Yong-Chien Ling
ARC Centre of Excellence for Electromaterials
Department of Chemistry
Science
National Tsing Hua University
University of Wollongong
Hsinchu, Taiwan
Wollongong, New South Wales, Australia

Xianxi Liu Mihrican Muti

Faculty of Mechanical and Electrical Engineering Analytical Chemistry Department
Kunming University of Science and Technology Faculty of Pharmacy
Kunming, China Ege University
Izmir, Turkey
Grzegorz Lota
and
Institute of Chemistry and Technical
Electrochemistry Chemistry Department
Poznan University of Technology Faculty of Sciences
Poznan, Poland Adnan Menderes University
Aydın, Turkey
Katarzyna Lota
Central Laboratory of Batteries and Cells G.-P. Nikoleli
Institute of Non-Ferrous Metals Division in Poznan Laboratory of Inorganic and Analytical
Poznan, Poland Chemistry
National Technical University
of Athens
Nguyen Dang Luong Athens, Greece
Department of Biotechnology and Chemical
Technology
Aalto University D. P. Nikolelis
Espoo, Finland Department of Chemistry
University of Athens, Panepistimiopolis-Kouponia
Athens, Greece
Giulio Malucelli
Department of Applied Science and
Argo Nurbawono
Technology
Department of Electrical and Computer Engineering
Politecnico di Torino
National University of Singapore
Alessandria, Italy
Singapore

Alberto Mariani Jinhui Peng

Department of Chemistry and Pharmacy National University of Yunnan
University of Sassari Kunming, China
Sassari, Italy
Preeti Pratap
Daniele Marino Department of Bioengineering
Department of Neurosciences University of Illinois at Chicago
University of Messina School of Medicine Chicago, Illinois
Messina, Italy
D. Pribat
Lucia Merlo Department of Energy Science
Department of Neurosciences Sungkyunkwan University
University of Messina School of Medicine Suwon, South Korea
Messina, Italy
xvi Contributors

Jigneshkumar V. Rohit Haolin Tang

Department of Chemistry State Key Laboratory of Advanced Technology for
S. V. National Institute of Technology Materials Synthesis and Processing
Surat, Gujarat, India Wuhan University of Technology
Wuhan, China
Hatef Sadeghi
Physics Department
Lancaster University Brianna C. Thompson
Lancaster, United Kingdom Mechanical and Aerospace Engineering
Nanyang Technological University
Montree Sawangphruk Singapore
Department of Chemical and Biomolecular Engineering
Vidyasirimedhi Institute of Science and Technology and
Rayong, Thailand Intelligent Polymer Research Institute
ARC Centre of Excellence for
Jukka Seppälä
Electromaterials Science
Department of Biotechnology and Chemical
University of Wollongong
Technology
Wollongong, New South Wales, Australia
Aalto University
Espoo, Finland
Ahsan Uddin
Andrzej Sikora Department of Electrical Engineering
Division of Electrotechnology and Materials Science University of South Carolina
Electrotechnical Institute Columbia, South Carolina
Wroclaw, Poland

Amol Singh Jean-Baptiste Verlhac

Department of Electrical Engineering Institut des Sciences Moléculaires
University of South Carolina CNRS UMR 5255
Columbia, South Carolina University of Bordeaux
Talence, France
Madhulika Sinha
Department of Chemistry
National Tsing Hua University Anil Verma
Hsinchu, Taiwan Department of Chemical Engineering
Indian Institute of Technology Delhi
Jakub Sołtys New Delhi, India
Interdisciplinary Center for Mathematical and
Computational Modeling
University of Warsaw Gordon G. Wallace
Warsaw, Poland Intelligent Polymer Research Institute
ARC Centre of Excellence for
Michael Stroscio Electromaterials Science
Department of Electrical and Computer University of Wollongong
Engineering Wollongong, New South Wales, Australia
and
Department of Bioengineering
University of Illinois at Chicago Guoxiu Wang
Chicago, Illinois Centre for Clean Energy Technology
School of Chemistry and Forensic Science
Zhu-Yin Sui University of Technology
National Center for Nanoscience and Technology Sydney, New South Wales, Australia
Beijing, China

Bronislaw Szubzda M. Willander

Division of Electrotechnology and Materials Science Department of Science and Technology
Electrotechnical Institute Linköping University
Wroclaw, Poland Norrköping, Sweden
Contributors xvii

Hui-Fen Wu Minggang Zeng

Department of Chemistry Department of Electrical and Computer Engineering
National Sun Yat-Sen University National University of Singapore
and Singapore
College of Pharmacy
Kaohsiung Medical University Beibei Zhan
and Institute of Advanced Materials (IAM)
Institute of Medical Science and Technology Jiangsu National Synergistic Innovation Center for
National Sun Yat-Sen University Advanced Materials (SICAM)
Kaohsiung, Taiwan Nanjing University of Technology (NanjingTech)
Nanjing, China
Ke Xu
Department of Electrical and Computer Engineering Ding Zhou
University of Illinois at Chicago National Center for Nanoscience and Technology
Chicago, Illinois Beijing, China
Section I
Biomaterial
 1 Design and Applications of
Graphene- and Biomolecule-Based
Nanosensors and Nanodevices
Ke Xu, Preeti Pratap, Mitra Dutta, and Michael Stroscio

CONTENTS
Abstract.......................................................................................................................................................................................... 3
1.1 Graphene and Graphene-Based Field-Effect-Transistor-Like Structures............................................................................. 3
1.2 Design of Graphene- and Aptamer-Based Biosensors......................................................................................................... 5
1.2.1 Design of Aptamer-Based Optical and Electrochemical Biosensors....................................................................... 5
1.2.2 Design of Aptamer-Based Biosensors with Graphene-Based Field Effect Transistor Structures............................ 6
1.3 Sensing Elements on Graphene-Based Substrates................................................................................................................ 6
1.3.1 Raman Spectroscopy and Its Application in Nanosensing....................................................................................... 7
1.3.2 Raman Spectroscopic Studies of Graphene.............................................................................................................. 7
1.3.3 Raman Spectroscopy of Proteins on Graphene and Graphene-Binding Peptides.................................................... 9
1.4 Summary.............................................................................................................................................................................. 9
Acknowledgment......................................................................................................................................................................... 10
References.................................................................................................................................................................................... 10

ABSTRACT Graphene has exceptional electrical, optical, mechani-

In this chapter, the design of graphene- and biomolecule-based
nanosensors and nanodevices is surveyed with emphasis on
using graphene-based field-effect-transistor (GFET)-like
structures as sensing substrates and DNA aptamers as sensing
elements. In the context of designing nanobiosensors, the ele-
ments of sensing, Raman spectroscopy techniques and their
application in this process, and functionalization of graphene
using peptides are delineated. To understand such devices,
background materials are discussed and a combination of
theoretical considerations and empirical observations are
reviewed on a case-by-case basis.
1.1 GRAPHENE AND GRAPHENE-BASED FIELD-
EFFECT-TRANSISTOR-LIKE STRUCTURES
Graphene is a two-dimensional ordered structure consists
of single-layer carbon atoms. The sp2-bonded carbon atoms
are arranged in a honeycomb lattice. When graphene layers
are stacked vertically to form multilayer structures with a
particular orientation between neighboring planes, a three-
dimensional structure known as graphite is formed, in which
graphene sheets are bounded by weak van der Waals forces.
It is to be noted that the name graphene is also being used to
describe few-layer graphite. Graphite can have up to 10 layers
and still be called multilayer graphene. When going from one
layer to several layers, the properties of graphene can change
significantly.
cal, and thermal properties due to to its atomic structure
and special band structure [1]. Graphene is a zero-bandgap
semiconductor. Wallace [2] first studied the band structure of
graphene theoretically and revealed its unusual semi-metallic
behavior. While the zero bandgap in intrinsic graphene makes
graphene uniquely interesting, the lack of a bandgap can be a
major engineering issue. Owing to its zero bandgap, graphene
is particularly difficult to switch from a conductive state (on)
to a nonconductive state (off), and thus difficult to be used as
a solid state switch. Bilayer graphene or graphene nanorib-
bon (GNR) structures do not suffer from this problem because
both of them can have a bandgap under the right conditions. It
is to be noted that the zero bandgap of large-area graphene is
not an issue in radio frequency (RF) applications.
Among graphene’s electrical properties, high electron
mobility [3] and ballistic transport of charge carriers [4] are of
intense interest to researchers. Similar to the carbon nanotube
(CNT), the pseudospin nature of the charge carries in gra-
phene can cause the absence of backscattering and result in
high mobility [5]. In the meantime, the near defect-free lattice
and high sound velocity can also contribute to the high cur-
rent density and current sustainability of graphene. Graphene
can sustain current densities of up to 5 × 108 A/cm2, which
is about 1 µA per atomic row of carbon atoms [6]. The high
mobility and the quantization of conductance in narrow chan-
nels can contribute to ballistic transport of charge carriers in
the submicron range [4]. Graphene technology is especially
promising because it can be easily integrated into the existing
3
4 Graphene Science Handbook

TABLE 1.1
Three Major Fabrication Methods for Single- and Few-Layer Graphene
Method Description Property of Graphene References
Mechanical Manual cleaving process from graphite or highly oriented Random sized and distributed flakes [1,7]
exfoliation pyrolytic graphene (HOPG). Easily applicable. Typically used varying from single to few layers. Not
as adhesive tape to pull graphene films off a graphite crystal. scalable.
Epitaxial growth on Epitaxial growth on silicon carbide substrate by desorption of Si Single- to few-layer graphene with size up [8–10]
SiC at 1250–1450°C. Industrially controllable but very high cost to to a wafer scale. Graphene is typically
produce SiC wafers. The number of graphene layers can be metallic due to heavy doping by charges
controlled by varying the heating time and temperature. transferred from the substrate.
Chemical vapor CVD is brought about by dissolving carbon onto metal Able to grow large area, single-layer [11–14]
deposition (CVD) substrates or by decomposition of a gaseous precursor and graphene with high uniformity.
transit directly onto metal substrates such as iridium, nickel,
and copper. Graphene films can be transferred to oxide
substrate by using disposable PMMA or PDMS films.

planar processing infrastructure, grown on various substrates
including silicon dioxide which can be processed by con-
ventional semiconductor methods. As a result of graphene’s
exceptional electronic properties, the possibility of ultrafast
electronic devices operating in up to THz frequency range is
being explored by the research community.
There are three major approaches to fabricate single- and
few-layer graphene: mechanical exfoliation, epitaxial growth
on a silicon carbide substrate, and chemical vapor deposition.
Each of the methods has its own advantages and disadvan-
tages. A detailed description and comparison for these meth-
ods are listed in Table 1.1.
Graphene has practical applications in various fields
including graphene thin film electrodes, graphene-based
nanocomposites, and GFET [15,16]. The structure of a GFET
is similar to that of a silicon FET. A typical field-effect tran-
sistor (FET) is an electronic device with three terminals. A
terminal known as a gate can create an electric field to con-
trol the conductivity between the other two of the terminals
known as the source and the drain. The free carrier density
in the channel between the source and the drain can be tuned
by the gate voltage, leading to a current change controlled
directly by the gate voltage. This change in the current func-
tions as a switch which indicates an “on” state when the cur-
collaboration with the Army Research Laboratory using
low-pressure chemical vapor deposition (LPCVD) on cop-
per foil and transferred onto a Si/SiO2 substrate. The Si/
SiO2 substrate consists of 525 µm of n++ Si wafer coated with
296 nm of SiO2. The thickness of graphene layers was later
confirmed with Raman spectroscopy as consisting of 6% sin-
gle-layer and 94% bilayer graphene. The FET structure was
fabricated on top of graphene surface with 45-nm-thick chro-
mium and 5-nm-thick gold as source and drain electrodes.
Channel length and width were both set at 2 mm for easy
application in future measurement. Voltage was applied on
degenerately doped silicon which was used as the gate ter-
minal. Conductivity between the source and the drain can be
effectively modulated by a gate voltage. When the gate volt-
age varied from −50 to –50 V, the conductance of the device
decreased, indicating a p-type semiconductor behavior under
ambient conditions.
× 10–4
3
2
Source–drain current (A)

rent value is high and an “off” state when the current in the
channel is low. The GFET as well as the CNT-based FET are 1
being considered by the semiconductor industry as possible
alternatives to conventional silicon FETs [17]. In the case of
0 Gate voltage
CNTs, all constituent atoms are at the surface and any small
–50 V
change on the surface can lead to a large change in electrical
–30 V
current, which has made possible the development of sensors –1
–10 V
with exceptional sensitivity. While offering electronic prop- 0V
erties similar to CNTs, the fact that graphene has a planar –2 10 V
geometry and its ability to be processed with current com- 30 V
50 V
plementary metal-oxide-semiconductor (CMOS) technology
–3
gives graphene a significant advantage over CNTs. –2 –1.5 –1 –0.5 0 0.5 1 1.5 2
Figure 1.1 shows the typical source–drain current (Ids) Source–drain voltage (V)
versus source–drain voltage (Vds) characteristics of GFET
sensors. Single-layer and bilayer graphene were used as FIGURE 1.1  Voltage–current characteristic of a graphene-based
the sensing substrate. Graphene structures were grown in FET structure.
Design and Applications of Graphene- and Biomolecule-Based Nanosensors and Nanodevices
1.2 DESIGN OF GRAPHENE- AND
APTAMER-BASED BIOSENSORS
1.2.1 Design of Aptamer-Based Optical
and Electrochemical Biosensors
A GFET structure can be used in combination with nucleic-
acid aptamer technology to fabricate graphene-based and
aptamer-based biosensors and devices with high selectiv-
ity and sensitivity. To design such devices, it is necessary to
consider the underlying principles and mechanisms by which
these graphene-based biosensors function.
Aptamers are short strands of featured oligonucleic acid
sequences typically 9–20 nm long containing about 30–80
oligonucleotides. Aptamers can recognize specific ligands
or molecules in analytes and bind to those target molecules.
Aptamers can detect a wide range of molecules including
ions, nucleic acids, small molecules, proteins, and even tis-
sues, cells, and organisms. Within a short period of time in
1990, three separate groups independently developed in vitro
selection and amplification technique for the isolation of spe-
cific nucleic acid sequences that are able to bind to target mol-
ecules with high affinity and selectivity [18–20]. Both RNA
and DNA aptamers are found by a process called selection
evolution of ligands by exponential enrichment (SELEX).
During the process, aptamers are selected and isolated
from vast populations of random sequences, and engineered
through repeated rounds of in vitro selection to be able to bind
to specific molecular targets. Aptamers are sometimes called
synthetic antibodies because they have similar properties in a
number of applications.
Biosensors are integrated devices capable of detecting the
existence of target molecules or ligands by using a particu-
lar recognition element and then providing semiquantitative
or quantitative analytical information. Biosensors detect the
presence of the target by monitoring the optical, electronic,
or mass changes generated from the interaction between the
recognition component and the target analyte. When aptam-
ers are used as the recognition element, it is also called an
aptasensor [21]. Aptamer-based biosensors can take advan-
tage of the high selectivity and tunable properties of aptam-
ers. Compared with antibodies, aptamers have a wide range of
advantages such as smaller size, chemical stability, ability to
bind to drugs and toxic substance, ability to be labeled with-
out affecting affinity, and low cost compared with antibodies.
On the basis of different sensing mechanisms, the two types
of biosensors most widely used are known as the optical bio-
sensor and the electrochemical biosensor. Optical biosensors
utilize fluorescent detection techniques to detect optical bio-
assays. Since aptamers have the ability to be labeled without
affecting affinity, fluorescent dyes, different fluorophores, and
quenchers can be easily functionalized at the ends of aptamers.
Fluorescent detection also has the advantage of inherent capa-
bility for real-time detection. One of the first examples of an
optical aptamer-based sensor was reported by Kleinjung et al.
for the detection of L-adenosine. They managed to immobi-
lize a biotinylated RNA aptamer on streptavidin-derivatized
5
optical fibers [22]. The approach evaluated the association and
dissociation kinetic and showed the utility of aptamers for the
submicron scale detection of specific analytes. Several other
approaches have been developed for converting aptamers into
fluorescent sensing probes. A frequently adopted method
employs aptamer-based molecular beacons. A molecular
beacon is a nucleic acid probe that undergoes spontaneous
conformational change when encountering specific target or
complementary nucleic acids and translated the conforma-
tional change into a variation in fluorescent properties. An
aptamer-based molecular beacon is a modified version of
traditional molecular beacon and is usually called an apta-
beacon [23]. It places an aptamer sequence in a hairpin struc-
ture, and functionalizes the two ends with a fluorophore and a
quencher. Theoretically, any known aptamer can be converted
into a molecular aptamer beacon by adding a small sequence
of nucleotides to its 3′-end as well as to its 5′-end [23]. For
example, a quencher can be covalently attached to the 3′-end
and a fluorophore can then be added to the 5′-end. When the
target ligand is absent, the beacon will form a stem structure
placing the fluorophore and the quencher close to each other.
In this state, there will be no fluorescence signal because light
energy is transferred to the quencher and the fluorophore is
quenched. In the presence of ligand, the aptamer will bind to
the target ligand and form a probe. The binding of target is
more stable and stronger than the stem structure and thus it
can disrupt the stem, open the aptamer, separate the quencher
from the fluorophore, and result in fluorescence signals that
may be measured quantitatively or semiquantitatively [24].
In distinction to optical biosensors, electrochemical biosen-
sors monitor the electrical signal generated during the interac-
tion between the aptamers and target analytes. Typically, the
amplitude of the electrical signal is proportional to the ana-
lyte concentration. Based on the assay format and the method
of detection, the electrochemical aptamer-based biosensors
may be divided into three major types. The first type is called
sandwich and competition-type assay, which involves the use
of an electrode-bound aptamer to bring a complex composed
of the target and some redox-active targets to the electrode. In
the second type, electrochemical impedance spectroscopy is
used to detect targets adsorbed onto an aptamer-terminated
electrode surface. The third type uses electrochemistry to
monitor binding-related conformational changes in an elec-
trode-bound aptamer.
Xiao et al. [25] reported detection in a typical beacon for-
mat based on a 3D conformational change with the throm-
bin-binding aptamer. The aptamer undergoes a structural
rearrangement that allows thrombin detection using a beacon
without a stem loop. Thrombin is a proteolytic enzyme which
facilitates blood clotting by converting fibrinogen into fibrin,
which can also be used as a tumor marker in the diagnosis
of pulmonary metastasis. The aptamer molecular beacon was
constructed by binding a methylene blue molecule to one end
of the aptamer and a thiol group to the other end. The thiol
group functions as a linker that can be attached to gold elec-
trode surfaces. Before interaction with thrombin, the aptamer
was elastic and able to interact with the electrode surface and
6 Graphene Science Handbook
transferring electrons. However, after interaction occurred,
conformational change creates a longer electron-tunneling
distance and thus decreases the signal. A similar aptamer
molecular beacon approach was used by the team for the elec-
trochemical detection of platelet-derived growth factor in the
picomolar range, and demonstrated this aptamer-based bio-
sensor directly in blood serum [26].
Compared with the “signal-off” structure in which the
electrical signal decreases as a result of binding, an improved
“signal-on” architecture was later discovered by Radi et  al.
[27] in which the binding of the target analyte resulted in an
increase in the signal. In this case, the aptamer molecular bea-
con had a ferrocene label with shorter spacers on both ends.
Detection was conducted using cyclic voltammetry, DPV, and
impedance measurements. Before thrombin is introduced to
the structure, the ferrocene label is far from the electrode sur-
face and could not provide any electron transfer to the sur-
face. When thrombin is present, the aptamer would form a
G-quadruplex and the ferrocene label would bend close to the
electrode allowing effective electron transfer as well as signal
generation. With the use of DPV, a detection limit of 0.5 nM
can be achieved with a linear range of 5–35 nM. Xiao et al.
[28] made similar efforts to modify their previous structure
and fabricate a “signal-on” electrochemical aptamer sensor.
They started with double-stranded DNA consisting of a short
DNA sequence tagged with methylene blue (MB) that can
hybridize with an aptamer and a sequence complementary to
it, which contained the antithrombin aptamer sequence. The
duplex of DNA maintained the redox label at “standing” posi-
tion with a long enough distance from the electrode surface.
When thrombin is added to the complex, the complementary
sequence would be displaced and the single-stranded DNA
with MB tagged in one end would approach the electrode sur-
face and produce the electric current.
1.2.2 Design of Aptamer-Based Biosensors
with Graphene-Based Field Effect
Transistor Structures
The merit of using aptamers in graphene-based biosensors
with FET structures lies in their small size. One critical
consideration here is the Debye length, which is the typi-
cal distance required for screening surplus charges contrib-
uted by mobile electric carriers present in a nanostructure.
Antibodies are widely used as sensing elements. However, the
size of antibodies is about 10 nm, which is much larger than
the Debye length or the electrical double layer that is about
3 nm in 10 mM ionic concentration. As a result, the recogni-
tion of target-binding process might occur outside the elec-
trical Debye length and lead to very weak potential changes
observed on the electrical contacts. Aptamers, on the other
hand, have an average of 10 nm for 30 bases, which is within
the Debye length and can enable the perturbation of the gate
potential by target analytes that interact with the aptamers.
Prior to the GFET structure being used in biomolecule
sensors, the CNT-based FET structure has been massively
researched in developing chemical and biological sensors.
So et al. fabricated a single-walled carbon nanotube (SWNT)
FET to monitor the binding processes between an aptamer
and a thrombin [29]. It is known that SWNTs behave as
p-type semiconductors in ambient atmosphere. SWNTs were
immobilized between the source and drain electrodes, and
antithrombin aptamers were attached on the SWNTs. The
reaction between an aptamer and a thrombin altered conduc-
tance between the source and the drain, thus enabling electri-
cal detection of thrombin.
However, the applications of CNTs are often plagued by
several problems. For example, it is difficult to separate semi-
conducting nanotubes from metallic nanotubes. In addition,
when only a few CNTs are used, in many cases it is challenging
to manipulate them for device fabrication because they are too
small compared with large-sized biomolecules. On the con-
trary, graphene, with similar properties as CNT, but comes in
a flat structure, is an ideal substrate for fabricating biosensors.
Xu et al. reported a graphene-based and an aptamer-based
biosensor with cocaine as the detection target [30]. One end
of the aptamer is attached with MB which functions as an
electron donor. 1-Pyrenebutanoic acid, succinimidyl ester
(merchandise name: P130) is used as linker molecule which
contains the pyrene group that can noncovalently bind to
the graphene surface. Owing to the overlapping π-bonds
between the aromatic side chains, the highly aromatic pyrene
group can interact strongly with the basal plane of graphene
via π-stacking. As a result of the small size of the cocaine
aptamer which is about 2-nm in length with 30 bases, the
whole structure is within the Debye length. When the target
cocaine molecule is present, the aptamer will undergo a con-
formation change and lead to a reduced distance between the
MB and the graphene surface. When the MB bends within
the proximity of the graphene surface, it can provide elec-
trons and cause a current shift in the I–V characteristics of the
graphene–FET.
A similar structure had also been introduced by Huang
et al. [31] using large-sized chemical vapor deposition (CVD)-
grown graphene films. The graphene-based structure was
configured for real-time biomolecular sensing. As glucose
or glutamate molecules are oxidized by the specific redox
enzyme (glucose oxidase or glutamic dehydrogenase) which
functions as a mediator to attach to the graphene surface,
conductance of the graphene transistor will change and target
molecules can be detected. These results from current gra-
phene-based and aptamer-based biosensors show exceptional
electronic response and the ability to support cell adhesion
and growth, which proves the promising potential of graphene
in making nanoscale biomolecule sensors as well as applica-
tions in detecting dynamic bimolecular analytes.
1.3 SENSING ELEMENTS ON GRAPHENE-
BASED SUBSTRATES
The bond between molecular sensing elements and the sub-
strate plays a very significant role in the sensitivity of bio-
sensors designed on graphene-based substrates. The most
important factor to be considered during binding is that the
Design and Applications of Graphene- and Biomolecule-Based Nanosensors and Nanodevices
transport properties of the carbon-based substrate should
be unaffected. An effective method would be noncovalent
functionalization, as opposed to covalent functionalization
[32], which does not disrupt the substrate as no atomic scale
defects are created. These defects significantly affect the per-
formance of graphene-based substrates and hence should be
reduced [33].
Graphene’s excellent electrochemical properties open the
way for varied uses in the sensing of biomolecules [34]. One
of the earliest of such graphene-based sensors was for glu-
cose wherein the graphene is functionalized by polyethyleni-
mine and nanocomposites of these were used to modify the
electrode, producing excellent range of sensitivity (from 2 to
14 mM of glucose), and good reproducibility [35]. In addi-
tion, graphene exhibits good catalytic activity toward nico-
tinamide adenine dinucleotide (NADH) oxidation and hence
is a useful sensor for detecting ethanol [36]. The antidiuretic
acid-graphene-glassy carbon (ADH–graphene–GC) setup has
been shown to have a good range of detection and low limit of
detection. These factors have been attributed to the inherent
biocompatibility of graphene [37].
Other examples of graphene-based biosensors have been
developed by antibody modification [38] and by making use
of aptamers [39]. In the first case, the linker, 1-pyrenebutanoic
acid, succinimidyl ester is used which is then incubated in
suitable antibody solution and used for the detection of E. coli
bacteria, with excellent sensitivity and low detection limits.
In the case of aptamer modification, graphene oxide (GO)
and reduced graphene oxide (RGO) are used as substrates
to detect Staphylococcus aureus and it has been shown that
RGO has lower levels of noise, but both substrates have good
sensitivity with very short detection times and limits [39].
1.3.1 Raman Spectroscopy and Its
Application in Nanosensing
Discovered by Chandrashekara Venkata Raman in 1928,
Raman spectroscopy is the phenomenon in which light is
scattered inelastically. In this phenomenon, the frequency of
radiation of the scattered molecules is different from that of
the incident beam causing a shift of wavelength. This type
of  inelastic scattering is known as the Raman effect. The
change in wavelength is dependent on the chemical structure
of the molecules [40]. The molecular vibrations give informa-
tion about the electronic environment, structure, bonding of the
molecule and symmetry, and this information is obtained from
the scattered light. Hence, a qualitative and quantitative repre-
sentation of the individual compounds can be achieved [40].
Being a spectroscopic technique, Raman spectroscopy is
used in studying biological structures such as proteins, chro-
mosomes, and DNA. It provides useful information on the
chemical composition, the chemicals surrounding the particu-
lar subunits, the characteristics of the material being studied,
and the secondary structure [41].
A non-ionizing laser is used as the excitation source in a
Raman spectroscopy setup. The photons can be absorbed,
pass through the material without any interaction or without
7
getting scattered. Absorption occurs primarily when the
energy difference between the ground state and the excited
state of the molecule matches the incident photon’s energy,
promoting the photon to the excited state. Fluorescence
occurs when the excited electron emits the energy and relaxes
to a lower energy state. Scattering occurs when a phonon is
emitted or absorbed during the process and the absorbed pho-
ton is reemitted with different energies. In the case of Raman
scattering, the difference in energy between the absorbed
and reemitted photons corresponds to the energy required to
excite a molecule to a higher vibrational mode.
The two types of scattering that occurs with visible light
are Rayleigh and Raman scattering. Rayleigh scattering is
more intense and occurs when there is distortion of electron
clouds. This is an elastic process because no exchange of
energy occurs. Energy transfer occurs when the molecule’s
vibrational state is changed from the molecule to photon or
from the photon to the molecule. Owing to the occurrence of
energy transfer, Raman scattering is a weak process because
only one in about 106 –108 scattered photons is involved [42].
Raman scattering is classified as Stokes or anti-Stokes
based on the direction in which the energy transfer occurs,
either from the molecule to the photon or from the photon to
the molecule. In the case of Stokes scattering, the incident
photon transfers its energy to the molecule (phonon absorp-
tion) which is in a lower energy state, thus exciting it to the
higher vibrational state. In anti-Stokes scattering, the mol-
ecule releases energy (phonon emission) on interaction with
the photon which is possibly due to prior excitation of the
molecule before interaction with the incident photon, return-
ing to a lower energy state. Hence, the energy of the photons
scattered during an anti-Stokes scattering is higher than that
of Stokes scattering [42]. The most dominant Raman scatter-
ing process is the Stokes scattering since the molecules are all
in the ground state at room temperature. The Raman shift is
the difference between the incident photons and the scattered
photons and is expressed in wave number in units of cm−1.
The setup of a Raman spectrometer includes an incident
laser which irradiates the sample of interest (in many cases)
through an optical microscope, whereas the photons that are
scattered are collected in a spectrometer followed by appropri-
ate filtration. Although there are different kinds of lasers that
can be employed to excite the sample such as the Ti: sapphire
laser (650–1100 nm) and the HeNe laser (533 nm), the ones
typically used for biological samples are those with longer
wavelengths in order to avoid a fluorescence background [42].
There are also disadvantages associated with using the
Raman spectroscopy technique for biological samples. The
scattering cross-section of the sample is very small so this calls
for high concentrations of the sample, which is difficult to pre-
pare in large amounts. Added to this is the fact that a laser of
very high power (300 mW) would be needed for excitation [41].
1.3.2 Raman Spectroscopic Studies of Graphene
Raman spectroscopic measurements on graphene show the
characteristic presence of two peaks at 1580 and 2700 cm−1,
8 Graphene Science Handbook
known as the G band and the G′ band, respectively. The G
band or the graphite band corresponds to the in-plane carbon–
carbon stretching which is of the lowest frequency of Raman-
allowed signal from one single photon [43,44]. The G′ band
is a two-photon phenomenon of highest frequency wherein
the momentum (q) is not equal to zero and a single photon
gives rise to the formation of two phonons within the crystal
­(second-order interaction). The very intense G band produced
in graphene is highly unique and much higher in intensity than
that of graphite. When observing the Raman spectra of a crys-
talline sample with a size smaller than that of the wavelength
of light, an additional peak was observed at 1350 cm−1 [43,44].
This has been attributed to the breathing of the carbon hexa-
gons at the border of the crystallite areas that achieve Raman
activity due to loss of translational symmetry. Since this peak
occurs due to defects in an otherwise perfect infinite graphene
sheet, it is called as the D-band (D for defect).
By changing the energy of the laser used for excitation, the
effects of coupling due to the interlayer can be observed [45].
Different substrates and gates that have been developed on
graphene substrates have been studied in great depth, based
on parameters such as charge transfer effects, strain, and dis-
order. Owing to these studies that reveal accurate character-
ization of graphene, Raman spectroscopy is now being used
to study the doping concentration present in graphene-based
electronic devices.
Graphene has unique electronic dispersion characteristics
with no energy gap between the valence band and conduc-
tion band, and having linear relationship of dispersion near
the Fermi level, the G-band phonons produced during interac-
tion with the excitation source has the capability to promote
electrons from the ground state (valence band) to the excited
state (conduction band) [46]. Owing to these characteristics,
the sensitivity of the electronic structure is highly increased
and depends on the electron–hole coupling [47].
Raman spectroscopy is a very powerful tool for the deter-
mination of defects in graphene. These defects present highly
valuable Raman peaks that lead to an effective character-
ization of the graphene structure. In an otherwise symmet-
ric graphene structure, it is the defects that contribute to the
transport properties and to the relaxation of the electrons that
have been excited by incident photons. Raman spectroscopy is
very sensitive to disorder detection, which depends on crystal
symmetry [48,49].
On exciting graphene with argon ions and thus producing
point defects, two specific peaks are observed at 1345 and
1646 cm−1, which are referred to as D and D′ (D for disor-
der). These peaks are dispersive meaning that they change in
their value depending on the wavelength of the incident laser
source. The presence of disorder peaks is attributed to the
double resonance model wherein, apart from the incoming or
the outgoing resonance from the incident or the scattered pho-
tons which matches the energy level of an allowed electronic
transition, the initial incident excitation itself undergoes a real
transition. This tends to enhance the Raman cross-­section.
These disorder peaks are a result of loss of momentum
conservation which occurs owing to excitation of photons at
the interior points of the Brillouin zone. The Brillouin zone is
defined as the primitive cell within a reciprocal space which
is the Fourier transform representation of the original lat-
tice. This event takes place instead of excitation of only those
photons in the center of the Brillouin zone, which are of first
order, Raman-allowed, and have a momentum equal to zero
due to symmetry considerations. Hence, introducing disorder
affects translational symmetry which may lead to other dis-
tortions, break other symmetry conditions and excite photons
that are not in the Brillouin center. In addition, it has been
shown that the ratio of the intensities between the D band
(disorder-induced band) and the G band (first-order graphene
band) is inversely proportional to the grain size of the sample
[43,44]: Id/Ig = A/La, where A is the excitation frequency, a
constant.
There are many different properties of G band peaks
observed in graphene and some of the common ones are:
G1, which occurs at 1585 cm−1 and represents the signature
of sp2 carbons; G2, which represents the hydrostatic pressure
exerted on graphene and is identified by a frequency shift; G3,
which represents stretching of graphene on a uniaxial plane
and usually observed as G3+ and G3− which refer to stretching
of atoms along the direction of stretching and in the direc-
tion perpendicular to stretching. These can be identified by
a redshift in both the frequencies, caused by increasing the
stretching. G4, which represents doping of graphene and can
be identified by blueshift or redshift, depending on the level
of doping; G5, which is observed by a redshift during tem-
perature change; G6, which is observed as a relative change
in intensity of G+ and G− when the layer of graphene is inho-
mogenously strained; G7, which is observed when the width
of the spectral line from the laser is changed; and G8, which
is observed when the graphene sheets are bent.
The G′ band that is observed at around 2650 cm−1 also
has a number of characteristic properties indicating differ-
ent parameters. G′1 is observed as a single or a multipeak,
characteristic of sp2 carbons, in the range of 2500–2800 cm−1.
The G′2 and G′3 are indicative of the number of layers of the
graphene sample, owing to sensitive dispersive properties. G′4
represents the stacking of graphene and can be used to easily
differentiate between stacking order by the number of peaks
(single or double) obtained in the Raman spectrum. With the
help of G′5, the wave vectors of the electrons and phonons
within the Brillouin zone can be probed.
The D band also has multiple properties signifying differ-
ent aspects of disorders in graphene. D1 is the Raman signa-
ture of disorder in graphene in the range of 1250–1400 cm−1.
D2 refers to the D band frequency which is dispersive and
is mostly seen at around 1350 cm−1 for a laser source with
energy 2.41 eV. D3 provides information about the band
intensity using which the disorder can be quantified, whereas
D5 gives an idea about the graphene edge type. No scattering
takes place when the edge is zigzag, so this can be used to dif-
ferentiate zigzag edges from armchair edges, where scattering
takes place [50].
Design and Applications of Graphene- and Biomolecule-Based Nanosensors and Nanodevices 9

1.3.3 Raman Spectroscopy of Proteins on
Graphene and Graphene-Binding Peptides
Raman spectroscopy of proteins has been researched for
many years now and it has been shown to provide conclu-
sive information about the secondary structure [51], specific
side-chain interactions along with reasonable data for band
assignment [52]. The structure, intensity, and the band posi-
tions of certain measured and spectral correlation is per-
formed for unknown samples. Hence, Raman spectroscopy
for biological samples depends largely on the assignment of
spectral features. For example, spectral information obtained
for smaller, model compounds such as amino acids or short
peptides can be applied to a large molecule of the same kind,
that is, polypeptides.
Phage display has been used to determine the sequences
of a few peptide sequences that bind to graphene. Different
variations of graphene-based substrates and peptides are used.
Each of these systems has their own characteristics, which are
described in detail in Table 1.2.
1.4 SUMMARY
Graphene with its exceptional electronic properties, 2D
structure, and the ability to support DNA immobilization
has proved to be an excellent platform for fast, selective, and
sensitive detection of biomolecules. Raman spectroscopy
is a very powerful tool for the identification and character-
ization of graphene and DNA aptamers in nanostructures.
Aptamer-based biomolecular devices relying on the unique
physical properties of aptamers are largely new to the sensing
arena. These devices include a number of sensing schematics
based on the binding-induced folding of aptamers and exhib-
iting constant detection limits as well as great selectivity to

TABLE 1.2
Electronic Systems That Use Peptides for Binding to Graphene
Type of Graphene
Substrate Peptide Sequence/Type Description, Properties, and Uses References
Potato-shaped graphene EPLQLKM Peptide binds to the edges due to π–π interactions, which define the [53–55]
mechanical and electronic properties. Graphene is terminated by
positively charged hydrogen and the peptide sequence EPLQLKM
reacts with this through the glutamate residue, E.
Potato-shaped graphene HSSYWYAFNNKT This peptide interacts with graphene plane by π–π stacking of the [54,55]
aromatic rings present in the residue, H-Y-W-Y-F
Graphene oxide GGGRKRIHIGPGPAFYTT and To determine protein–peptide interactions, 1-pyrenebutyric acid, [56–59]
GGGNSWGCAFRQVC a pyrene moiety, is attached to the N-terminus of peptides.
Fluorophores based on pyrenes are a good choice for optical
contrast agents in molecular beacons as they reemit light upon
excitation and the number of times a specific event occurs per
photon adsorbed is very high. Owing to the π bonds present,
reaction with CNTs and graphene is noncovalent. The fluorescence
of pyrene is quenched due to the proximity of graphene oxide layer
to pyrene but when the peptide binds to the protein, owing to the
adhesive properties of pyrene, desorption and dequenching of
pyrene occurs due to competition between pyrene and target
protein for the graphene oxide layer, which helps in detecting the
target protein.
Graphene Self-assembling peptide sequence: A high level of symmetric formation was observed when the [60]
IMVTESSDYSSY (wild type) capability of the peptide to form highly ordered structures over
graphene were determined using AFM. This is attributed to the
hexagonal structure of graphene. Moreover, there is a transition
from the amorphous state to an orderly state during the formation
process of a peptide over graphene. Different domains of a peptide
contribute to different characteristics of the peptides. Research has
shown that the aromatic domain of a peptide corresponds to the
binding ability of the peptides while the hydrophilic and the
hydrophobic domains correspond to the diffusion and the
self-assembly of the peptide.
Graphene GAMHLPWHMGTL α-Helical structure originally in powder form but on binding with [61]
graphene, the form is very different from its original structure.
Tryptophan has been shown to be an essential amino acid required
for binding to graphene and also incubation of peptide has been
shown to have no effect on the binding, as confirmed by Raman
spectra.
10
work directly in blood serum and other complex structures.
Combined with aptamer technology, graphene- and aptamer-
based sensor is a promising candidate for the development of
an integrated and multiplexed biomolecular sensor.
ACKNOWLEDGMENT
Dr. Barbara Nichols and Dr. Eugene Zakar of US Army
Research Laboratory, Washington, DC are acknowledged
for providing graphene samples used in the fabrication of the
FET devices discussed in the chapter. Support under an ARO
MURI W911NF-11-1-0024 is also acknowledged.
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 2 Graphene-Based DNA Sensors
Hatef Sadeghi

CONTENTS
Abstract........................................................................................................................................................................................ 13
2.1 Introduction........................................................................................................................................................................ 13
2.2 DNA and Its Properties...................................................................................................................................................... 14
2.2.1 DNA Structure........................................................................................................................................................ 14
2.2.2 DNA Electrical Properties...................................................................................................................................... 14
2.3 DNA Sensing Methods....................................................................................................................................................... 15
2.4 Graphene-Based Sensors.................................................................................................................................................... 15
2.5 Graphene and Its Configurations........................................................................................................................................ 16
2.6 Graphene Properties........................................................................................................................................................... 17
2.7 Graphene for DNA Sensing................................................................................................................................................ 17
2.7.1 Carbon Nanotube.................................................................................................................................................... 18
2.7.2 Graphene Sheet....................................................................................................................................................... 18
2.7.3 Graphene Oxide...................................................................................................................................................... 18
2.7.4 Graphene Nanoprobe, Nanowall, and Nanofiber.................................................................................................... 19
2.8 Outlook............................................................................................................................................................................... 19
2.8.1 Edge and Surface Effects........................................................................................................................................ 20
2.8.2 Doping Effects........................................................................................................................................................ 20
2.8.3 Defect Effect........................................................................................................................................................... 20
2.8.4 Functionalization Effect......................................................................................................................................... 20
2.8.5 Novel Hybrid Carbon Nanomaterial....................................................................................................................... 20
2.8.6 Environmental Issues.............................................................................................................................................. 21
2.9 Conclusion.......................................................................................................................................................................... 21
References.................................................................................................................................................................................... 21

ABSTRACT DNA sensing and sequencing, challenges still remain. In this

Advances in miniaturization of electronic devices down
to nano/molecular scales are starting to attract attention.
Deoxyribonucleic acid (DNA) nanosensors are new devices
that offer an alternative to very expensive and time-consum-
ing conventional DNA detection methods. Electrochemical
DNA sensing works by recording changes in the electrical
properties of the platform, such as variation of its current or
conductance, upon adsorption of the target DNA. The discov-
ery of the many exotic properties of graphene, a new single
planar sheet of sp2-bonded carbon atoms in honeycomb lat-
tice, such as high surface area, low electrical and frequency
noise, and high conductivity and stability, potentially allow
the cost-effective design of sequence-selective label-free DNA
electrochemical sensors. Recent theoretical and experimen-
tal works have demonstrated the efficacy of the method. For
instance, graphene nanopores and hybrid and functionalized
carbon-based materials have been shown to be very promis-
ing not only toward DNA bases sensing but also in sequenc-
ing of the DNA strand. Although there is no doubt that the
carbon-based nanomaterials show excellent sensitivity for
chapter, recent advances in graphene-based DNA sensors will
be reviewed and the main challenges of using these methods
will be addressed.
2.1 INTRODUCTION
Opening new doors in paternity tests, genetic and cancer
research, forensic analyses, sex and ancestry determina-
tion, transcriptome of specific genes, and disease diagnostic
needs a careful look at deoxyribonucleic acid (DNA) diag-
nosis. Reading the sequence of DNA could lead to person-
alized medicine for improving human health [1,2]. It could
provide information about the molecular interactions and
kinetics hidden in measurements [3]. Therefore, the develop-
ment of cost-effective and sequence-selective [4] rapid and
highly sensitive [5,6] DNA sensors is needed. Conventional
technologies based on fluorescence detection [2] are already
in a working state but physical approaches, especially electri-
cal detection of chemical and biological species using novel
nano and molecular structure-based devices, have recently

13
14
attracted substantial attention [7] due to their rapid and inex-
pensive nature as the long timescales, error, and cost asso-
ciated with sample preparation and amplification could be
avoided. A variety of different technologies for inexpensive
and rapid single-molecule DNA sequencing was reviewed by
Xu et al. [2]. However, there is still a need for new techniques
for improved sensitivity and fast dynamics [3,8].
The IUPAC (International Union of Pure and Applied
Chemistry) defines “electro-chemical biosensor” as “a self-
contained integrated device, which is capable of providing
specific quantitative or semi-quantitative analytical informa-
tion using a biological recognition element which is retained
in direct spatial contact with an electrochemical transduc-
tion element” [9]. Biosensing involves the monitoring of sub-
stances that are usually apparent within biological systems
[10]. Biosensors consist of two elements: a receptor that is a
material with a specific interaction with biomolecule and a
transducer that converts chemical information into a measur-
able signal [11].
Single-molecule DNA sequencing is a method used to
determine the base sequences of individual DNA elements
[2] which is implemented in three steps: (a) immobilization
of single-stranded oligonucleotide probes onto a substrate, (b)
hybridization, and (c) reading. DNA sensors, commonly, rely
on the immobilization of a DNA probe onto the transducer
surface, the subsequent hybridization with the DNA target
triggering a signal either directly or indirectly [6].
2.2  DNA AND ITS PROPERTIES
In the last decades, there has been an increasing interest in the
study of molecular electronic devices, which exhibits inter-
esting electronic behaviors for developing new technological
applications. The birth of molecular electronics can be traced
back to 1974 when Aviram et al. proposed a rectifier based on
a single organic molecule. Interconnecting single molecules
in nanoelectronic devices is challenging; however, after the
invention of the scanning tunneling microscope, fabrication
of nano and molecular structure became possible. However,
structural changes in the molecules, which affect the response
of devices could be induced by contacts between molecules
and electrodes [12].
DNA is an important biological polymer carrying genetic
information, and its unique features cannot be found in other
polymers. DNA has a self-assembling ability by forming
hydrogen-bonded base pairs of adenine and thymine (A–T)
and of guanine and cytosine (G–C), which makes it error
free. Due to its very small intervals (0.34–0.36 nm), it could
A C
FIGURE 2.1  Four DNA bases: (A) adenine, (T) thymine, (G) guanine, and (C) cytosine.
Graphene Science Handbook
be used as a template for aligning molecules without any fine
processing. In some studies, DNA is considered a one-dimen-
sional (1D) system conductor whereas other studies have
doubted it, as we will discuss later. DNA as a conductor could
be applied for use in molecular wires since the frontier orbits
of the bases, the highest occupied molecular orbital (HOMO)
and the lowest unoccupied molecular orbital (LUMO), are
p-electrons existing perpendicular to the molecular plane [8].
Recently, DNA field-effect transistor (DNA-FET) using car-
bon nanotube (CNT) as source and drain have been fabricated
where its channel was 50 nm DNA [13]. However, a typical
method to measure electronic properties of the DNA is using
two gold nanoparticles to connect it to metal electrodes [14].
2.2.1  DNA Structure
DNA sequence consists of four bases called (A) adenine, (T)
thymine, (G) guanine, and (C) cytosine, as shown in Figure
2.1. Based on these four bases, several DNA structures could
be formed, such as Z, A, B, and C″, where 12, 11, 10, and 9
base pairs form a pitch, respectively [8].
Most DNA molecules consist of two polymer elements
(double-stranded DNA structure [dsDNA]) bound noncova-
lently together in a helical fashion. The two strands can be
melted to form two single-stranded DNA (ssDNA) molecules
by high temperature, low salt, and high pH [15].
2.2.2  DNA Electrical Properties
Oxygen could modify the conductance of the poly (dG)–poly
(dC) DNA molecules, which is a characteristic behavior of a
p-type semiconductor. In addition, the poly (dA)–poly (dT)
DNA molecules behave as an n-type semiconductor [16]. The
transport properties of DNA molecules are still an interest-
ing issue reported by a variety of experimental studies [17,18].
Since the observation of electric conduction in DNA by Eley
and Spivery [19] in 1962, different observations have been
reported. Superconducting [20], conducting [21–25], semi-
conducting [23–34], or insulating [35–42] behavior has been
observed in DNA. These reports show that depending on the
type and composition of the considered systems, the DNA
molecules show different behavior [16,43]. Base sequence,
buffer, sample shape, measurement environment, and method
are the factors that modify the electronic behavior of a DNA
system [8]. Quantum fluctuations in the transport properties
of DNA could be observed due to its nonlinear behavior [43].
The conductivity is associated with the π-electron overlap
of the paired bases, A–T and G–C, arranged one on top of
Hydrogen
Nitrogen
Oxygen
Carbon
G T
Graphene-Based DNA Sensors
the other with an interplane spacing of 0.34 nm, similar to
the one found in graphite [44]. An important aspect of DNA
electrical conductivity is the electron (hole) transfer rate that
involves quantum mechanical tunneling for short distances
where photo-excited carrier moved from a G–C pair to the
next one by coherent tunneling through the A–T pair and ther-
mally activated hopping in the case of large spacing between
G–C pairs. The short-distance transport mechanism could be
explained by Marcus theory that transfer efficiency is propor-
tional to e−βd, where d is the length of a molecule, and β is
a value proportional to the overlap integral of the acceptor
molecule and the donor molecule [8,45].
2.3  DNA SENSING METHODS
Active nano/bio-electronic devices such as zero-dimensional
(0D) nanoparticles, 1D nanowires, and two-dimensional (2D)
networks have shown excellent detection ability for both
molecular (e.g., DNA) and nanoscale (e.g., viruses) biocom-
ponents [46].
There are several methods for sequencing DNA (Table 2.1)
such as the chain-termination methods (Sanger method [47]),
amplification and clonal selection, high-throughput sequenc-
ing, single-molecule sequencing, etc. [48]. Nowadays, Sanger
sequencing is a reliable, highly accurate method for DNA
sequencing. The key element is the use of dideoxynucleo-
tide triphosphates as DNA chain terminators and fluorescent
dye detection. However, it is too slow (8 days run to achieve
99.995% accuracy) and costly for reading personal genetic
codes. It costs an estimated US$ 10–25 million to sequence
a single human genome and $20,000–$50,000 to sequence a
microbial genome [2].
Single-molecule sequencing can be classified into fluo-
rescence sequencing, direct sequencing by using transmis-
sion electron microscopy (TEM), and electronic sequencing
by using nanopore, scanning tunneling microscopy (STM),
and nano-knife-edge probes. Xu et  al. [2] in their excellent
paper have reviewed all these methods. They conclude that
the success of single-molecule sequencing relies heavily not
only on detection techniques but also on the preparation of
DNA samples.
TABLE 2.1
Comparison between the Sanger Method and
Single-Molecule Sequencing
Sequencing Method Remarks References
Chain-termination Reliable, highly accurate, but too [47]
methods (Sanger slow and costly
method)
Single-molecule Fluorescence sequencing [2]
sequencing Direct sequencing by using TEM
Electronic sequencing by using
nanopore, STM, and nano-knife-
edge probes
15
In the last decades, success in miniaturization of the
electronic devices have turned the attention toward DNA
electrochemical nanosensors that are an attractive alterna-
tive for label-free, sensitive, and rapid measurement [4]. Not
only they can provide chemically stable nucleic acid recog-
nition layers without defects, after hybridization and reading
step, the initial sensing surface could also be chemically or
electrochemically renewed and reused. The transduction of
DNA hybridization could require a label in indirect trans-
duction methods or rely on the label-free techniques in the
direct detection methodologies [6]. A typical electrochemi-
cal DNA sensor involves a solid electrode such as mercury,
gold, and carbon electrodes [49], which could generate cor-
responding electrochemical signals based on the interactive
bind between probe and hybridized double-stranded DNA or
covalently tagged with the DNA elements [50]. Compared to
conventional methods, electrical transduction provides low
cost and low power requirement, portability, independence of
sample turbidity, ease of miniaturization, and compatibility
with manufacturing nanotechnologies. They could be imple-
mented based on the voltammetric detection, the impedimet-
ric detection, as well as the field-effect modulation based on
FETs where the change in the surface charge consecutive to
hybridization is detected, which opens the way to real-time
detection [6,51].
The growing demand for biological and biomedical
research led to developing low-cost and new, faster ways to
sequence DNA that enables large-scale sequencing of com-
plex genomes [2]. However, the electrochemistry of DNA is an
issue [49]; for instance, the chemical modifications based on
TEM and fluorescence not only change the structures of DNA
nucleotides but also add extra steps that slow the sequencing
procedure.
Nano and molecular electronic approaches may be a better
path since they offer rapid, low decreased energy consump-
tion, and highly sensitive measurement in comparison with
the current methods, which are time consuming (normally
taking hours to days) [7,52]. Recently, carbon-based electri-
cal devices have been widely developed for high-performance
label-free chemical/biological sensors due to their particular
structure, excellent electrical properties, and high chemical
stability [6,7,49].
2.4  GRAPHENE-BASED SENSORS
After the isolation of graphene in 2004 [53], its extraordi-
nary properties in many fields such as electronics, mechanics,
physics, and chemistry have been attracting the attention of
researchers all over the world. Many research groups are now
working on this material. The electrochemical properties of
graphene are also very interesting. Besides the high poten-
tial of graphene to develop the next generation of biobatter-
ies, bioprocess analysis tools, genetic devices, ultrathin solar
cells, smart circuits, enzymatic biofuel cells, supercapacitor,
and molecular transistors, it shows excellent characteristic as
bioelectronic devices and sensing applications such as sens-
ing of gaseous species, metal ions, and various biomolecules,
16 Graphene Science Handbook

Graphene-based pH sensors have also been experimentally

TABLE 2.2
Graphene-Based Sensors
Sensing Material References
Glucose [10,51,55–59]
pH [51,60,61]
H2O2 [5,62–66]
Enzymes [67]
NADH [63,68–70]
Dopamine [63]
H2 [71,72]
2,4,6-Trinitrotoluene (TNT) [73]
Paracetamol [74]
Lectins [75]
NO2, NH3, DNT, NO, H2O, alcohol, H2S, Pb2+, Cd2+ [9,51]
including DNA, glucose, and proteins [10,46,49,52] as sum-
marized in Table 2.2. It has a wide electrochemical potential
window as it has high surface area, low charge resistance, and
well-defined redox peaks, which lead to increased sensitiv-
ity [54]. Here, we will show some graphene sensing applica-
tions, and later discuss its extraordinary properties for sensing
proposes.
The performance of graphene for biosensor applications
has been reviewed by different authors. All agree that it
shows the superior performance for future biosensing appli-
cations [5,9,10,51,74,76]. Shao et al. [63] showed that graphene
exhibits excellent performance in the direct electrochemistry
of enzyme, electrochemical detection of small biomolecules,
and electroanalysis, specifically superior performance for
sensing heavy metal ions. Graphene exhibited good sensitiv-
ity and selectivity toward the detection of glucose, cholesterol,
Hb, small biomolecules, DNA, heavy metal ions, and poison-
ous gaseous molecules [5].
Since CNTs and graphene demonstrate faster response
times and higher sensitivity than traditional electrodes at
extremely low working potentials, some works were car-
ried out to use this material for glucose sensing [55]. Shan
et al. [56] experimentally showed that graphene could sense
glucose. Chen et  al. [57] fabricated the glucose sensor by
using gold nanoparticles on the bilayer graphene. Baby et al.
[58] showed that platinum–gold nanoparticle on graphene
nanosheet could sense glucose too. In addition, graphene-
based FET sensors [51,55] as well as graphene modified elec-
trodes [10] and reduced graphene oxide (rGO)/nafion hybrids
[59] were applied to sense it.
studied [60]. Ohno et  al. [61] showed that nonfunctionalized
single-layer graphene FET could detect pH and the channel con-
ductance increased linearly by pH. In another work, epitaxially
grown single-, double-, and triple-layer graphene sheets were
used in solution-gate FETs to sense pH variation [51].
A new electrocatalyst MnO2/graphene oxide (GO) hybrid
nanostructure, as well as nonfunctionalized graphene, was
successfully synthesized for the detection of H2O2 [62–65].
Nitrogen-doped graphene exhibited excellent electrocata-
lytic activity for the reduction of H2O2 [5] and fast electron
transfer kinetics of glucose oxidase, and high sensitivity and
selectivity for glucose biosensing [66]. The recent develop-
ments in enzyme-based biosensors have been reviewed by
Ispas et al. [67].
Reduced β-nicotinamide adenine dinucleotide (NADH),
which has received considerable interest in developing
amperometric biosensors, biofuel cells, and bioelectron-
ics, could be sensed by graphene-based sensors [63,68–70].
Dopamine that plays a significant role in the central nervous,
renal, hormonal, and cardiovascular systems could also be
detected by this material [63]. Graphene also has been used
for NO2, NH3, DNT, NO, H2O, alcohol, H2S, Pb2+, and Cd2+,
as reviewed by He et al. and Puerma et al. [9,51]. In addition,
H2 [71,72], 2,4,6-trinitrotoluene (TNT) [73], paracetamol [74],
and lectins [75] could be sensed by graphene.
2.5  GRAPHENE AND ITS CONFIGURATIONS
Graphene is a one-atom-thick planar sheet of sp2-bonded
carbon atoms in a honeycomb crystal lattice [54], which was
isolated in 2004 by Novoselov et al. [53]. For this isolation,
the 2010 Nobel Prize in Physics was awarded to Andre Geim
and Konstantin Novoselov [77]. As shown in Figure 2.2,
graphene could be formed in different structures. It can be
wrapped up into 0D fullerenes, rolled into 1D nanotube, or
stacked to produce few-layer (2–10) or multilayer graphene,
which is called 3D graphite. Ideally, for graphene to preserve
its distinct properties, its use should be narrowed to single-
or few-layer morphology. The number of layers needed for
graphene’s properties to fully match those of bulk graphite is
over 100 [54]. Monolayer graphene could be in a 2D form like
a sheet. It could be cut as zigzag or armchair edge nanorib-
bon. Two-layer graphene could have two configurations AA
or AB, of which the latter is more stable [78–80]. One of the
layers in bilayer graphene could be rotated in order to form
twisted bilayer graphene. Trilayer graphene has two stable

FIGURE 2.2  (a) 0D fullerenes, (b) 1D nanotube, (c) 2D graphene, and (d) 3D graphite.
Graphene-Based DNA Sensors
configurations named ABA and ABC. In addition, this clean
configuration could be oxidized or doped with some impuri-
ties such as oxygen, nitrogen, etc. to achieve new electrical,
optical, and chemical properties [81,82]. Nanopore, which is
a small hole in a sheet, is another configuration, which shows
sensing properties in other materials. Clean graphene nano-
pore has also been recently studied, and it shows good sensing
properties [83].
2.6  GRAPHENE PROPERTIES
Graphene shows very interesting electrical, chemical, and
mechanical properties, promising for next-generation elec-
tronic devices used in quantum electrical devices, channel
materials for FETs, transparent electrodes, nanocomposites,
electromechanical resonators, sensors, active material for
energy storage, etc. due to its remarkable electronic, optical,
mechanical, thermal, and electrochemical properties. It is the
hardest material in the world, even harder than diamond [54].
As a result of its ultrahigh individual molecule sensitivity and
low-frequency noise, graphene is an exceptionally low electri-
cal noise material that is extraordinarily wonderful for sensor
applications [51,84]. In addition, it offers high flexibility, large
surface area, and facile chemical functionalization instead of
other sensing platforms. Based on its 2D one atomic thickness
nature, all atoms could potentially interact with the target,
promising ultimate sensitivity [51].
Graphene, which has drawn attention for its massless Dirac
Fermions, has an extraordinary mobility (~27,000 cm2 V−1 s−1
at room temperature and ~200,000 cm2 V−1 s−1 for suspended
graphene at electron densities of ~2 × 1011 cm−2 [85,86]: the
latter is 200 times higher than in silicon [87]), which remains
high even at high concentrations in both electrically and
chemically doped devices. However, the electronic properties
of graphene are highly sensitive to change in the Coulomb
potential that could be modified by charged inorganic impuri-
ties or the dielectric environment [88].
The electrical conductivity of graphene has been calcu-
lated to be ~64 mS cm−1, which is approximately 60 times
more than that of single-walled CNTs, which remains stable
over a vast range of temperatures ranging as low as liquid-
helium temperatures [10,89]. Additionally, graphene con-
tains an amazing current-handling capability that can carry a
supercurrent up to ~108 A cm−2 [90], which is 10 times higher
than the maximum allowable current density of copper [91],
a very high thermal conductivity (~3080−5300 W m−1 K−1
[92]), high mechanical strength (200 times greater than steel)
[9], and a long mean free path (~1 μm at room temperature
[93]) with Fermi velocity (as high as vF = 106 m s−1 even at
room temperature) that means graphene charge carriers can
travel thousands of interatomic distances without scattering
and a linear conductivity extending beyond room temperature
[94,95]. For these combined reasons, graphene has become an
attractive material for electronic device applications [96,97].
Moreover, ballistic transport phenomena at room temperature
[98,99], anomalous quantum Hall effect (half-integer quan-
tum Hall effect) [100–102], and tunable bandgap (in bilayer
17
graphene [87]) or band overlap (in trilayer graphene [85]) by
applied perpendicular electric and magnetic fields have been
observed experimentally [103–106]. More importantly for the
sensing application, graphene has a very large surface area
(at 2630 m2 g−1, 300 times higher than graphite and two times
that of single-walled CNTs).
2.7  GRAPHENE FOR DNA SENSING
Highly sensitive charge carrier modulation upon interaction
with various biological species and large surface area are two
factors that make graphene-based materials very promising
for biodevices [9,10,46,52,107,108] than the other materials
such as silicon nanowires [6]. In addition, low electrical noise,
low electric power consumption, and modifiable bandgap
from semimetallic to semiconducting, high thermal stability,
flexibility, lack of metallic impurities, and readily renewable
surface besides the potential for miniaturization make gra-
phene superior for biosensing [7,54,88]. Their miniaturiza-
tion potential is superior to the limitation of bulk channels,
which restricts the interaction between target molecules and
channel [51]. For the first time, graphene-based nanomaterials
for electrochemical sensing have been applied by Shang et al.
[109]. The presence of oxygen-containing groups at graphene
edges or surface is its major advantage as it could greatly
influence its electrochemical performance [10]. Its high den-
sity of edge-plane defect sites provides multiple active sites
for electron transfer to biospecies. Graphene shows better per-
formance compared to CNT due to the larger ratio of edges
and, therefore, a higher amount of edge defects that are ideal
for heterogeneous electron transfer [54]. Carbon-based sen-
sor technology is relatively cheap to produce, lightweight, and
compact with a low environmental impact that leads to high
commercial development potential [11,110].
The use of nanomaterials, including nanoparticle (quantum
dots or metal nanoparticles), nanowires/tubes, and new 2D
materials such as graphene as sensing materials have attracted
increasing interest to develop [6,81,111–115] cost-effective and
sequence-selective rapid and highly sensitive DNA sensors.
Recently, carbon-based DNA biosensors have been experi-
mentally realized by employing CNT, pristine graphene, or
GO as a sensing platform [4]. They exhibit high sensitivity
and selectivity and low cost for the detection of selected DNA
sequences [63]. For the first time, Mohanty et al. demonstrated
a graphene-based DNA hybridization device with excellent
sensitivity [46]. Typically, there are several graphene-based
sensing methods such as electrochemical sensing, biosens-
ing enhancement of graphene with metal nanoparticles, FET
biosensors, and optical biosensors [3,54,116–118]. Although
silicon-based FET DNA detector showed good performance,
their production is expensive [119,120].
A few theoretical studies have been carried out on the inter-
action of DNA with carbon-based materials. First-principles
study of physisorption of nucleic acid bases on small-diameter
CNTs [121] and graphene [122] has been done by Gowtham
et al. They conclude that the interaction strength of nucleic acid
bases is smaller for the tube, and therefore surface curvature
18
reduces the binding energy between the base molecule and the
substrate. Rajesh et al. [123] studied the interaction of aromatic
amino acids with graphene and single-walled CNT based on
density functional theory (DFT) implemented by Vienna ab-
initio simulation package (VASP). Seung et  al. reported an
ultrasensitive and fast DNA sequencing method with a gra-
phene-embedded nanochannel device based on first-principles
DFT-NEGF (nonequilibrium Green’s function formalism)
transport calculations. They showed that their device effectively
controls the motion of nucleobases via π–π interaction [124].
Molecular dynamics simulations have been carried out by Zhao
et  al. to investigate the self-assembly properties of short and
long DNA segments on the graphene surface and the surface
of CNT arrays [107,125] as well as C60 [126,127] implemented
by NAMD software package. They found that short DNA seg-
ments (up to 12 base pairs) on graphene or CNT array surfaces
form stable hybrid structures that either rotate from a parallel to
a perpendicular orientation on the surface to form a forest-like
structure or attach flat on the surface based on the π stacking
interaction between the hydrophobic DNA base pairs and gra-
phitic carbon rings in both cases. The self-assembly patterns on
CNT surface is similar to DNA–graphene. However, the hybrid
systems formed by DNA and CNT surface is less intensive than
those from DNA and graphene due to the slightly more noisy
fluctuations in the π stacking parameters. They concluded that
the π stacking forces between nucleotides and surfaces with
carbon rings play a significant role [107].
A real-time DNA sensor based on a solution-gate graphene
FET (GFET) was demonstrated by monitoring the current
change upon addition of the target ssDNA. It is believed that
similar to direct n-doping effect should be observed when
DNA is attached to the graphene sensor that could be con-
firmed by the negative shift of the transfer curve and the Dirac
point [51]. The dispersed gold and platinum nanoparticle on
graphene has been used in some studies as an electrochemical
sensor [114,128], which shows enhanced result. Pumera et al.
compared the performance of an analytical electrochemical
method for the determination of free DNA bases (G, A, T,
and C) with graphene and CNTs. They showed that the sen-
sitivity of the graphene-based electrode was about 2–4 times
greater than that of (impurity-free) multiwall CNTs [9]. Their
result also indicated that electrochemical response of graphene
sheets is independent of the number of layers from a single
graphene sheet to multilayer stacked graphene nanoribbons for
dopamine and ascorbic acid [129] which has been questioned
later. In addition, their results showed that multilayer graphene
nanoribbons exhibit larger capacitance than their few-layer and
single-layer graphene counterparts [130]. The effect of pH and
DNA concentration on organic thin-film transistor biosensors
has been studied by Khan et al. [131], which indicates that the
DNA solution became the dominant factor to limit the detec-
tion of more than one-base mismatch target.
Carbon nanostructures such as CNT, carbon nanodot,
and CNF (carbon nanofiber) have been used for this purpose
[5,132,133]. Recently, Lu et al. [134] used graphene for single
DNA detection of four free bases (G, A, T, and C) and Bo
et al. [133] reported good current responses of graphene and
Graphene Science Handbook
PANIw-based sensor to detect DNA. Moreover, single DNA
probe has been used as an electrode for the detection of vari-
ous target molecules [135].
2.7.1 Carbon Nanotube
Some works used CNTs as a DNA sensing platform [136].
The molecular modeling shows that single DNA can bind to
CNTs through π stacking [6,137–139]. CNTs enable immobi-
lization of DNA molecules and amplify signal transduction of
hybridization and could work as a novel indicator of hybrid-
ization [50,140]. In addition, CNT-based FET devices have
also been experimentally reported, which could provide label-
free detection of DNA hybridization [3,116,117]. However, the
reproducibility and defect control difficulties of CNTs are
problems compared to graphene [10].
2.7.2 Graphene Sheet
DNA sensor using pristine graphene was experimentally real-
ized by Ye et al. Their result indicates fast response times with
complete and rapid recovery to baseline at room tempera-
ture [141]. Epitaxially grown graphene on SiC used to detect
dsDNA shows that adding oxygenated groups onto graphene
largely improved electrode performance [112]. Hall effect mea-
surements-based method on CVD grown graphene was used
for single-base sequence-selective detection of DNA [142].
Electrical detection of DNA hybridization using CVD gra-
phene in FET structure was recently reported by Chen et  al.
[143]. Lin et al. experimentally reported a simple ssDNA sensor
based on the π–π stacking interaction between DNA sequence
and gold–silver dispersed graphene. They showed that silver
staining on the gold nanoparticle improved the performances of
the electrochemical DNA sensor [144]. Liquid-gated transistors
were fabricated by a mono- and few-layer CVD-grown large-
sized graphene films for DNA sensing. Adding AuNPs on the
surface of graphene devices can extend the upper limit of DNA
detection [4]. In addition, with DNA hybridization technique,
label-free cancer cell sensor has been experimentally realized
based on graphene-modified electrodes [145,146]. However,
Kasry et al. [147] showed that the unmodified graphene surface
does not allow nonspecific binding.
2.7.3 Graphene Oxide
Most studies in graphene-based DNA sensor have been car-
ried out based on GO or rGO [5,46,81,148–151]. For the first
time, Mohanty et al. demonstrated an electronic DNA sensor
using a GO sheet that exhibited excellent sensitivity to DNA
hybridization [54]. Their electrical measurements showed
that the hybridization of the ssDNA on GO led to a 128%
increase in conductivity. Roy et al. and Loo et al. investigated
the suitability of different chemically modified graphene sur-
faces and found that GO is the most sensitive surface for elec-
trochemical sensors [152–154]. Lu et al. [134] and Liu et al.
[155,156] applied GO in an array to detect DNA hybridiza-
tion focusing on fluorescence quenching properties of GO to
Graphene-Based DNA Sensors
construct a highly sensitive, selective, and economic sensor.
When the DNA binds to the target, the fluorescence quenched
is restored. However, the binding energy between DNA and
graphene was found to be small [54].
Jang et al. developed a new GO-based platform for the assay
of duplex-DNA unwinding activity. Their results show that
real-time monitoring is possible with GO platform by following
the change in fluorescence [157]. Zhou et al. [135,158] prepared
chemically rGO electrodes and quantum dots for label-free
electrochemical detection of four DNA bases. Huang et al. used
rGO with abundant –COOH groups to detect G and A DNA
bases. They explained the high sensitivity of their demonstra-
tion with the electrostatic attraction between negatively charged
–COOH groups and positively charged DNA bases, and the
strong π–π stacking interaction between the nucleobases and
carbon atoms in the honeycomb lattice [159]. Wan et  al. [81]
showed that the presence of silver in GO could be employed for
DNA detection. In another work, the effect of Fe3O4 nanopar-
ticles was studied, it indicated that a doped rGO by Fe3O4
nanoparticle helps to improve the electron transfer rate [160].
Using gold nanoparticle, Du et al. fabricated a doped rGO and
applied to detect single DNA. They showed that this platform
could separate the oxidation signal of T from A’s [161]. Wang
et al. also used gold nanoparticle to produce functionalized GO.
Their experiment result shows that Au-deposited GO can detect
target DNA with very high sensitivity as low as 100 fM, that is,
0.5 amol DNA in 5 mL solution [162]. In addition, the presence
of Ru(bpy)32+ in the detection buffer could enhance the current
response of the sensor [163]. Moreover, the –SO3 group on the
rGO surface provides strong binding sites for immobilization
of DNA probe [112]. Muti et al. [164] also detected a hepatitis
B virus-specific sequence by using GO modified electrode of
DNA hybridization.
It is shown that the network of rGO nanoribbons exhib-
its a higher sensitivity than graphene or rGO film [112,165].
Sulfonated rGO also shows sensitivity to DNA [166]. It is
interesting to note that hybridization of a pair of target and
probe ssDNA under dry conditions in GO platform produces
one-sixth quantum of the hole (p-doping) [4]. In addition, the
mechanism of the sensing by GO could be generally explained
as high conductivity and an excellent electrocatalytic environ-
ment that is provided by rGO, and the conducting polymer
interact with π–π stacking [167].
2.7.4 Graphene Nanoprobe, Nanowall,
and Nanofiber
Recently, new graphene-based nanomaterials such as gra-
phene nanopore, nanofibers, and carbon quantum dots were
fabricated for sensing applications [49,168,169].
Nanopore structure, which is a hole made in a membrane,
shows potential in DNA sequencing. Common membrane
materials are insulators such as silicon nitride, silicon oxide,
and aluminum oxide. However, recently some experiments
showed that graphene nanopore could be used to sense DNA
although it is not an insulator [112,170]. Using graphene as a
nanopore provides direct electrical potential controllability
19
and sensibility at the nanopore. Sadeghi et al. [168] showed that
with proper signal processing method, direct electrical current
could be used to selectively sense DNA bases in bilayer gra-
phene nanopore device. Within a two terminal and three termi-
nal geometry, they demonstrate that changes in the electrical
properties of the graphene ribbon containing a nanopore can
be used to discriminate between DNA bases. In addition, mul-
tilayer graphene-insulator devices could control the molecule’s
motion sufficiently. For these reasons, Merchant et  al. dem-
onstrated a graphene nanopore membrane to sequence DNA
and they observed larger blocked currents than for traditional
solid-state nanopores due to the thin nature of the graphene
membranes. Although ionic current noise levels of that sys-
tem are much higher than those for silicon nitride nanopores,
by deposition of 5 nm of titanium dioxide over the device,
they reduced this noise [83]. Saha et al. [1] in their theoretical
study showed that in a metallic graphene nanoribbon nanopore
(where pore bonded covalently to either hydrogen or nitrogen)
with zigzag edges passivated by hydrogen, a unique change in
device conductance is observed when each of the four DNA
bases inserted into the nanopore. They proposed that poor
signal-to-noise ratio of such a system could be resolved by
abandoning the usage of a small tunneling current. Although
nanopore electrical methods provide rapid DNA sequenc-
ing, they are coped with additional solution and base rotation
effects [2]. However, a research recently showed that the holes
in the graphene heal spontaneously by filling up with either
nonhexagon, graphene-like, or perfect hexagon 2D structures
at room temperature [171] which could raise significant ques-
tions in graphene nanopore device production. Recently, it has
also been experimentally shown that using graphene nanowall
could detect a single DNA [172]. Also, graphene quantum dot-
based sensor has been demonstrated by Zhao et al. [158] for
sensitive and selective detection of various target molecules.
Huang et al. [173] recently reviewed the application of nano-
fibers (CNFs) in sensor technology. CNFs have cylindrical
nanostructures with different stacking arrangements of gra-
phene sheets. The main difference between CNFs and CNTs
is the more edge sites produced by stacking varying shapes. It
is demonstrated that superior electrochemical performance for
the oxidation of DNA bases over CNTs could be achieved by
CNF platforms [49] due to the higher edge effect [112].
2.8 OUTLOOK
The graphene roadmap [174] suggests that those applications
that use lowest-grade, cheapest, and most available graphene
will be the first to be commercialized probably in a few years.
Since graphene used in sensing application does not require
very pure flake and it is extremely sensitive to the environ-
ment due to its 2D nature, it is highly likely that the sensor
technology will become one of the first technologies that
commercialize graphene.
There is no doubt that the carbon-based materials show excel-
lent sensitivity for DNA sensing and sequencing, but challenges
still remain. In general, the recovery time of graphene-based sen-
sors is relatively long, up to several hours [51]. Reproducibility is
20
still a common problem in graphene technology. Although the
rGO-based methods for producing graphene show very promis-
ing results [145,175] in terms of reproducibility, more studies to
enhance their performance and reliability are required.
The number of layers plays a significant role in the elec-
tronic properties of graphene-based materials [54,176,177].
New methods to control the number of layers in production
processes are needed. In addition, there are a few works, which
distinguish between graphene structures in terms of a num-
ber of layers. Systematic theoretical and experimental studies
still need to precisely address which structure of the graphene
among its different configuration such as mono-, bi-, and
trilayer structure, or mono- or few-layer nanoribbons, etc. could
perform the best sensitivity and selectivity. In addition, avoid-
ing surface contamination and limiting substrate effects should
be addressed [55,110]. Identification of the signature of the four
bases single-stranded DNA is a key factor in the sequencing
of the DNA, and in electrochemical sensors, this signature is
typically sensed based on changing the electrical properties
of the platform such as conductance, current, or capacitance.
However, the four DNA bases have a similar chemical structure
[2]; therefore, distinguishing methods with higher reliability is
needed to commercializing the graphene-based DNA sensors.
Graphene molecular sensing is possible since graphene is a
very good low-noise material. However, the immobilization of
nanoparticles in graphene could worthily affect its signal-to-
noise ratio. In general, nanoparticles could immobilize and label
the biomolecules and increase the stability, improve the cataly-
sis of electrochemical reactions, and enhance electron transfer.
High electric conductivity is a need for strong substrate–mole-
cule coupling [178]. However, the conductivity could be affected
by functionalizing with impurities, defect, or pore shape. As an
example, gold generally shows poor biomolecule adsorption that
results in high noise and weak substrate–biomolecule coupling.
Obtaining higher sensitivity at the cost of a lower signal-to-noise
ratio implies a trade-off that needs further investigation to find
the optimum point. In general, FET-based biosensors indicate
higher sensitivity, and selectivity with rapid response with min-
iaturization capability. Graphene FET-based DNA biosensor
still needs to be further investigated.
Although very few works [179] have been carried out in
characterizing the graphene nanoribbons biosensing capabili-
ties, they show a range of linear responses for both chemical
and physical adsorptions. Their capability in biosensing and
specifically in DNA sequencing has not been explored well
yet. Moreover, chemical modification of graphene-based
electrodes can tune the electrochemical properties. Specific
groups such as hydrogen and oxygen can play vital roles in
electrochemical sensing [10]. Therefore, the key factors that
could affect the sensitivity of graphene-based DNA sensors
could be addressed as the following.
2.8.1 Edge and Surface Effects
Heterogeneous electron transfer is faster in the edges [9]. The
surface physics and chemistry of graphene and interaction of
chemicals and biomolecules at the interface of graphene will
Graphene Science Handbook
play an important role in sensing technology [63,180] as avoid-
ing the surface contamination is still a particular challenge
[110]. The effects of oxygen moieties on the electrochemical
characteristics of the substrate still require clarification [54].
There are few works investigating the absorption mechanism of
molecules on graphene and its edge effect as well as the effect of
the orientation of biomolecules on the graphene transport prop-
erties. More theoretical studies need to be addressed in order to
clarify the transport through the graphene-based DNA sensors.
From a theoretical point of view, solvent effect [107] (related to
the binding free energy between the macromolecules in solu-
tion) is another important factor that should be investigated.
The rate of electron transfer has been shown to be surface
dependent. The creation of specific surface functional groups
can increase this rate significantly as it is feasible in the edges
of the rGO sheets holding oxygenated species [54], which
should be precisely considered.
2.8.2  Doping Effects
Chemical doping with foreign heteroatoms (nitrogen, boron,
etc.) will effectively modify the properties of graphene [112]
for instance, nitrogen regulates the electronic properties of
carbon materials significantly [181]. Its effect in improving
the performance of H2O2 and glucose oxide sensing devices
has been studied [66]. High temperatures required for nitro-
gen doping make graphene to restack more easily. Therefore,
alternative doping strategy should be developed. Heteroatom
doping in CNTs has shown to greatly improve the electrocata-
lytic activity [63]. Heteroatoms doping of different structure
of the graphene may open new doors in DNA sensing technol-
ogy, which should be addressed.
2.8.3  Defect Effect
Reduction of GO is the most effective method to prepare gra-
phene sheets, which commonly induces abundant structural
defects and functional groups [182]. Although the general
presence of the defect improves electrochemical activity,
defect effect in DNA-based sensors needs to be well studied.
2.8.4 Functionalization Effect
More functionality could improve the performance of car-
bon-based materials and may offer more capabilities [51].
Functional composites such as a combination of graphene with
polymers or inorganic composites may offer more sensitive
and selective structures with higher reproducibility. However,
little attention has been given to the combination of graphene
and metallic nanoparticles [54], which may open new doors.
2.8.5 Novel Hybrid Carbon Nanomaterial
Among the various structures of carbon-based materials,
graphite oxide is an excellent material and is promising for
biosensing [145,183]. The electrooxidative current of the G
and A bases in DNA is dramatically improved using GO
Graphene-Based DNA Sensors
rather than CNTs [175]. In addition, graphene outperforms the
CNTs-based electrochemical sensors since graphene does not
contain metallic impurities as CNTs usually do, and the pro-
duction of graphene is cheaper and more accessible [9,110].
Moreover, chemical activity improved with edge sides, which
is higher in graphene rather than CNTs [110]. However, study-
ing different structures of the graphene with various shape,
stack, and edge forms is still needed and should be inves-
tigated. Zhang et  al. [184] showed that a hybrid GO–multi-
walled nanotubes could be a novel and efficient platform
for biosensing. Therefore, more studies on hybrid graphene
nanomaterials are needed to find more sensitive and selective
structures. New hybrid carbon nanomaterial could be consid-
ered such as GO-nanofiber, GO-nanowall, etc.
2.8.6 Environmental Issues
Extensive work must be carried out to assess and optimize
the possible toxicity and health risks of carbon nanomaterials.
2.9 CONCLUSION
The sensing application of carbon-based materials has attracted
considerable attention in recent years, specifically after rapid
advances in device miniaturization down to nano and molecu-
lar scale. Sensing and reading of the DNA, the polymer that
carries genome information of human, play a very important
role in the disease diagnostic. In this chapter, the scientific
attempts for using carbon-based materials for DNA sensing
were reviewed. CNT and pristine and functionalized mono-
and multilayer graphene have been used for cost-effective
and sequence-selective label-free DNA sequencing. Although
there is no doubt that carbon-based materials show promising
sensing signatures, there are still unanswered questions toward
proposing a reliable, cheap sequencing method based on direct
electrical measurement of carbon-based platforms for future
DNA sequencing technology. Some of these questions posed
in this chapter could lead to important new developments.
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 3 Antimicrobial Perspectives for
Graphene-Based Nanomaterials
Archana Ramchandra Deokar, Madhulika Sinha,
Ganesh Gollavelli, and Yong-Chien Ling

CONTENTS
Abstract........................................................................................................................................................................................ 27
3.1 Introduction........................................................................................................................................................................ 27
3.2 Graphite, GO, and Reduced GO......................................................................................................................................... 28
3.3 Graphene and Antibacterial Activity: Effect of Synthesis Method, Size, and Shape of Graphene................................... 30
3.4 Antimicrobial Property of GO and Graphene-Metal/Polymer NC.................................................................................... 33
3.5 Graphene-Based Photothermal Antibacterial Therapy...................................................................................................... 35
3.6 Mechanistic Approach toward Antibacterial Property of Graphene-Based NMs............................................................. 36
3.7 Future Perspectives............................................................................................................................................................. 37
Acknowledgment......................................................................................................................................................................... 38
References.................................................................................................................................................................................... 38

ABSTRACT
Conventional antibiotic therapies are becoming less efficient
owing to the emergence of antibiotic-resistance bacterial
strains. The development of novel antibacterial material to
effectively inhibit or kill bacteria is crucial. During the last
decade, inorganic nanoparticles and semiconductors have
played an increasingly important role in combating bacte-
rial infections. Graphene, since its discovery in 2004, has
drawn tremendous attention from the scientific community as
a promising nanomaterial (NM) owing to its multiple prop-
erties such as its unique mechanical stiffness, outstanding
electronic transport, specific surface areas, thermal stability,
conductivity, optical properties, low toxicity, and last but not
the least, its excellent antibacterial property.
Here, a comprehensive view on the antibacterial proper-
ties of graphene-based NMs is summarized. In our group,
efforts were made to synthesize a graphene-based photother-
mal agent and magnetic reduced graphene oxide functional-
ized with glutaraldehyde for the efficient capture and effective
killing of both Gram-positive Staphylococcus aureus and
Gram-negative Escherichia coli bacteria upon near-infrared
laser irradiation. We also prepared a smart magnetic graphene
within 1 min by solid-state microwave reaction for drinking
water purification. It can effectively kill pathogens such as
E. coli, remove heavy metals, and is less toxic to zebrafish.
Nevertheless, the development of graphene-based antibac-
terial materials toward practical applications warrants the
understanding of their exact interaction mechanism. Hence,
the mechanism of action for graphene-based composites
toward bacteria is explored.
3.1 INTRODUCTION
Conventional antibiotic therapies have gradually become less
efficient owing to the emergence of the antibiotic-resistant
bacterial strains. For instance, bacterial infection caused
by the New Delhi Metallo-β-lactamase-1 type bacteria was
found to be multidrug resistant, causing severe nosocomial
infections worldwide (Kumarasamy et  al. 2010). The rising
numbers of drug-resistant diseases will eventually lead to an
increasing need to develop novel and effective antimicrobial
products that can combat these infections. Nanotechnology
is increasingly playing an important role in combating nos-
ocomial infections including but not limited to coating or
incorporating different nanoscale metal and metal-oxide into
surgical equipments (Park et al. 1998; Shah et al. 2008), medi-
cal implants (Banerjee et al. 2011), paints (Kumar et al. 2008),
and textiles (Shimanovich et al. 2012).
Carbon-based nanomaterials (CNMs) have shown great
promise for a number of revolutionary applications (Garg and
Ling 2013; Garg et al. 2014a, b; Ke et al. 2014). CNMs such
as fullerenes (C60) (Lyon et  al. 2006, 2008), carbon nano-
tubes (CNTs) (Liu et  al. 2009; Wang et  al. 2013), graphene
(J. C. Liu et al. 2011, S. B. Liu et al. 2011; Carpio et al. 2012),
and graphene quantum dots (GQDs) (Ristic et  al. 2014) are
emerging antimicrobial materials. Studies with pure micro-
bial cultures have shown that several CNMs have significant
antibacterial activity (Table 3.1). A focus area of research is to
harness this property for industrial applications (Mauter and
Elimelech 2008; Ahmed et al. 2012). An investigation of the
potential toxicity assay of nano-C60 results has shown that
in both Gram-positive and Gram-negative bacteria, nano-C60

27
28
TABLE 3.1
Antibacterial Efficacy of Different Carbon NMs
NMs Starting Material Synthesis Method Bacterial Species/Type
CNTs SWCNTs; Centrifugation-based E. coli, P. aeruginosa,
Co-MCM-41 sieve B. subtilis, and S. aureus
GO Graphite powder Chemical oxidation- E. coli
modified Hummers
Fullerene nC60+THF Solvent (H2O) based E. coli and B. subtilis
GQDs Graphite rods Electrochemical MRSA, E. coli
disrupts electron transport, punctures bacterial membranes,
or produces the radical-oxygen species that are toxic (Tsao
et  al. 2002). Carboxyfullerenes puncture the membranes of
some Gram-positive bacteria but not Gram-negative bacte-
ria. The earlier study, in which the toxicity of carboxyfuller-
enes toward 20 bacterial isolates was evaluated, identified
the mechanism of toxicity as membrane destabilization and
suggested that caboxyfullerenes could be considered as anti-
microbial agents against Gram-positive and Gram-negative
bacteria.
On the other hand, the antibacterial activity of CNTs has
been investigated as a surrogate market in a recent report
(Kang et al. 2007). The authors investigated the interaction of
well-characterized, low metal content, narrowly distributed,
and pristine single-walled carbon nanotubes (SWCNTs) with
a model bacterium, Escherichia coli K12. The most accepted
antibacterial mechanism of SWCNTs includes the direct
physical contact and piercing action of aggregated SWCNTs
(Kang et al. 2008). Oxidative stress from residual metal ions
in CNTs might partially contribute toward the antibacte-
rial activity. We have demonstrated that acid-functionalized
SWCNTs (AFSWCNTs) possess better antibacterial activity
toward Gram-positive bacteria. Better activity is attributed
not only to direct physical contact and piercing action, but
also to molecular-scale interactions with surface functional
groups of bacteria with CNTs (Deokar et al. 2013).
During the last two decades, two forms of CNMs, fuller-
ene and CNTs, have been explored intensively (Yamago
et al. 1995; Prato et al. 2008; Talyzin et al. 2011). Since the
seminal work of Novoselov et al. on free-standing graphene
sheets in 2004 , various forms of graphene sheets have been
actively explored with a wide range of technological applica-
tions such as transistors (Eda et al. 2008), solar cells (Tang
et al. 2010), and sensors (Ang et al. 2008). Graphene is a flat
monolayer of carbon atoms tightly packed into two-dimen-
sional (2D) honeycomb lattice, and is the basic building
block for graphitic materials of all other dimensionalities
(Figure 3.1) (Geim and Novoselov 2007). It can be wrapped
up into zero-dimensional fullerenes, rolled into the one-
dimensional CNTs, or stacked into three-dimensional (3D)
graphite. Theoretically, graphene has been studied for 60
years (Wallace 1947; Mcclure 1956; Slonczewski and Weiss
1958) and is widely used for describing the properties of var-
ious CNMs. It is one of the most fascinating carbon-based
Graphene Science Handbook
Antibacterial Activity References
Higher death rate if well dispersed Liu et al. (2009)
GO shows higher cell viability J. C. Liu et al. (2011),
than rGO S. B. Liu et al. (2011)
Higher cell toxicity; no ROS generation Lyon et al. (2008)
Effective in antibiotic resistance Ristic et al. (2014)
bac. sps.
nanostructures with unique superlatives such as thinnest
imaginable material, largest surface area (~2700 m 2/g),
strongest material ever measured (theoretical limit), stiff-
est known material (stiffer than diamond), most stretchable
crystal (up to 20% elasticity), record thermal conductivity
(outperforming diamond), highest current density at room
temperature (106 times than cooper), completely imperme-
able, intrinsic mobility (100 times more than in Si), conducts
electricity in the limit of no electrons, and the lightest charge
carrier (Geim and Novoselov 2007).
Recently, graphene has been explored for various biomedi-
cal applications owing to its superior biocompatibility (Chen
et al. 2008; Liu et al. 2008). High surface area and versatility of
surface functionalization made it a good scaffold for compos-
ite materials. However, the antibacterial activity of graphene-
based materials is still at a nascent stage. Commercialization
of graphene-based nanocomposites (NCs) for antibacterial
applications will be of great importance owing to their low-
cost mass-production and ease of preparation. Several research
groups made efforts to study the antibacterial activity of gra-
phene. The first direct evidence on graphene’s antibacterial
activity was reported by Hu et  al. (2010), a graphene-based
antibacterial paper. The authors questioned the interactions
between graphene oxide (GO) nanosheets (NSs) and bacterial
and mammalian cells, and they reported the novel findings
on excellent antibacterial activity and minimal cytotoxicity of
GO NSs. The mechanism of interaction is attributed to either
oxidative stress or the physical disruption of the cell mem-
brane unlike the other CNMs (CNTs and fullerene) (Kang
et al. 2007; Liu et al. 2009). The small diameter, high surface
area, strong cell adhesion and capturing ability, and syringe
like structure of individually dispersed SWCNTs played an
important role in governing CNTs antibacterial activity;
whereas in case of graphene, the high-surface area, geom-
etry of graphene-based nanomaterials (NMs), and thermal
conductivity played an important role in governing its anti-
bacterial activity. The study of the mechanism of action for
graphene-based NMs is crucial in order to combat the exist-
ing antibiotic resistance.
3.2  GRAPHITE, GO, AND REDUCED GO
3D graphite (Gt) is made of several single-atom thick sheets
of carbon atom, that is, graphene, synthesized through the
Antimicrobial Perspectives for Graphene-Based Nanomaterials 29

Graphene

GQD Fullerene

CNT

FIGURE 3.1  Schematic representation of CNMs: Graphene, GQD, CNT, and fullerene attack on bacteria.

micromechanical exfoliation of Gt. GO is a graphene sheet with antibacterial activity than larger diameter multiwall carbon
carboxylic groups at its edges and phenol, hydroxyl, and epox- nanotubes (MWCNTs) (Kang et al. 2008). Second, the authors
ide groups on its basal plane. GO can be chemically exfoliated compared the antibacterial efficiency of Gt with GtO. Although
from graphite oxide. Thermal annealing or chemical treatment they possesses almost the same particle size, Gt demonstrated
can eliminate functional groups on GO to produce reduced higher antibacterial activity than GtO owing to their differ-
GO (RGO) (Stankovich et al. 2007). Owing to the differences ent GSH oxidizing capacity. Metallic Gt can oxidize more
of graphene-based NMs (Gt, GtO, GO, and RGO) in electronic GSH than insulating GtO, this observation suggests that the
structure, dispersability, size, and oxidation capacity, Liu et al. metallicity of graphene plays an important role in its antibac-
(2009) made the effort to study their antibacterial properties terial activity. Third, the comparison between GO and RGOs
against Gram-negative E. coli bacteria. The correlation among
the antibacterial activities, glutathione (γ-L-glutamyl-L-
cysteinyl-glycine GSH [glutathione]) oxidation, and aggregate TABLE 3.2
size is summarized in Table 3.2, which can be examined from Correlation among Antibacterial Activities, Oxidative
three aspects. First, the different oxidizing forms of graphite Stress, and Particle Size
(GtO) and graphene (GO) are compared, they have similar
Loss of Cells (%) Loss of GSH (%) Particle Size (μm)
capacities in oxidizing GSH (GtO at 21.4 ± 1.1% versus GO
at 22.2 ± 0.7%); however, GO dispersion (69.3 ± 6.6%) can kill GtO 15.0 ± 3.7 21.4 ± 1.1 6.28 ± 2.50
much higher fractions of E. coli than GtO (15 ± 3.7%) disper- Gt 26.1 ± 4.8 29.9 ± 0.7 6.87 ± 3.12
sion. GtO and GO contain almost the same number of func- rGO 45.9 ± 4.8 94.2 ± 1.1 2.75 ± 1.18
tional groups, the only difference is their individual NS size. GO 69.3 ± 6.6 22.2 ± 0.7 0.31 ± 0.20
The results demonstrated that the aggregation of graphene Source: Reprinted with permission from Liu, S. B. et al. Antibacterial activ-
NSs played an important role in governing their antibacterial ity of graphite, graphite oxide, graphene oxide, and reduced gra-
activity. Materials having smaller size have higher cytotoxicity phene oxide: Membrane and oxidative stress. ACS Nano 5, no. 9,
than larger ones. The results are consistent with the observa- 2011: 6971–80. Copyright 2011 American Chemical Society.
tion for CNTs. SWCNTs with smaller diameter possess higher
30 Graphene Science Handbook

TABLE 3.3
Graphene-Based NCs: Physical Properties and Antibacterial Activity
Material Synthesis Method Shape Size Antibacterial Activity References
GO sheets Chemical oxidation- Sheets 0.01–0.75 μm2 E. coli Liu et al. (2012)
modified Hummers
GONWs Chemical exfoliation Perpendicular Single- and/or E. coli and S. aureus Akhavan et al. (2010)
sheets (nanowalls) multilayer
Graphene NSs Hydrothermal reduction of NSs Few layer E. coli and S. typhimurium, Krishnamoorthy et al.
GO (in alkaline conditions) E. faecalis and B. subtilis (2012)
GO, rGO paper Chemical oxidation- Sheets ~1.5 μm, E. coli Hu et al. (2010)
modified Hummers ~4.6 μm
GQDs MW-assisted cleaving and Spherical 5.1 nm E. coli and S. aureus Sun et al. (2014)
reduction process
GBP–OHP CVD Film Monolayer H. pylori, E. coli, and S. aureus Mannoor et al. (2012)
hRGO FET device Enzymic oxidation of GO Sheets Monolayer E. coli J. Chen et al. (2014),
Y. Chen et al. (2014)

antibacterial activity depicts that smaller size GO are much
more toxic than RGO toward E. coli. A comparative study sug-
gests that dispersibility, particle size, and oxidative capacity of
graphene-based NMs play an important role in governing their
antibacterial activity. The antibacterial mechanism is likely
to be a synergy of membrane and oxidative stress. Metallic
Gt could be a cheapest alternative among all graphene-based
NMs from the commercialization point of view. The authors
suggest that physicochemical properties of graphene-based
NMs such as density of functional groups, size, and conductiv-
ity can be tailored to either reducing their risks or increasing
their application potential.
3.3 GRAPHENE AND ANTIBACTERIAL ACTIVITY:
EFFECT OF SYNTHESIS METHOD,
SIZE, AND SHAPE OF GRAPHENE
Ever since the discovery of graphene in 2004, various syn-
thesis methods have been developed such as exfoliation and
cleavage, thermal chemical deposition, plasma enchanced
chemical vapor deposition (CVD), and chemical reduction
method. The physical, chemical and most importantly, anti-
bacterial properties of graphene and/or its subtypes vary
based on methods of synthesis, size, and shapes (Table 3.3).
The recent achievements on the synthesis of graphene by ther-
mal CVD have confirmed the reproducibility of good quality
graphene on centimeter scale substrate and successful transfer
to many other substrates including Si, glass, and polydimeth-
ylsiloxane (PDMS) (Li et al. 2009).
Single-atom-thick/monolayer, sp2 hybridized graphene is
of particular interest owing to its superior mechanical, elec-
trical, and sensing properties. Mannoor et al. (2012) printed
a CVD synthesized monolayer of graphene onto water-sol-
uble silk for wireless single bacterium detection on tooth
enamel. The authors’ innovation is a fully biointerfaced
sensing platform, which can be tuned to detect target ana-
lytes. They self-assembled antimicrobial peptides onto the
monolayer of graphene (Figure 3.2), further they incorpo-
rated two other major functionalities of a hybrid biosensor

(a) (b) (c) (d)

FIGURE 3.2  Biotransferrable graphene wireless nanosensor. (a) Graphene is printed onto bioresorbable silk and contacts are formed
containing a wireless coil. (b) Biotransfer of the nanosensing architecture onto the surface of a tooth. (c) Magnified schematic of the sens-
ing element, illustrating wireless readout. (d) Binding of pathogenic bacteria by peptides self-assembled on the graphene nanotransducer.
(Reprinted by permission from Macmillan Publishers Ltd. Nature Communications, Mannoor, M. S. et al. 3, 2012: 1–8, Copyright 2012.)
Antimicrobial Perspectives for Graphene-Based Nanomaterials 31

unit: a battery-free operation and remote wireless sensing
capability. Upon reorganization and binding of specific bac-
terial targets by the immobilized peptides, the electrical
conductivity of graphene film was modulated and wirelessly
monitored using an inductively coupled radio frequency
reader device. The key functionalities of the graphene/silk
hybrid sensing elements are thus derived from a synergistic
integration of the individual material’s properties and com-
ponents. This work represents a fundamentally new para-
digm in biochemical detection, and may provide an in situ,
first-order monitoring and detection system for applications
including point-of-care diagnostics, hospital sanitation mon-
itoring, and food safety analysis.
The interaction of biological cells varies with respect to
the surface area, number of layers, lateral dimensions, shape,
and aspect ratio of graphene. Liu et al. (2012) demonstrated
the effect of the lateral size of GO on Gram-negative bac-
terium. In particular, they prepared six different dimen-
sions of GO by making the use of the tip sonication method.
Spectroscopic analysis revealed that all six types of GO do
not differ in surface chemistry nor in chemical composition.
Based on time and concentration dependent experiments, the
large sized GO was demonstrated to have better antibacterial
activity than the smaller one. The atomic force microscopy
(AFM) images depict that large sized GO sheets (Figure
3.3c,d) wraps the bacteria, there-by isolating them from
growth medium which further seizes cell proliferation and
leads to a huge loss in bacterial cell viability (Figure 3.3a,b).
However, the small size of GO (Figure 3.3e,f) will hold on
the bacterial cell surface and cannot isolate the cells from
their environment. Overall, the originated antibacterial inac-
tivation occurs based on the size, chemical composition, and
surface chemistry of GO. Moreover, the results suggested
that the antimicrobial action is related to neither aggregation
nor oxidation.
In another work, Akhavan and Ghaderi (2010) have stud-
ied the geometry effect of graphene nanowalls (GNWs) toward
the Gram-positive Staphylococcus aureus (S. aureus) and
Gram-negative E. coli, suggesting that the toxicity mechanism
of CNTs includes oxidative stress, cutting off intracellular
­metabolic routes, and rupture of cell membrane through direct
physical contact with bacteria. The authors extended this obser-
vation to graphene. The sharp edges of the graphene-based
NSs with extremely high aspect ratio (the ratio of lateral size
to the atomic thickness) could be proposed as the ideal nano-
structure for effective direct interaction with microorganisms.
The authors employed an inexpensive and versatile technique,
electrophoretic deposition, for deposition of GNWs on steel
substrates. Further graphene-oxide nanowalls (GONWs) were
reduced to reduced graphene nanowalls (RGNWs). Figure 3.4
represents morphology of the GONWs. The single/multilayer
GONWs were deposited in high density and at random orienta-
tions, but some of them were almost perpendicular to surface
of the substrate. The mechanism of interaction of RGNWs was
investigated by measuring the intracellular efflux of material
from the damaged cell membrane of Gram-positive S. aureus

(a) (c) (e)

(b) (d) (f )

FIGURE 3.3  AFM amplitude and 3D images of E. coli cells after incubation with GO sheets. (a,b) E. coli incubation with deionized water
for 2 h, (c,d) E. coli incubation with the 40 μg/mL GO-0 suspension for 2 h, and (e,f) E. coli after incubation with the 40 μg/mL GO-240
suspension for 2 h. The scale bars are 1 μm. (Reprinted with permission from Liu, S. B. et al., Lateral dimension-dependent antibacterial
activity of graphene oxide sheets. Langmuir 28, no. 33, 2012: 12364–72. Copyright 2012 American Chemical Society.)
32 Graphene Science Handbook

(a) (b)

500 nm
100 nm

(c)
500 nm

FIGURE 3.4  SEM images of (a) the GONWs deposited on stainless steel substrate by EPD, (b) the nanowalls at a higher magnification
showing those are nearly perpendicular to the substrate, and (c) the cross-sectional view of the nanowalls. (Reprinted with permission from
Akhavan, O. and E. Ghaderi. Toxicity of graphene and graphene oxide nanowalls against bacteria. ACS Nano 4, no. 10, 2010: 5731–36.
Copyright 2010 American Chemical Society.)

or Gram-negative E. coli bacteria. RGNWs (16% ± 3%) were Gram-positive bacteria possesses a thick peptidoglycan layer
found to be much more toxic than GONWs (41% ± 8%) (Figure (~20–80 nm) (Akhavan and Ghaderi 2010; Tyagi et al. 2013).
3.5). The higher toxicity of GNWs was attributed to more The MIC of graphene-based NSs was compared with the com-
sharpening of the edges of the NWs resulting in stronger con- mercial antibiotic kanamycin (Table 3.4). MIC values dem-
tact interaction with the cell membrane and/or better charge onstrated that graphene-based NSs are much more toxic than
transfer. Owing to the high surface area and ease of function- kanamycin toward both bacteria. Moreover, the antibacterial
alization, one can play a lot of chemistry around graphene
either by chemical functionalization or by changing the geom- 100 100
E. coli
etry of the graphene-based NSs to make it a suitable candidate
Survival bacteria
for antibacterial application. Recently, efforts were made to
80 80
enhance graphene’s antibacterial property by functionalizing/ RNA
modifying with metal and metal oxide nanoparticles. Such
Survival bacteria (%)

NCs possess a synergistic effect that is usually not observed in 60 60

RNA (ng/mL)

the individual material.

Owing to the multiple drug resistance of bacterial strains,
Krishnamoorthy et  al. (2012) made an attempt to develop a 40 40
low cost and effective graphene-based antibacterial material
that could have a significant impact on environment and health
care. A graphene-based antibacterial material could be a 20 20
potential candidate among CNMs owing to their high thermal
stability, high mechanical properties, low cost, and superior
0 0
biocompatibility. The antibacterial activity of graphene-based
Control GONWs RGNWs
NSs synthesized by the hydrothermal approach (under alka-
line conditions using hydrazine hydrate) was evaluated based
FIGURE 3.5  Cytotoxicity of GONWs and RGNWs to E. coli, and
on minimum inhibitory concentration (MIC) against Gram- concentrations of RNA in the phosphate-buffered saline (PBS) of
negative E. coli, Salmonella typhimurium and Gram-positive the E. coli bacteria exposed to the nanowalls. (Reprinted with per-
Enterococcus faecalis, Bacillus subtilis. The differences in cell mission from Akhavan, O., and E. Ghaderi. Toxicity of graphene
wall structure are apparent. For example, Gram-negative bac- and graphene oxide nanowalls against bacteria. ACS Nano 4, no. 10,
teria possesses a thin peptidoglycan layer (~7–8 nm); whereas 2010: 5731–36. Copyright 2010 American Chemical Society.)
Antimicrobial Perspectives for Graphene-Based Nanomaterials
TABLE 3.4
MIC of Graphene NSs and Standard Drug Kanamycin
against Gram-Negative and Gram-Positive Bacterial
Strainsa
Graphene NSs MIC Kanamycin
Bacterial Strains (μg/mL) MIC (μg/mL)
Gram-negative strains
E. coli 1 64
S. typhimurium 1 64
Gram-positive strains
E. faecalis 8 128
B. subtilis 4 128
Source: Reprinted with permission from Krishnamoorthy, K. et al.
Antibacterial efficiency of graphene nanosheets against pathogenic
bacteria via lipid peroxidation. Journal of Physical Chemistry C
116, no. 32, 2012: 17280–87. Copyright 2012 American Chemical
Society.
a Results are mean ± standard deviation (n = 3).
efficiency of graphene-based NSs toward Gram-negative is
much better than Gram-positive bacteria. Similar observations
were reported by Hu et al. Oxidative stress or direct physical
contact of E. coli with graphene-based NSs resulted in the loss
of cellular integrity with the disruption of the cell membrane
(Stankovich et al. 2007; Akhavan and Ghaderi 2010; Hu et al.
2010). NM toxicity toward biological species not only relies
on the nature of the cell wall but is also dependent on cellular
enzymes and biochemical events. Toward this end, the authors
made efforts to study oxidative stress that results in damage to
cellular components such as DNA, lipids, and proteins. The
oxidation of fatty acids leads to the generation of lipid peroxi-
dation that stimulates a chain reaction, resulting in the disinte-
gration of the cell membrane followed by cell death.
3.4 ANTIMICROBIAL PROPERTY OF GO
AND GRAPHENE-METAL/POLYMER NC
The combination of two different NMs always leads to the
advancement of achieving better outputs with inherent prop-
erties and also leads to a synergistic effect. Over the past sev-
eral years, nanoparticulates, specifically, silver nanoparticles
(AgNPs) have been extensively studied (Panacek et al. 2006;
Pal et al. 2007) in the realm of antimicrobial action. Owing to
their superior antimicrobial action toward a broad spectrum
of pathogens, AgNPs have been used in food packing and
storage materials, plastics, catheters, bandages, textiles, deter-
gents, dental resin composites, and as a disinfection control-
ler in water purification technologies (Benn and Westerhoff
2008). However, the problems associated with aggregation as
well as releasing Ag+ ions somewhat limit their commercial
utility. To improve the dispersibility and minimizing the Ag+
release, at first AgNPs were immobilized on CNTs and later
on graphene and GO owing to their high surface area and
ease of functionalization. The immobilization of AgNPs on
33
graphene-based NMs not only enhances their dispersibility
but also permits more prominent antimicrobial action mini-
mizing their release into the environment. Toward this end,
Ma et al. (2011) made an attempt to decorate GO with well-
dispersed AgNPs in water and the as-obtained composite
exhibited enhanced antibacterial activity. The antibacterial
efficacy of Ag, GO, and Ag–GO was evaluated on Gram-
negative E. coli bacteria. The results demonstrated that GO
and Ag exhibited less antibacterial activity than the Ag–GO
NCs. Morphological observations demonstrated substantial
loss of cellular integrity of E. coli upon 30 min interaction
with Ag–GO composite as compared with the control set. It
is believed that the antibacterial action of AgNPs originates
from the amount of Ag+ ions present in the bacterial solu-
tion, which was ~0.5 mg/L. To investigate the possibility of
toxicity caused by Ag+, the authors measured the amount
of Ag+ ions released from Ag–GO, which was found to be
~0.05 mg/L. This concentration was too low to induce the
obtained antibacterial activity with Ag–GO. Hence, a possible
antibacterial action of the Ag–GO composite is proposed by
preventing nourishment of bacteria in growth medium and
wrapping of the entire surface of bacteria using the Ag–GO
composite. The oxygen functional groups present on the GO
may form hydrogen bonds with the E. coli surface contain-
ing phosphates and sugars. Furthermore, the AgNPs present
on the GO surface directly contact the bacteria cell wall and
trigger the bacteria cell wall to rupture significantly even in
a very short-time period of 5 min. Very recently, oxidation
debris fragments, a by-product adsorbed on the surface of
GO, have been found crucial for the nucleation and growth of
AgNPs (de Faria et al. 2014). The experimental results have
shown that the GO–Ag composite influences bacterial adhe-
sion. In another interesting work, carbon nanoscrolls filled
with AgNPs have been evaluated with enhanced antifungal
activity (Li et al. 2013).
Sreeprasad et  al. (2011) made efforts to synthesize mul-
tifunctional GO/RGO composite films for medical and
environmental remediation application. GO/RGO-based
composite films are transparent, luminescent, and antibac-
terial. The antibacterial activity of GO/RGO was enhanced
by functionalizing with lactoferin (NLf), NLf protected gold
(Au), chitosan (Ch), and combinations thereof. The addition
of Ch to RGO/GO helped not only in forming stable disper-
sions but also in fabricating large (cm2) surface area films
through a simple solvent evaporation technique. Further, pho-
toluminescence properties were incorporated by anchoring
Au@NLf onto the films. The as-formed composite showed
stable luminescence in the presence of various metal ions
in the solid state. The composite showed reasonable stabil-
ity against pH and temperature variations as well. The as-
prepared films were found transparent and the transparency
could be modulated by controlling the concentration of GO/
RGO with ease. The luminescent films were stable under vari-
ous environmental conditions and against various metal ions
demonstrating their usefulness in water purification and med-
ical applications. The authors claimed that it could be appli-
cable as a reverse osmosis membrane and on medical devices
34
Erasable/rewritable
luminescent pattern
N+
luminescence for
–
O
applications
barcode
Stable
Large area
luminescent
films
Au@Lf
Ch
FIGURE 3.6  Various composites made and their proposed utility. (Reprinted with permission from Sreeprasad, T. S. et al. Transparent,
luminescent, antibacterial, and patternable film forming composites of graphene oxide/reduced graphene oxide. ACS Applied Materials and
Interfaces 3, no. 7, 2011: 2643–54. Copyright 2011 American Chemical Society.)
such as catheters. Figure 3.6 represents the schematic of vari-
ous composites synthesized and their proposed utility. RGO/
GO–NLf–Ch and RGO/GO@Ag–NLf–Ch composite mate-
rial demonstrated synergistic antibacterial activity relative to
that of GO/RGO (Figure 3.7). Apart from that use of bare Ch
and/or AgNPs, recently, surface engineering of graphene sub-
types with ethylenediamine triacetic acid (Carpio et al. 2014),
zinc oxide NPs (Wang et al. 2014), Fe3O4 NPs (Santhosh et al.
2014), magainin I (J. Chen et al. 2014, Y. Chen et al. 2014), and
magnetic Ch (Abdelhamid and Wu 2013) have resulted a wide
range of NCs for antibacterial applications.
Recently, we also designed a multifunctional smart mag-
netic graphene (SMG) for the removal of heavy metal ions,
and to disinfect disease causing bacteria utilizing a green
microwave technique (Golavelli et al. 2013). Time- and con-
centration-dependent studies demonstrated that SMG (100 μg/
mL) possesses 100% killing efficiency toward Gram-negative
E. coli. The SMG exhibits low cytotoxicity toward zebrafish
as an animal model. One of the possible reasons toward high
antibacterial activity could be the roughness of SMG that
leads to the disruption of the cell membrane of bacteria. This
observation is in good agreement with Akhavan’s findings;
where the sharp edges of the GONWs disrupt the bacteria cell
wall (Akhavan and Ghaderi 2010). Another possibility could
be the presence of hydrogen bonding between OH groups of
GO and bacterial cell membrane. All aforementioned factors
lead to the 100% disinfection ability of bacteria in drinking
Graphene Science Handbook
Ch
A
nt
i
ac bac
tiv te
ity ria
Lf l
Large area
Ch films
Antibacterial
membranes
coating for
Erasable/rewritable
pattern
water. Furthermore, with the increased near-infrared (NIR)
absorbance of SMG compared with GO, one can disinfect
bacteria photothermally. Within a few minutes of interaction
time, SMG (100 μg/mL) was able to disinfect ~80% of E. coli.
Extending the interaction time to 1 h, a lower concentration of
SMG (10 μg/mL) was able to disinfect ~95% of bacteria dem-
onstrating its rich potential as a disinfectant in water research.
Modern life is highly dependent on polymer-based materi-
als such as carry bags, table tops, and water pipes. Due to close
association with these materials, there are several possibilities to
get infected with microbial diseases. It is therefore very impor-
tant to use intrinsic antimicrobial polymers to prevent patho-
genic actions or to coat the polymers with antibiotics, quaternary
ammonium salts, and metal NPs. The usage of organic antimi-
crobial agents such as antibiotics exhibit several disadvantages
such as shorter life times, high decomposability, and low heat
resistance (Kenawy et al. 2007). In this regime, coatings with
well-known inorganic NMs such as Ag, ZnO, and TiO2 have
appeared quite promising. However, their relative toxicity to
humans and high production costs have motivated researchers to
search for potential alternatives. To this end, graphene subtypes
are quite promising owing to their ease of preparation and avail-
ability. The recent in vitro and in vivo studies have demonstrated
that graphene/GO is nontoxic. Graphene/GO is compatible with
polymers and serve as reinforcing agents owing to their supe-
rior mechanical strengths. Santos et al. have fabricated GO with
poly-N-vinyl carbazole (GO–PVK) and tested the antimicrobial
 Antimicrobial Perspectives for Graphene-Based Nanomaterials
3
2.5
2
OD at 600 nm
1.5
0.5
0
IC Lf Ch GO RGO
Added materials in growth medium
FIGURE 3.7  Comparison of antibacterial activity of different materials tested. (Reprinted with permission from Sreeprasad, T. S. et al.
Transparent, luminescent, antibacterial and patternable film forming composites of graphene oxide/reduced graphene oxide. ACS Applied
Materials and Interfaces 3, no. 7, 2011: 2643–54. Copyright 2011 American Chemical Society.)
action of as-prepared GO–PVK NC film against E. coli. The
GO–PVK NC thin film has shown more effective antibacterial
activity than GO and unmodified PVK films alone (Santos et al.
2011). Very recently, a GO–PVK-modified membrane filter
was effectively used for the removal of B. subtilis and E. coli
(Musico et al. 2014). Despite this, it is crucial to design nontoxic
composites with potent antibacterial activity. In this manner,
Some et al. used poly (l-lysine) (PLL) to fabricate graphene and/
or GO. PLL is a polycationic homopolymer containing naturally
occurring peptide l-lysine and possesses appreciable antibac-
terial activity, yet promotes the growth of human cell culture.
In particular, PLL was modified onto the graphene/GO surface
via electrostatic and covalent interactions and further explored
in designing antibacterial plastic gloves. In addition, GO–PLL
and graphene–PLL composites also promote cell growth (Some
et  al. 2012). In view of these reports, it is quite reasonable to
expect that graphene/GO-polymer composites are nontoxic to
humans and possess rapid antimicrobial action toward certain
pathogens.
3.5 GRAPHENE-BASED PHOTOTHERMAL
ANTIBACTERIAL THERAPY
After the pioneering work by Yang et al. (2010), it is now widely
admitted that graphene or RGO possesses inherent photothermal
properties. Recently, we designed a graphene-based photother-
mal agent by functionalizing magnetic RGO with glutaral-
dehyde (MRGOGA). Upon NIR irradiation, the as-prepared
MRGOGA composite was found to efficiently capture and kill
both Gram-positive S. aureus and E. coli Gram-negative bac-
teria (Wu et al. 2013). The glutaraldehyde serves as an efficient
35
Initial
After 24 h
GO-Lf RGO-Lf GO-Ch-Lf RGO-Ch-Lf GO-Ch-AuLf RGO-Ch-AuLf
capturing agent toward both bacteria, the magnetic characteris-
tics of MRGOGA allow the bacteria to be readily trapped into
small volume by the external magnet. The synergistic effect
increases the heating extent of MRGOGA upon NIR laser
irradiation and trigger the killing of the captured bacteria. The
antibacterial efficiency of MRGOGA was evaluated under both
batch and continuous operation modes. Specifically, the batch
mode was operated with a still bacteria solution, whereas the
continuous mode was operated with a flowing bacteria being
continuously pumped through a microfluidic chip. In contrast
to MRGO and functionalized CNTs (MCNGA—single-walled
CNTs [SWCNTs] functionalized with magnetic NPs and GA
[glutaraldehyde]), MRGOGA demonstrated better antibacterial
efficiency as demonstrated in Table 3.5. The survival rate and
membrane integrity assay demonstrate that 80 ppm MRGOGA
solution provided rapid (10 min) and effective killing up to 99%
of both bacteria. The key factors toward the effective killing of
bacteria include the capturing ability of GA and photothermal
effects of graphene, which is capable of absorbing light and
subsequently releasing the energy as a heat. Heat produced by
MRGOGA upon NIR laser irradiation raised the temperature
to ~50°C. At this temperature the enzymes denature, inhibit the
necessary intracellular reactions, damage proteins and lipids on
the cell membrane, and finally lead to bacteria death. Moreover,
the MRGOGA cross-linked bacteria can be easily controlled
by an external magnetic field and aggregated at small volumes
allowing the efficient use of NIR laser irradiation to increase
local heating for effective bacteria killing.
By making the use of noncovalent interactions, Wang et al.
(2013) also undertook graphene-based antibacterial photother-
mal therapy by functionalizing nano RGO (NRGO) with anti-
S. aureus polyclonal antibody (Ab). Here, the Ab adsorbed on
36 Graphene Science Handbook

materials will be of particular interest among CNMs owing

TABLE 3.5 to their low-cost and bulk production at laboratory scale.
Survival Rate of S. aureus and E. coli for 80 ppm Oxidative stress or direct physical contact of bacterial strains
MRGO, MRGOGA, and MCNGA Solution after with graphene-based NSs is the most acceptable mechanism
Photothermal Treatments under Batch Operation Mode of interaction that has been demonstrated (Stankovich et  al.
2007; Akhavan and Ghaderi 2010). Several researchers have
Survival Rate (%) n = 3
carried out antibacterial studies of graphene-based NMs.
Under Dark NIR Laser Irradiation However, the fundamental mechanistic approach toward bac-
Agent S. aureus E. coli S. aureus E. coli terial strains is still at the nascent stage. Moreover, some liter-
None 155 ± 15 102 ± 14
ature reports on antibacterial studies of graphene-based NMs
MRGO 143 ± 50 117 ± 34  45 ± 14  39 ± 12
are contrary to others. For example, some studies claim that
MRGOGA 147 ± 20 108 ± 15 0.4 ± 0.1 0.1 ± 0.1
GO is toxic toward bacteria; whereas it was also reported that
MCNGA 110 ± 9 133 ± 32 8.7 ± 2  20 ± 6
GO can also enhance E. coli growth nonspecifically (Ruiz
et  al. 2011). In our group, we made an attempt to explore a
Source: Reprinted with permission from Wu, M. C. et al. Graphene-based novel antibacterial mechanism of SWCNTs toward both
photothermal agent for rapid and effective killing of bacteria. ACS Gram-positive and Gram-negative bacteria. We have made
Nano 7, no. 2, 2013: 1281–90. Copyright 2013 American Chemical systematic spectroscopic and microscopic studies to explore
Society. the mechanism of interaction of graphene’s sister CNTs. So far
direct physical contact, piercing action, and oxidative stress
from residual metal ions are the well-known killing mecha-
NRGO by noncovalent interactions helps to retain the struc- nisms of CNTs toward bacteria (Kang et al. 2007, 2008). Our
tural characteristics of Ab. The Ab-NRGO was incubated with research team made an attempt to study the molecular-scale
bacteria and exposed to NIR light. Upon NIR exposure, the interactions of AFSWCNTs with surface functional groups of
Ab-NRGO selectively killed S. aureus, however, the killing effi- bacteria (Deokar et  al. 2013) (Figure 3.8). X-ray photoelec-
cacy was less prominent against E. coli and human cells under tron spectroscopic measurements demonstrated that molec-
similar experimental conditions. Recently, a variety of nanopar- ular-scale interactions might be possible in Gram-positive
ticulates or a luminescent rare-earth complex is combined with bacteria in addition to the aforementioned mechanisms. This
graphene domains (Table 3.6) for optical labeling, tracking, and might be owing to the difference in the chemical composi-
photothermal ablation of bacteria (Lin et  al. 2014; Tian et  al. tion of the cell membranes of these two bacterial strains. The
2014; Xu et al. 2014; Yang et al. 2014). These reports certainly Gram-positive S. aureus restrains a thick peptidoglycan layer
signify the importance of graphene-based composites in photo- (~20–80 nm) which is composed of amino acids, teichoic
thermal antibacterial therapy and may provide new insights for acids, surface proteins, and lipoids. The peptidoglycan acts as
future medical applications where drug-resistant pathogens in a chelating agent and makes for the possibility of molecular-
human systems can be selectively and specifically photo ablated. scale interactions such as hydrogen bonding and electrostatic
In line with this, the visible light-induced inactivation property interactions. The Gram-negative E. coli consists of an outer
of graphene composites may be used for indoor air disinfection. membrane (~10–15 nm), a peptidoglycan layer (~7–8 nm), and
a cytoplasmic membrane (~7 nm), hence is less susceptible
3.6 MECHANISTIC APPROACH TOWARD toward the action of AFSWCNTs. Both the cytoplasmic mem-
ANTIBACTERIAL PROPERTY OF brane and the outer membrane contain a lipid bilayer struc-
ture. The intermediate thin peptidoglycan layer (~7–8 nm) is
GRAPHENE-BASED NMs
covered with a thick outer membrane, hence becoming more
The development of CNMs toward commercial antibacterial resistant toward the action of AFSWCNTs. This mechanistic
applications warrants the understanding of their interaction approach might be applicable to graphene, as SWCNTs are
mechanism with bacterial cells. Graphene-based antibacterial made of one-atom thick sheet of graphene.

TABLE 3.6
Graphene-Based Composites for Photothermal and Photodynamic Therapy
Laser Power Intensity Irradiation Type of
NM Wavelength (nm) (W/cm2) Time (Min) Bacterial Species/Type Treatment References
GO-IONP-Ag 808 1.5 7 E. coli and S. aureus PTT Tian et al. (2014)
MRGOGA 808 1.5 10 E. coli and S. aureus PTT Wu et al. (2013)
Ab–NRGO 808 1.0 10 S. aureus PTT Wang et al. (2013)
(Au@Rubpy/GO) SERS tags 785 400 mW 10 E. coli and S. aureus PTT Lin et al. (2014)
Eu-Van-rGO 808 1.5 3 DR-E. coli, DR-S. aureus PTT Yang et al. (2014)
GQD 470 1.0 15 E. coli and S. aureus PDT Ristic et al. (2014)
Antimicrobial Perspectives for Graphene-Based Nanomaterials 37

(a)

2 2

1 1

Molecular-scale interaction Direct physical contact and

piercing action

(b)

Only direct physical contact and

piercing action

FIGURE 3.8  Schematic demonstrating the interaction of AFSWCNTs toward (a) Gram-positive S. aureus and (b) Gram-negative E. coli
bacterial cell wall. (1) Cytoplasmic membrane, (2) peptidoglycan, (3) outer membrane. (Reproduced from Deokar, A. R. et al. Journal of
Materials Chemistry B 1, no. 20, 2013: 2639–46.)

Very recently, Tu et  al. (2013) explored mechanistic
insights for the antibacterial activity of graphene by experi-
mental and theoretical approaches using E. coli as a model
bacterium. The viable changes in the E. coli morphologies
can be roughly detected at three different stages. In stage I,
E. coli showed resistance toward the antibacterial action of
GO, especially at low concentrations. In stage II, the E. coli
cell got partially damaged and at stage III, E. coli had totally
lost its cell integrity by the ‘Blade’ like action of GO. The
molecular dynamics simulation studies revealed that gra-
phene can extract huge amounts of phospholipids from the
inner and outer membranes of E. coli, owing to its destructive
action and strong dispersive interaction with phospholipids.
According to recent reports (Hui et al. 2014), bare GO intrinsi-
cally kills both bacteria and mammalian cells, whereas mask-
ing its basal planes via noncovalent adsorption renders GO
inactive against bacteria. Another mechanism for the bacteri-
cidal effect of GO shows mechanical wrapping of the patho-
gens and locally damaging their cell membrane resulting in
cell lysis (J. Chen et al. 2014; Y. Chen et al. 2014). This is most
likely owing to local perturbation of the cell membrane and
decreased membrane potential in bacteria eventually leading
to a leakage of electrolytes of fungal spores. Apart from this,
Abdelhamid et  al. (2014) demonstrated that GO effectively
absorbs gramicidin (GD), which is water-insoluble, through
physical interactions and improves its antibacterial activity.
These emerging mechanistic approaches in conjunction with
cytotoxic and/or genotoxic studies toward the antibacterial
property of graphene-based NMs (Ocsoy et al. 2013; Guo and
Mei 2014; Sametband et al. 2014; Sun et al. 2014) may provide
new insights in designing graphene-based antibiotics in the
near future.
3.7  FUTURE PERSPECTIVES
The unique physicochemical and photothermal properties, low-
cost bulk production, high-surface area, and ease of functional-
ization in graphene have made it an attractive candidate toward
the development of commercial antibacterial applications.
There is still plenty of room left to explore and understand the
antimicrobial mechanism of graphene-based NMs. With the
ease of functionalization and high-surface area, one might play
a lot of chemistry by functionalizing 2D graphene. Moreover,
graphene could also be utilized for wound healing and sensing
applications by tuning the size, shape, and number of layers.
However, the synthesis of single-layer graphene on an industrial
scale still remains a big challenge for researchers. We anticipate
that owing to low cytotoxicity and superior biocompatibility of
38
graphene-based NMs, graphene might replace antibiotics for
multi-drug resistant bacteria in the twenty-first century.
ACKNOWLEDGMENT
Financial support by National Tsing Hua University and
the Ministry of Science and Technology (101-2113-M-007-
006-MY3, 104-2113-M-007-008-MY3) and (104-2627-B-
007-001) of Taiwan is gratefully acknowledged.
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 4 Biomedical Applications of Graphene
Maria Caffo, Lucia Merlo, Daniele Marino, and Gerardo Caruso

CONTENTS
Abstract........................................................................................................................................................................................ 41
4.1 Introduction........................................................................................................................................................................ 41
4.2 Chemical Characteristics and Properties of Graphene....................................................................................................... 42
4.3 General Applications of Graphene..................................................................................................................................... 42
4.4 Biomedical Applications of Graphene................................................................................................................................ 43
4.4.1 Drug Delivery......................................................................................................................................................... 43
4.4.2 Gene Delivery......................................................................................................................................................... 45
4.4.3 Photothermal and Photodynamic Cancer Therapy................................................................................................. 46
4.4.4 Biosensing and Bioimaging.................................................................................................................................... 47
4.5 Multifunctional Nanoplatforms.......................................................................................................................................... 47
4.5.1 Organic NGO Platforms......................................................................................................................................... 47
4.5.2 Hybrid NGO Platforms........................................................................................................................................... 48
4.6 Toxicity............................................................................................................................................................................... 48
4.7 Graphene in Neuro-Oncology............................................................................................................................................ 50
4.8 Opened Challenges and Future Directions......................................................................................................................... 51
References.................................................................................................................................................................................... 51

ABSTRACT revolutionizing medical treatments, imaging, faster diagno-

Graphene is a versatile two-dimensional nanomaterial thanks
to its unique physical and chemical characteristics. It has
shown great potentials in different fields and revealed to be
promising in biomedical research. The application of nano-
technology to health care through nanomedicine devices is
revolutionizing medical approaches, imaging, and treat-
ment. Numerous experimental studies have also been made
to employ graphene as a vehicle for antitumoral therapies.
Patients affected by brain tumor can greatly benefit from it.
However, graphene remains an experimental material, and its
in vitro and in vivo toxicity has been so far tested with con-
troversial results. We will describe the chemical and physi-
cal properties of graphene, its main current uses in different
fields, focusing on its putative role in neuro-oncology, and its
possible long-term toxicity.
4.1 INTRODUCTION
Notwithstanding the progress of medicine, morbidity and
mortality in oncological patients still remains high, and new
treatments barely defeat the diseases. In this specific field,
brain tumors represent a challenge: the particular environ-
ment they develop in being hard to reach by most of the mol-
ecules known today, due to the presence of the blood–brain
barrier (BBB). Nanotechnology can reveal a useful tool in
overcoming this obstacle. Nanomedicine, the application
of nanotechnology to health care, holds great promise for
sis, drug delivery, and tissue regeneration [1–3]. Nanoparticle
(NP) systems in cancer therapies provide better penetration
of therapeutic and diagnostic agents, and a reduced risk in
comparison to conventional treatments [1–3]. By using nano-
technology, it is possible to deliver the drug to the targeted
tissue across the BBB, release the drug at a controlled rate,
and avoid degradation processes. Reduction of toxicity to
peripheral organs and biodegradability can also be achieved
with these systems.
Graphene is an innovative two-dimensional (2D) nano-
material. Thanks to its particular chemical configuration, it
possesses unique physical, electronic, optical, thermal, and
mechanical characteristics [4–6]. This molecule together
with its related derivatives, such as its oxide, has shown poten-
tials not only in the field of nanoelectronics [7], composite
materials [8–10], energy technology [11,12], sensors [13], and
catalysis [14–17], but has also found promising applications
in biomedical research. In recent years, graphene has been
widely applied in targeting controlled drug/gene delivery, as
well as photothermal and photodynamic cancer therapy, bio-
sensing, and bioimaging [18]. However, as an experimental
material, its in vitro and in vivo toxicity has been tested with
controversial results.
The purpose of this chapter is to describe the main current
uses of graphene, also focusing on its preliminary therapeu-
tic and diagnostic uses in oncology and neuro-oncology, its
possible long-term toxicity, and to illustrate possible future
employments in these fields.

41
42
4.2 CHEMICAL CHARACTERISTICS AND
PROPERTIES OF GRAPHENE
Graphene is a carbon allotrope with a bidimensional hexago-
nal structure. Specifically, it is composed of a single layer of
sp2-bounded carbon atoms possessing unique physical and
chemical properties (Table 4.1). Its peculiarities reside in (1)
high specific surface area (2630 m2/g); (2) high charge carri-
ers mobility (200,000 cm2/V s); (3) mechanical strength (high
Young’s modulus: ~1100 GPa); (4) high thermal conductiv-
ity (~5000 W/m/K); (5) high optical transmittance (~97.7%);
(6) intrinsic biocompatibility; and (7) low cost of production
and simple functionalization [17,19].
Graphene can be synthesized either through chemical
vapor deposition [20–22] or from the chemical exfoliation
of graphite, the latter being the most widely adopted proce-
dure because it is technologically simple, highly efficient,
and of low cost [23]. The exfoliation of graphite requires
the oxidation of the aromatic structure in order to weaken
the Van der Walls interactions between the carbon planes.
The complete exfoliation produces colloid suspensions
of f­ew-layer carbon sheets. The intermediate compounds
obtained through this reaction are grouped as graphene
oxide (GO), a planar carbon structure with a high density
of oxygen functional groups, which can be subsequently
reduced into ­g raphene typically by chemical [24] or ther-
mal [25] methods.
GO itself possesses peculiar physical and chemical prop-
erties, making it a versatile material for various applications
[26]. Even in the field of nanotechnology, nano-GO (NGO)
has shown enormous potential derived from its simple chem-
ical structure and morphology. NGO is obtained from GO by
using exfoliation followed by ultrasonication [27] in order to
convert the micrometric lateral dimensions of the GO sheets
to the nanometric size (<100 nm). The hexagonal structure of
NGO contains carboxylic and carbonyl groups on the edges,
and hydroxyl and epoxy groups in the basal planes. Its unique
morphology, surface chemistry, and structure can be the key
point for the development of new multifunctional materials
for cancer therapy. The surface presence of the oxygen func-
tional groups, conferring an oxidized state thanks to the neg-
ative surface charge and reactive sites for functionalization
[15], allows GO to be used in different chemical reactions
[28,29] such as acylation to form the covalent attachment of
molecular precursors [20–22,30,31]. The aromatic structure
of GO can form noncovalent hydrophobic interactions as
well [13,32,33].
TABLE 4.1
Physical and Chemical Characteristics of Graphene
High specific surface area 2630 m2/g
High charge carriers mobility 200,000 cm2/V/s
High mechanical strength Young’s modulus: ~1100 GPa
High thermal conductivity ~5000 W/m/K
High optical transmittance ~97.7%
Graphene Science Handbook
The importance of the functionalization of GO has been the
key for the biological and biomedical applications of graphene
[15,18,34,35]. NGO has a high value of a specific surface area
given by the bidimensional structure of carbon atoms with
dimensions below 100 nm and atomic thickness. This high
aspect ratio allows a linear, semiflexible configuration with a
high rate of functionalization; thus, NGO maximizes the inter-
action with the interstitial matrix than do comparable- sized,
rigid spherical molecules [36]. Moreover, the GO aromatic
structure allows light absorption in the near-infrared (NIR)
range (700–900 nm), also called the “therapeutic window”
[37] as it is a noninvasive, harmless, and skin-penetrating
irradiation. Specifically, the strong NIR absorption of reduced
GO (rGO) is principally due to the oxygen groups present at
the edge of the molecule, which are susceptible of structural
modifications in order to tailor the light absorption at different
spectral positions [38]. This property is particularly suitable
for photothermal therapy applied to the tumor treatment [39–
41]. Graphene itself showed photoluminescent properties [42].
It emits light across the visible spectral range when excited
by ultrashort laser pulses [42]. Photoluminescence was also
observed in its derivatives [43,44]. After being excited in the
NIR region, NGO has also been discovered able to up-convert
fluorescence without the interference of auto-fluorescence
from tissues. This ulterior property makes biodetection and
bioimaging feasible by using NGO [45–49]. Another applica-
tion of this property can also be found in early cancer detec-
tion [50] and chemotherapy response, overcoming the limits
of specific proteins [51] or telomerase, [52] which have to be
usually overexpressed in tumors.
4.3  GENERAL APPLICATIONS OF GRAPHENE
The use of graphene and its derivatives in various fields of
science has been growing strongly in recent years (Table 4.2).
This is mainly due to the structural and chemical versatility
of this molecule, which makes it suitable to different practical
applications. The use of graphene specially treated with meth-
ods of molecular engineering, such as solubilization, doping,
and chemical functionalization, allows its exploitation for
TABLE 4.2
General Applications of Graphene
Field Processing/Properties
Nanoelectronics Solubilization, doping, and chemical
functionalization
Nano-optics, conductors, Hybridization with metals or oxides
and CNTs
Nano-electrocatalyst and Excellent conductivity
biofuel cells
Supercapacitors Chemical stability increasing the
capacitance
Electrochemical-, immune-, Promoter for the exchange of electrons and
and fluorescent sensors support material for immobilizing
different targets
Biomedical Applications of Graphene
the creation of nanoelectronic devices and composite mate-
rials. Actually, the chemical functionalization of graphene
has focused on improving its solubility and processability in
both water and organic solvents in order to tune, introduce, or
enhance its new function or properties [53]. For this reason,
in recent years, some organic reactions such as nucleophilic
ring-opening [54,55], 1,3-dipolar cycloaddition [56], diazo-
nium [57,58], amide bond formation [59], and carbodiimide-
activated esterification [60] have been reported. In parallel,
the chemical doping of graphene has been studied, with the
aim of being able to control its unique electrical properties.
This allowed its use as a component for the creation of elec-
trochemical sensors and field-effect transistors (FETs) [61,62].
One of the most fascinating fields of application and devel-
opment opportunities for graphene concerns its hybridization
with other molecules, in order to enhance their performance.
However, in order to obtain a real advantage of this type of
hybrid, some essential requirements must be satisfied, such
as (1) the presence of a “molecular glue” that can adhere the
NP on the surface of graphene; (2) controlling the morphol-
ogy and size of nanomaterials; and (3) the presence in the
hybrid of a monolayer of graphene so as to not lose its native
characteristics. Although the hybridization of graphene with
other materials is still a developing field, there are already a
number of techniques that allow the creation of hybrid nano-
materials based on graphene [53]. Different materials allow,
through hybridization techniques, to amplify the properties
of graphene: (1) some metals (e.g., Au, Ag, Pt, Pd, and Cu),
thus creating new compounds to be used in the electrochemi-
cal and analytical fields; (2) various oxides (such as SiO2,
Fe2O3, TiO2, Co[OH]2, SnO2, ZnO, Al2O3, Co3O4, MnO2, and
Fe3O4) [63–73], with which it is possible to achieve significant
improvements in technological fields such as nanoelectronics,
nano-optics and conductors, conversion, and storage devices;
and (3) carbon nanotubes (CNTs), through which graphene
can greatly increase its conductivity, placing them as sepa-
rators of the individual layers, thus increasing the surface
[74,75].
Graphene is also suitable to be used in the field of ener-
getics, thanks to its large surface area, excellent conductiv-
ity, and good mechanical performance [76]. It has been the
object of research studies looking for the creation of fuel cells
through new materials. Many of these are based on NPs act-
ing as nano-electrocatalysts: graphene possesses the ability
to strengthen their electrocatalytic activity also thanks to its
typical 2D conformation [53]. Furthermore, besides the tra-
ditional fuel cells, biofuel cells have also been developed in
recent years, thanks to the progressive miniaturization of
electronic devices. Even in this case, numerous studies have
demonstrated the excellent adaptability of graphene as an
enhanced material for the biofuel cell, being able to simul-
taneously immobilize the enzyme, premising the increase of
the electron shuttling, and also keeping it active so as to make
effective and stable biofuel cells [77].
The ductility of graphene in the energy sector has
been taken into consideration in the area of supercapaci-
tors, currently divided into two broad categories (electrical
43
double-layer capacitance and pseudocapacitance). These are
now popular in large scale, possessing long life, wide thermal
operating range, and low maintenance cost, as well as a higher
capability. Graphene fits very well in this context thanks to
its peculiar features of good chemical stability, excellent
mechanical properties, and potential low manufacturing cost.
Several recent studies have shown how the use of graphene
paired with other materials such as CNTs and polyaniline
can increase the capacitance, a fundamental characteristic
in supercapacitors [4,78,79]. Parallel to the supercapacitors
described above, recently hydrogen-based storage models
have been proposed, thus following the growing interest in
clean energy techniques. Also, in this case, the carbon-based
molecules, and therefore graphene have also been proposed as
a hydrogen storage material [80].
Another interesting area of development and application of
graphene concerns its use in the construction of electrochemi-
cal [81], immune- [82], and fluorescent sensors, exploited in
many modern industries. Graphene, in fact, can be adapted
both as a promoter for the exchange of electrons between ana-
lytes and electrodes, and as a support material for immobiliz-
ing different targets, due to its very large surface area.
4.4 BIOMEDICAL APPLICATIONS
OF GRAPHENE
The biomedical applications of graphene represent a new field
with significant potential that ranges from drug/gene delivery,
photothermal and photodynamic cancer therapy, biological
sensing, and imaging, to multifunctional nanoplatforms. The
intensive research on the biomedical applications of graphene
and its derivatives is due to its intrinsic biocompatibility, low
cost of production, and ease in the processes of functionaliza-
tion [17,83].
In the field of oncology, NGO has been studied for the treat-
ment of different types of tumors, both as a native molecule,
and as a drug-delivery vehicle [84–86]. As an example, non-
targeted NGO was tested for the treatment of primary tumors,
given its enhanced permeability and retention effect [87].
Moreover, tailoring its surface with specific ligands as targets
for proteins expressed in cancer cells, nontargeted NGO could
improve its role in tumor treatment. Instead, other researches
were conducted in targeted nanomaterials to detect, visualize,
and destroy cancer cells with minimal side effects on normal
cells [84,88].
NGO has also been experimentally employed as a bioimag-
ing agent in different techniques, including magnetic resonance
(MR) and radionuclide-based imaging [89–91] (Figure 4.1).
4.4.1  Drug Delivery
Drug-delivery technologies modify the drug release pro-
file, absorption, distribution, and elimination for the benefit
of improving product efficacy and safety, as well as patient
convenience and compliance. Anatomic features such as the
BBB, the branching pathways of the pulmonary system, and
the tight epithelial junctions of the skin make it difficult for
44
Gene
y
deliver
Drug
y
deliver
aging
Bioim
ensing
Bios
Photo py
nal
unctio
Multif tforms
la
nanop
FIGURE 4.1  Schematic representation of biomedical graphene applications.
drugs to reach many desired physiological targets [3]. In addi-
tion to the commonly used oral and injection routes, drugs can
also be administered through other means, including trans-
dermal, transmucosal, ocular, pulmonary, and implantation.
Several drugs are limited by their poor solubility, high toxic-
ity and high dosage, aggregation due to poor solubility, non-
specific delivery, in vivo degradation, and short-circulating
half-lives [3].
Drug-delivery carriers are macromolecular assemblies
that can incorporate imaging and therapeutic compounds
of a distinct nature, such as small chemicals, fluorophores
and biosensors, peptides and proteins, oligonucleotides, and
genes. Current efforts in the area of drug delivery include the
development of targeted delivery, in which the drug is only
active in the target area and sustained release formulations in
which the drug is released over a period of time in a controlled
manner.
GO is an ideal and versatile nanocarrier for efficient drug
and gene delivery. GO used for drug delivery is usually 1–2 nm
thick, with size ranging from a few to several hundred nano-
meters [16,88]. Its planar structure rich in oxygen molecules
renders GO biocompatibility, physiological solubility and sta-
bility, and capability of transporting drugs or genes. The reac-
tive COOH and OH groups when conjugated with polymers
[55] or biomolecules (e.g., biotargeting ligand [88], deoxyribo-
nucleic acid [DNA] [92], protein [93,94], quantum dots [QDs]
[95], and Fe3O4 NPs [96]) allow different applications.
A premise that should be made is that most aromatic drugs
are water insoluble; although NGO colloids are soluble in
water, their functionalization with polyethylene glycol (PEG)
facilitates the cell internalization [97]. The PEGylation is a
common method used to gain molecular stability by surface
covalent attachment of PEG polymer chains. The main impor-
tance of PEGylation resides in preventing the opsonization of
particles by the macrophages [98,99]. Moreover, PEG is a non-
toxic and nonimmunogenic compound, approved by the Food
and Drug Administration (FDA) for internal use in humans.
Graphene Science Handbook
dynam
ic
Photo py
thera
therm
al
thera
For these reasons, PEGylation has already been validated to
increase the biocompatibility and reduce thrombogenicity of
NGO [100]. A different kind of PEGylation used (linear or
branched) has been shown to also influence the NGO uptake
kinetics in different human and murine cell lines, apart from
the specific characteristics of the cell types, demonstrating
that the linear configuration is internalized more simply [101].
Starting from the initial experimental concept that CNTs
could be used for drug delivery [102–104], NGO was also
tested for the same purpose [105]. The first NGO-PEGylated
carrier was developed to deliver water-insoluble aromatic
anticancer drugs into cells [105]. The compound complete
of the drug (SN-38) exhibited a cytotoxicity for human colon
cancer cells line 1000-fold higher than irinotecan, an SN-38
prodrug approved for the treatment of colon cancer. Another
experimental study employing a CD20+ antibody-conju-
gated NGO–PEG demonstrated that the NGO drug delivery
is pH dependent [88]. Following this report, the pH-related
drug release has been tested and confirmed by many differ-
ent NGO-delivery systems [8,84,106]. A more recent paper
also inferred a thermo-responsive drug delivery using the
capability of the poly-N-isopropylacrylamide (PNIPAM) to
pass from the hydrophilic to the hydrophobic phase at 33°C.
PNIPAM-grafted graphene sheets were conjugated with a
water-insoluble anticancer drug, camptothecin (CPT), and all
these molecules were linked by hydrophobic interactions. The
PNIPAM–graphene complex was able to load the drug with
a superior capacity and did not exhibit toxicity in vitro. The
same complex showed an elevated capacity of killing cancer
cells in vitro, demonstrating it as an effective vehicle for anti-
cancer drug delivery [107].
The combined use of multiple drugs is widely adopted in
cancer therapy. Nevertheless, few reports on nanomaterial-
based multiple drug-delivery systems have been addressed so
far due to technical difficulties. A paper by Zhang et al. ana-
lyzed the use of NGO as a carrier for the delivery of two anti-
cancer drugs. NGO was conjugated with folic acid (FA) and
Biomedical Applications of Graphene
then loaded with doxorubicin (DOX) and CPT. This complex
exhibited specific targeting and high cytotoxicity to human
breast cancer cells with FA receptors. More importantly, it
showed a higher cytotoxicity than when loaded with only one
drug [84].
The versatility of graphene allowed for different experi-
mental attempts at improving its use in the field of antitu-
mor therapy by using different mechanisms of delivery. To
enhance the anticancer effect, Yang et  al. [108] used the
magnetic properties of graphene, testing an NGO–Fe3O4
NP hybrid loaded with DOX in vitro. Their experiment was
specifically addressed against human breast cancer cells,
resulting in a clear controlled release of the drug. Dong and
colleagues investigated the potentialities of an NGO–PEG
system on the delivery of zinc phthalocyanine (a photosensi-
tizer [PS] for photodynamic therapy [PDT]) toward Michigan
Cancer Foundation-7 (MCF-7) breast carcinoma cells line.
Apart from a drug-loading efficiency up to 14 wt%, they dem-
onstrated a high phototoxicity under xenon light irradiation
[109]. Wen et  al. [110] developed an NGO disulfide-linked
PEG system for DOX delivery, subject to redox environments
by detachment of PEG chains. Moreover, in vitro studies with
human cervical carcinoma (Henrietta Lacks [HeLa]) cells
showed that DOX is 1.55 times more effectively released by
NGO disulfide-linked PEG than by the NGO–PEG system
alone. The authors hypothesize that the incorporation of a
stable PEG molecule on the NGO/DOX system can decrease
the drug release. Dembereldorj et al. [111] investigated both
in vitro and in vivo glutathione-triggered DOX release in real
time from the NGO–PEG platform. In vitro studies on A549
cells demonstrated a drug-delivery efficiency of 23.5 wt%
after treatment with 2-mM glutathione within 15 min. They
also observed an increase of 2.5 times in vitro drug release
on cells by externally triggering glutathione ethyl ester rather
than endogenous glutathione. In vivo studies demonstrated
the possibility to monitor the real-time release of DOX by
fluorescence images after an external trigger with glutathione.
NGO can also be functionalized with other types of highly
hydrophilic and biocompatible polymers, such as polyvinyl
alcohol (PVA). The complex made up by NGO–PVA and CPT
had a higher cytotoxicity when compared to free CPT.
A lot of other molecules were tested to further increase
the stability of NGO in water and physiological fluids, among
these gelatin (GE) [112] and chitosan (CS) [85]. GE can medi-
ate the drug release in vitro. The compound NGO–GE–
DOX showed high toxicity for MCF-7 cells, in comparison
with the NGO–GE that was shown to be not toxic under the
same experimental conditions for concentrations higher than
200 µg/mL [112]. The covalent functionalization of NGO
with CS exhibits an interesting potential as a drug-delivery
platform with high cytotoxicity to human hepatocellular car-
cinoma cells line (HepG2) and HeLa cells when compared
with the delivery of the CPT alone [85]. The same study
demonstrates that cationic GO–CS nanoplatform can also be
applied as a vector for gene therapy due to the ability to con-
dense plasmid DNA on its surface: the in vitro experiments
with HeLa cells exhibit transfection efficiency.
45
The evolution of NGO studies as an oncologic drug delivery
allowed to shift the interest toward the employment of NGO-
based drug-delivery systems in other diseases. Thus, NGO
exhibited a capability in anti-inflammatory drug (Ibuprofen)
delivery, controlled by the pH value [113].
4.4.2 Gene Delivery
Gene therapy is a novel and promising approach to treat
genetic diseases requiring efficient and safe gene vectors that
not only enable an efficient cellular uptake, but also protect
oligonucleotides from enzymatic cleavage [114].
NGO is a promising gene delivery nano-vector with low
cytotoxicity and high transfection efficiency. When NGO is
conjugated with positively charged polyethylenimine (PEI),
it allows the condensation of plasmid DNA onto its surface
through electrostatic interaction. The complex NGO–PEI per-
mits the development of carriers for the delivery of genes or
oligonucleotides, as vectors. PEI and its derivatives have been
recognized as some of the most effective and powerful cat-
ionic gene-delivery vectors due to their high cationic-charge
density at physiological pH that improves the DNA and ribo-
nucleic acid (RNA) binding and condensation efficiency, while
being able to release the loaded DNA or RNA into the nucleus
or cytoplasm, respectively, when the amine groups of PEI are
protonated [115]. The complex NGO–PEI can be obtained by
covalent linking via amide bond formation [116] or noncova-
lent linking based on electrostatic and hydrogen interactions
[117]. Several options have been developed for gene therapy
based on NGO–PEI with DNA [116–119] or RNA [120,121],
showing high transfection efficiency and low cytotoxicity
in vitro. A high DNA transfection rate was surprisingly dem-
onstrated in HeLa cells after GO­–PEI delivery even in the
presence of 10% fetal bovine serum [116]. Although PEI is
widely used in gene transfection due to its high transfection
efficiency, PEI grafted to other compounds usually leads to a
decrease in transfection efficiency. Moreover, serum protein
can hinder cellular uptake, thus reducing the transfection effi-
ciency [116]. The reasons of this phenomenon need further
studies to be elucidated. Another experiment confirmed the
bond between NGO–PEI with plasmid DNA for intracellular
transfection in HeLa cells [119]. PEI can be conjugated in dif-
ferent molecular weights, 1.2 or 10 kDa: both complexes are
stable in physiological solutions. Feng et al. [122] examined
the transfection efficiency of GO–PEI-1.2k and GO–PEI-10k
and compared them with the unbound polymers PEI-1.2k and
PEI-10k, respectively. Their experiment demonstrated that
grafting PEI to GO not only significantly lowered the cyto-
toxicity of the cationic polymer, but also improved the trans-
fection efficiency of the polymer, suggesting that GO–PEI can
be a promising candidate for efficient gene delivery. A paper
by Zhang et  al. showed that GO–PEI can load siRNA and
DOX efficiently, and deliver both into cancer cells obtaining
a synergistic effect to enhance chemotherapy efficacy [123],
confirming the role of GO in anticancer gene therapy.
Starting from the hypothesis that the cytotoxicity is the main
problem in gene delivery caused by the high concentration of
46
DNA-condensing compounds required for an efficient uptake
of DNA, Zhou et al. [118] reported a new NGO–PEI system
with an ultrasmall GO. Removing the free PEI and ensuring a
high PEI density on small-sized graphene, they obtained high
transfection efficiencies combined with a very low cytotoxic-
ity. Plasmid DNA could be transfected into mammalian cell
lines with up to 95% efficiency and 90% viability compared to
efficiencies of 30% or lower for established transfection tech-
nologies available.
With the aim of increasing the effectiveness of NGO
platforms, sequential delivery of DOX and Bcl-2-targeted
siRNA to HeLa cells using a GO–PEI nanocarrier was per-
formed. The cytotoxicity assay revealed that the GO–PEI–
Bcl-2-targeted siRNA complexes dramatically enhanced the
cytotoxicity of the GO–PEI–DOX, compared to the GO–PEI
siRNA complexes, confirming a strong synergistic antican-
cer effect of the GO–PEI–DOX and GO–PEI–Bcl-2-targeted
siRNA [124].
The synthesis of GO–CS sheets and their application for
drug and gene delivery has also been investigated. GO–CS
can condense plasmid DNA into stable NPs, transfecting
DNA with a high efficiency in HeLa cells [85].
4.4.3 Photothermal and Photodynamic
Cancer Therapy
Photothermal and photodynamic therapies use infrared elec-
tromagnetic radiation to treat various medical diseases. The
basic model employs a PS excited with a specific band light.
This activation brings the sensitizer to an excited state where
it releases vibrational energy in the form of heat. Unlike PDT,
photothermal therapy does not require oxygen to interact with
the target cells or tissues. Moreover, current studies show that
photothermal therapy is able to use longer-wavelength light,
which is less energetic and therefore less harmful to other
cells and tissues.
The photoluminescence of NGO was also investigated
along with the potential application on photothermal cancer
cell therapy. Li et al. [125] observed that intensive microbub-
bling can be induced by irradiation at a laser power lower than
4 mW in the presence of NGO causing instant cell damage.
Further studies demonstrated that, after cell internalization,
NGO is preferentially localized on F-actin filaments inducing
cell-cycle alterations, apoptosis, and oxidative stress [126].
Although the majority of studies concerning the application
of graphene in drug delivery have been performed through
in vitro tests, Yang et al. [127] for the first time studied the
in vivo tumor uptake and photothermal therapy with NGO
PEGylated using xenograft tumor mouse models. They
observed very high tumor uptake of the PEG-modified GO
due to a highly efficient tumor-passive targeting of GO caused
by the enhanced permeability and retention effect. Moreover,
a highly efficient tumor ablation was achieved under the low-
power NIR laser irradiation, thanks to the strong absorbance
of GO in the NIR region. Reduced NGO (rNGO) with a
strong optical absorption in the NIR region due to the higher
restructuration of the aromatic structure combined with the
Graphene Science Handbook
noncovalent bond PEG shell, showed a remarkable improve-
ment in the in vivo photothermal cancer treatment. The
results obtained an efficacy of 100% on tumor elimination
after intravenous injection at a lower power density (0.15 W/
cm2) [41]. This new approach showed a higher efficiency in
the in vivo tumor treatment when compared with non-rNGO
PEGylated. Markovic et al. [39] compared the photothermal
anticancer activity of NIR-excited graphene and CNT in
human glioma cells. Despite its lower NIR-absorbing capac-
ity, polyvinylpyrrolidone-coated graphene NPs display higher
photothermal responsiveness, and induce photothermal cell
death because of oxidative stress, mitochondrial membrane
depolarization, and activation of the necrosis and apoptosis
processes in comparison with single-walled CNT. Zhang et al.
[40] developed an NGO–PEG–DOX for the antitumor effect
in vitro and in vivo by the combination of photothermal and
chemotherapies. The combined chemo-photothermal therapy
exhibited a synergistic effect that leads to better cancer killing
than chemotherapy or photothermal therapy alone.
Important limitations in the in vivo use of graphene
nanosheets for photothermal therapy are to be considered
[128]. The limited penetration depth of NIR irradiation in
body tissues causes inefficient ablation of deeply located
tumors as well as large tumors. Although this problem can be
overcome by using NIR irradiation having a relatively high
optical power [39,40], this energy can damage the surface and
the surrounding healthy tissues. Meanwhile, since graphene
exhibited some concentration-dependent cytotoxic [129] and
genotoxic [130] effects mainly originating from the genera-
tion of reactive oxygen species (ROS) [131,132], a safe con-
centration of graphene (corresponding to ≈10 μg/mL or less)
[130,133] should be used in the clinical setting. Therefore, the
design and fabrication of new structures of graphene-based
nanomaterials that, despite their low concentrations, can
be effective in photothermal therapies are highly required.
Nevertheless, no investigation on photothermal therapy of
cancer using a safe concentration of graphene at an ultralow
laser power has been reported yet.
Graphene and its derivatives are also the subject of PDT
studies. PDT allows the noninvasive treatment of diseases with
low toxicity and high stability under physiological conditions
[134]. Unlike photothermal therapy, PDT requires oxygen to
interact with the target cells or tissues, and involves the uptake
of PSs by cancer cells followed by irradiation. One of the PS
molecules most used is Chlorine6 (Ce6), due to its capacity to
generate cytotoxic singlet oxygen when exposed under light
excitation. However, the lower solubility on biological fluids
remains a problem. Huang et al. [135] reported the application
of FA and sulfonic acid-conjugated GO loaded with porphy-
rin PSs for targeting PDT. GO was loaded with a PS with
high efficiency via hydrophobic interactions. Such a system
significantly increased the accumulation of PSs in stomach
cancer cells, leading to a remarkable concentration-dependent
photodynamic effect on tumor cells under irradiation. Tian
et al. [136] further studied photothermally assisted PDT using
GO loaded with a PS and demonstrating that such combined
treatment yields a remarkably improved cancer-killing effect.
Biomedical Applications of Graphene
4.4.4  Biosensing and Bioimaging
A biosensor is a physicochemical analytical device used for
the detection of a specific biological molecule. Nanomaterials
are exquisitely sensitive chemical and biological sensors.
Nanoscale materials demonstrate unique properties: their
large surface area to volume ratio can achieve rapid and low-
cost reactions, using a variety of designs.
Graphene derivatives, including not only GO, but also
pristine graphene, chemically rGO, [137] and doped graphene
[61] have been studied for their applications in biosensing and
detection of biomolecules such as thrombin [138], adenosine
triphosphate (ATP) [15], oligonucleotide [139], amino acid
[140], and dopamine [141]. Several types of GO-based bio-
sensors have been built, which include (1) novel fluorescence
resonance energy transfer (FRET) [15,138,139]; (2) FET-type
biosensors [142]; (3) controllable self-assembling of graphene
biomolecules to build highly ultrasensitive biosensors for the
detection of DNA and other molecules [139,143]; (4) graphene-
based nanoplatforms for matrix-assisted laser desorption/
ionization time-of-flight mass spectrometry (MALDI-TOF
MS) [140,144]; and (5) GO-based novel biosensors via elec-
trochemical principles [141,145].
The exploration of the possibilities of GO in biological
imaging is a relatively new field [16,88,96,146]. For the first
time, Sun et  al. [88] examined the cellular uptake of GO
PEGylated loaded with chemical drugs using intrinsic fluo-
rescence of GO in the NIR region. Later, another group [112]
studied GE-grafted rGO labeled with a fluorescence dye for
cellular imaging and drug delivery. Today, it is becoming pos-
sible to prepare NGO with a size of 10 nm or less—graphene
quantum dots (GQDs)—from chemical oxidation of graph-
ite [40,45] or a different solubilization chemistry [47]. These
GQDs exhibit intrinsic fluorescence, and can be used for
bioimaging. Pan et  al. [147] synthesized weakly fluorescent
GQDs with blue emission color through hydrothermal cutting
of GO, not useful for the current bioimaging. Treating these
same GQDs by exposing them to hydrazine vapor, the fluores-
cence significantly improved [45]. Surface functionalization
of GQDs with alkylamine also helps in enhancing the fluo-
rescence [46]. Recent papers confirmed that, compared with
other types of QDs, GQDs show excellent biocompatibility,
physiological solubility, and low cytotoxicity, and, moreover,
they can be used directly for intracellular imaging without
further surface processing or functionalization [48–49]. In
addition, GQDs possess unique optical properties such as pH
dependent and upconversion fluorescence behaviors [148]. The
upconversion fluorescence property of GQDs allows them to
be excited at the NIR region, making both in vitro and in vivo
biodetection and imaging efficient, safe, and without interfer-
ence from auto-fluorescence from the cells, organs, or tissues
in this region [149]. GO was also demonstrated as useful as
the contrast agent for cellular MR [96] in the form of com-
posites of dextran-coated Fe3 NPs and GO (Fe3O4 –GO). The
Fe3O4 –GO compound possesses good O4 physiological stabil-
ity and low cytotoxicity and exhibits significantly enhanced
cellular MR, able to detect cells at an iron concentration of
47
5 µg/mL with cell density of 2 × 105 cells/mL, compared with
isolated Fe3O4 –NPs.
The photoluminescence of NGO is the subject of research
for optical bioimaging [148]. Strong photoluminescence from
two-photon excitation can be induced in NGO by an ultra-
fast pulsed laser and this photoluminescence can be tailored
through varying the size of the nanosheets. The application of
this technique to cancer cell imaging has already been inves-
tigated in the gastric cancer cell line (AGS) [125], BT549
breast cancer cells line, and MG-63 human osteosarcoma
cell line [48]. Another combination deserving attention is
the NGO PEGylated applied in bioimaging after the func-
tionalization of terminal PEG amine groups with different
organic dyes (fluorescent labeling) [101,146]. It developed an
NGO-PEGylated platform functionalized with fluorescein for
intracellular imaging: this nanocomposite material showed
high rates of internalization on HeLa cells and excellent pH-
tunable fluorescent properties [146]. Specifically, NGO–PEG
functionalized with fluorescein isocyanate (FITC) allowed
the detection of biodistribution during in vitro cell internal-
ization [101,126]. The radiolabeling, binding different atoms
on NGO, such as 125I [100], 64Cu [150], and 66Ga [151] and
investigating their biodistribution through positron emission
tomography (PET) imaging, possesses very promising results
both in vitro and in vivo, demonstrating to be a much more
sensitive and accurate method in quantitatively tracking the
labeled substances in vivo.
4.5  MULTIFUNCTIONAL NANOPLATFORMS
The potential of NGO is to combine different therapy
approaches, such as chemotherapy, photothermal therapy, and
oxygen PDT, with bioimaging in order to develop a targeted
multifunctional nanoplatform with synergistic effects for
a more efficient cancer therapy. Multifunctional NGO plat-
forms can combine high targeting efficiency, good imaging
contrast, and extraordinary therapy efficacy for cancer cells.
The possibility of combination could be varying depending
on the “biostructure” of the specific tumor cells to be treated.
4.5.1 Organic NGO Platforms
The NGO-PEGylated compound possesses both higher bio-
logical stability thanks to the presence of the PEG and intrin-
sic photoluminescence of NGO for bioimaging. When the
NGO platform was targeted with the antibody anti-CD20 to
increase cell selectivity, and loaded with the anticancer drug
DOX, the effects of chemotherapy in vivo resulted in higher
selectivity and efficacy on the cancer cells, in comparison
to DOX alone or the same nanoplatform without targeting
units [88]. Another in vivo experiment with NGO PEGylated
loaded with DOX demonstrated a synergistic effect on the
elimination of the tumors without weight loss or recurrence
[40]. An NGO multimodal drug-delivery carrier platform
with active molecular targeting was developed by Zhang et al.
[84] through the covalent bonding of FA molecules to its sur-
face, to specifically target MCF-7 cells. The nanoplatform
48
NGO–FA was further functionalized with two anticancer
drugs, DOX and CPT via hydrophobic interactions show-
ing a high level of targeting efficiency to MCF-7 cells, and
high cytotoxicity when compared to NGO loaded with either
DOX or CPT only. Another multifunctional NGO platform
developed by Shen et al. [152] involves NGO–PEG–FA and
is further complemented with gadolinium (Gd3+) before being
loaded with DOX. In vitro MR testing of this multifunctional
platform showed a superior targeting imaging efficiency over
Gd3+ free materials and demonstrated drug release effective-
ness under tumor physiological conditions (pH 5.5), finally
resulting in a clear cytotoxic effect for HepG cells. rNGO
exhibits a sixfold higher NIR absorption, resulting in a more
efficient on-cell photothermal ablation. In order to increase
the physiological stability of rNGO, Robinson et  al. [129]
performed surface modification of rNGO with amphiphilic
PEG by covalent bonding. Afterwards, they targeted the sys-
tem with the peptide Arg-Gly-Asp (RGD) or control peptide
RAD in order to increase the selectivity to the U87MG cells.
In  vitro tests showed low cytotoxicity of rNGO–RGD plat-
forms; however, after NIR irradiation, they showed a high
efficacy for photoablation of cells. PDT uses the combination
of the PS Ce6 with GO nanocarriers previously modified with
the targeting molecule FA through simple noncovalent inter-
actions [135]. The resultant system can efficiently deliver Ce6
to the tumor due to high affinity of the targeting molecules to
MGC803 cells and can increase the photodynamic efficiency
upon irradiation. The combination of GO with Ce6 can result
in an efficacious and controlled drug-delivery system [136].
4.5.2 Hybrid NGO Platforms
Inorganic NPs have demonstrated a clear potential in a wide
range of cancer therapies [153,154]: iron oxide [155] and gold
NPs [156] are the ones most studied due to their intrinsic
properties. Several organic and inorganic hybrid materials
based on these kinds of NPs are already present in preclini-
cal stages or even in marketing. Their combination with NGO
could develop a powerful platform with synergistic effects.
A multifunctional NGO platform with Fe3O4, further loaded
with DOX, showed interesting magnetic and pH-triggered
controlled magnetic properties that make it a promising can-
didate for controlled targeted drug delivery [157]. The same
hybrid nanoplatform was developed by adding a targeting
molecule of FA [108]. A singular NGO platform with iron
oxide NPs was created by adding polyacrylic acid (PAA) for
linking the fluorescein o-methacrylate (FMA): this has been
made to increase the hydrophilic behavior and fluorescent
properties [158]. In vitro studies with HeLa cells showed that
nanoplatforms locate only in the cytoplasm and evidence
low cytotoxic effects. An immediate employment of NGO
loaded with iron oxide NPs is in the field of MR imaging.
This nanoplatform showed a good physiological stability, low
toxicity, and good internalization on HeLa cells. In addition,
imaging studies demonstrated the significant enhancement of
cellular MR when compared with iron oxide NPs alone [96].
Graphene Science Handbook
A truly multifunctional NGO platform with iron oxide NPs
was recently developed [159] assembled with posterior non-
covalent functionalization with PEG. It resulted in excellent
physiological stability, strong NIR optical absorbance, and
superparamagnetic properties, and has been used as a ther-
anostic agent for in vivo triple-modal imaging (fluorescence,
photoacoustic, and MR) and effective photothermal ablation
[159]. NGO modified with gold NPs also revealed an inter-
esting multifunctional nanoplatform for cancer imaging and
therapy. Wang et al. [160] performed the surface modification
of GO by electrostatic interactions with dodecanethiol–cetyl
trimethylammonium bromide (CTAB)-capped gold NPs with
rGO subsequently loaded with DOX. In vitro results showed
that these new nanoplatforms can cause the inhibition of
HepG2 cells and allow cellular imaging due to the surface
plasmon band of gold NPs. The system seems to have potenti-
alities for multimodal probes and as a drug carrier for target-
ing. Semiconductor QDs are high potential biomaterials, due
to brighter fluorescence, lower photoleaching, high resistance
to chemical degradation, and potential to perform photother-
mal therapy; however, they exhibit a high toxicity. In order to
reduce the levels of toxicity, Hu et al. [91] developed a new
multifunctional-based NGO platform with QDs by the use of
a spacer agent (an amphiphilic polypeptide, poly[l-lysine])
and targeted it with FA. In vitro studies with HeLa and MCF-7
cells demonstrated internalization by cells and revealed
insignificant cytotoxicity, with approximately 92% of cell via-
bility. The authors also evaluated the photothermal therapy
effects on MCF-7 cells irradiated at NIR wavelength at the
power of 2 W/cm2 for 4 min. They verified the efficiency of
the nanoplatforms with synergistic effects of NIR absorption
by GO–QDs. The design of GO-based theranostic platforms
with multifunctionalities and multimodalities is a new chal-
lenging field allowing thousands of possible combinations.
4.6 TOXICITY
Currently, a complete evaluation of the size, shape, compo-
sition, and aggregation-dependent interactions of NPs with
biological systems is lacking, and thus, it is unclear whether
the exposure of humans, animals, and plants to engineered
nanostructures could produce harmful biological responses
[3]. NPs constitute a part of particulate matter, and human
exposure to NPs has increased in the past century because of
the industrial revolution.
However, for the newly developed graphene and its deriva-
tives, such information is generally lacking to date. It is
evident that, thanks to the versatility of the NGO aromatic
molecular structure and the richness of its surface functional
groups allowing functionalization with small molecules,
graphene represents a key molecule to build up new hybrid
systems that can be useful in the imaging and treatment of
cancer. These approaches have already been explored with
both single- (SWCNTs) and multiwalled carbon nanotubes
(MWCNTs). However, some limitations, such as the pres-
ence of metallic impurities, homogeneous size, and length
Biomedical Applications of Graphene
distributions, argued the possible toxic effects [161]. In addi-
tion, their morphology, similar to that of asbestos [162], has
limited their potential biological applications. Some graphene
nanomaterials have aerodynamic sizes that can lead to inha-
lation and substantial deposition in the human respiratory
tract, which may impair lung defense and clearance leading
to the formation of granulomas and lung fibrosis [163]. The
limited literature on in vitro toxicity suggests that graphene
can be either benign or toxic to cells, and it is hypothesized
that the biological response will vary across the material fam-
ily depending on layer number, lateral size, stiffness, hydro-
phobicity, surface functionalization, and dose. The generation
of ROS in target cells is a potential mechanism for toxicity,
although the extremely high hydrophobic surface area of
some graphene materials may also lead to significant interac-
tions with membrane lipids leading to direct physical toxic-
ity or adsorption of biological molecules leading to indirect
toxicity. Limited in vivo studies demonstrate systemic bio-
distribution and biopersistence of graphene following intra-
venous delivery. Similar to other foreign bodies, graphene
has the potential to induce foreign body tumors. Long-term
adverse health impacts must be considered in the design of
graphene family nanomaterials (GFNs) for drug delivery, tis-
sue engineering, and fluorescence-based biomolecular sens-
ing [163]. With regard to the photothermal in vivo treatment,
both in vivo and in vitro toxicity studies did not show evi-
dence of cross effects under the level of experimental condi-
tions. A few in vitro studies compared the biocompatibility
between SWCNT and graphene. SWCNT showed inhibition
on cell proliferation in neuroendocrine cells, oligodendroglia,
and osteoblasts in contrast to rGO [164]. Moreover, SWCNT
generated higher lactate dehydrogenase levels in neural pheo-
chromocytoma-derived PC12 cells as compared to graphene
[131]. Anyway, the in vitro [131,132] and in vivo [165] studies
on the biocompatibility of graphene derivatives are still in a
preliminary stage, with only a few publications specifically
addressed [100,131,132,165–167] on this matter.
The functionalization degree of CNTs decreases their toxic-
ity and GO is generally more highly functionalized than CNTs
according to the oxygen content [132,168]. Therefore, good
biocompatibility of GO is generally expected in this regard.
Another aspect that might contribute to the high biocompatibil-
ity is the 2D structure of GO. Although the effect of shape on the
toxicity is still unknown in detail to date, many previous results
show that the shape affects the biological activity of nanoma-
terials [169]. Obviously, the physicochemical properties of GO
are closely related to its cytotoxicity and in vivo biodistribution
[14], with mechanisms that seem related to oxidative stress and
damage of the cell membrane. At low doses, GO induces ROS
generation, but no obvious toxicity is observed. The oxidative
stress may contribute to the slight viability decrease of GO
at high concentration. The oxidative stress induced by GO is
moderately low when compared to fullerenes and CNTs. NGO
includes a large variety of nanostructures with variable charac-
teristics and properties [132]. Consequently, due to the resul-
tant immunotoxicological heterogeneity, it is very complicated
49
to provide a complete safety evaluation. Moreover, variations
may occur such as interactions with immune cells, different
inflammatory responses, different antigen-specific hypersen-
sitivity reactions, etc. This is the reason why opposite and
conflicting findings have commonly been reported. In vivo
studies on a mice model of NGO PEGylated evidenced that
after intravenous administration, NGO PEGylated mainly
accumulates in the reticuloendothelial system including the
liver and spleen, and it can be gradually cleared up, most prob-
ably by both renal and fecal excretion [100]. Additional in vivo
studies found a highly efficient tumor-passive targeting and
relatively low retention in reticuloendothelial systems [127].
After intravenous administration of GO in a mice model, GO
doses of 0.1 and 0.25 mg did not exhibit toxicity. However,
GO doses of 0.4 mg exhibited chronic toxicity. Careful analy-
sis showed that administration of high doses of GO leads to the
lung granuloma formation. However, other studies showed no
significant toxicity after 3 months of injection of GO at 20 mg/
kg in a mice model both in blood analysis and histological
examinations [100,127]. Most in vitro studies agree that GO
promotes cytotoxicity mainly through generating ROS in a
dose-dependent manner that induces oxidative stress [99,158].
Graphene can generate ROS in neural pheochromocytoma-
derived PC12 cells by time/concentration dependence and also
cause apoptosis for concentrations up to 10 μg/mL [131]. The
induction of apoptosis was also observed in human fibroblasts
for GO concentrations of 50 μg/mL. In human lung epithelial
cells, GO doses of more than 50 μg/mL showed no toxicity
in vitro [132], but higher GO concentrations cause a dose-
dependent oxidative stress in these cells and a slight loss of cell
viability. Other parameters such as the hydrophilic character
[166], dose levels, and lateral dimensions [170] of graphene
make a decisive contribution to the assessment of biocom-
patibility. In vitro studies of NGO PEGylated assessed the
cytotoxicity when bound to 1,2-distearoyl-sn-glycero-3-phos-
phoethanolamineN-(amino[polyethyleneglycol]) (DSPE) with
four different types of cells: HeLa cells derived from cervical
cancer tissue, National Institute of Health 3T3 mouse fibroblast
cells (NIH-3T3), Sloan Kettering breast cancer cells (SKBR3),
and MCF-7 breast cancer cells. The results suggested that the
NGO compound has different cytotoxic effects on the four
cell lines, HeLa being the one that exhibited greater toxicity
compared to the other cell lines. In the human lung adenocar-
cinoma epithelial cell line A549, NGO PEGylated suggested
no cytotoxicity effect [171]. Conversely, a study [132] on the
toxicity of GO performed in A549 cells revealed that GO does
not enter the cell and has no obvious cytotoxicity, but can cause
a dose-dependent oxidative stress and induce a slight loss of
cell viability at a high concentration. These effects are dose
and size related.
These results suggest that graphene derivatives have a mul-
titude of chemical structures and morphologies and possibili-
ties of combination that requires long-term studies of toxicity
and biocompatibility in order to assess dose and specificity on
different tissues before becoming of current use in biomedical
human applications.
50
4.7  GRAPHENE IN NEURO-ONCOLOGY
Cerebral gliomas account for about 45% of all primary cen-
tral nervous system tumors and 77% of all malignant primary
brain tumors [172]. The overall diagnosis of brain tumors is
growing. The American National Cancer Institutes of Health
estimate 23,130 new cases of brain tumors in the United
States in 2013 with 14,080 deaths (http://www.cancer.gov/
cancertopics/types/brain).
Current therapy of brain glioma is unsatisfactory due to
the low therapeutic efficiency and strong systemic side effects
of postsurgical chemo- and/or radiotherapy protocols. The
prognosis still remains poor with less than 2 years of median
survival [173]. Overcoming the BBB would significantly
improve the delivery of targeted drugs to malignant glioma
cells. Moreover, the synergy between chemo- and photother-
mal targeted therapy would enhance specificity, decreasing
side effects. In this view, nanotechnology and nanoengi-
neered devices developed for medical purposes can represent
ideal devices for the delivery of specific compounds to brain
tumors, across the BBB [1–3].
Graphene nanoplatelets, namely single layers of carbon
atoms having nanoscale lateral dimensions, are insoluble and
possess a difficult interfacial interaction with the targeting
matrix [174]. They absorb insoluble molecules via noncovalent
binding [175], with low drug-loading efficiency. The coating of
silica NPs, which are good vectors for insoluble chemothera-
peutic drugs [176,177], on a graphene nanosheet could improve
the interfacial properties of graphene. It has also been consid-
ered that the morphology of different glioma cells, the molecu-
lar status of cell lines, and the concentration of graphene may
regulate the biological response of tumoral cells.
One of the first attempts at using graphene for the treat-
ment of gliomas employed its property as a carrier [178]. The
chemotherapeutic drug 1,3-bis(2-chloroethyl)-1-nitrosourea
(BCNU), widely used for the treatment of brain tumors, has
poor thermal stability and a short half-life. Immobilization of
BCNU on a nanocarrier might increase its stability and extend
its half-life. NGO was conjugated with PAA to improve the
aqueous solubility and increase the cell penetration efficacy,
and used as a nanocarrier for BCNU. This nanocarrier sig-
nificantly prolonged the half-life of bound BCNU from 19 to
43 h and showed an efficient intracellular uptake by GL261
cancer cells. The in vitro anticancer efficacy of PAA–GO–
BCNU was demonstrated by a 30% increase in DNA inter-
strand cross-linking and a 77% decrease in the half-maximal
inhibitory concentration of the drug [178].
The photothermal activity of graphene has also been inves-
tigated in the treatment of brain tumors [39]. The mechanisms
of graphene-mediated photothermal killing of cancer cells
apparently involved oxidative stress and mitochondrial mem-
brane depolarization resulting in mixed apoptotic and necrotic
cell death characterized by caspase activation/DNA frag-
mentation and cell membrane damage, respectively. Despite
a lower NIR-absorbing capacity, a suspension of polyvinyl-
pyrrolidone-coated graphene sheets exposed to NIR radiation
generated more heat than CNTs under the same conditions.
Graphene Science Handbook
Subsequently, graphene NPs performed significantly better in
inducing photothermal death of U251 human glioma cells in
vitro. The superior photothermal sensitivity of graphene sheets
could be largely explained by their better dispersivity [39].
A more recent study combined the chemo-photothermal
targeted therapy of glioma within one novel multifunc-
tional drug-delivery system using a targeting peptide (IP)-
modified mesoporous silica-coated graphene nanosheet
(GSPI) [179]. DOX was conjugated with the GSPI-based
system (GSPID), showing synergistic chemo-photothermal
properties. Cytotoxicity experiments demonstrated the high-
est rate of death of glioma cells compared to that of single
chemotherapy or photothermal therapy. Furthermore, the IP
modification could significantly enhance the accumulation of
GSPID within glioma cells [179]. A study by Jaworski et al.
[180] examined the toxicity of graphene platelets in U87
and U118 glioma cell lines. They revealed that graphene is
toxic to glioma cells, indicating the potential applicability of
graphene platelets in glioma therapy. Because of their large
surface area, graphene platelets did not enter into glioma
cells, but adhered to them. The mechanism they explained
concerns the different biological impacts of graphene elec-
trons on various cell and tissue types, and the subsequent
interaction with cell membranes and receptors, blocking the
supply of nutrients, inducing stress, and activating apopto-
sis. This direct interaction between platelets and tumor cells,
caused by their chemical or/and physical properties, indi-
cates that this effect might depend on the surface morphol-
ogy of the cells. In fact, the properties of glioma cells may
vary depending on the cell line [181]. Exposure to graphene
induced apoptosis in both glioma cell lines but with different
results: 68% in U87 and 99% in U118 cells. The activation
of apoptosis was also observed in a study on the influence of
graphene and nanotubes on the U251 glioma cell line, which
was treated photothermally [39]. Moreover, mechanisms
of necrosis were also present—24% in U87 cells and 0.2%
in U118 cells. U118 cells have a reduced expression of the
antiapoptotic gene Bcl2 and of the suppressor gene PTEN,
allowing for apoptosis, in contrast with U87 cells. The pre-
cise mechanism of apoptosis is still unknown. However, it
is clear that because of a mutation of the gene p53 in U118
cells, this gene is not involved in apoptosis activation [182].
Recently, graphene nanoplatelets have been employed as one
of the most promising nanomaterials in photothermal can-
cer therapy [35,183]. Akhavan and Ghaderi [128] developed
an ultraefficient in vivo photothermal cancer therapy using
reduced graphene oxide nanomeshes (rGONMs) in mouse
models. By this method, simultaneous application of an
ultralow concentration (10 μg/mL) of injected rGO-based
composites and an ultralow laser power irradiation in an in
vivo tumor ablation with 100% efficiency was provided. Such
a high efficiency was principally assigned to the extraordi-
nary NIR absorbance of the rGONMs (as one of the novel
structures of graphene) as compared to the absorbance of
the rGO sheets and the rGONPs (as known graphene-based
nanomaterials are usually applied for investigations on
advanced photothermal therapy). Meanwhile, effective tumor
Biomedical Applications of Graphene
targeting by the RGD-functionalized rGONM (due to target-
ing αβ integrin receptors overexpressed on U87MG cells
by the RGD-based peptide) was found to be another impor-
tant parameter in improving the efficiency of the therapy, as
indicated by fluorescence imaging. The results of this work
suggest that rGONM–PEG–Cy7-RGD is one of the most
promising nanomaterials in the development of ultraefficient
cancer diagnosis and therapy with low side effects.
4.8 OPENED CHALLENGES AND
FUTURE DIRECTIONS
Graphene provides fascinating opportunities in various sci-
entific fields, and the research on the biomedical applications
of graphene has made a rapidly dramatic progress [184]. The
new field opened thanks to graphene is encouraging, but has
to face the challenges that are present when it has to be applied
to human beings.
One such challenge is the thorough understanding of gra-
phene–cell interactions, especially the cellular uptake mecha-
nism. Such knowledge certainly facilitates the development
of more efficient GO-based nanoplatforms. It is mandatory to
have a deep understanding of the integration of the immuno-
logical, metabolic, and pharmacological processes to provide
insight into how cells respond to NGO. The development of
suitable chemical synthesis and functionalization approaches
for precise control over the morphology and distribution of GO
is closely related to the performance and safety of GO-based
nanomaterials for biomedical applications.
The in vitro and in vivo toxicity of GO is another major
concern. At the current stage, there are only a few publica-
tions in this regard [100,131,132,165–167], and no study has
been ethically admitted nor performed in humans. Thus, it
is necessary to identify potential toxicities for each mate-
rial, including physiology, biodistribution, phagocytosis, and
endocytosis and establish risk/benefit considerations for every
nanoplatform system.
For GO-based biosensing based on the FRET principle,
tuning the electronic property of GO and the development
of techniques to integrate GO into practical devices with
high sensitivity and selectivity is hampered by an acceptable
reproducibility, reliability, and low cost. As for GO-based
bioimaging, although the GQDs have distinct advantages
over QDs, the weak fluorescence intensity and broad emis-
sion band are major obstacles for their use in biodetection
and labeling; so, more efforts must be made to prepare GQDs
with a good control of size and distribution, surface defects,
and functionalization. GO is able to accelerate the growth,
differentiation, and proliferation of stem cells, and therefore
holds great promise in tissue engineering and regenerative
medicine. The research on GO-based materials for cell cul-
ture is a relatively new direction. Specifically, neural stem
cell (NSC)-based therapy requires a scaffold to provide a cell
growth microenvironment and appropriate synergistic guid-
ance. Li et  al. [185] report the first utilization of graphene
foam, a three-dimensional (3D) porous structure, as a novel
scaffold for NSCs in vitro. The three-dimensional graphene
51
foams (3D-GFs) not only supported NSC growth, but also
kept cells at a more active proliferation state with upregula-
tion of the Ki67 expression than that of 2D graphene films.
Moreover, phenotypic analysis indicated that 3D-GFs plat-
form can enhance the NSC differentiation toward astrocytes
and neurons. It is highly probable that the current research on
the delivery of drugs and genes will extend to the employment
of various proteins such as growth factors, not only for cancer
but also to treat other diseases.
Concluding, there is currently no definitive study regarding
the potentialities or risks of NGO systems. They offer many
opportunities for cancer therapy, but their interaction with
biological tissues: normal or carcinogenic has not yet been
fully elucidated. Overall, an improved specificity to tumor
cells is expected from these therapeutic agents to allow for
shorter recovery times and a diminution of side effects.
The ultimate goal of NGO research as a therapeutic agent
in cancer therapy will be the improvement of life expectancies
and a reduction in the cost of treatments of oncologic patients.
The commercialization of a new versatile material such
as graphene is still uncertain. It is at an experimental level,
especially in the biomedical field, and for this reason, it has
to be tested under different settings. Moreover, there is often
a considerable time lag between the experimental scientific
results, the development of a new technology, its validation,
and its adoption by industries. Notwithstanding, the pivotal
role of graphene in the near future is testified by the fact that
in 2013, the European Commission announced a 1-billion
euro funding for a large-scale project aimed at studying gra-
phene and developing its production and applications [186].
Naturally, the more this nanomaterial is used, the more its
cost will dramatically drop; moreover, optimized techniques
of synthesis caused an additional reduction: while in 2008,
graphene was one of the most expensive materials, costing
about $100,000,000/cm2, now, it is possible to buy rGO for
approximately $270/g [187].
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 5 Graphene Biodevices
Xiaochen Dong, Beibei Zhan, and Wei Huang

CONTENTS
Abstract........................................................................................................................................................................................ 57
5.1 Introduction........................................................................................................................................................................ 57
5.2 Applications of Graphene-Based FETs for Biosensors...................................................................................................... 57
5.2.1 DNA Detection....................................................................................................................................................... 57
5.2.2 Protein Detection.................................................................................................................................................... 59
5.2.3 Cells or Bacteria Detection..................................................................................................................................... 63
5.2.4 Glucose Detection................................................................................................................................................... 66
5.2.5 Other Applications for Biosensors.......................................................................................................................... 67
5.3 Conclusion.......................................................................................................................................................................... 68
References.................................................................................................................................................................................... 69

ABSTRACT doubt that graphene-based sensors will attract more interest

Graphene has attracted tremendous attention in recent years
because of its unique electronic, thermal, and mechanical
properties. Here, the development of sensitive and selective
field-effect transistors (FET) biosensors based on graphene is
systematically reviewed. It indicates that graphene FETs are
promising candidates for the development of nanoelectronic
biosensors.
5.1 INTRODUCTION
It is well known that graphene possesses a large amount of
extraordinary properties involving electrical, physical, struc-
tural, and mechanical performances compared with con-
ventional carbon materials.1–4 Graphene, as an exciting new
material, is considered as a promising candidate for high-
frequency devices and has attracted a great deal of interest
in optical science, materials science, nanoelectronics, and
bioscience.5,6 The applications of graphene-based electronic
(field effect transistors) or electrochemical (electrodes) sen-
sors have rapidly broadened in the biological and chemical
field owing to these outstanding performances, especially
high intrinsic carrier mobility and bipolar field-effect char-
acteristics together with perfect flexibility and transparency.7,8
Reduced graphene oxide (RGO) obtained by thermal, chemi-
cal, or photothermal reduction of graphene oxide (GO) is
substantially different from pristine graphene due to the oxi-
dative process. However, the scalable and simple synthesis
and good biocompatibility of RGO still make it show high
potential in the detection of sensors with high sensitivity and
selectivity.9 In addition, compared with pristine graphene,
the superior advantage of RGO is that the chemical groups
on its surface are beneficial for modifications to accurately
identify the specific sensing targets. Moreover, the different
structures of graphene (nanoribbon or nanomesh, and so on)
cause distinguishing detection characteristics.10,11 There is no
to be employed in the sensing field including the chemical
molecules (gaseous molecules,12,13 metal ions14 or pH,15,16 etc.)
and biological molecules, as shown in Table 5.1.
In this chapter, we mainly describe some fabrication meth-
ods and various biosensing applications based on graphene
field-effect transistors (FETs). Finally, the perspectives and
current challenges of graphene for biosensors are mentioned
and some available suggestions are provided for further explo-
ration. It will give the researchers possible promise and indi-
cate the forward direction for the development of biomolecule
detection with novel and excellent graphene materials.
5.2 APPLICATIONS OF GRAPHENE-
BASED FETs FOR BIOSENSORS
With its unique combination of structural and electronic prop-
erties, graphene becomes a promising candidate material for
sensors that are vital to biological or chemical fields. On the
other hand, graphene possesses superior biocompatibility and
extremely high chemical stability, which makes it possible to
open up exciting opportunities for social problems including
healthcare, security, and life science. The common opera-
tional principle of graphene bioelectronic sensors is based on
the change of graphene electrical conductivity after adsorp-
tion of molecules on its surface. In this section, the role of
biosensing applications based on graphene FETs is discussed
in detail with emphasis on the detection mechanisms and
their relative advantages. Some of the biosensing applications
based on graphene FETs are summarized in Table 5.2.
5.2.1  DNA Detection
Graphene has received more and more attention and has been
widely employed in the detection of nucleic acids, such as sin-
gle-stranded DNAs, nucleobases, nucleotides, and so on. The
π–π interaction between the graphene hexagonal carbon ring
57
58 Graphene Science Handbook

TABLE 5.1
Applications of Graphene Materials on Electronic and Electrochemical Sensors
Electronic Sensors Electrochemical Sensors
Biological Field Chemical Field Physical Field Biological Field Chemical Field
DNA, RNA, protein, cells, Gas (NO2, SO2, NH3, H2, Phototransistor, thermal DNA, protein, glucose, hydrogen Gas (NO2, NH3, H2, etc),
bacterials, glucose, etc.), pH, metal ionic, etc. transistor, magnetism, peroxide, dopamine, etc. metal ionic, organic
hydrogen peroxide, etc. strain, etc. molecules, etc.

TABLE 5.2
Applications of Biosensors Based on Graphene FETs
Detected Biomolecules Biomolecules Detection Mechanisms Detection Limit References
Nucleic acids DNA P-doping effect 17
N-doping effect 0.01 nM 18
Proteins Immunoglobulin E (IgE) Field effect 0.29 nM 19
Immunoglobulin G (IgG) Scattering effect 13 pM 20
Fibronectin N-doping effect 0.5 nM 21
Cells and bacteria E. coli bacteria Field effect 10 cfu mL−1 22
Neuroendocrine PC12 cells P-doping effect 23
Others biomolecules Glucose P-doping effect 0.1 mM 24
Gutamate 5 μM
Adenosine triphosphate (ATP) P-doping effect 5 μM 25

and the ring structure in nucleic acid provides the convenient
conditions to ensure accurate detection. As a matter of fact, the
first significant investigation on DNA detection was reported by
Mohanty and Berry in 2008.17 In this experiment, the electri-
cal characterizations of the hybridization between probe DNAs
anchored on graphene sheet and complementary DNAs or non-
complementary DNAs were considered as an important biomo-
lecular transistor parameter. In detail, the increased response
current was chiefly attributed to the generation or removal of
one quanta of hole after the complementary strands in DNAs
that functionalized with fluorescence groups were added to
hybrid with the probe DNAs. However, there was no variation
after the addition of non-complementary DNAs. From this pos-
itive variation conductivity, the target DNAs can be selectively
detected easily. The result gave researchers a deep impres-
sion and indicated the forward direction of the development
of highly sensitive biosensors with graphene materials. Then,
a large amount of outstanding and valuable reports involving
label-free and sensitive detection of DNAs based on graphene
FET have been delivered. Dong et al.18 fabricated electrical
devices with chemical vapor deposition (CVD)-grown large-
size graphene sheets for DNA detection, which was similar with
that of the aforementioned experiment. From the Ig − Vg curves
(Figure 5.1), it was observed that the infusive result showed a
high detection sensitivity (~0.01 nM) in buffer solution, which
was more sensitive than doubled-walled carbon nanotube
(DWNT) network devices.26 Moreover, the device was able to
distinguish the single base mismatch DNA according to the

(a) (b) Bare

5.0 × 10–4 Bare Complementary Mismatched
2.5 × 10–4 Probe
Probe 0.01 nM 0.01 nM
4.0 × 10–4 0.1 nM
2.0 × 10–4

3.0 × 10–4
Id (A)

Id (A)

1.5 × 10–4 1 nM
0.1 nM
1 nM 10 nM
2.0 × 10–4 10 nM 1.0 × 10–4 100 nM
100 nM
500 nM
500 nM
1.0 × 10–4 0.5 × 10–5
–0.5 0.0 0.5 1.0 1.5 –0.5 0.0 0.5 1.0 1.5
Vg (V) Vg (V)

FIGURE 5.1  Illustration of transfer curves for bare graphene FET, after immobilization with probe DNA, and after hybridization of
(a) complementary or (b) one-base mismatched DNA molecules with different concentrations.
Graphene Biodevices
shift of Vg,min. Compared with Berry, Dong et al. demonstrated
a different opinion on the identical mechanism that the negative
shift of Vg,min owing to electron transfer (electronic n-doping
effect) from DNA molecules to graphene instead of the non-
specific binding between complementary DNAs and graphene,
electrostatic gating effect and the impurity screening mecha-
nism. Furthermore, the upper detection limit could be extended
to 500 nM from primary 10 nM after the modification of gra-
phene surface with Au nanoparticles (NPs). The detailed detec-
tion mechanism was also demonstrated.
In addition, a facile and cost-effective approach to fabricate
label-free and sensitive DNA sensors based on graphene FET
was described by Guo and coworkers.27 However, there was a
different point that 1-pyrenebutanoic acid succinimidyl ester
was used to functionalise the graphene surface to ensure high
conductivity and sensitivity for biomolecules. It was a pity that
the detection limit could reach as low as 3 nM, which is higher
than that of the previous reports. Ohno et al.28 also made some
efforts to detect DNA and give a quantitative analysis of elec-
trical biosensing based on graphene FETs. The results showed
that one probe DNA could be attached on the active channel per
100 nm2. And among that, 30% of attached probe DNAs was
hybridized with 200 nM full-complementary DNA, while only
5% of probe DNAs was bound to the noncomplementary DNA.
Since graphene-based devices possess great application
potential in biosensors, more and more workers have explored
various methods to achieve the best detection state. For example,
researchers have made an attempt to improve the DNA detec-
tion sensitivity of a graphene device through optimizing the
gate materials, buffer concentration, and graphene surface con-
dition.29 Effects of gate materials including silver wire, natural
graphite needle, and platinum filament on detection sensitivity
was studied first. As shown in Figure 5.2a, owing to the fact
that the charge neutrality point, VCNP (the applied gate voltage
corresponding to the minimum conductance) is too high, plati-
num filament is not preferred as the gate material. However, the
lowest VCNP of the device with natural graphene needle or silver
wire electrode was still selected as the best material for DNA
detection to avoid the undesirable electrochemical reactions at
the exposed graphene edges. After that, they concluded that the
lower concentration of electrolytes resulted in higher detection
sensitivity, as shown in Figure 5.2b. On the contrary, a very low
concentration was obviously not beneficial for solution gating
operation. In addition, the authors tried to use Au as a trans-
fer supporting layer rather than the commonly used PMMA
in the transfer process; the result turned out to be successful
according to the relatively much cleaner surface, Figure 5.2d
and e. Combing the aforementioned content, the optimized liq-
uid-gated graphene device for short-chain DNA sensing could
achieve high detection sensitivity as low as 1 pM.
Graphene has exhibited great application potential in biosen-
sors, but the low yield of pristine graphene obtained through
mechanical cleavage and the CVD process greatly limits its
development, which stimulated researchers to make further
relative study. Dong et  al. carried on another experiment to
explore the potential of graphene–Au nanocomposites FET in
nanoelectronic biosensing. The g­ raphene–Au nanocomposites
59
were obtained from chemically RGO assisted by microwave
irradiation (MWI) in aqueous media.30 Apparently, the thio-
lated probe DNAs could immobilize on Au NPs, and then the
complementary target DNAs were added by hybridization and
made the corresponding current changes. They demonstrated
that RGO-Au sheet FETs exhibited higher hole mobility with
~9.0 cm2/Vs (slope of the Id − Vg curve at p-region) compared
with that (~0.015 cm2/Vs) of bare RGO FETs. The DNA detec-
tion results indicated that the resulting FET presented excellent
DNA sensing properties, Figure 5.3. It enlightened researchers
that the Au NPs were useful for conjugating biomolecular probes
on the channel surface, improving the DNA detection sensitivity.
Different from Dong, Yin31 and his colleagues used Pt NPs
to decorate RGO FET and realized DNA detection. First, an
RGO thin film was produced through the Langmuir–Blodgett
(LB) method32 followed by thermal reduction, and then Pt
NPs were synthesized onto RGO surface directly by photo-
chemical reduction. Pt NPs became the linker between thi-
olated probe DNA and RGO surface. To one’s satisfaction,
the detection limit of the RGO biosensor for real-time detec-
tion of a single-stranded DNA could reach as low as 2.4 ​nM.
Recently, an ultrasensitive label-free DNA sensor based on
RGO FET was reported by Cai.33 In this experiment, peptide
nucleic acid (PNA) with great sequence-specific affinity and
stability instead of the conventional DNA was selected as a
probe to hybridize with target DNA. Similarly, the left shift
of the Id − Vg curves of the device due to the n-doping effect
was measured and the DNA detection limit can reach 100 fM.
From the aforementioned contents, it can be concluded
without doubt that graphene-based nanoelectronic biosensors
leave a good impression on the researchers, and it is significant
to strive for further exploration in label-free DNA detection.
5.2.2 Protein Detection
 Similarly with the mechanism of DNA detection, the most
common method for protein detection is that antibody protein
firstly anchored onto the graphene surface through π–π reac-
tion. Then, the target protein is added to react with the probe
antibody, where the electron or hole transfer causes the shift
in the Ig − Vg curve to realize detection. This part depicts the
studies on protein detection in detail.
Ohno et al.19,34–36 made lots of efforts to study the vari-
ous protein detection methods with graphene-based FET in
the past few years. First, they investigated the detection of
bovine serum albumin (BSA) using electrolyte-gated gra-
phene FET without any decorations.34 In this work, BSA
molecules were directly adsorbed onto the graphene sur-
face instead of protein–protein interaction. The conduction
increased with the increasing of BSA concentration and the
detection limit achieved as low as 0.3 nM. They found the
conductance changes caused by BSA adsorption were quite
small, which could be explained by three interpretations: the
contact resistance of the graphene electrode, desorption of
BSA molecules, and inappropriate isoelectric point. In 2010,
Ohno19 continued to discuss the sensing properties for immu-
noglobulin E (IgE) based on aptamer-modified graphene FET.
60 Graphene Science Handbook

(a)

Drain current (μA) 24

(d) Annealed PMMA-graphene 10 nm

22
Gating wires
Silver
Graphite
20 Platinum

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Gate voltage (V)
(b)
0.00 10 μM probe DNA

–0.03 5 μm –10 nm
ΔVCNP

–0.06

10× PBS
–0.09 1×
0.1× (e) Gold-transferred graphene 10 nm

–0.12
1E – 3 0.01 0.1 1 10 100
Concentration of complementary DNA (nM)

(c)
0.00 10 μM probe DNA

–0.03
ΔVCNP

–0.06

With PMMA coating

–0.09 Annealed PMMA-graphene 5 μm –10 nm
Gold-transferred graphene

–0.12
1E–3 0.01 0.1 1 10 100
Concentration of complementary DNA (nM)

FIGURE 5.2  (a) Transfer curves of graphene FET operated with various gate electrodes (silver wire, natural graphite needle, and platinum
filament). (b) Summary of VCNP shift of the devices with different PBS buffer concentrations. (c) Summary of VCNP shift of the devices with
different transfer-supporting layers. (d) and (e) AFM images of PMMA- and gold-transferred graphene, respectively.

(a) 2.0 × 10–7 (b) 3.0 × 10–7

Bare device Bare device
Immobilized 2.5 × 10–7 Immobilized
1.5 × 10–7 Complementary Single base mismatch
2.0 × 10–7
–5.30%
Id (A)

Id (A)

1.0 × 10–7 –13.5% 1.5 × 10–7

1.0 × 10–7
0.5 × 10–8
0.5 × 10–8

0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.1 0.2 0.3 0.4 0.5
Vd (V) Vd (V)

FIGURE 5.3  Drain current versus drain voltage of different disease states (bare graphene–Au device, after immobilization probe DNA,
and after reaction with (a) complementary and (b) single-mismatched DNA strand) at Vg = 40 V.
Graphene Biodevices
It found that the drain current of functionalized graphene FET
decreased with the increase of IgE concentration. The low
and upper detection limits were around 0.29 nM and 160 nM,
respectively. A similar result on IgE detection using aptamer-
modified immunoglobulin sensor was also published in
2011.35 Okamoto and Ohno36 fabricated graphene FETs using
an antigen-binding fragment for heat-shock protein (HSP)
detection. The limit of detection could be as low as 100 pM.
Compared with the above, the latter was a little more prefect,
which may be ascribed to the antibody–antigen interaction
combined with higher affinity.
The previous reports indicate that RGO fabricated FETs
possess high sensitivity and selectivity for biomolecules. On
the basis of the literatures, Mao20 fabricated a kind of FET with
thermally RGO and realized the detection of immunoglobulin
G (IgG), as shown in Figure 5.4. The surface of RGO was
decorated with Au NP–antibody conjugates through a com-
bination of electrospray with an electrostatic-force-directed
assembly. The introduction of target protein (IgG) made sig-
nificant electrical changes due to the increase in the number
of scattering centers and local geometric deformation after
the binding of IgG to anti-IgG. The specificity of the sensor
was verified through the sensor resistance changes with vari-
ous subjects as mismatched proteins. The results indicated
that the detection limit of RGO-based FET for IgG can reach
2 ng/mL (13 pM). After that, they reported another similar
biosensing results based on thermally RGO FET labeled with
Au NP-anti-IgG for IgG detection.37 In this contribution, the
detection limit was around 0.2 ng/mL, lower than that of car-
bon nanotube FETs.38,39 On the basis of these researches, new
protein FET sensors were fabricated using vertically oriented
graphene (VG) sheets decorated with Au nanoparticle-anti-
body conjugates.40 The VG sheets were grown and assembled
with plasma-enhanced CVD method in one step. Owing to
the unique vertical orientation and open structure, VG can be
served as an ideal sensing material. It can make the analyte
molecules access the entire FET surface easily. The sensing
results indicated that the new protein sensors possessed high
sensitivity and excellent selectivity for IgG.
TRGO
sheet
Au
SiO2
Si
FET and direct current
measurements
FIGURE 5.4  Schematic diagram of the RGO FET biosensor fabrication process.
61
Generally, metals were commonly used as electrodes in
FET. Recently, an all-RGO thin film transistor was fabricated
by He21 and his team, as shown in Figure 5.5. It combined
RGO electrodes obtained by a spin-coating method with RGO
as the active channel through the microfluidic method. The
all-RGO FET presented excellent reproducibility, flexibil-
ity, and transparency. It was used to detect the nonspecific
absorption of fibronectin in buffer solution and the detection
limit can reach 0.5 nM. Moreover, the Dirac point presented
a negative shift in Ig − Vg curve owing to the n-doping effect
caused by the introduction of negatively charged fibronectin,
which was different from the electrostatic gating effect.18,41
It is well known that the graphene electrode can be widely
applied for electrochemical biosensing with high sensitivity
and selectivity. For example, Mao and his teams42 fabricated
an electrochemical immunosensor to detect the prostate-­
specific antigen (PSA) for prostate cancer diagnosis. The elec-
trode was fabricated with graphene sheets, methylene blue,
and chitosan (GS-MB-CS), which can be used to immobilize
the antibody of in advanced. The result demonstrated that the
current decreased linearly with the increase of PSA concen-
tration in a range of 0.05–5.00 ng.mL −1, and the sensor could
achieve a low detection limit (as low as 13 pg.mL −1). However,
it has been reported by several articles that RGO-based FETs
can exhibit higher sensitivity for label-free detection of PSA.
Differently, Kim43 selected the prostate-specific antigen/
α1-antichymotrypsin (PSA-ACT) as the prostate cancer bio-
marker. Immunoreaction between PSA-ACT and PSA mono-
clonal antibodies on the surface of RGO would cause Vg,min
to linearly shifted against the target protein concentration
in a different pH solution. The detection limit of the PSA–
ACT complex could reach 100 fg/mL in PBS solution, which
is higher than that of the earlier-mentioned electrochemical
electrode device. Moreover, alanine aminotransferase was
also determined by Hera et al.44 using the graphene FET bio-
sensor. They proved that there was a direct link between the
conductance of GFET and values of pH. On the basis of the
fact that pH value can be changed by the generation of H+
ions in the reaction between alanine aminotransferase and
Au NP-anti IgG
conjugates
Blocking
buffer
IgG
62 Graphene Science Handbook

APTES-coated PET
Spin coating GO film
of GO solution

Scratching

PDMS stamp

GO solution
1. Vacuum-assisted drying Buffer solution
2. Removal of PDMS stamp Insulation
GO micropattern Pt electrode

Vg

1. Reduction with hydrazine

2. Insulation of electrodes
Vds

FIGURE 5.5  Schematic fabrication process of all-RGO thin film transistors.

L-alanine with α-ketoglutarate, this biosensor was employed
to detect alanine aminotransferase.
Not only the two-dimensional graphene, but three-dimen-
sional graphene structure can also be used as an active channel
of FET for target biomolecule detection with high sensitivity
and selectivity. For example, Myung et  al.45 fabricated FET
biosensors using RGO encapsulating NPs as the channel for
the detection of human epidermal growth factor receptor 2
(HER2) and epidermal growth factor receptor (EGFR), which
are both overexpressed in breast cancers. As shown in Figure
5.6, first, GO assemble on amine-terminated SiO2 (GO-NPs)
via electrostatic interaction. At the same time, the photoresist
was patterned on silicon dioxide substrates with functional-
ized gold electrodes. Then, the self-assembled monolayers
(SAMs) of positively charged 3-aminopropyltriethoxysilane
(APTES) was used to functionalize the exposed silicon oxide

(a) (d)
Graphene oxide GO-NPs

SiO2
50 nm
Amine-terminated SiO2 NP Centrifugation NP assembly

(b) (c) APTES on SiO2 (e) rGO-NPs

Au Au
Au Au Photo resist

Substrate Substrate Substrate

Fabrication of electrodes PR Patterning and Removal of PR Patterns
and surface functionalization surface functionalization and reduction of GO (rGO)

FIGURE 5.6  Schematic diagram for the construction process of biomolecular sensor based on RGO-encapsulated NPs.
Graphene Biodevices
surface and cysteamine for gold surface (Figure 5.6c). After
that, the apparatus was centrifuged in a solution of GO-NPs to
promote the assembly of the negatively charged GO-NPs on
the positively charged SAMs. After removing the patterned
photoresist using acetone and reducing the GO through an
overnight exposure to hydrazine vapor, the powerful and
cost-effective device was fabricated successfully. The detec-
tion concentrations of HER2 and EGFR can reach 1 pM and
100 pM, respectively.
Maybe there are many difficulties in protein detection, but
more and more powerful, convenient, and green chemical
approaches are proposed to synthesize and optimize graphene
materials for high-performance nanoelectronic biosensors.
We should keep optimistic and expect further development of
graphene FET biosensors.
5.2.3 Cells or Bacteria Detection
The development of graphene-based FETs as a sensitive plat-
form for detecting biological bacteria or cells is a great break-
through. As a matter of fact, no matter what types of cells
or bacteria are investigated, graphene interface with the cell
needs to contact with the frequently charged cell wall or mem-
branes directly, which are influenced by the cell’s internal
bioactivity.46 Therefore, the interfaced graphene device can
be stimulated to attain the corresponding electronic proper-
ties due to the various effects, including changes in Coulomb
potential caused by charged inorganic impurities,47 screening
effects arising from the dielectric environment,48,49 or the var-
ied local dipole moment on the interfaced graphene.50 In the
followed section, we will depict the development in bacteria
or living cells detection in detail.
In 2008, bacteria-interfaced graphene devices were fab-
ricated by Mohanty and Berry18 using amine-functionalized
graphene (GA) as the sensing channel. Significant conduc-
tance increase (a sharp 42% increase) was observed after the
binding of a single bacterium on the GA surface. The conduc-
tance increase was attributed to two factors: (a) high p-dop-
ing on the GA (around 1400 holes per bacterium) between
the positively charged GA and the oppositely charged bac-
terial wall and (b) to the confinement of the doped carriers
within the few-atom-thick nanostructure. However, Liu et al.9
proposed an opinion that the device could not be applied in
practice owing to the sensor being without specificity to dis-
criminate the bacterial species.
After that, Huang and coworkers22 demonstrated a specific
FET biosensor based on a large-sized graphene film grown by
CVD. The FET functionalized with E. coli antibodies via the
linker molecule (1-pyrenebutanoic acid succinimidyl ester)
presents strong specificity and high sensitivity for E.  coli
bacteria. The detection limit can reach as low as 10 cfu/mL.
To make sure the strong specificity of the device, succinimi-
dyl esters without reaction with E. coli antibodies and the
uncoated graphene area had been quenched and passivated
with ethanolamine and Tween 20, respectively, as shown in
Figure  5.7. The Id − Vd curves indicated the gradually cor-
responding response before and after exposure to E. coli at
63
various concentrations from 0 to105 cfu/mL. Meanwhile, the
conductance have no response to 105 cfu/mL P. aeruginosa,
indicating the highly selectivity for E. coli. More interest-
ing, the E. coli-modified device presented high sensitivity to
glucose-induced metabolic activities of the bound E. coli bac-
teria in real time. Recently, graphene FETs are indeed highly
sensitive to the pH variation have been verified.34,15 The sig-
nificance of the research is that it detects the metabolic activi-
ties of bacteria in real time successfully with a simple method,
which provides a possibility for functional studies and screen-
ing of antibacterial drugs.
The solution-gate graphene device for bacteria or single
cell detection has been developed and explored from the
static to dynamic state. Aimed at revealing specific micro-
scopic information of the disease, in 2011, Ang et al.51
reported on the detecting results for malaria-infected red
blood cells with graphene transistor arrays integrated with
microfluidic technology at the single-cell level. It is well
known that the disease cell expresses specific surface anti-
gens and produces detectable different surface charge densi-
ties; these principles form the foundation for a bioelectronic
sensor. The irreversible structural modifications of the para-
sitized red blood cells (PEs) induced by P. falciparum (the
most virulent for malaria) infection include several mani-
festations: loss of deformability and the export of parasite
proteins and development of positively charged knob-like
protrusions on the cell surfaces. However, coupling charac-
teristic dwell times with the conductance changes of gra-
phene FET induced by these structural modifications could
be used to distinguish two stages of infection: trophozoite
(T-PEs) and schizont (S-PEs) stages, as shown in Figure
5.8b. In this work, the endothelial CD36 receptors were
selected to functionalize graphene to capture the malaria-
infected cells. The final results indicated that the average
dwell times caused by S-PEs were longer and the conduc-
tance was higher than that of T-PEs’.
Furthermore, the prominent graphene materials have
aroused great interest in the development of nanoelectronic
sensing for living cells or its dynamic secretion detection. For
example, highly uniform parallel arrays of RGO sheets with
centimeter-long, ultrathin (1–3 nm), and electrically continuous
micropatterns were fabricated by He and his workers23 for mon-
itoring hormonal catecholamine molecules and their dynamic
secretion from living neuroendocrine PC12 cells. In this device,
PC12 cells were cultured directly on the top of RGO transistor.
The current response in the device was observed when a high
K+ solution was introduced into the recording chamber. The
recording chamber depolarized the cell membrane and allowed
Ca2+ influx through the voltage-gated Ca2+ channels on the cell
membrane to the underlying RGO. Vesicular secretion of cate-
cholamine molecules released from PC12 cells into membrane-
FET interacted with RGO sheets via strong π–π interaction,
which caused the p-doping effect and corresponding current
spike (Figure 5.9). It is in coincidence with that of carbon nano-
tube network-based FET device.52
With the development of biosensors, coupling between
graphene and silicon nanowires FET was demonstrated  by
64 Graphene Science Handbook

(a) (b)
Graphene Linker Antibody 40

Ethanolamine
Tween 20 500 nm 30

E. coli

Ids (μA)
Vg
20 0 cfu/mL
10
Insulation Insulation 100
Source 10 1000
Drain 10,000
100,000
Quartz
0
Vds = 100 mV 0.00 0.05 0.10 0.15 0.20
Vds (V)
(c) (d)

Δ Conductance (%)
40 29.0 0.5 mM 6
4
28.5 2
30
0
28.0 0.0 0.5 1.0 1.5 2.0
Ids (μA)

Ids (μA)
20 Glucose (mM)
27.5
Bare 1 mM 1.5 mM
10 1 mM 2 mM
P. aeruginosa 27.0 27.9 2 mM
E. coli 27.8
0 0 50
0.00 0.05 0.10 0.15 0.20 0 100 200 300
Vds (V) Time (s)

FIGURE 5.7  (a) Illustration of graphene-FET functionalized with anti-E. coli antibody for detection of E. coli. The upper inset shows
scanning electron microscopy image of E. coli on graphene. (b) Drain current versus drain voltage curves of graphene biosensor before and
after fixing various concentrations of E. coli at Vg = 0 V. (c) Drain current versus drain voltage curves of the graphene device after exposure
to P. aeruginosa and E. coli for specificity identification. (d) Real-time current recording of the graphene device immobilized with E. coli
after addition of glucose at different concentrations. Lower inset: no response after addition of glucose into graphene without E. coli. Upper
inset: Percentage conduction change versus glucose concentration.

(a) Ag/AgCl
Parasitized
erythrocyte
Blood flow
Conductance

PDMS

Photoresist

Quartz

Time
(b)
210
Trophozoite-PE T1 T2 T3
Schizont-PE
205 S2
Conductance (μS)

200
T2

195
T1 T3 S1 S2 S3
190

185 S1 S3

0 5 10 15 20 25 30 35 40
Time (s)

FIGURE 5.8  (a) (Left) Schematic of flow sensing with an array of graphene transistors. (Right) Distinct conductance change with specific
binding between CD36 receptors on graphene channel and ligands located on membrane knobs. (b) Illustration of conductance versus time
for different disease states (T-PEs and S-PEs) on the left (Vg = 0.1 V) and the corresponding differential interference with graphene FET
array contrast (DIC) images on the right.
Graphene Biodevices 65

(a) Reduce graphene oxide

Vesicle
Ca ion channel

Insulation Insulation
Ca2+ Ca2+

rce

in
Sou

Dra
+/–

5 nA
(b)

5 nA
5 ms
5 ms
10 nA

5s

FIGURE 5.9  (a) Schematic of the interface between living neuroendocrine PC12 cell and RGO FET. (b) Real-time current response of
vesicular secretion of catecholamine molecules released from PC12 cells with Vds = 100 ​mV and Vg = 0 V.

Lieber53 to extracellularly detect the electrical potential
change of cardiomyocyte cells, as shown in Figure 5.10a and
b. Owing to the large interfacial area between graphene and
the cell, the spontaneously beating embryonic chicken car-
diomyocytes exhibited regulated change in cell potential and
yielded well-defined extracellular signals on graphene FET
with a frequency of 1.1 Hz (signal-to-noise ratio routinely > 4).
As shown schematically in Figure 5.10c, the magnitude of the
conductance peak at various water gate potentials highlighted
the necessity of recording explicit device sensitivity to inter-
pret the corresponding voltages. Figure 5.10d shows that the
nature of the recorded signals could be tuned by selected gate
potentials transferring the device from p-type to n-type. We
can anticipate that graphene nanoribbons or nanomesh with
a large bandgap and edge ratio can attract more interest in
developing the field of cellular bioelectricity detection.
In addition, Hess and Garrido54 extended the previous
work and realized the detection of the electronic activity
of the electrogenic cells using CVD-grown large-area gra-
phene FET. In this work, cardiomyocyte-like HL-1 cells
were cultured directly on the surface of graphene-based
solution-gated transistors (G-SGFET). The action potentials
from the cells could be detected with G-SGFET directly.
Here, the graphene Fermi level and conductance could be
controlled by the applied gate voltage via the electrolyte.
Figure 5.11b shows the current response of eight graphene
transistors over tens of seconds and (c) the amplified simul-
taneous current recordings over hundreds of milliseconds.
The current spikes were induced by the propagation of
action potential across the cells. This study clearly indicated
the outstanding electronic and electrochemical properties of
graphene FET for cellular-interfaced sensing. It should be a

(a) (c)
+0.05 V

+0.10 V

+0.15 V

S NW D (d)
(b)
Cell

S Gra D

FIGURE 5.10  (a) Schematic of coupling between graphene and silicon nanowires. (b) Representation of the cardiomyocyte cell inter-
faced to integrate device. (c) Temporal response of the graphene device, the recorded traces at various applied water gate potentials with
+0.05, +0.1 and +0.15 V, respectively. (d) Representative expanded peaks for selected gate potentials. Blue traces was p-type polarity of
graphene FET, red peaks represented n-type device polarity, and the green peak was recorded near the Dirac point.
66 Graphene Science Handbook

(a) (b) (c)

T1

T2

T3

T6

T7

T16 T9

T11
T9 0.1 μA
200 μV T16
50 ms 10 s 0.1 s

FIGURE 5.11  (a) (Top) Optical microscopy image of eight transistors in one FET array. (Bottom) Exemplary single spikes of current
response corresponding to extracellular voltage signal. (b) and (c) Simultaneous current response of eight transistors in one FET array over
tens of seconds and hundreds of milliseconds, respectively.

true breakthrough and have a bright prospect in the field of
bioelectronics.
In a word, the recent developments in graphene-based
FETs for monitoring bacteria or living cells have been widely
explored. The detection mechanism and specificity of gra-
phene-based cellular devices will be improved and perfected
gradually.
5.2.4 Glucose Detection
The worldwide increase in the number of diabetic patients
has encouraged scientists to pay more attention into the field
of glucose biosensors. Now, most graphene-based FET glu-
cose sensors are functionalized with glucose oxidase (GOD).
The GOD can catalyze glucose to gluconic acid and H2O2.
H2O2 can change the local potential and cause the correspond-
ing current response to realize the identification of glucose
quickly and accurately. For example, Huang et al.24 fabricated
a glucose sensor based on graphene transistor decorated with
GOD via linker molecules (1-pyrenebutanoic acid succinimi-
dyl ester), as shown in Figure 5.12. It can be seen that the
drain current increased quickly with the introduction of glu-
cose (0.1 mM) owing to the effect of H2O2 catalyzed by GOD.
With the increase in concentration, the drain current increases
directly. The lower inset indicates that the saturation current
appeared at about 10 mM. In the control experiment, it can be
found that the other oxidation product of glucose (D-glucono-
1,5-lactone) could not cause appreciable current increase,
indicating the high specificity of the graphene-based sensors
for glucose. What’s more, the glutamic dehydrogenase (GluD)
modified graphene transistors can realize the detection of
glutamate with high sensitivity and selectivity. Further stud-
ies indicated that its detection mechanism was similar to the
aforementioned glucose nanoelectronic biosensor. The detec-
tion limit of graphene-based enzymatic sensors for glucose
and glutamate could achieve 0.1 mM and 5 µM, respectively,
which are superior to SWNT network sensors55.
With the development of technology and maturity of knowl-
edge for nanoelectronic sensors, it is critical to fabricate high-
performance graphene biosensors, which has not only high
sensitivity and strong specificity, but also simple and costless
synthesis method, portable and wearable feasibility. To meet this

(a) (b) Glucose (c) 2 mM

Graphene Gluconic acid Adding H2O2 1.5 mM
0.5 μA

10 mM
Glucose O2
GOD GOD Linker 100 s 2 mM
H2O2 1 mM 3 mM
NH

0.1 mM
NH

Insulation Insulation 4
0.1 mM 0.05
Δ| (μA)

Drain Source Gluconolactone

0.5 mM 2 1 mM
0.5 μA

0.1 μA
1 μA

Quartz
0
+– 500 s 0 5 10 40 s
Vds = 100 mV 200 s
Glucose (mM)

FIGURE 5.12  (a) Schematic of graphene glucose sensor functionalized with GOD. (b) Current responses to the addition of various con-
centrations glucose into the recording chamber. Upper inset: no response to 10 mM glucose under GOD-free graphene FET. The lower inset
shows the response change curve of graphene FET to various glucose concentrations. (c) Current responses to the addition of H2O2 and
D-glucono-1,5-lactone (1 mM) from glucose oxidation.
Graphene Biodevices 67

(a) Pt G
Electrolyte Vg

PDMS
Ag paint well

D
S
Graphene PSE GOD

PET substrate Vds

(b) –140.0μ PBS @ Vds = –0.2

(c)
1.82 mM @ Vds = –0.2
3.33 mM @ Vds = –0.2
–120.0μ 5.71 mM @ Vds = –0.2
7.5 mM @ Vds = –0.2
9.47 mM @ Vds = –0.2
–100.0μ 10.91 mM @ Vds = –0.2
PBS @ Vds = –0.2
–120.0μ 1.82 mM @ Vds = –0.2
3.33 mM @ Vds = –0.2
5.71 mM @ Vds = –0.2
7.5 mM @ Vds = –0.2
–100.0μ 9.47 mM @ Vds = –0.2
10.91 mM @ Vds = –0.2

–80.0μ
–80.0μ
Ids (A)

Ids (A)
–60.0μ
–60.0μ

–40.0μ G –40.0μ G
PET
PET
–20.0μ –20.0μ

–1.0 –0.5 0.0 0.5 1.0 1.5 –1.0 –0.5 0.0 0.5 1.0 1.5
Vg (V) Vg (V)

FIGURE 5.13  (a) Experimental instrument of the flexible glucose sensor based on CVD-grown graphene functionalized with GOD. (b)
and (c) show the source–drain current curves in response to the increasing glucose concentrations from 0 to 10.8 mM at Vds = −0.2 V for
detection of the flat and bended substrate sensor, respectively.

requirement, flexible graphene-based sensors have been manu-
factured. The novel flexible graphene FET glucose sensor with
polyethylene terephthalate (PET) as a substrate was first fabri-
cated by Kwak and his team.56 Partially in keeping with Huang’
experiment, the graphene surface also was functionalized with
GOD instead of GDH via the same linker molecules, which
can induce catalytic reaction of glucose and produce H2O2. To
elucidate the feasibility of the resulting flexible glucose sensor,
glucose detections for flat and bended substrates (the radius of
the deflected device was 6.625 cm) were performed, as shown
in Figure 5.13. The results of the transfer curves of both condi-
tions were similar and both of the Dirac points were shifted to
the left. Moreover, the flexible FET exhibited ambipolar behav-
ior and prominent glucose detecting properties in the range of
3.3–10.9 mM covering the reference range of medical examina-
tion for the diagnosis of diabetes. This flexible graphene-based
sensor provides excellent detection performance even during
deformed or continuous real-time monitoring. Besides, it holds
great potential especially for portable, wearable, and implant-
able glucose level monitoring applications.
5.2.5 Other Applications for Biosensors
Graphene devices decorated with different biomolecules
exhibit high potential in disease diagnostics, food safety, and
environmental monitoring. There is an outstanding article on
the bioelectronic nose (B-nose).57 This bioelectronic olfactory
system based on graphene FET could discriminate various
odorants rapidly and precisely. After treated with O2 and NH3
plasma and formed p-type (PG) and n-type (NG) graphene,
human olfactory receptors 2AG1 (hOR2AG1: OR), binding
to the particular amyl butyrate (AB), was conjugated with a
modified bilayer graphene platform, as shown in Figure 5.14a.
After introducing AB molecules gradually from 0.04 fM to
400 pM, the B-nose PG showed better responses to AB mol-
ecules than that of B-nose NG. This phenomenon can be
attributed to the decrease charge carriers of n-type B-nose
neutralized by oxygen atom of the H2O or O2 in the liquid
solution (Figure 5.13b). The detection limit for amyl butyr-
ate could achieve as low as 0.04 fM. After that, the research-
ers made some comparisons among different numbers of OR
loading, and verified the response intensity followed the order
1OR < 2OR < 4OR. At last, it realizes the modulation of the
performance of B-noses by the OR loading. Additionally, the
long-term stability was tested. It indicated that the sensitivity
only decreases by about 5%–6% in dry air in a sealed vessel at
25°C for 10 days. This successful experiment demonstrated a
new direction for the detection of odorants with high sensitiv-
ity and specificity. A wide range of other applications will be
broadened successively.
In addition, it has been found that graphene nanoribbon-
based devices present predominant performance, including
68 Graphene Science Handbook

(a) (b)
20 40 pM
Vg 400 fM 4 nM
hOR2AG1
(OR) AB 4 fM

[Δ/II0]ds (%)
10 OR-OG
0.04 fM
Liquid Pristine-MBLG
gate 0
OR-OG

D
0.4 fM
S –10 40 fM 4 pM 400 pM
0 1000 2000 3000
Time (s)

FIGURE 5.14  (a) Schematic of modified bilayer graphene FET B-nose conjugated with olfactory receptors. (b) Real-time current record-
ing and a calibration curve of FET B-nose based on OR-conjugated OG, NG, and without OR-conjugated sensor measured at Vds = 10 mV
and Vg = 0 V with application of AB molecule at various concentrations.

(a) Vd (b) 480

+ – H2N

Vg 470 O O O
N
N

+ – –
O P O P O P O N N
460 – – – O
Ag/AgCl O O O

450 5 μM OH OH

Id (nA)
10 μM
GNRs Insulation 440
20 μM
D S 430 30 μM

SiO2 420 40 μM
Vd = 0.5V 50 μM
Si 410
0 100 200 300 400
Time (s)

FIGURE 5.15  (a) Schematic of the RGONR network device. (b) Real-time current response of device at various ATP concentrations at
Vd = 0.5 V and Vg = 0 V.

high sensitivity and high selectivity owing to the large band
gap and edge ratio.58 Dong et al.25 prepared a graphene
nanoribbon network FET with chemically RGO nanoribbons
(RGONRs) (Figure 5.15). This kind of FET presents much
higher on/off ratios and detection sensitive for adenosine tri-
phosphate (ATP) than that of common graphene or carbon
nanotube-based FET. It is due to the n-doping effect of ATP
rather than electrostatic gating that the conductance change
was opposite to that of single-walled carbon nanotubes
(SWCNTs).59 The minimum detection limit could reach 5​
µM. To decrease the contact resistance between graphene and
electrodes, abundant number of approaches had been imple-
mented. For example, Xu et al. synthesized graphene grown
on quartz substrates directly using a two-temperature-zone
CVD system and fabricated FET sensor.60 Serving as ATP
sensors, the ATP detection range was about 0.002–5 mM.
Additionally, Yue fabricated a new FET with indium tin oxide
(ITO) as the drain and source electrodes and Au electrode as
the gate electrode.61 The ATP detection limit of this kind of
FET could reach 10 pM.
Recently, Park et al. prepared a rapid-response and high-
sensitivity biosensor based on a liquid-ion-gated FET toward
H2O2.62 Graphene–polypyrrole (PPy) nanotube composites were
used as the sensing channel. The device presented good electrical
conductivity and p-channel behavior. For H2O2 determination,
the detection limit can reach 100 pM, which was more favorable
than those previously reported biosensors for H2O2.
5.3 CONCLUSION
In summary, the above-mentioned perspective results outline
the recent developments of graphene-based devices in the field
of biological sensing. Moreover, the electrical characteristics
and detection mechanisms of graphene-based devices for
monitoring various target molecules was discussed. Owing
to its exceptional electrical properties, electrochemical prop-
erties, and structural properties, graphene-based FETs show
great promise in the fields of electronics and electrochemi-
cal sensors with good sensitivity and high selectivity. It also
demonstrates more excellent advantages as compared with the
conventional carbon nanotube-based FETs.
However, the lack of simple and low-cost methods for
controllable and scalable preparation of graphene sheets
hinders further development and widespread applications in
biological or chemical fields. Moreover, the major bottleneck
in the development of graphene-based nanoelectronic biosen-
sors is the sensitivity and selectivity. Despite there are still
many unresolved issues and challenges; more and more fea-
sible measures can be taken to amplify much room for future
development on scientific researches and applications of
Graphene Biodevices
graphene-based FETs. First, a full understanding of the detec-
tion mechanisms and interactions between graphene active
channel and target molecules is significant. It is beneficial for
researchers to make full use of disciplines and technology to
enhance the detection sensitivity. Second, enhancement of the
FET performance is important to increase its sensitivity. The
results have demonstrated that the sensitivity of the graphene
material-based biosensors can be improved and perfected by
using graphene bilayers46 and by altering graphene sheets
to nanoribbons,25 nanomesh,63,11 or nanoneedle64,65 channel.
Third, making specific functionalizations on graphene sur-
face through metal NPs or other linkers and developing novel
modified graphene devices can optimize its electrical charac-
teristics greatly. We suppose and envision the rapid develop-
ment and the bright future of graphene-based biosensors.
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 6 Antibacterial and Antifungal Activities
of Graphene Nanosheets
Montree Sawangphruk

CONTENTS
Abstract........................................................................................................................................................................................ 71
6.1 Introduction........................................................................................................................................................................ 71
6.2 Structures of Graphene and Its Related Materials.............................................................................................................. 72
6.3 Bacterial Cell Structures..................................................................................................................................................... 73
6.4 Overview of Antibacterial Mechanisms of General Antibiotics........................................................................................ 74
6.5 Proposed Antibacterial Mechanisms of Graphene-Based Materials................................................................................. 74
6.5.1 Alteration of Bacterial Plasma Membrane............................................................................................................. 74
6.5.2 Oxidative Stress Mediated by Graphene-Based Materials..................................................................................... 74
6.5.3 Destructive Extraction of Phospholipids from Cell Membrane by Graphene Nanosheets.................................... 75
6.6 Lateral Size Effect of Graphene Oxide Nanosheets on Their Antibacterial Activity........................................................ 75
6.7 Synergistically Enhanced Antibacterial Activity of GO/Silver Nanoparticles.................................................................. 75
6.8 Photoinactivation of Bacteria by Graphene Coated on TiO2 Thin Film for Use in Solar Light......................................... 76
6.9 Antibacterial Graphene-Based Paper................................................................................................................................. 76
6.10 Antibacterial Activity of Graphene Coated on Stainless Steel.......................................................................................... 76
6.11 Fungal Cell Structures........................................................................................................................................................ 77
6.12 Antifungal Activity of rGO................................................................................................................................................ 77
6.13 Summary and Perspectives................................................................................................................................................. 78
Acknowledgments........................................................................................................................................................................ 78
References.................................................................................................................................................................................... 79

ABSTRACT
Antibacterial and antifungal agents are widely used for the
prevention of public health issues. Graphene is a material
consisting of a monolayer of sp2-bonded carbon atoms. It is
of interest due to its high surface area (~2630 m 2 g−1), high
electrical conductivity (~2000 S ​cm−1), high thermal con-
ductivity (4840−5300 W m−1 K−1), high electronic carrier
mobility (200,000 cm 2 V−1 s−1), and high Young’s modu-
lus (~10 TPa) leading to various potential applications.
Interestingly, graphene can inhibit the growth of bacterial
cells (e.g., Escherichia coli and Staphylococcus aureus) and
fungal cells (e.g., Aspergillus niger, Aspergillus oryzae, and
Fusarium oxysporum). Graphene can damage bacterial and
fungal cell membranes with their extremely sharp edges.
Graphene with diluted oxygen-containing reduced graphene
oxide (rGO) can in addition oxidize glutathione, which is
a redox state mediator in bacteria. Its oxidation leads to
inhibition of bacterial growth. The inhibitory concentration
(IC50) of rGO, a measure of the effectiveness of graphene
in inhibiting the fungi against F. oxysporum, A. niger, and
A. oryzae are 50, 100, and 100 µg mL −1, respectively. We
believe that graphene may find important environmental and
clinical applications.
6.1 INTRODUCTION
Antimicrobial is defined as an agent, which can kill and/or
inhibit the growth of microorganisms. The definition of anti-
microbial includes antibacterial and antifungal. In medicine
antibacterial is generally known as antibiotic, which is used
against bacteria, while, “antifungal” means destroying or
inhibiting the growth of fungi. Apart from the prefix “anti,”
the suffixes “cide” and “cidal” meaning “killing” excluding or
“inhibiting” are also used in this research area such as biocide
(noun), biocidal (adjective); bactericide (noun), bactericidal
(adjective); and fungicide (noun) and fungicidal (adjective).
Antimicrobial materials has important roles in treat-
ing infectious diseases caused by pathogenic bacteria and
fungi.1 However, general antibiotics lead to microbial resis-
tance, resulting in failure treatment efficiency. The rapid
development of nanomaterials, for example, nanoparticles
(0D), nanotubes and nanowires (1D), nanosheets (2D), and
nanofilms (3D) in the past decades opens up new opportu-
nities in antimicrobial research. Among many nanomaterials
reported as antibacterial agents, graphene has been found to
be an antimicrobial material. The antimicrobial mechanism
of graphene-based nanosheets is based on “physical damage”
of the cell membrane2; thus, they will not face a concern about

71
72 Graphene Science Handbook

(a)
TABLE 6.1
Graphene-Related Materials and Their Mechanisms
of Action on Bacteria
Graphene-Related Mechanisms
Materials Bacteria/Fungi of Action References
Graphene Escherichia coli Damage the 2
nanosheets cell membrane
GO and rGO as Escherichia coli Damage the 4
well as their paper cell membrane
Graphene and GO Escherichia coli, Damage the 5
nanowalls Staphylococcus cell membrane
aureus
GO and rGO Escherichia coli Damage the 6 (b) HO O HO O
cell membrane OH
Graphene film on Escherichia coli Electron charge 7 O O
Cu and Ge transfer
substrates between HO
O
bacteria and
OH
graphene film OH
O
O
O
OH
OH
TABLE 6.2
OH OH
Graphene-Related Materials and Their Mechanisms HO
of Action to Fungi O O
O
Graphene- Mechanisms
OH
Related Materials Fungi of Action References O OH O OH
GO Fusarium Damage the 8
graminearum, cell
Fusarium oxysporum membrane (c) O OH O OH
O
rGO Aspergillus niger, Damage the 9
Aspergillus cell OH OH
oryzae, Fusarium membrane
O
oxysporum
GO-silver Candida albicans, Endocytosis 10 O
nanocomposites Candida tropical pathway of
silver ion OH
HO

O
“antibiotic resistance,” which is a major drawback of antibiot-
O
ics, metal ions, and quaternary ammonium compounds typi-
cally used as antimicrobial agents.3,4 Tables 6.1 and 6.2 list HO OH
the antimicrobial mechanisms of graphene-related materials
to bacteria and fungi, respectively. O
HO O HO O

FIGURE 6.1  Structures of (a) graphene, (b) graphene oxide, and

6.2 STRUCTURES OF GRAPHENE AND
ITS RELATED MATERIALS
Graphene is a single atomic sheet of graphite (see Figure
6.1a), which can be produced by a number of techniques, for
example, mechanical exfoliation method,11 epitaxially grown
graphene on SiC12 and on metal substrate,13 large-scale roll-
to-roll production of 30 in. graphene films using chemical
vapor deposition,14 and chemical exfoliation with subsequent
reduction.15 Graphene has a high theoretical surface area
(~2630 m2 g−1),16 high electrical conductivity (~2000 S cm−1),17
(c) reduced graphene oxide.
high optical transmittance (~97.7%), high thermal conductiv-
ity (4840−5300 W m−1 K−1),18 high electronic carrier mobility
(200,000 cm2 V−1 s−1),19 and high Young’s modulus (~10 TPa)20
leading to various potential applications such as thin, flex-
ible, durable display screens, electric transistors, batteries and
supercapacitors, solar cells, medical applications, polymer/
graphene composites, as well as chemical and industrial pro-
cesses enhanced by the use of graphene-based nanosheets.21−27
Antibacterial and Antifungal Activities of Graphene Nanosheets
Graphene oxide (GO) is an atomic sheet of carbon having
carboxylic groups at its edges and phenol and epoxide groups
on its basal plane (see Figure 6.1b).28,29 GO is an insulating
material (0.02 S/m)30 and rather stable as the colloidal suspen-
sion sheets in water.29,31 The structures of GO with different
oxygen-containing groups due to different exfoliation meth-
ods used in the preparation process may result in differences
in the physical, chemical, and biological properties of GO.32
For example, GO can be synthesized by using a modified
Hummer’s and Offeman method15 as follows. Graphite powder
(3.0 g) and NaNO3 (1.5 g) were put to a concentrated H2SO4
(150 mL) while stirring (100 rpm) in an ice bath for an hour.
KMnO4 (8.0 g) was slowly added to the mixture at room tem-
perature (25°C) for a couple of hours without stirring. Deionized
and ultrapure water (90 mL) was added to the suspension and
kept stirring (100 rpm) at 95°C for 12 h. Then, H2O2 (30% v/v,
30 mL) was slowly added to the diluted suspension. For purifi-
cation, the mixture was filtered through a nanomembrane, that
is, polyester fiber. The filtrate was centrifuged at high speed
(6000 rpm) for about 15 min and the remaining solid mate-
rial (GO) was then washed in succession with ultrapure water
(200 mL), 30% v/v HCl (100 mL), and ethanol (100 mL). This
process was repeated more than three times. The final product
GO powder was collected by filtration and vacuum dried.9,33
Thermal annealing or chemical reduction can eliminate the
oxygen-containing groups on GO nanosheets to produce rGO
nanosheets.9,33 The rGO is more conductive (225.3 S m−1),
than GO but lower conductive than graphene without an
oxygen-containing group.34 The carbon-to-oxygen ratios of
graphene, GO, and rGO are, for example, 1:0, 3:1, and 10.3:1,
respectively35,36 depending on the reduction conditions used.
The carboxylic functional groups are still found at the edge of
rGO nanosheets and there are some defects on the basal plane
of graphene (see Figure 6.1c).31
Graphene and its related materials are of interest in many
research applications. Especially in the field of biomedicine,
biosensing,37 drug delivery,38,39 gene transfection,40,41 and
tumor imaging/therapy42 have received great attention. More
recently, it was found that graphene and its related materials
have antimicrobial properties.1,9 Compared with other carbon
materials, for example, fullerenes (C60) and carbon nano-
tubes (CNTs), a few studies on the antimicrobial activities
(a)
Lipoteichoic acid
Peptidoglycan
cell wall
Plasma membrane
FIGURE 6.2  (a) Gram-positive and (b) Gram-negative bacterial cell walls.
73
of graphene and its related materials have been found in the
literature.6,9 The antibacterial mechanism of graphene and
its related materials has been attributed to membrane stress
induced by sharp edges of graphene nanosheets, which may
result in “physical damages” on cell membranes.
6.3  BACTERIAL CELL STRUCTURES
To understand the antibacterial activity and mechanism of gra-
phene and its related materials, first of all, we need to know the
bacterial cell structures. The size of a bacterium is about one-
hundredth the size of a human cell (10–100 µm). There are
two types of cell walls in bacteria, the so-called Gram-positive
and Gram-negative related to Gram-staining characteristics.
Gram staining, originally developed by Hans Christian Gram,
can differentiate bacteria in two groups by the chemical and
physical properties of the cell wall of bacteria by detecting
peptidoglycan. The peptidoglycan is present in a thick layer in
Gram-positive bacteria for which after staining Gram-positive
bacteria show a purple-blue color while Gram-negative bacte-
ria shows a pink-red color. In general, the cell wall of Gram-
positive bacteria such as S. aureus is thicker than that of the
Gram-negative bacteria E. coli (see Figure 6.2).
The cell wall of Gram-positive bacteria (Figure 6.2a) con-
sists of multilayers of peptidoglycan backbone cross-linked
with other biochemicals.43 Peptidoglycans are made up of a
polysaccharide backbone consisting of alternating N-acetyl
muramic acid and N-acetyl glucosamine residues in equal
amounts. The cell wall is also composed of lipoteichoic acids,
that is, ribitol teichoic acids and glycerol teichoic and gener-
ally lack lipids and proteins located on the surface of Gram-
positive bacteria. Peptidoglycans, which are about 40%–60%
of dry weight of the cell wall, provide rigidity to the cell wall;
the cell walls of Gram-positive bacteria may contain multi-
layers of peptidoglycan, conferring significant mechanical
strength. Although the peptidoglycan is responsible for the
mechanical strength and shape of bacterial cells, it has suffi-
cient plasticity and dynamic turnover to allow cell growth and
division. Notably, The cell wall of Gram-positive bacteria can
be completely dissolved by the enzyme lysozyme.
In contrast, Gram-negative organisms (Figure 6.2b) have
a thinner layer of peptidoglycan about one-twentieth of the
(b)
Outer lipid
membrane
Peptidoglycan
cell wall
Plasma
membrane
74
thickness of the peptidoglycan layer found in Gram-positive
organisms. Although they have a thinner cell wall, the outer
cell wall has proteins, phospholipids, and lipopolysaccha-
rides, which has the ability to protect the internal structures
of the bacteria from damaging chemicals. The weight content
of peptidoglycan is about 5%–10% of the dry cell wall. The
outer membrane can protect the Gram-negative bacteria with
resistance to lysozyme and the antibiotic penicillin. However,
alternative medicinal treatments such as lysozyme with EDTA
and the antibiotic ampicillin have been developed to combat
the protective outer membrane of Gram-negative organisms.
Both bacteria have plasma membrane or cytoplasmic mem-
brane consisting of a phospholipid bilayer. The plasma mem-
brane acts as a permeability barrier of molecules and serves
as the location for the transport of molecules into the cell.
6.4 OVERVIEW OF ANTIBACTERIAL
MECHANISMS OF GENERAL ANTIBIOTICS
Typical antibiotic mechanisms of general antibiotics are
listed in Table 6.3.44–47 For a typical antimicrobial mecha-
nism of antibiotics, for example, penicillin, vancomycin, and
bacitracin, they can inhibit the cell wall synthesis or dam-
age the cell wall because of the fact that most bacteria have
peptidoglycan-based cell walls. The bacterial growth can
be prevented by inhibiting peptidoglycan synthesis. Thus
most antibiotics only work for actively growing bacteria.
The cell wall of new bacteria that grew in the presence of
cell-wall-synthesis inhibitors is deprived of peptidoglycan.
These bacteria will be subjected to osmotic lysis. In addition,
TABLE 6.3
General Antibiotics and Their Mechanisms of Action
General Antibiotics Mechanisms of Action
Penicillins Inhibition to cell wall synthesis or damage
Cephlasporins to cell wall
Glycopeptides
Monobactams
Vancomycins
Bacitracins
Trimethoprims Inhibition to folic acid metabolism or
Sulfonamides inhibiting the reduction of dihydrofolic
acid (DHF) to tetrahydrofolic acid (THF)
finally leading to inhibit the DNA synthesis
Polymyxins Disruption of cell membrane function such
Polyenes as binding to lipopolysaccharide leading to
damage to cytoplasmic membrane of fungi
Quinolones Inhibition to DNA and RNA syntheses
Rifampins
Nalidixic acid
Erythromycins Inhibition to protein biosynthesis
Chloramphenicol
Tetracyclines
Streptomycins
Gentamycin
Macrolides
aminoglycosides
Graphene Science Handbook
the Gram-negative bacteria generally are less susceptible to
inhibitors of cell wall synthesis than the Gram-positive bac-
teria. Antibiotics fail to reach the cell wall because they are
blocked by the Gram-negative outer membrane. Penicillin is
the classic of an antibiotic that inhibits cell wall synthesis.
Other antibacterial mechanisms involve the inhibition of pro-
tein synthesis, DNA and RNA syntheses, and mycolic acid
and folic syntheses.
6.5 PROPOSED ANTIBACTERIAL MECHANISMS
OF GRAPHENE-BASED MATERIALS
6.5.1  Alteration of Bacterial Plasma Membrane
The GO and rGO sheets having different contents of oxygen-
containing groups can damage the plasma membranes of
bacteria leading to cell death due to the leakage of cell organ-
isms.4,6 For example, after GO or rGO had interacted to the
cell membrane of E. coli cells, the flattened E. coli cells were
observed. They eventually lose their cellular integrity.4,6 The
damages are also induced on bacterial cells after direct con-
tact with GO or rGO materials. This mechanism is based on
“physical damage” of the bacterial cell membrane. This is
similar to the antibacterial activity of CNTs. A comparison
of cells interacting with GO and rGO shows that E. coli mix
with GO and rGO in different ways. The aggregation/disper-
sion of graphene-based materials plays an important role in
their antibacterial activities.6
6.5.2 Oxidative Stress Mediated by
Graphene-Based Materials
The oxidative membrane stress of bacteria is induced by the
direct “physical contact” of graphene or its related materi-
als to the bacterial cell wall. Oxidative stress is well defined
as an antibacterial mechanism of C60 and CNTs.48,49 While,
oxidative stress mediated by graphene-based materials is not
yet totally clear and may come from several paths, one is
reactive oxygen species (ROS)-mediated oxidative stress, in
which oxidative stress is induced by ROS generated by gra-
phene and its related materials.50 Notably, the GO and rGO at
100 μg mL −1 concentration exposure induces the production
of superoxide radical anion of about two- and one-fold when
compared with the control after 4 h incubation.51 In compari-
son with the control group, lipid peroxidation, the oxidative
degradation of lipids in the cell membrane, was observed in
the system having graphene sheet using a lipid peroxidation
assay.52 The degree of degradation was increased by 117%
and 109% after exposure to 10 and 5 μg mL −1 of graphene,
respectively.50 The oxidation of fatty acids by graphene and
its related materials leads to the lipid peroxides that stimu-
late a chain reaction, resulting in the disintegration of a cell
membrane followed by cell death. The other possible path is
ROS-independent oxidative stress, in which graphene-based
materials may disrupt a specific microbial process by dis-
turbing or oxidizing a vital cellular structure or component
without ROS production.53
Antibacterial and Antifungal Activities of Graphene Nanosheets
6.5.3 Destructive Extraction of Phospholipids from
Cell Membrane by Graphene Nanosheets
Recently, it has been found that the graphene nanosheets
can penetrate into and extract large amounts of phospho-
lipids in the cell membranes of E. coli. The strong disper-
sion interaction between hydrophobic graphene nanosheets
and lipid molecule is a key driving force in killing and/or
inhibiting the growth of bacterial cells. The recent study
offers a fundamental understanding to the antimicrobial
mechanism of graphene.2 The penetration of graphene into
the cell membrane and subsequently the destructive extrac-
tion of phospholipids from the bacterial cell membrane is
most possibly an exact antibacterial mechanism of graphene
nanosheets.2 Experimentally microscopic and theoretical
molecular dynamics simulation studies2 show that pristine
graphene and GO nanosheets can induce the degradation of
inner and outer cell membranes of E. coli via the interactions
with phospholipids of bacterial cell membrane (see Figure
6.3). Graphene-based nanosheets can penetrate into and then
remove large amounts of phospholipids from the cell mem-
brane because of the strong interactions between graphene
and lipid molecules. This destructive extraction leads to the
death of bacterial cells.2
There are three rough stages of membrane degradation,
which were observed during the 2.5 h incubation process of
E. coli in 100 µmmL −1.2 The change of E. coli cell morphol-
ogy over incubation time was observed from the transmission
electron microscopy (TEM) images. In stage I, the E. coli
cells can tolerate GO nanosheets for a short period of time for
which the morphology of treated E. coli is more or less similar
to the normal untreated E. coli cells. In stage II, the cell mem-
branes of E. coli are partially damaged, with some display-
ing a lower surface phospholipid density. However, the cell
membrane is not yet broken nor cut by graphene nanosheets.
In stage III, the cell membranes of E. coli cells were harshly
damaged and even lost their cytoplasm.2 All three stages were
observed within 2.5 h incubation; however, the exact time of
each stage is not known yet.
FIGURE 6.3  Cartoon showing the destructive extractions of
phospholipids from E. coli cell membrane by graphene nanosheets.
(Adapted from Y. Tu et al., Nature Nanotechnology, 2013, 8, 594–
601 and the Zhejiang University NEWS “Scientists Discovered the
Truth of Graphene Killing Bacteria” July 10, 2013.)
75
60
50
E. coli cell viability (%)
40
30
20
10
0
0 0.2 0.4 0.6 0.8
Average lateral surface area of GO (μM2)
FIGURE 6.4  Correlation between the E. coli cell viability and
the average lateral surface area of GO nanosheets after 2-h incuba-
tion. (Adapted from T. Hayashi et al., Biochemical and Biophysical
Research Communications, 1983, 115, 1108–1113.)
6.6 LATERAL SIZE EFFECT OF GRAPHENE
OXIDE NANOSHEETS ON THEIR
ANTIBACTERIAL ACTIVITY
The antibacterial activity of GO nanosheets against E. coli
cells depends on their lateral sizes. Larger the GO sheets,
higher will be the antibacterial activity compared with the
smaller ones.54 This is because the larger ones can cover
most of the E. coli cell surface whereas the smaller ones
cannot during the 2 h incubation.54 The viability of E. coli
cells in Figure 6.4 decreased by 97.7 ± 1.0%, 91.5 ± 0.5%,
87.8 ± 2.09%, 71.2 ± 6.0%, 60.7 ± 8.8%, and 45.5 ± 5.5%
after incubating with GO nanosheets with different average
lateral surface areas of about 075, 0.1, 0.075, 0.025, 0.01, 0
(control) µm2, respectively.54
6.7 SYNERGISTICALLY ENHANCED
ANTIBACTERIAL ACTIVITY OF
GO/SILVER NANOPARTICLES
Silver nanoparticles (AgNPs) are well recognized as a pow-
erful antimicrobial agent.55 The antibacterial activity of
graphene-based materials/silver nanoparticles is currently
of interest.1,56 GO/AgNPs nanocomposites were prepared by
reducing silver ion by sodium citrate in the presence of sus-
pended GO nanosheets.1,56 The 100 μg mL −1 composite could
decrease the cell viabilities of E. coli and S. aureus cells by
up to about 45% when compared with pure AgNPs. Unlike
the GO/AgNPs nanocomposite, pure GO and pure AgNPs at
the same dose showed no obvious effect on the viabilities of
both E. coli and S. aureus cells. Therefore, the remarkably
enhanced antibacterial activity of the GO/AgNPs composites
is not simply the additive effects of the two components; they
separately function in this system. The unique physicochemi-
cal structure of the nanocomposite with high dispersion might
provide a very good interaction or contact with different bac-
teria inducing the synergistic effect.
76
This might explain the need of the optimal AgNPs to GO
ratio. A ratio lower than 1:1 represents insufficient AgNPs
on GO sheets, whereas a ratio higher than 1:1 (e.g., 2:1) not
only results in larger AgNPs but also leads to partial aggrega-
tion of AgNPs on GO sheets, which sequentially could alter
the interface and reduce the active area for the interaction of
AgNPs with GO sheets and/or the interaction of GO/AgNPs
with bacteria.1,57 When compared with AgNPs, GO/AgNPs
nanocomposite with an optimal weight ratio (1:1) of AgNPs
to GO is highly effective and shows synergistically enhanced,
strong antibacterial activities at a very low concentration of
2.5 μg mL −1.1
6.8 PHOTOINACTIVATION OF BACTERIA
BY GRAPHENE COATED ON TiO2 THIN
FILM FOR USE IN SOLAR LIGHT
Exfoliated GO nanosheets, deposited on photocatalytic ana-
tase TiO2 thin films and subsequently annealed at 400°C in
air, resulted in partial formation of a Ti−C bond between the
GO sheets and the TiO2 thin film.58 UV−visible light-induced
reduction of the GO in the annealed GO/TiO2 composite
films immersed in ethanol for 4 h can reduce 85% of oxygen-
containing groups. GO structures turned to rGO ones. The
antibacterial activity of the rGO/TiO2 composite films tested
against E. coli is about 7.5-fold highly active than that of the
pure anatase TiO2 thin film. The rGO nanosheets were rather
stable after the photoinactivation of the bacteria.58 The effect
of the presence of rGO nanosheets is a sensitizer of the TiO2
photocatalyst.
6.9  ANTIBACTERIAL GRAPHENE-BASED PAPER
Macroscopic, freestanding, robust, and flexible papers of GO
and rGO were prepared by filtering their suspensions through
polymer, polyvinylidene difluoride (PVDF), filter membranes
with a diameter of 47 mm and a pore size of 220 nm using
a one-step vacuum filtration at room temperature.4 The GO
and rGO papers with thicknesses of about 1.5 and 4.6 μm,
respectively, peeled off from the PVDF membranes were used
for their antibacterial activity testing against E. coli using air-
borne bacteria tests.4 After E. coli cells were spread on the
as-prepared paper, Luria–Bertani (LB) growth medium (with
1.5% agar) was then spread. The paper was then left over-
night and incubated at 37°C. No cell growth on the GO paper
was observed and only a limited number of E. coli colonies
appeared on the rGO paper. This indicated the superior anti-
bacterial effect of GO over rGO-based paper. Control studies
without using either GO or rGO paper showed a great number
of colony-forming units (CFU).
6.10 ANTIBACTERIAL ACTIVITY OF GRAPHENE
COATED ON STAINLESS STEEL
A GO suspension in alcoholic solvent can be easily prepared
by dispersing GO powder (1 mg/mL) in isopropyl alcohol.
Then magnesium (II) ion, for example, magnesium (II)
Graphene Science Handbook
nitrate, as a charger was added to the GO suspension in order
to make positively charged graphene nanosheets. The weight
ratio of the GO to Mg2+ was fixed equally. By using this
method, a uniform and stable Mg2+ -GO sheet suspension was
obtained as the electrolyte applicable in the electrophoretic
deposition of GO nanosheets.5 Two polished stainless-steel
substrates were used as electrodes. The distance between
the two electrodes was about 5 mm, and the applied volt-
age of 150 V was applied to the electrodes immersed in the
Mg2+ -GO electrolyte. By applying the voltage, the positively
charged Mg2+ -GO sheets were moved toward the negative
electrode and subsequently reduced and eventually depos-
ited on the stainless-steel electrode. The deposition time
was rather short, about 2 min to obtain the GO nanowalls on
the stainless-steel substrate. Some of the prepared GO were
also reduced by hydrazine vapor for 1 h, the so-called rGO
nanowalls.5
By using antibacterial drop test,5 the bactericidal activi-
ties of graphene-coated stainless-steel samples were inves-
tigated against E. coli and S. aureus used as Gram-negative
and Gram-positive representatives, respectively. Prior to the
antibacterial tests, all graphene-coated samples and glass-
ware were sterilized by autoclaving at 120°C for 10 min.
After the bacteria were cultured on a nutrient agar plate at
37°C for 24 h, the cultured bacteria were added in 10 mL of
phosphate buffer saline (PBS) solution to reach a concen-
tration of bacteria of 108 colony-forming units per milliliter
(CFU mL −1). After that, a portion of the bacterial suspen-
sion was diluted to 106 CFU mL −1. For the antibacterial drop
test, each sample was placed in a sterilized Petri dish. Then,
100 μL of the diluted bacterial suspension was spread on
the surface of the graphene-coated sample. After sonication
of the sample for 60 min at 37°C, the bacteria were washed
from the surface of the sample with 5 mL of PBS in a steril-
ized Petri dish. Then, 100 μL of each bacterial suspension
was spread on a nutrient agar plate and incubated at 37°C for
24 h. The surviving bacterial colonies were counted using
an optical microscope. The total number of the cell-forming
units was determined by area-based estimation. The reported
data were the average value of three separate similar runs.5
After the antibacterial drop test, the bactericidal activity
of the GO and rGO nanowalls against E. coli was shown in
Figure 6.5a. For the control sample, the bare stainless-steel
substrate, no considerable antibacterial activity was observed
but the rGO nanowalls exhibited considerable antibacterial
activities. In fact, after 1 h, 41 ± 8% and 16 ± 3% of the bac-
teria could survive on the surface of the GO and the rGO,
respectively. The antibacterial activity of the rGO is also
comparable with the antibacterial activity of singlewalled car-
bon nanotubes (SWCNTs), which can inactivate 87 ± 7% of
E. coli in 1 h.5 Figure 6.5b shows a similar study on S. aureus.
Once again it was found that the nanowalls were toxic to
bacteria. On the contrary, the nanowalls exhibited stronger
antibacterial activities against S. aureus than their activi-
ties against E. coli. In fact, only 26 ± 5% and only 5 ± 1% of
the bacteria could survive on the surface of the GO and the
rGO nanowires after 1 h, respectively. Therefore, although
Antibacterial and Antifungal Activities of Graphene Nanosheets
(a) 120
100
% Survival bacteria
80
60
40
20
0 0
Control GO rGO
FIGURE 6.5  Survival bacteria, that is, (a) E. coli and (b) S. aureus on graphene-coated stainless steel using antibacterial drop test.
(Adapted from S. Gurunathan et al., International Journal of Nanomedicine, 2012, 7, 5901–5914.)
the synthesized nanowalls were toxic to both Gram-negative
and Gram-positive bacteria, they were more toxic to Gram-
positive bacteria (S. aureus). In addition, for each model of the
bacteria, the rGO nanowalls exhibited stronger toxicity than
the GO nanowalls.5
6.11  FUNGAL CELL STRUCTURES
Fungi are eukaryotes like mammalian cells including
human cells. The similarity of fungal and mammalian cells
lead to the problems for designing antifungal agents, which
selectively inhibit or kill pathogenic fungal cells but not
the human host cells. The fungal cell wall in Figure 6.6 is
mainly composed of protein, chitin, glucan, and the phos-
pholipid bilayer. The chitin, glucans, and glycoproteins are
covalently cross-linked together on top of the phospholipid
bilayer and the cross-linking is a dynamic process that
occurs extracellularly.59
6.12  ANTIFUNGAL ACTIVITY OF rGO
The antifungal activity of rGO was tested with three fungi
that is, A. oryzae, A. niger, and F. oxysporum. A. niger and
F.  ­oxysporum are phytopathogenic fungi that cause diseases
on vegetables and fruits.9 On the contrary, A. oryzae is a ben-
eficial fungus used for the production of traditional Japanese
FIGURE 6.6  Cell wall structure of fungi.
77
(b) 120
100
% Survival bacteria
80
60
40
20
Control GO rGO
fermented foods such as sake, rice vinegar, and soy sauce
as well as for heterogeneous enzyme production. A.  ­oryzae
is generally recognized as safe by US Food and Drug
Administration (FDA) and the World Health Organization
(WHO).60
The rGO nanosheets were dispersed in 15 mL potato dex-
trose agar (PDA) at 50°C and poured into sterilized Petri
dishes (90 mm in diameter). After solidification, agar disks
(5 mm diameter) covered by fungal growth were aseptically
removed from a young (5 day old) PDA fungal culture. The
disks were aseptically placed at the center of the PDA agar
plates containing rGO nanosheets with different concen-
trations. All Petri plates were incubated at 25°C for 7 days.
Experiments were performed with five replicates. The average
fungal colony diameters were determined. Growth inhibition
of A. niger, F. oxysporum, and A. oryzae was proportional to
the concentrations of the rGO nanosheets in PDA.9
The concentrations of rGO nanosheets, which can inhibit
the mycelia growths of A. niger, A. oryzae, and F. oxysporum,
are at 500, 500, and 250 µg mL−1, respectively (see Figure 6.7).
The reason, why the rGO nanosheets were effective to inhibit
fungi, is probably due to the direct contact with the cell walls
FIGURE 6.7  Mycelial growth of A. niger on the PDA media con-
taining different concentrations of rGO nanosheets (unpublished
images).
78
FIGURE 6.8  Cartoon showing the destructive extraction of phospholipids from the microbial cell membrane: (a) before and (b) after
extraction of phospholipids. (Adapted from Y. Tu et al., Nature Nanotechnology, 2013, 8, 594–601.)
of fungi.9 After the contact, the reactive oxygen-containing
functionalities of several small rGO nanosheets could chemi-
cally react with the organic functional groups of chitin and
other polysaccharides on the cell walls of fungi.61 Notably, the
antibacterial mechanism of graphene-related materials based
on the direct contact with the bacterial cells was previously
reported.5,6 It was also reported that the antifungal mechanism
of essential oils containing oxygen-species functional groups
(e.g., phenol) was due to the direct contact with the cell walls of
fungi.62−64 Interestingly, it was recently reported that the cyto-
toxicity of GO nanosheets on A549 human cells occurred as
a result of direct interactions between the cell membrane and
GO nanosheets.65 Another possible mechanism is based on the
destructive extraction of phospholipids in the cell membrane
of fungi similar to that in bacteria.2 Similar to phospholipids in
the fungal membrane as in the bacterial membrane, graphene-
based nanosheets may initially penetrate into and then remove
large amounts of phospholipids from the cell membranes. This
process may lead to the death of fungal cells.2
As the extent of fungal growth inhibition was dependent on
the concentration of rGO used, the half-maximal inhibitory
concentration (IC50) values were then determined by plot-
ting the logarithm of the concentration of the rGO (µg mL −1)
versus the mycelial growth inhibitory activity (%). The IC50
values of the rGO nanosheets against F. oxysporum, A. niger,
and A. oryzae are 50, 100, and 100 µg mL −1, respectively.
This might be because the rGO can easily get attached to the
external cell wall of F. oxysporum via hydroxyl oxygen spe-
cies of glycoproteins.66
6.13  SUMMARY AND PERSPECTIVES
Antibacterial and antifungal agents are widely used for the
prevention of public health issues. Graphene is a material con-
sisting of a monolayer of sp2-bonded carbon atoms. It is of
interest due to its high surface area (~2630 m2 g−1), high elec-
trical conductivity (~2000 S cm−1), high thermal conductiv-
ity (4840−5300 W m−1 K−1), high electronic carrier mobility
(200,000 cm2 V−1 s−1), and high Young’s modulus (~10 TPa)
leading to various potential applications. Interestingly,
Graphene Science Handbook
graphene can inhibit the growth of bacterial cells (e.g., E. coli,
S. aureus) and fungal cells (e.g., A. niger, A. oryzae, and F.
oxysporum). Graphene can kill or damage bacterial and fungal
cell membranes with their extremely sharp edges. Graphene
with diluted oxygen-containing functionalities, the so-called
rGO can in addition oxidize glutathione, which is a redox state
mediator in bacteria. Its oxidation leads to bacterial growth
inhibition. The half-maximal inhibitory concentration (IC50)
of rGO, a measure of the effectiveness of graphene in inhibit-
ing the fungi, against F. oxysporum, A. niger, and A. ­oryzae
are 50, 100, and 100 µg mL −1, respectively. We believe that
graphene may find important environmental and clinical
applications. The most possible antimicrobial mechanism of
graphene-based nanosheets with evidence recently published
in Nature Nanotechnology2 is the destructive extraction of
phospholipids from microbial membranes (see Figure 6.8).
As graphene-based nanosheets can enter the cell mem-
brane with destructive extraction of the phospholipids from
the cell membrane, graphene nanosheets can also induce
serious membrane stress, and thus significantly reducing cell
viability. The resulting antibacterial and antifungal activities
of graphene-based nanosheets increase with increasing lat-
eral size and concentration of graphene. As a result, graphene
could be a great antibacterial material in the near future since
its antimicrobial mechanism is based on “physical damage.”
A current concern of bacterial resistance to antibiotics could
be easily overcome if graphene was used as an antibiotic
agent. It is also necessary to note here that cytotoxicity stud-
ies of graphene and its related materials and their influence on
plant, animal, and human cells are also needed.
ACKNOWLEDGMENTS
The author thanks the Faculty of Engineering, the Kasetsart
University Research and Development Institute, the Thailand
Research Fund (TRG5680043), the Commission on Higher
Education, Ministry of Education (“the National Research
University Project of Thailand” and “Postgraduate Education
and Research Programs in Petroleum and Petrochemicals and
Advanced Materials”) for their financial support.
Antibacterial and Antifungal Activities of Graphene Nanosheets
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 7 Applications of Graphene in Biosensing
D. P. Nikolelis, Z. H. Ibupoto, G.-P. Nikoleli, and M. Willander

CONTENTS
Abstract........................................................................................................................................................................................ 81
7.1 Introduction........................................................................................................................................................................ 81
7.2 Graphene-Based Glucose-Sensing Application.................................................................................................................. 83
7.3 Graphene and Its Composite-Based Hydrogen Peroxide Sensors...................................................................................... 84
7.4 Dopamine Sensor Based on Graphene Nanosheets............................................................................................................ 85
7.5 Cholesterol Biosensor Based on Graphene Nanosheets..................................................................................................... 85
7.6 Cytochrome c Biosensor Based on Graphene.................................................................................................................... 85
7.7 NADH Biosensor Based on Graphene................................................................................................................................ 85
7.8 DNA Sensors Based on Graphene...................................................................................................................................... 86
7.9 Lipid-Modified Urea Biosensor.......................................................................................................................................... 86
7.10 Lipid-Modified Cholesterol Biosensor................................................................................................................................ 87
7.11 Conclusion and Future Challenges..................................................................................................................................... 87
Acknowledgments........................................................................................................................................................................ 88
References.................................................................................................................................................................................... 88

ABSTRACT novel and attractive functional materials with the emergence

Graphene experiences two-dimensional nanostructures com-
posed of particles of few nanometer thickness. The small
thickness of graphene nanosheets endorses its wide use in
biosensing applications due to ultra-high conductivity and
mechanical strength, high surface area, simple function-
alization, and other unique and attractive physiochemical
characteristics. Since the last 3–4 years the number of bio-
sensors based on graphene as the primary transducer has
been proposed for the detection of various compounds.
Graphene-based biosensors are accompanied by high sensi-
tivity, selectivity, fast response time, stability, and low limit
of detection. Graphene-based biosensors have the advantage
of functionalization with both nonpolar and polar biosensitive
materials over the metal–oxide–semiconductors where nonpo-
lar molecules cannot be functionalized effectively. Moreover,
through the graphene-based biosensor, direct detection of
biomolecules has also been realized with acceptable sensitiv-
ity and selectivity. On the basis of high selectivity, sensitiv-
ity, simplicity, and potential usability in real-time samples for
the graphene-based biosensor, the following chapter provides
a brief review of graphene-based biosensors. The chapter
includes the fundamental principles involved during the func-
tionalization and the type of electronic sensors based on the
graphene material. Examples of biosensors based on graphene
include the biosensing of dopamine, glucose, hydrazine, nitric
oxide, β-­ nicotinamide adenine dinucleotide (NADH), and
paracetamol. Modification of the graphene biosensor surface
with a lipid film increases the sensitivity of detection. Typical
examples of this modification are the biosensing of urea, cho-
lesterol, etc. There has been a growing interest in the use of
of new bioreceptors; therefore, the present time can be con-
sidered to witness the birth of a new generation of biosensors
which has been realized and adapted.
7.1 INTRODUCTION
In graphene, each carbon atom is sp2 hybridized which when
combined together gives a two-dimensional array of gra-
phene, such bonding renders graphene its excellent electronic,
optical, thermal, and mechanical properties (Novoselov et al.
2004, Latil and Henrard 2006, Balandin et al. 2008, Rao et al.
2009, Zhang et al. 2010). The novel synthetic routes and the
functionalization approaches make graphene and its deriva-
tives find a variety of applications at a high speed. Graphene
and its composite structures have been used in various fields
such as, nanoelectronics (Xuan et al. 2008), composite mate-
rials ((Bai et al. 2010, Fan et al. 2010, Fang et al. 2010, Yang
et al. 2010b, Sun and Wu 2011), fuel cells and hydrogen stor-
age (Stoller et al. 2008, Wang et al. 2009, Liu et al. 2010a),
sensors (Lu et al. 2009a), and catalysis (Qu et al. 2010).
Several synthetic routes have been found for the produc-
tion of graphene (Park and Ruoff 2009, and Rao et al. 2009).
For the first time, graphene was synthesized by Geim and
coworkers (Novoselov et  al. 2004) using mechanical exfo-
liation of well-oriented pyrolytic graphite. The scotch tape
method (Geim 2009, and Park and Ruoff 2009) is widely
used for the production of graphene in many laboratories
for fundamental research and for the development of related
devices. However, this method is not suitable for mass pro-
duction and the other reported method which gives the
81
82
perfect graphene is the exfoliation of graphite (Hernandez
et  al. 2008, Li et  al. 2008a, Bourlinos et  al. 2009, Lotya
et  al. 2009). This method also give less yield of graphene
(Hernandez et al. 2008). Other existing methods for the pro-
duction of graphene are termed as thermal decomposition of
SiC wafer under ultrahigh vacuum conditions (Berger et al.
2006, Rolling et al. 2006, De Heer et al. 2007, Emtsev et al.
2009) or by chemical vapor deposition technique using the
metal substrate such as ruthenium (Sutter et al. 2008), nickel
(Kim et al. 2009, and Reina et al. 2009), and Cu (Li et al.
2009c) or without the use of a substrate (Dato et al. 2008).
The chemical vapor deposition method is considered as a
mass production method for the production of graphene for
electronic applications (Hass et al. 2008, Obraztsov 2009).
In addition to the chemical vapor deposition as a mass pro-
duction method for graphene synthesis, the technique of
chemical- (Gilje et  al. 2007, Stankovich et  al. 2007, Fan
et al. 2008, and Li et al. 2008b) or temperature-dependent
reduction of graphite oxide (GO) is also used. From electro-
chemistry point of view, graphene is mostly prepared by the
reduction of GO. The graphene obtained from the reduction
of GO is known as functionalized graphene sheets or chemi-
cally reduced graphene oxide (RGO), which is accompanied
by several defects (Schniepp et  al. 2006) and containing
functional groups that are more favorable for electrochemi-
cal measurements (Banks et al. 2005, Wang 2005, McCreery
2008, Dumitrescu et al. 2009).
Graphene is largely used in sensing applications by detect-
ing various analytes such as dopamine (Kim et al. 2010), glu-
cose (Kang et  al. 2009, Liu et  al. 2010b), hydrazine (Wang
et al. 2010), nitric oxide (Wu et al. 2010b), NADH (Lin et al.
2009), and paracetamol (Kang et  al. 2010). The use of gra-
phene material for sensing applications has proved to be an
excellent transducer by improving the sensitivity and selec-
tivity of the sensor device in addition to low limit of concen-
tration detection and a rapid response time (Brownson and
Banks 2010, Kang et al. 2010). The surface modification of the
sensor electrode also improves the performance of the device.
The Nafion film due to its distinctive properties and unique
ion exchange and biocompatibility is extensively employed
for the modification of electrode surfaces and for the develop-
ment of amperometric biosensors (Wang et al. 2003, Li et al.
2009b). For instance, graphene-modified electrodes showed
excellent performance compared with carbon nanotubes
(CNTs) by detecting adenine and guanine (Yin et  al. 2010).
Similarly, graphene nanosheets and Nafion composite film
(Li et al. 2009b) demonstrated superior response during the
detection of lead and cadmium ions.
Currently, due to these fascinating properties of gra-
phene-based electrodes, these electrodes have been used in
the research areas of chemical sensors and biosensors to a
large extent. It has been shown that graphene possessed high
electrocatalytic activity for different biomolecules and there-
fore provides the perfect environment for the immobiliza-
tion of different enzymes (Hong et al. 2010, Liu et al. 2010c,
Shan et al. 2010a, Wu et al. 2010b, Zhou et al. 2010, Wang
et  al. 2011a,b). Different nanomaterials have been used for
Graphene Science Handbook
the fabrication of electrochemical biosensors such as metal
nanoparticles, CNTs, and metal oxides and are success-
fully used for the analysis of samples in medical and such
industries (Pellegrini et  al. 2004, Alwarappan et  al. 2009b,
Prabhulkar et  al. 2009, Zhang et  al. 2009). The functional
graphene or CNTs are very much appropriate for ultracapaci-
tor and energy storage applications; however, the usability
of graphene for electrochemical biosensing for the detection
of bioactive species and biomolecules detection is also suit-
able (Kusakari et al. 2008, Li et al. 2008c, Alwarappan et al.
2009a, Wang et al. 2009).
It has been reported that graphene carries a large number
of reactive functional groups which combines with the free
–NH2 terminals of the enzyme or proteinaceous biosensi-
tive material, finally resulting a firm amide covalent linkage
(Subbiah et  al. 2010). The fabrication of chemical sensors
using graphene as a primary transducer with high sensitivity
is due to the two-dimensional structure of single atomic layer
of graphite which may provide better binding among the sur-
face dopants and ascorbate. Graphene exhibits less Johnson
noise compared with CNTs (Novoselov et  al. 2005, Zhang
et al. 2005, Geim and Novoselov 2007) and a small change
in carrier concentration could result in a significant change in
electrical conductivity (Ao et al. 2008).
The electrochemical properties of graphene have not been
fully explored yet; however, it is observed that the fast elec-
tron transfer between enzymes and electrodes takes place
because of the extraordinary electronic properties of graphene
(McCreery 2008, Shang et al. 2008, Tang et al. 2009). As the
carbon atom in graphene is sp2 hybridized and one p orbital
of carbon is not involved in the hybridization which forms the
delocalized π bonds above and below the plane, these delocal-
ized π-electron system gives strong electrical conductivities
and mobility within the graphene planes (Yang et al. 2010b).
The usability of graphene for biosensing application prevents
the difficulties that arose during the use of transition metals
such as Fe, Ni, Co, etc. In graphene, the rapid electron trans-
portation, high thermal conductivity, good mechanical flex-
ibility, and biocompatibility provide excellent transducers for
biosensing applications.
The glucose sensors have been reported using the bion-
anocomposite film–oxidase/Pt/functional graphene sheets/
chitosan (Wu et al. 2009) and PVP-protected graphene-GOD-
PFIL-modified glassy carbon electrode (Shan et  al. 2009).
Zhou has developed a novel graphene-modified glassy car-
bon electrode for electrochemical sensing and biosensing
of various electroactive substances (Zhou et  al. 2009). The
electrochemiluminescence sensors based on Ru(bpy)32+/
graphene/Nafion-modified electrode has been reported by
Li by detecting the oxalate (Li et  al. 2009a). Graphene has
been widely used for the sensing of different analytes and the
sensing applications of graphene have been described in many
reviews (Shao et al. 2010, Yang et al. 2010a, Jiang 2011, Kuila
et al. 2011, Ratinac et al. 2011, Zhigang et al. 2012).
Modification of the graphene biosensor with a lipid mem-
brane increases the sensitivity of biosensing and offers an
attractive route for the detection of biomolecules such as urea,
Applications of Graphene in Biosensing
cholesterol, etc. Herein, we discuss about the usability of gra-
phene in the detection of a diverse wide range of analytes.
7.2 GRAPHENE-BASED GLUCOSE-
SENSING APPLICATION
Graphene exhibits high electrocatalytic activity for H2O2
and reasonable and worthy direct electrochemical response
for the glucose oxidase; thus, it can be considered a potential
candidate for the direct electrochemistry of glucose oxidase
(Zhou et al. 2009, Shao et al. 2010). Shan et al. developed for
the first time, a glucose biosensor using graphene electrode
modified with polyvinylpyrrolidone which could be mixed
in water (Shan et al. 2009). This has shown acceptable elec-
trochemical reduction for H2O2. After the immobilization of
glucose oxidase, the sensor device obtained a direct electron
transfer rate between the immobilized glucose oxidase and
the graphene electrode. The proposed glucose sensor showed
a linear response for concentrations of 2–14 mM and good
reproducibility and stability. Alwarappan et  al. designed an
enzyme-doped graphene-nanosheets-based glucose biosen-
sor (Alwarappan et al. 2010). The graphene nanosheets were
chemically obtained and covalently linked to glucose oxidase.
The covalently linked graphene/glucose oxidase was function-
alized on the glassy carbon electrode surface. It was modified
with porous polypyrrole. Polypyrrole/graphene/glucose oxi-
dase showed a good sensitivity of 3 µM with signal/noise = 3.
Wu et  al. presented a new trend toward the fabrication of
glucose biosensor by electrocatalytic reduction of oxygen at
the glucose oxidase–graphene–glassy carbon electrode (Wu
et al. 2010b). It was found that on successive addition of glu-
cose, the reduction current was lowered. The developed glu-
cose biosensor exhibited linear response for the concentration
range of 0.1–10 mM having a sensitivity of 110 µA mM−1 cm−2
with a detection limit of 10 ± 2 µM. Kang et al. used a glu-
cose oxidase–graphene–chitosan-modified electrode mate-
rial (Kang et al. 2009), herein, the bioactivity of immobilized
enzyme was retained by the chitosan and graphene was well
dispersed in the chitosan solution. A heavy loading of enzyme
was obtained at about 1.12 × 10−9 mol/cm2 compared with the
bare glassy carbon electrode surface. The presented glucose
sensor showed a sensitivity of 110 ± 3 µA mM−1 cm−2 with a
linear range of 0.1 to 10 mM and also a low concentration
limit of detection (10 ± 2 µM) was observed.
To improve the performance of glucose biosensors based
on graphene electrode, the metal nanoparticles are widely
used along with the graphene itself. Wang et al. has fabricated
the composite electrode made of graphene and cadmium
sulfide for a better microenvironment for the immobiliza-
tion of enzymes, especially the immobilization of glucose
oxidase (Wang et al. 2011b). The graphene–cadmium sulfide
nanomatrix has shown better electron transfer properties for
glucose oxidase by showing a rate constant of 5.9 s−1. The fab-
ricated glucose biosensor exhibited a linear range from 2 to
16 mM and a detection limit of 0.7 mM was also observed
with negligible response to common interferences. Zeng
et al. have developed palladium nanoparticle/chitosan-grafted
83
graphene-based nanocomposite for the detection of glucose
(Zeng et  al. 2011). The biocompatibility and hydrophilicity
of graphene was improved. First, it was functionalized with
chitosan and further palladium nanoparticles were deposited
on the electrode using in situ reduction. The fabricated bio-
sensor device showed an excellent electrocatalytic tendency
for H2O2 and heavy loading of enzyme was also noticed. The
presented device exhibited a sensitivity of 31.2 µM−1 cm−2
for glucose in the linear range of 1 µM to 1 mM. The strong
affinity for glucose by the enzyme was observed by show-
ing a low Michaelis–Menten of 1.2 mM. Yang et  al. (2011)
constructed a novel nanocomposite of electrochemically
RGO and gold–palladium (1:1) bimetallic nanoparticles in the
absence of a reducing agent. The prepared nanocomposite has
shown excellent biocompatibility, improved electron transfer
rate, and high electroactive surface area in addition to high
sensitivity and stability for the reduction of oxygen. The linear
range for this sensor device was found to be 3.5 mM with a
sensitivity of 266.6 µA mM−1 cm−2. Hasan et al. (2012) have
developed a glucose sensor using the functionalized graphene.
A combination of positively charged polymeric ionic liquid
and glucose oxidase provides the suitable microenvironment
for the glucose oxidase thereby retaining its bioactivity for
a long-term period. The proposed sensor has shown a linear
response for a wide range of glucose concentrations of up to
100 mM with a sensitivity of 5.59 µA/decade. The obtained
results indicate that the functionalized graphene may have
potential for the detection of glucose in clinical samples.
Graphene and its nanocomposites have been used for the
development of nonenzymatic sensors. Non-enzymatic is
accompanied by several advantages such as no use of expen-
sive enzyme and the loss activity is avoided by this way. This
is a novel approach toward the construction of enzyme-free
glucose sensors using graphene as an electroactive material/
composite nanostructures of graphene. Kong et al. fabricated
high-density gold nanoparticles using thionine functionalized
GO through the chemical reduction of HAuCl4 with sodium
citrate (Kong et al. 2012). The thionine enhances the adsorp-
tion of negatively charged AuCl4– on the GO surface which
further helps in the heavy loading of gold nanoparticles. The
glassy carbon electrode functionalized with GO–thionine–
gold has shown a significant electrocatalytic tendency for
the enzyme-free oxidation of glucose with a linear range of
0.2–13.4 mM and a low concentration limit of detection of
0.05 µM.
Luo et  al. developed a nonenzymatic glucose sensor
through potentiostatic electrodeposition of metallic copper
nanoparticles on graphene nanosheets (Luo et al. 2012). The
enhanced electrocatalytic response for glucose was observed
for copper–graphene nanosheet electrodes relative to that of
unmodified graphene sheet electrodes. The copper–graphene
nanocomposite showed a linear range of up to 4.5 mM glu-
cose concentration with a detection limit of 0.5 µM (signal/
noise = 3) using a detection potential of 500 mV. Gao et  al.
developed an enzyme-free glucose sensor by one-step elec-
trochemical synthesis of platinum and nickel nanoparticle
composite with graphene (Gao et  al. 2011). The fabricated
84
TABLE 7.1
Glucose Sensors Based on Graphene
Material
Graphene/polyvinylpyrrolidone
Graphene/glucose oxidase
Glucose oxidase–graphene
Enzyme chitosan/graphene
Graphene/cadmiun sulfide
Nanoparticle/chitosan-grafted graphene
Graphene oxide and gold–palladium and bimetallic nanoparticles
Graphene oxide–thionine–gold
Metallic copper nanoparticles on graphene nanosheets
Platinum and nickel nanoparticle composite with graphene
nanocomposite shows plenty of attractive properties such
as well-dispersed nanoparticles with alloy behavior, heavy
loading of nanoparticles, and remarkable reduction of GO.
The response of the proposed sensor device was linear up
to 35 mM having a sensitivity of 20.42 µA cm−2 mM−1 at a
negative potential of −0.35 V. The most noticeable thing in
the developed sensor device is that it is capable of working at
a negative potential which ensures no oxidation of common
interferents. Typical examples of sensors based on graphene
for glucose sensing are summarized in Table 7.1.
7.3 GRAPHENE AND ITS COMPOSITE-BASED
HYDROGEN PEROXIDE SENSORS
Selvakumar Palanisamy et  al. reported on enzyme-free
amperometric sensors for hydrogen peroxide using electro-
chemically synthesized RGO and zinc oxide nanocomposite
by the electrodeposition technique (Selvakumar Palanisamy
et al. 2012). The RGO and zinc oxide composite was depos-
ited on glassy carbon electrode. The amperometric technique
was used for the measurement of electrochemical response
and the sensor showed excellent performance for the detec-
tion of H2O2 at −3.8 V. The linear range was found to be
0.02–22.48 µM. A fast response time of less than 5 s was also
observed in addition to acceptable operation and storage.
Yalin Xia et al. prepared a novel and enzyme-free electro-
chemical sensor using the polynucleotide–silver nanoclusters/
graphene composite film for the sensing of hydrogen peroxide
(Yalin Xia et al. 2013). Graphene-modified glassy carbon elec-
trode was used due to many attractive properties of graphene
such as good conductivity, biocompatibility, and high surface
area to volume ratio. The graphene composite film showed
excellent electrocatalytic activity for the reduction of hydro-
gen peroxide and simplicity in the immobilization of enzyme
on the surface of graphene. The presented sensor showed a
linear range of 15–23 mM, good selectivity, and repeatability
in addition to anti-interference ability.
Liu et  al. adapted different approaches for the develop-
ment of hydrogen peroxide sensor electrodes (Liu et  al.
2011). The sensor electrode was prepared by layer by layer
Graphene Science Handbook
Sensitivity Linear Range Reference
2–14 mM Shan et al. (2009)
Alwarappan et al. (2010)
110 µA mM−1 cm−2 0.1–10 mM Wu et al. (2010a,b)
110 ± 3 µA mM−1 cm−2 0.1–10 mM Kang et al. (2009)
2–16 mM Wang et al. (2011a,b)
31.2 µM−1 cm−2 1 µM–1 mM Zeng et al. (2011)
266.6 µA mM−1 cm−2 Up to 3.5 mM Yang et al. (2011)
0.2–13.4 mM Kong et al. (2012)
0.5–4.5 mM Luo et al. (2012)
20.42 µA cm−2 mM−1 up to 35 mM Gao et al. (2011)
combination of negatively charged iron oxide nanoparti-
cles and positively charged poly(diallydimethylammonium
chloride) through ­ electrostatic attraction. The use of
poly(diallydimethylammonium chloride) and graphene
enhanced the catalytic performance of iron oxide nanopar-
ticles due to its high surface area and good electrical conduc-
tivity. Owing to these advantages of the composite film, it
has shown significant and dominant electrocatalytic tendency
for the detection of H2O2 with a linear range of 20 µM to
6.25 mM and also a fast response time at successive addition
of H2O2 and a low concentration limit of detection of 2.5 µM
(signal/noise = 3) was noticed.
Li et  al. fabricated the MnO2/GO composite structures
for the enzyme-free detection of hydrogen peroxide (Li et al.
2010b). The hybrid material showed high electrochemical
activity for the determination of H2O2 in basic medium. The
nonenzymatic sensor showed excellent performance at low
working potential with high sensitivity, low concentration
limit of detection, and longer lifetime stability. This perfor-
mance shown by the developed sensor could be due to the
high surface area of GO for the deposition of MnO2 nanopar-
ticles. The obtained information from this experiment showed
that a novel nanocomposite with high surface area and better
electrocatalytic activity can be used as a potential candidate
for the development of nonenzymatic sensors.
Ali A. Ensafi et  al. reported H2O2 sensor using Nafion/
exfoliated GO/Co3O4 nanocomposite on the glassy carbon
electrode (Ensafi et al. 2013). The modified GO-based elec-
trode showed acceptable and stable redox signal when it was
tested in basic and neutral mediums with enhanced electro-
catalytic activity for the oxidation of hydrogen peroxide. A
low concentration detection limit (ca. 0.3 µmol L −1) and a
sensitivity of 560 µA mmol−1 cm−2 were observed. A response
time of the sensor electrode (95% steady-state current) of 4 s
was observed. The proposed sensor electrode was used for the
monitoring of H2O2 in milk samples with reasonable recovery
values. The sensor electrode was very selective, stable, and
reproducible. The fascinating performance of this analytical
device including noticeable catalytic activity, simple method
of fabrication supports this new nanocomposite electrode
Applications of Graphene in Biosensing
TABLE 7.2
H2O2 Sensors Based on Graphene
Material Sensitivity
Graphene oxide and zinc oxide
Polynucleitide–silver nanoclusters/ graphene
Nafion/exfoliated graphene oxide/Co3O4 560 µA mmol−1 cm−2
Poly(diallydimethylammonium chloride)/graphene
potential candidate for the engineering of potential H2O2 sen-
sor. Typical examples of sensors based on graphene for hydro-
gen peroxide sensing are summarized in Table 7.2.
7.4 DOPAMINE SENSOR BASED ON
GRAPHENE NANOSHEETS
Xiuli Niu et al. reported on the selective and sensitive dopa-
mine electrochemical sensor using the graphene nanosheets
and multiwall CNTs functionalized with 3, 4, 9, 10-perylene
tetracarboxylic acid in an ionic liquid (IL) modified glass car-
bon electrode (Xiuli Niu et al. 2013). The modified electrode
demonstrated excellent electrocatalytic activity for the oxida-
tion of dopamine. The developed sensor detected a wide range
of dopamine in the concentration range of 0.03–3.82 mM. The
detection limit for the presented dopamine sensor was found
to be 1.20 × 10−9 M (S/N = 3). The graphene-nanosheet-based
modified electrode shows excellent catalytic activity, good
sensitivity, reproducibility, selectivity, and stability.
Li et al. developed a nanocomposite of Pt nanoparticles/IL/
graphene for the determination of ascorbic acid and dopamine
at the same time (Li et al. 2010a). The two oxidation peaks dif-
fered by more than 200 mV, which is enough to distinguish
between ascorbic acid and dopamine. The distinctive three
peaks have been observed by the Pt/IL/graphene-modified
electrodes from the human urine sample which contains ascor-
bic acid and dopamine. These electrodes have reliable shelf life
and reproducibility. Hence, IL-functionalized graphene can
have a contributing role from the clinical point of view in the
analysis of samples containing ascorbic acid and dopamine.
7.5 CHOLESTEROL BIOSENSOR BASED
ON GRAPHENE NANOSHEETS
Israr et al. have developed graphene-nanosheet-based poten-
tiometric cholesterol biosensor using uniform exfoliation
mono- and double-layer graphene nanosheets on copper wire
where the graphene nanosheets were dispersed in N-methyl-
pyrrolidone solution (Israr et al. 2011). Graphene nanosheets
were immobilized with cholesterol oxidase by the physi-
cal adsorption method. The proposed cholesterol biosensor
exhibits good selectivity and sensitivity (i.e., 82 mV/decade)
in the range of 1 × 10−6 to 1 × 10−3 M of cholesterol. The sen-
sor showed a fast response time of 4 s in addition to good
stability and repeatability.
85
Linear Range Response Time Reference
0.02–22.48 µM 5s Selvakumar Palanisamy
et al. (2012)
15–23 mM Y. Xia et al. (2013)
Detection limit 0.3 µmol L−1 4 s Ensafi et al. (2013)
20 µM–6.25 mM Liu et al. (2011)
Cholesterol and its ester derivatives are important compo-
nents of all animals and cells. Cholesterol and its derivatives
are the main constituents of many bioanalytes including bile
acid and steroid hormones. The increasing level of cholesterol
in the human body is responsible for many diseases such as
cardiac diseases, cerebral thrombosis, and arthrosclerosis.
Thus, the precise measurement of cholesterol is essential from
the medical point of view (Dey and Raj 2010). Dey and Raj
have constructed a sensitive amperometric biosensor using
the hybrid material based on the composition of Pt nanopar-
ticles and graphene for sensing H2O2 (Dey and Raj 2010). The
cholesterol biosensor was prepared by immobilizing choles-
terol oxidase and cholesterol esterase on this hybrid material.
The sensitivity and low concentration limit of detection were
2.07 ± 0.1 µA µM−1 cm−2 and 0.2 µM, respectively. The high
sensitivity and low concentration limit of detection could be
due to the interactive nature of graphene and Pt nanoparticles.
7.6 CYTOCHROME c BIOSENSOR
BASED ON GRAPHENE
Direct electron transfer rate between cytochrome c and the elec-
trode is becoming more popular because of its biological reac-
tivity (Xiang et al. 2008). It is observed that bare glass carbon
electrode does not show voltametric response for cytochrome
c because of the slow electron transfer rate between the elec-
trode and the electrolyte interface. The carbon-based modified
nanofiller electrodes have solved these hurdles by the develop-
ment of cytochrome c electrodes. Wu et al. have reported on
a cytochrome c biosensor using chitosan (CS)–graphene elec-
trode of direct electron transfer rate between the electrode and
the electrolyte interface (Wu et al. 2010a). The formal potential
for this modified electrode was found to be 0.28 V. The elec-
tron transfer rate constant for the modified graphene electrode
was found to be 1.95 s−1, which is superior to the conventional
electrodes. Thus, cytochrome c preserved its bioactivity on the
surface of CS–graphene modified electrode and performed like
an enzyme for the reduction of nitric oxide.
7.7  NADH BIOSENSOR BASED ON GRAPHENE
NADH is considered an essential coenzyme that is involved
in a large number of dehydrogenase-based enzymatic reac-
tions (i.e., more than 300) (Liu et  al. 2009). The electro-
catalytic oxidation of NADH has been studied as part of an
86
experiment during the construction of dehydrogenase analyti-
cal biodevices.
It has been investigated that the electrochemical oxidation
of NADH at bare glass carbon electrode in neutral medium of
solution is found at high overpotential (0.5 V) due to slow elec-
tron transfer rate and backing up of electrode (Raj and Ohsaka
2001). Liu et al. developed a NADH sensor using electrostatic
functionalized graphene with water-soluble electroactive
methylene green (MG) (Liu et al. 2009). For bare glass carbon
electrode in the case of NADH, the oxidation peak is found at
+0.55 V. However, it occurred at +0.40 V and +0.14 V respec-
tively for the modified electrodes of C-reduced graphene and
C-reduced graphene functionalized with MG. Shan et al. fab-
ricated an IL-functionalized graphene biosensor for the detec-
tion of NADH by electrochemical method (Shan et al. 2010b).
The amperometric measurement for this electrode showed a
stable 95.4% and 90 % of initial activity after 10 and 30 min,
respectively, for a 1 mM NADH solution as compared with
that of bare glass carbon electrode (68% and 46% for the same
condition of measurement). In addition, the IL-CS-graphene-
modified electrode showed an acceptable linearity from 0.25
to 2 mM and maximum sensitivity of 37.43 µA mM−1 cm−2.
7.8  DNA SENSORS BASED ON GRAPHENE
It is highly valuable to have devices which are sensitive, selec-
tive, fast, and cheap for the detection of biomolecules and for
clinical diagnosis.
Currently, Lu et  al. (2009a,b,c) showed that a combina-
tion of graphene and ssDNA may have high potential for the
determination of biomolecules. The (G, A, T, and C) bases are
detectable by the electrochemical method and for the develop-
ment of DNA sensors (Lu et al. 2009a).
Wan et  al. explored that the incorporation of silver
nanoparticles in GO sheets suits to signal amplification and
determination of bacteria (Wan et  al. 2011a,b). Thus, GO
sheet modified with silver nanoparticles keeps strong poten-
tial for the quick analysis of protein and DNA. Zhao et al. fab-
ricated graphene electrode combined with probe ssDNA for
the selective and sensitive determination of different analytes
Urea
Glass fiber
filter
et
she
phene
Gra
FIGURE 7.1  ​Schematic image of urea biosensor.
Graphene Science Handbook
(Zhao et  al. 2011). Bo et  al. reported a DNA biosensor and
the fabrication of electrode was carried out by electrodeposi-
tion of Prussian blue (PB) on chemically treated carbon paste
electrode (Bo et al. 2011). It was noticed that by coupling the
PB electrode with graphene increases the current output. The
detection of bacteria by using a graphene-based biosensor
has attracted great attention among the scientific community
(Mohanty and Berry 2008, Wan et  al. 2011a,b). Recently, a
selective, sensitive, simple, and accurate impedimetric immu-
nosensor based on graphene electrode has been reported for
the determination of marine pathogenic SRB.
7.9  LIPID-MODIFIED UREA BIOSENSOR
A miniaturized potentiometric urea lipid film-based biosen-
sor on graphene nanosheets was recently presented in the
literature (Nikoleli et  al. 2012). A simplistic approach of
dropwise dispersion of graphene has been utilized to scatter
graphene nanosheets on a copper wire. Stabilized lipid films
were prepared by polymerization with a procedure similar to
that previously described (Nikolelis et al. 2006). A measure of
0.15 mL of a mixture containing 5 mg of a mixed lipid pow-
der [composed of 35 (w/w) DPPA and 65 (w/w) of DPPC],
0.070 mL of methacrylic acid, 0.8 mL of ethylene glycol
dimethacrylate, 8 mg of 2,2′-azobis-(2-methylpropionitrile),
and 1.0 mL of acetonitrile were spread on a glass fiber micro-
filter. The filter with the mixture was then irradiated using
a UV deuterium lamp. Raman spectrometry was used to
monitor the kinetics of the polymerization process (Nikolelis
et al. 2006). Urease was incorporated into these BLMs prior
to polymerization by spreading 15 µL of enzyme suspen-
sion with the polymerization mixture. The preparation of the
potentiometric urea biosensor has been finalized by encapsu-
lation of the filter-supported polymerized lipid film onto the
copper wire containing graphene nanosheets. Reproducibility
and repeatability have been investigated with five repeated
experiments from a single biosensor. It has been observed that
the urea biosensor reveals excellent reusability with negligible
change in the measured EMF values. A schematic diagram of
the experimental setup is shown in Figure 7.1.
2NH3 + CO2
Urease
Copper wire
Applications of Graphene in Biosensing
Structural characterization of graphene nanosheets for
miniaturization of potentiometric urea lipid film-based bio-
sensors has been studied through atomic force microscopy
(AFM) and transmission electron microscopy (TEM) mea-
surements. UV-Vis and Fourier transform IR (FTIR) spectros-
copy have been utilized to study the pre- and postconjugated
surfaces of graphene nanosheets. The presented potentiomet-
ric urea biosensor exhibits good reproducibility, reusability,
selectivity, rapid response times (~4 s), long shelf life, and
high sensitivity of ca. 70 mV/decade over the urea logarithmic
concentration range from 1 × 10−6 to 1 × 10−3 M.
7.10 LIPID-MODIFIED CHOLESTEROL
BIOSENSOR
A novel potentiometric cholesterol biosensor has been fabri-
cated through the immobilization of the stabilized polymeric
lipid membrane onto graphene electrode (Nikoleli et al. 2013).
The stabilized polymeric lipid membrane is composed of cho-
lesterol oxidase enzyme and polymerization mixture; which
holds paramount influence on the properties of cholesterol
biosensor. The presented biosensor reveals appreciable repro-
ducibility, good selectivity, and high sensing capability with a
linear slope curve of ~64 mV/decade. The strong biocompat-
ibility among the stabilized polymeric lipid membrane and
human biofluids provides the possibility to use for real blood
samples/practical applications.
The advantages of this chapter as compared with our previ-
ous (Israr et al. 2011) are summarized in the following:
1. The highly suitable microenvironment for the attach-
ment of cholesterol molecules due to the same chem-
istry of lipid membrane and cholesterol molecules.
2. The stabilized lipid membrane has the ability to
increase the lifetime of the biosensor compared with
previously reported biosensors without lipid mem-
brane on the transducer surface.
3. The wide range of cholesterol concentrations is
detected by the proposed biosensor.
Bioreceptor
- Enzyme
- Whole cell
- Antibody Generated
- DNA
Graphene
biological
Immobilization
- Cross-linking
- Adsorption
- Encapsulation
- Confinement
- Covalent binding
FIGURE 7.2  Schematic diagram for future development of graphene sensors.
87
4. The negligible response to the common interferents
demonstrates the good selectivity of the presented
biosensor.
5. The detection limit of the present sensor is lower
than that previously described.
7.11  CONCLUSION AND FUTURE CHALLENGES
Various approaches have been adapted for the development
of novel biosensors which used either graphene or graphene-
like materials for sensing applications. The two-dimensional
graphene-based analytical devices such as sensors have
shown excellent sensitivity and selectivity for the detection
of glucose (Kuila et  al. 2011). Still there is plenty of room
for more research using graphene as the primary transducing
element for the construction of nanodevices with enhanced
performance. Chemical vapor deposition technique provides
graphene with a high surface area which can be used for the
detection of small biomolecules including DNA, gaseous ele-
ments, and heavy metal ions. A lot of concern are associated
with the potential usability of graphene in sensing area such
as how to prepare consistent and reproducible graphene and
sensors in large volume. The first concern is to develop a con-
trolled synthetic route and methodology for graphene. How
to control the number of layers, minimizing folding, bend-
ing during processing, and limiting substrate effects need
to be addressed (Yang et  al. 2010a,b). The electrochemical
response of IL combined with graphene has to be discovered.
To prepare single-layer graphene in huge quantity is still a
big challenge. Graphene being a two-dimensional material,
the nanosensors based on graphene show high sensitivity
and selectivity for the detection of different analytes such as
glucose, hydrogen peroxide, cholesterol, dopamine, ascorbic
acid, NADH, and DNA sensors. Owing to the hydrophobic
nature of graphene, it can easily be contaminated by differ-
ent substances, especially hydrocarbons (Dai 2007, Malard
et al. 2009). Two-dimensional structure of graphene makes it
a more severe problem of contamination because of its large
lateral surface area. It is highly demanded that the unwanted
Physical
-Piezoelectric
-Thermometric
electron Optical
by
-Photometric
Devices
Signal -Fluorescence
and -Electrochemical
chemical luminescence
reaction
Electrical
-Potentiometric
-Amperometric
-Impedometric
88
contamination must be avoided during the fabrication process
in order to prevent the effects on the sensing response of the
fabricated device. A schematic diagram for future develop-
ment of graphene sensors is represented in Figure 7.2.
ACKNOWLEDGMENTS
The authors acknowledge the financial help of the Greek
Ministry of Development, General Secretariat of Research
and Technology and the European Commission (in particu-
lar the European Regional Development Fund and National
Resources) which cofunded the current research project in the
framework of Greece–Slovakia bilateral projects (contract
12SLO_ΕΤ30_1036).
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 8 Graphene-Based Biosensor Technologies

Arzum Erdem, Ece Eksin, and Mihrican Muti

CONTENTS
Abstract........................................................................................................................................................................................ 91
8.1 Introduction........................................................................................................................................................................ 91
8.2 Graphene-Based Biosensor Technologies and Applications.............................................................................................. 92
8.2.1 Nucleic Acids Detection......................................................................................................................................... 92
8.2.2 Glucose Detection................................................................................................................................................... 94
8.2.3 Hydrogen Peroxide Detection................................................................................................................................. 95
8.2.4 Dopamine Detection............................................................................................................................................... 96
8.2.5 Detection of Other (Bio)Molecules......................................................................................................................... 97
8.3 Conclusion........................................................................................................................................................................ 100
Acknowledgment....................................................................................................................................................................... 100
References.................................................................................................................................................................................. 100

ABSTRACT
Graphene is a novel material that is a two-dimensional honey-
comb crystalline single layer of the carbon lattice. Due to the
high electron mobility, high specific surface area, quantum
Hall effect, and upstanding electric conductivity of graphene,
it is also an ideal material for the construction of various types
of biosensors.
This chapter overviews the implementation of a novel
material “graphene” and graphene-based nanomaterials into
the biosensor technologies by presenting its importance with
numerous applications on various analytes such as nucleic
acids, glucose, cholesterol, hydrogen peroxide, dopamine,
proteins, and other different small (bio)molecules.
8.1 INTRODUCTION
Biomolecule analysis is a very important topic for many
applications such as food and medicine industry, diagnostic,
security, forensic science, and environmental protection. The
ideal analytical tool should provide a fast, reliable response,
which is cost-effective, and widely applicable for most of the
applications. In this case, the biosensors, which are analytical
devices, can provide many advantages for the recognition of
one specific molecule in the complex mixtures.
With the recent advances in nanotechnology, a significant
progress has been made in the development of nanomateri-
als-based biosensors. Label-free monitoring of biorecogni-
tion events provides a promising platform, which is simple,
cost-effective, and requires no external modification to bio-
molecules. Nanomaterials have been applied to modify metal,
glass, or carbon surfaces in connection with electrochemi-
cal (EC) (Fojta and Palecek 1997, Palecek et al. 1998, Wang
2002, Kerman et  al. 2004, Lucarelli et  al. 2005, 2008) and
optical (Homola et al. 1999, Gauglitz 2005, Huang and Chen
2006, Leung et al. 2007, Proll et al. 2007) sensing. Biosensors,
especially EC biosensors in combination with various types
of nanomaterials have become simple, and efficient tools to
measure the concentration of analytes in short response-time
functions of target biomolecules to the drugs or the toxic
reagents (Wang 2003, Hernandez-Santos et  al. 2004, Katz
et al. 2004, Luo et al. 2006, Kerman et al. 2008).
Graphene (GRP), a two-dimensional honeycomb crystal-
line single layer of carbon lattice discovered by Geim et al. in
2004 (Novoselov et al. 2004), has introduced a new dimen-
sion to biosensor research. Due to its fast electron mobility,
high specific surface area, quantum Hall effect, and upstand-
ing electric conductivity, GRP is becoming an ideal material
for the construction of biosensors (Geim and Novoselov 2007,
Li et al. 2008, Park and Ruoff 2009).
In recent years, GRP-based biosensors and nanodevices
have been applied to the investigation on the nucleic acid
hybridization, protein electrochemistry, and small-molecule
detection (Shan et  al. 2009, Wang et  al. 2009, Zhou et  al.
2009, Bonanni and Pumera 2011) (Scheme 8.1).
Papakonstantinou and coworkers (Shang et al. 2008) were
the first researchers, who applied the GRP-based nanomate-
rials for EC sensing of (bio)molecules. They used substrate-
lift-up method for the rapid growth of uniform multilayer
graphene nanoflake films (MGNFs) on the silica substrate for
the selective discrimination of dopamine (DA) in the presence
of ascorbic acid (AA) and uric acid (UA). For the character-
ization of MGNFs, the surface morphology scanning elec-
tron microscopy (SEM), transmission electron microscopy
(TEM), Raman spectroscopy, near-edge x-ray absorption fine
structure spectroscopy, and high-resolution x-ray photoelec-
tron spectroscopy were used. It was shown in their study that
the MGNFs enabled the simultaneous discrimination of AA,

91
92 Graphene Science Handbook

Nucleic acids
Proteins
H2O2

Glucose H
CH2OH
Dopamine O O
O
OH H Amino acids
NH2 OH OH
OH R
HO O
H2 N
OH
OH

Graphene

Electrode

Electrochemical measurement
• Amperometry
• Voltammetry
• Electrochemical impedance spectroscopy

SCHEME 8.1  Graphene-based biosensors developed for electrochemical detection of nucleic acids, aminoacids, proteins and small (bio)
molecules.

DA, and UA as well as the sensing ability of DA with the
detection limit (DL) of 0.17 µM.
8.2 GRAPHENE-BASED BIOSENSOR
TECHNOLOGIES AND APPLICATIONS
8.2.1 Nucleic Acids Detection
GRP materials have been most commonly used for the devel-
opment of advanced nucleic acid biosensors to achieve the
goal of affordable and rapid testing for genetic and infectious
diseases related to the specific deoxyribonucleic acid (DNA)
sequences (Loo et al. 2013) (Table 8.1).
Niu et  al. (2013) developed an EC DNA biosensor based
on gold electrode modified by GRP and gold nanoparticles
(AuNPs). They modified gold electrode with sulfur graphene
(GRP-SH) and then covalently grafted it with AuNPs via sul-
fur–gold affinity. After the linkage of thiolated probe DNA to
the functional GRP via Au–S bond, there is a hybridization of
the probe with its target DNA from Escherichia coli.
DNA EC biosensor based on thionine–GRP nanocompos-
ite-modified gold electrode was introduced by Zhu et al. (2012).
The DNA hybridization was then monitored using differential
pulse voltammetry (DPV) in the presence of an electroac-
tive intercalator daunomycin with a limit of detection (LOD)
of 1.26 × 10−13 M for the complementary oligonucleotide.
Another nanocomposite-based sensor was developed using
GRP and AuNPs to detect the surviving gene, which was cor-
related with osteosarcoma by Liu et al. (2013).
Bo et al. (2011) fabricated a DNA biosensor based on oxidiz-
able GRP and polyaniline (PANI) nanowires-modified glassy
carbon electrode (GCE). The conductive and biocompatible
nanostructure was characterized with SEM, cyclic voltamme-
try (CV), and electrochemical impedance spectroscopy (EIS).
In another study (Sun et al. 2012a), the surface modifica-
tion of GCE was performed with carboxyl-functionalized
graphene oxide (GO-COOH) and electropolymerized poly-
l-lysine for the detection of the polymerase chain reaction
(PCR) products of tlh gene from oyster samples. Polymer
interface for the fixation of GO-COOH nanosheets, was
established with poly-l-lysine film and used as the platform
for the immobilization of the tlh-specific ssDNA sequences.
Additionally, GO-COOH and poly-l-lysine provided a car-
boxyl-functionalized interface with a high surface area and
good conductivity.
Chitosan (CS) has an important role in the development of
advanced biosensor technologies since it forms the stable film,
which could fix the materials tightly onto the electrode surface.
Qi et  al. (2012) reported Co3O4 nanorods (nano-Co3O4),
GRP, and CS-modified carbon ionic liquid electrode (CILE),
which exhibited a low LOD (4.3 × 10−13 M) for PCR amplifi-
cation products of Staphylococcus aureus nuc gene sequence.
Graphene-Based Biosensor Technologies 93

TABLE 8.1
Nucleic Acid Biosensors Developed Using GRP-Based Nanomaterials
GRP Type Analyte Method DL References
GRP DNA UV–vis, CV, and EIS 8.33 × 10−12 M Niu et al. (2013)
GRP DNA CV, EIS, and DPV 1.26 × 10−13 M Zhu et al. (2012)
Oxidizable GRP DNA CV, EIS, and DPV 3.25 × 10−13 M Bo et al. (2011)
GRP DNA EIS and DPV 4.3 × 10−13 M Qi et al. (2012)
Reduced GRP DNA CV and EIS 2.9 × 10−13 M Sun et al. (2012)
GRP DNA CV, EIS, and amperometry 3.4 fM Liu et al. (2013)
GRP DNA CV, EIS, and DPV 3.59 × 10−13 M Sun et al. (2011)
COOH-functionalized GRP DNA FTIR, EIS, and DPV 1.69 × 10−13 M Sun et al. (2012)
GO DNA Colorimetry 9.46–9.67 × 10−8 M Xiang et al. (2012)
GO DNA Fluorescence 20 pM Zhao et al. (2012)
GO DNA CRET 9 fM Chen and Li (2013)
GO DNA CRET – Bi et al. (2012)
GRP nanosheets DNA Colorimetric – Wei et al. (2013)
GRP nanosheets DNA ECL – Xu et al. (2013)
GO DNA Ion exchange 1 nM Balapanuru et al. (2010)
GO DNA Colorimetric 8 nM Thavanathan et al. (2014)

Due to the presence of nano-Co3O4 and GRP at the surface,
the effective surface area and electrical conductivity were
increased.
Sun et al. (2011) also used the CS for the construction of
a biosensor using PCR product of the soybean Lectin gene
sequence. The amount of ssDNA adsorbed on the electrode
surface increased by combining the specific properties such
as the biocompatibility and big surface area of Fe3O4 micro-
spheres, the excellent electron transfer ability of GRP, the
good film-forming ability of CS, and the high conductivity of
CILE. They also fabricated a DNA biosensor by using den-
dritic AuNPs and electrochemically reduced GRP composite-
modified CILE as the platform. GRP film decorated on the
CILE surface by EC reduction.
Then, dendritic nanogold electrodeposited on the surface
of GRP/CILE to get a modified electrode as Au/GRP/CILE,
and methylene blue was used as the EC indicator for monitor-
ing of DNA hybridization related to Listeria monocytogenes
with the detection limit of 2.9 × 10−13 M (Sun et al. 2012b).
As an electrode material, EC properties of chemically syn-
thesized GRP nanosheets were characterized in the study of
Alwarappan et al. (2009) by using Raman spectroscopy and
TEM, and then, the results were compared with the ones of
single-walled carbon nanotubes (SWCNTs). It was concluded
that GRP has better features than SWCNTs such as high
conductivity and high negative charge on the surface with a
greater sp2 character. In addition, the detection of neurotrans-
mitters such as DA and serotonin (ST) was performed both
on GRP and SWCNT-modified electrodes. It was shown that
GRP electrodes exhibited a better stability and signal-to-noise
ratio than SWCNTs when employed in DA and ST.
The application of graphene oxide (GO) integrated at the
single-use pencil graphite electrode for detection of the label-
free DNA hybridization related to Hepatitis B virus sequences
by Muti et al. (2011). It was concluded that the modification
of electrodes using GO facilitated a higher surface coverage
by providing enhanced adsorption of nucleic acids, and thus,
they offer enhanced DNA response within a high sensitiv-
ity. In one of the studies presented by Erdem et al. (2012),
the GO-integrated disposable EC sensor for the detection of
nucleic acids and monitoring of the surface-confined inter-
actions between the anticancer drug mitomycin C (MC) and
DNA was developed and the interaction was monitored by
using differential pulse voltammetry and EIS techniques. A
signal enhancement was observed for both signals of MC
and guanine due to the fact that GO provides a higher area at
the electrode surface for the binding of drug or nucleic acids
(Erdem et al. 2012).
Chen and Li constructed liquid-gated-based field-effect
transistors based on single-layer chemical vapor deposition
GRP (Chen and Li 2013). The transfer curve change upon
DNA immobilization and hybridization under various envi-
ronments was investigated with a low DL as 1 pM (10−12 M)
of target DNA.
A colorimetric biosensor for multiplexed DNA analysis
was developed by Xiang et al. (2012). In this study, a fluores-
cence-based colorimetric droplet sensor allows the simultane-
ous DNA determination by using GO nanoprobe as a quencher
for the ssDNA probes labeled with carboxyfluorescein (FAM)
and 6-carboxy-X-rhodamine (ROX). It was reported that this
colorimetric droplet biosensor exhibited a quantitative capa-
bility for simultaneous detection of two different target DNAs
with the detection limits of 9.46 and 9.67 × 10−8 M, respec-
tively. It was also reported that this biosensor platform can
become a promising detection tool in high-throughput appli-
cations due to the low consumption of reagents.
Based on fluorescence-quenching efficiency of GO and
exonuclease III (Exo III)-aided signal amplification, a sensi-
tive, rapid, and cost-effective method was developed for DNA
detection (Zhao et al. 2012). For this study, the 5′ end of the
94
probe DNA was labeled with fluorophore FAM. In the absence
of target DNA, Exo III was unable to catalyze the removal of
bases from the probe DNA. Following the addition of GO, the
fluorescence of FAM was significantly quenched due to the
strong binding between ssDNA and GO (Zhao et al. 2012).
A chemiluminescence (CL) biosensing platform for ultra-
sensitive DNA detection was developed by Chen and Li
(2013). In this Exo III-amplified chemiluminescence reso-
nance energy transfer (CRET) system, the luminol–hydrogen
peroxide (H2O2)–horseradish peroxidase (HRP) CL reaction
is used as the energy donor, and fluorescein, with its high fluo-
rescent quantum yield, is chosen as the energy acceptor. The
GO was used as a superquencher and Exo III was used as an
amplifying biocatalyst to develop a facile, sensitive, and cost-
effective method for DNA detection. The probe DNA was
labeled with fluorescein amidite (FAM). Due to the strong
noncovalent binding between GO and ssDNA, the FAM-
labeled probe DNA was adsorbed onto the GO surface, in the
presence of target DNA, the CRET signal could be observed,
and the CRET-sensing signal was amplified using an Exo III-
based target-recycling strategy. And, the biosensing platform
for DNA detection achieved a detection limit of 9 fM in 2.5 h,
with excellent selectivity that discriminates single-nucleotide
polymorphisms (SNPs).
Another study performed by the CRET system was
achieved by Bi et al. They used luminol–H2O2–HRP–fluores-
cein CRET system for the determination of ssDNA and throm-
bin. In the proposed CRET system, luminol acts as both a CL
substrate and donor, and fluorescein acts as both an enhancer
and acceptor. FAM-labeled ssDNA probe assembled on GO.
The excellent quenching efficiency of GO on fluorescein and
the subsequent CRET recovery induced by the formation of a
duplex or quadruplex–thrombin with a relatively weaker bind-
ing to GO achieved the sensitive and selective detection of
DNA and thrombin, respectively (Bi et al. 2012).
A colorimetric method for detection of DNA damage was
developed by using hemin–graphene nanosheets (H–GNs)
(Wei et al. 2013). The as-prepared H–GNs possessed both the
ability of GRP to differentiate the damaged DNA from intact
DNA and the catalytic action of hemin. The damaged DNA
made H–GNs coagulated to different degrees from the intact
DNA. As a result, the corresponding centrifugal supernatant
of H–GNs solution showed a different color in the presence
of 3,30,5,50-tetramethylbenzidine (TMB) and H2O2, which
could be discriminated by naked eyes or by ultraviolet–visible
(UV–vis) spectrometer. Based on this, a label-free colorimet-
ric method was developed to detect ss-DNA.
Graphene-nanosheet-based highly porous magnetite nano-
composites (GN-HPMNs) have been prepared by Xu et  al.
and used as an immobilization matrix for the fabrication of a
solid-state electrochemiluminescence sensor on paper-based
chips. The relatively highly porous GN-HPMNs combined
with Nafion were applied as the composite film for the immo-
bilization of Ru(bpy)32+. As an application example, assisted
by the electrochemiluminescence sensor developed, a 0.5-nM
single-nucleotide mismatch could be detected on the paper-
based chips (Xu et al. 2013).
Graphene Science Handbook
GO was implemented as a functional matrix to develop
fluorescent sensors for the amplified multiplexed detection of
DNA, and aptamer–substrate complexes in the study of Liu
et al. (2012a). The fluorophore-labeled DNA strands acted as
probes for two different DNA targets that were adsorbed onto
GO, leading to the quenching of the luminescence of the fluo-
rophores (Liu et al. 2012a).
Balapanuru et  al. reported a simple ion-exchange strat-
egy for electrostatic complexation of GO with a synthetic
dye namely, 4-(1-pyrenylvinyl)-N-butylpyridinium bromide
(PNPB) to form an energy- or charge-transfer complex.
They found that GO–organic dye charge-transfer complex
exhibits enhanced properties for biosensing and optical lim-
iting. A positively charged dye interacted with a negatively
charged GO to form a fluorescence-quenched charge-transfer
complex, named PNP+GO−. The operating principle of the
PNP+GO− sensing platform was based on the unique electro-
static and noncovalent interactions between the analyte and
PNP+, which will “turn on” the quenched fluorescence. The
selectivity of PNP+GO− for double-stranded DNA (dsDNA)
over other biomolecules was tested with proteins, ribonucleic
acid (RNA), carbohydrates, and surfactants. The LOD of their
assay was recorded as 1 nM for DNA (Balapanuru et al. 2010).
8.2.2 Glucose Detection
Glucose detection is clinically significant for diagnosis and
management of diabetes. EC detection of glucose can be real-
ized by using glucose oxidase as the recognition element of
the biosensor. It catalyzes the electron transfer from glucose
to oxygen accompanied by the production of gluconolactone
and hydrogen peroxide (H2O2) (Baby et al. 2010). The quan-
tification of glucose can be achieved via EC detection of the
enzymatically liberated H2O2. A conducting porous matrix,
which gives a large effective detection surface and high
enzyme-loading capacity, can be made by GRP (Table 8.2).
Ruan et al. (2013) reported a polydopamine–GRP hybrid
film-modified glucose oxidase enzyme electrode for glucose
detection. In the presence of GRP that provides a huge surface
area, fast electron transfer-ring rate, and good biocompatibil-
ity, and glucose oxidase, which enables a high and selective
activity toward glucose, enzyme electrode exhibited the high
detection sensitivity, low LOD, short response periods, wide
linear range, and low Michaelis–Menten constant.
Semiconductor quantum dots are quasi-zero-dimensional
materials that have gained a great deal of research inter-
est in the past decade. CdTe–CdS is an excellent core–shell
quantum dot, which can offer ultrafast charge carrier and
charge transfer (Li et al. 2010, Kim et al. 2011). In addition,
the introduction of a highly conductive material, such as
metal nanoparticles (Hirakawa and Kamat 2005) and GRP
nanosheets is also an efficient method to improve charge sep-
aration of the semiconductor quantum dots. Hence, Zhiguo
et  al. (2011b) integrated CdTe–CdS core–shell quantum dot
(CdTe–CdS), graphene–gold nanocomposite (GRP–AuNP),
and AuNP in a biosensor fabrication for glucose detection,
in which the CdTe–CdS was employed for electron transfer
Graphene-Based Biosensor Technologies 95

TABLE 8.2
Glucose Biosensors Developed Using GRP-Based Nanomaterials
GRP Type Analyte Method DL References
GRP Glucose XRD, FT IR 0.1 µM Ruan et al. (2013)
GRP Glucose XRD EIS, CV, and amperometry 3 × 10−12 M Chen et al. (2012)
GRP nanosheets Glucose CV and amperometry 1 µM Baby et al. (2010)
GRP Glucose CV and EIS 5 µM Huang et al. (2013)
GRP Glucose XPS and CV 180 µM Shan et al. (2010)
GO Glucose XRD, UV–vis, FTIR, EIS, and CV 0.34 µM Huang et al. (2013)
GRP paper Glucose XPS, EIS, CV, EDX, and amperometry 0.02 mM Xiao et al. (2013)
GRP Glucose XPS, CV, and amperometry 1 µM Hsu et al. (2012)
RGO Glucose CV, ATR spectra, XRD, and amperometry – Unnikrishnan et al. (2013)
RGO Glucose CV and amperometry 0.4 µM Yang et al. (2013)
GO Glucose UV–vis, CV, and amperometry 30 nM Guo et al. (2011)
Nitrogen-doped GRP Glucose XRD, amperometry, and CV 1.3 µM Jiang et al. (2014)

relay between GRP–AuNP and AuNP. The resulted biosensor
presented high sensitivity, selectivity, and long-term stability
toward the detection of glucose.
Due to the good biocompatibility and intrinsic porous
structure of Pt and AuNPs, the fabricated glucose biosen-
sor shows a high sensitive response and can detect as-low-as
1-µM glucose. Using platinum–gold (Pt–Au) and AuNP spac-
ers, decorated GRP nanosheets show an efficiently expanded
linear range and sensitivity (Baby et al. 2010).
A novel EC affinity nanobiosensor with “on–off” switch-
able property was designed for the ultrasensitive determina-
tion of glucose by Huang et  al. This ultrasensitive glucose
nanobiosensor exhibited broad linearity between the decrease
in electron transfer resistance and the glucose concentration
over a range from 5.0 to 9.0 mM with a detection limit as low
as 0.34 mM (Huang et al. 2013a).
GRP–carbon nanotube (CNT) hybrid material-based bio-
sensor was designed and implemented for the detection of
glucose oxidase and glucose by Chen et  al. It was reported
that this three-dimensional (3D) hybrid not only has a high
surface area, but also exhibits a good electronic conductiv-
ity. Moreover, this nanohybrid has been found as beneficial to
the electron transport and direct electrochemistry of glucose
oxidase as an electrode for glucose sensing (Chen et al. 2012).
Xiao et al. developed a nonenzymatic amperometric glu-
cose sensor by using an electrodeposition protocol for growing
structurally integrated Pt–Au alloy and MnO2 on free-stand-
ing GRP paper (Xiao et  al. 2013). This group reported that
the Pt–Au–MnO2 binary nanostructure-decorated GRP paper
exhibited an enhanced sensing performance such as a wide
linear range, high sensitivity, low detection limit, satisfactory
selectivity, excellent reproducibility and stability, and toler-
ability to mechanical stress.
A different nonenzymatic glucose biosensor was developed
by Hsu et  al. In their study, CuO/GRP nanocomposite was
synthesized for the glucose detection after its modification
onto GCE. A wide linear range was obtained by using CuO/
GRP-modified electrode with the detection limit as 1 µM.
This group reported that CuO/GRP nanocomposite exhibits
a great degree of potential for use as a novel nonenzymatic
glucose biosensor (Hsu et al. 2012).
One of the recent study by a colorimetric biosensor for
glucose detection was introduced by Guo et al. (2011) using
hemin-functionalized graphene nanosheets-modified GCE.
The hybrid nanomaterial not only showed the good electrical
and large-surface-area properties of GRP nanosheets but also
exhibited the excellent electrocatalysis and artificial enzyme
mimetic properties of hemin. This biosensor exhibited intrin-
sic peroxidase-like activity that can catalyze H2O2 to oxi-
dize 3,3,5,5-TMB to produce a blue color reaction. Based on
these properties, the simple, economical, and highly sensitive
amperometric and colorimetric biosensors for H2O2 and glu-
cose have been developed with its detection limit as 30 nM.
The results demonstrate that nanocomposites that were
used in the fabrication of biosensors such as GRP–glucose
oxidase biocomposite (Unnikrishnan et al. 2013), TiO2–GRP
nanocomposites (Jang et  al. 2012), glucose oxidase–GRP–
nanocopper nanocomposite film (Huang et al. 2013), glucose
oxidase–GRP–CS (Kang et  al. 2009, Yang et  al. 2013), or
GRP–AuNP–CS nanocomposite film (Shan et  al. 2010) can
offer a new and promising immobilization material for the
biosensor design.
8.2.3 Hydrogen Peroxide Detection
H2O2 is an enzymatic product of many biological processes;
thus, the detection of H2O2 has a great importance (Table 8.3).
Silver nanocrystals on GRP thin-film electrode were used
for fabricating H2O2 biosensor utilized by Zhong et al. (2013).
The interaction between two components in bimetallic
alloys generally shows many favorable properties comparing
with the corresponding monometallic counterparts (Cui et al.
2006, Grace and Pandian 2006, Qian and Yang 2006), which
include higher catalytic activity, catalytic selectivity, and bet-
ter resistance to deactivation. Therefore, Sheng et  al. (2011)
developed H2O2 biosensor based on HRP-induced deposition
of PANI on the designed GRP–CNT–Nafion/gold–platinum
alloy nanoparticles-modified GCE. The nanocomposite film
96
TABLE 8.3
Hydrogen Peroxide Biosensors Developed Using GRP-Based Nanomaterials
GRP Type Analyte Method
GRP H2O2 CV and amperometry
GRP H2O2 CV, EIS, SWV, and UV–vis
GRP H2O2 XRD, EIS, Raman spectrum, CV, and DPV
GRP nanopellet H2O2 UV–vis, CV, EIS, and amperometry
RGO H2O2 EIS, CV, and amperometry
COOH-functinalized GO H2O2 UV–vis and FTIR
GO sheets H2O2 FTIR, UV–vis, SWV, and amperometry
GRP sheets H2O2 UV–vis, FTIR, and SPR
GRP H2O2 CV and amperometry
by combining the advantages of GCE–CNT and bimetallic
AuPt NPs provided a biocompatible microenvironment for
the immobilization of the enzyme, on the other side, PANI on
the designed electrode, improved the sensitivity, and detection
limit for H2O2 determination.
Zhiguo et al. integrated the GRP–AuNPs, CdTe–CdS, and
AuNPs and HRP in the sequence of a gold electrode in a bio-
sensor fabrication to exploit electrocatalytic synergy on the
improvement of biosensor characteristics with its high sensi-
tivity, low detection limit (3.2 × 10−11 M), and good long-term
stability (Zhiguo et al. 2011a).
In another study relevant to the H2O2 biosensor, HRP
enzyme was selected as a model to form the single-layer gra-
phene nanoplatelet–tetrasodium 1,3,6,8-pyrenetetrasulfonic
acid–horse radish peroxidase (SLGnP–TPA–HRP) composite
film that enhanced electron transfer between the enzyme and
electrode surface. This system also adapts to other enzymes,
such as glucose oxidase, catalase, and xanthine oxidase (Lu
et al. 2010).
In one of the recent works of Mohammad-Rezaei and
Razmi (2012), a different H2O2 biosensor was developed
(Mohammad-Rezaei and Razmi 2012). The carbon ceramic
electrode (CCE) was first modified with GO and GO was con-
verted into reduced graphene oxide (RGO) on the surface of
CCE. Then, the cadmium sulfide-hemoglobin (CdS-Hb) was
immobilized onto the surface of the RGO/CCE. In their study,
RGO was used as a conductive nanomaterial with good bio-
compatibility to CdS nanoparticles. In this way, a new highly
sensitive biosensor for H2O2 was developed. This group
reported that the CdS-Hb-modified RGO/CCE has a higher
surface coverage and also a smaller apparent Michaelis–
Menten constant compared to other modified electrodes that
confirms excellent loading of Hb in the matrix, promotion in
electron transfer ratio, and a high affinity of the biosensor for
H2O2 (Mohammad-Rezaei and Razmi 2012).
Carboxyl-functionalized GO was used as a mimetic perox-
idase and 3,3′,5,5′-TMB was used as a substrate for sensitive
EC H2O2 determination by using linear sweep voltammetry.
The low detection limit was observed as 1.0 nM in the con-
centration range of 0.006–0.8 µM (Sun et al. 2013).
A sensitive biosensor incorporating myoglobin (Mb)
within graphene oxide nanosheets and Nafion composite
Graphene Science Handbook
DL References
2.49 × 10−7 M Zhong et al. (2013)
1.7 × 10−7 M Sheng et al. (2011)
3.2 × 10−11 M Zhiquo et al. (2011)
1.05 × 10−7 M Lu et al. (2010)
0.24 µM Mohammad-Rezaei and Razmi (2012)
1 nM Sun et al. (2013)
2.5 µM Guo et al. (2012)
1 µM Mao et al. (2011)
0.2 µM Li et al. (2014)
film (Mb-GO-Nafion) was developed for the H2O2 detection
(Guo et  al. 2012). First, the GO sheets were synthesized by
Hummers method and the nanosheets were employed to fabri-
cate a thin-film-modified electrode. Mb was then incorporated
into GO sheets and Nafion composite films. It was reported
that Mb–GO–Nafion films provided a favorable microenvi-
ronment for Mb to display good EC and catalytic activities
toward different substrates of biological and environmental
significance. It was also presented that the films exhibited
an excellent analytical performance for the determination of
H2O2 in a wide linear range with a good sensitivity and a low
detection limit. Therefore, such multicomponent films with
integrated GO sheets, Nafion binder, and Mb have potential
applications in developing novel EC biosensors or bioreactors
(Guo et al. 2012).
In one of the recent works (Mao et al. 2011), the EC and
surface plasmon resonance (SPR) detection of H2O2 was
introduced by using polyelectrolyte-functionalized ionic liq-
uid-decorated graphene sheets (PFIL-GS) composite. This
composite was synthesized and characterized by UV–vis
absorption, Fourier transform infrared, and Raman spectros-
copy, and then used to detect H2O2 by electrochemical surface
plasmon resonance (EC-SPR) spectroscopy.
8.2.4  Dopamine Detection
DA is an important catecholamine neurotransmitter that
broadly consists of the central nervous system. It implicates
in many human behaviors, such as cognition, reward, motiva-
tion, and motor function and plays a critical role in learning
and memory. There have also been some reports on DA detec-
tion using GRP-based sensors (Liu et al. 2012b, Liu B. et al.
2012, Liu S.Q. et al. 2012, Liu Q. et al. 2012) (Table 8.4).
For instance, the detection of DA and UA was explored
using reduced graphene oxide and AuNPs entrapped in
chitosan/silica sol–gel hybrid membranes (RGO-AuNPs-
CSHMs) by Liu et al. The RGO encapsulated in the CSHMs
and negatively charged AuNPs also tightly adsorbed within
CSHMs containing robust positively charged amino groups
by electrostatic interactions. The electrochemistry of the
nanocomposite film was investigated in their study (Liu
et  al. 2012b) by using SEM, EIS, and CV. It was reported
Graphene-Based Biosensor Technologies 97

The fabrication of cholesterol biosensor based on AuNPs-

TABLE 8.4 decorated GRP nanopellets has been reported by Aravind
DA Biosensors Developed Using GRP-Based et al. (2011). AuNP-decorated GRP nanoplatelets acted as a
Nanomaterials suitable support for the deposition of AuNPs immobilized
onto the GCE. It was shown that the combination of function-
GRP Type Analyte Method DL References
alized GRP and AuNPs facilitated the amperometric detec-
GRP DA CV and DPV −7
6.0 × 10  M Liu et al.
tion of cholesterol, and also the anti-interference ability of the
nanosheets (2012)
GO DA–UA CV and EIS 0.3 and Liu et al.
biosensor. In another similar work (Manjunatha et al. 2012),
0.7 µM (2012) an amperometric bienzymatic cholesterol biosensor devel-
GRP DA CV, EIS, and 0.2 nM Liu et al. oped by the immobilization of cholesterol oxidase and cho-
amperometry (2012) lesterol esterase onto functionalized GRP-modified graphite
GRP DA XRD, ATR-IR, 1 × 10−11 M Liu et al. electrode, resulting in a more sensitive detection of H2O2 than
EIS, CV, DPV, (2012) the bare graphite electrode.
and amperometry A different cholesterol biosensor was developed by using
cerium oxide (CeO2)–GRP composite matrix for the efficient
cholesterol detection. The CeO2–GRP composites were pre-
that the integration of RGO and AuNPs enhanced the signal pared by depositing CeO2 onto graphene, and then, the electro-
of electro-oxidation of DA and UA, and consequently, the generated chemiluminescence (ECL) technique was applied
proposed EC sensor exhibited good selectivity and accept- for detection of the analyte. It was reported that the experi-
able reproducibility and could be used for the detection of mental results demonstrated that CeO2–GRP could catalyze
DA and UA in real samples. the ECL of a luminol–H2O2 system to amplify the luminol
The sensitive determination of DA in the presence of AA ECL signal greatly. In addition, while using the CeO2–GRP
was achieved this time by using GRP nanosheets as the bio- composite, a better biocompatible microenvironment could
sensor component for signal amplification by Liu et al. (Liu be provided for the immobilized enzyme, resulting in excel-
S.Q. et al. 2012). CV and differential pulse voltammetry was lent stability and a long lifetime of the ECL biosensor. It was
used for EC detection of DA. The amperometric DA detection reported that this biosensor exhibited the linear range from
based on GRP-modified sensors was performed by Liu et al. 12 µM to 7.2 mM (Zhang et al. 2013a).
(Liu Q. et  al. 2012) using polyvinylpyrrolidone/graphene- Taking Hb as a model protein, Huang et al. (2012) dem-
modified glassy carbon electrode (PVP/GRP/GCE). onstrated a biosensor based on CS–ionic liquid–ferrocene/
Molecularly imprinted polymer-modified EC sensor based GRP composite film. Due to the synergistic beneficial char-
on GRP–CS composite was constructed for DA detection acteristics of Fc, Grand IL for Hb-designed biosensor showed
(Liu B. et al. 2012). In that study, after the dispersion of CS an electrocatalytic activity toward the reduction of H2O2 and
in GRP mixture, the functional matrix was used as the tem- exhibited high stability and a low detection limit as 3.8 µM.
plate molecule through a co-electrodeposition film onto the In a different study for Hb detection (Sun et al. 2012c), the
surface of GCE for DA detection. A sensor developed by Liu CILE was used as a working electrode, and then, GRP and
and coworkers presented the good analytical performances silver nanoparticle (AgNP) were electrodeposited onto the
such as sensitivity, selectivity, and rapid response toward DA surface of CILE with a potentiostatic method. It was reported
determination. that GRP nanosheets and AgNPs exhibited synergistic effects
on the electrode surface, which provided a specific 3D struc-
ture with high conductivity and good biocompatibility. It was
8.2.5  Detection of Other (Bio)Molecules
also shown that Hb-modified electrode showed an excellent
Some of the representative studies have been summarized in electrocatalysis to the reduction of trichloroacetic acid in the
this section (Lin et  al. 1998, Imeri et  al. 2000, Konstantin concentration range from 0.8 to 22.0 mM with a detection
et al. 2008, Aravind et al. 2011, Liu et al. 2011, Qi et al. 2011, limit of 0.42 mM.
Tonini et  al. 2011, Abdelhamid and Wu 2012, Boks et  al. In another study, using CS to obtain a composite film that
2012, Ge et al. 2012, Han et al. 2012, Huang et al. 2012, Kim contains GRP, ionic liquid, and 1-ethyl-3-methylimidazolium
et al. 2012, Lian et al. 2012, Loforte et al. 2012, Manjunatha tetrafluoroborate was performed by Ruan et al. (2012) for Mb
et  al. 2012, Meethal and Atwood 2012, Ruan et  al. 2012, detection. Due to the large surface-to-volume ratio and high
Shi et  al. 2012, Sun et  al. 2012c,d, Zhou et  al. 2012, Alava conductivity of the GRP, the high ionic conductivity of the IL,
et al. 2013, Gao et al. 2013, Huang et al. 2013, Jin et al. 2013, and the high biocompatibility of the carpal tunnel syndrome
Labroo and Cui 2013, Lin et al. 2013, Liu et al. 2013, Ni et al. (CTS) enhanced the absorption of the Mb and promoted the
2013, Wua et  al. 2013, Zhang et  al. 2013a,b). For example, direct electron transfer between the Mb and the electrode.
the GRP sheets prepared through the exfoliation of graphite The determination of l-cysteine was performed using GO
oxide leave behind some defects and vacancies (Konstantin and Au nanoclusters composite-based electrode (Ge et  al.
et al. 2008), and these defects can act as good anchoring sites 2012). It was shown that this composite matrix provided a suit-
for the deposition of metal nanoparticles, which can be used able catalytic platform for l-cysteine, which greatly facilitated
for cholesterol biosensor applications (Table 8.5). the electron exchange between l-cysteine and the electrode,
98 Graphene Science Handbook

TABLE 8.5
Other Biosensors for Detecting Various (Bio)Molecules Based on GRP-Based Nanomaterials
GRP Type Analyte Method DL References
GO Amino acid UV–vis, FTIR, CV, and amperometry 0.02 µM Sun et al. (2012)
GRP Hb UV–vis, FTIR, CV, EIS, and amperometry 3.8 µM Huang et al. (2013)
GRP nanopellets Cholesterol FTIR, CV, and amperometry 5 µM Aravind et al. (2011)
GRP Cholesterol CV, EIS, and amperometry 15 µM Manjunatha et al. (2012)
GRP Mb UV–vis, FTIR, and CV 0.583 mM Ruan et al. (2012)
GRP nanosheets Hb UV–vis, CV, and EIS 0.42 nM Sun et al. (2012)
GO Toxin UV–vis 0.5 − 0.3 µg/L Shi et al. (2012)
GRP nanosheets ST XPS, EIS, CV, DPV, and CA 5 × 10−9 M Kim et al. (2012)
GRP Erythromycin CV, UV–vis, and amperometry 2.3 × 10−8 M Lian et al. (2012)
GRP Drug (NSAID) FTIR and UV–vis 1 µM Abdelhamid and Wu (2012)
GRP Tumor marker CV and DPV 3.4 pg/mL Han et al. (2012)
GRP Tumor marker DPV, CV, and EIS 0.06 ng/mL Lin et al. (2013)
GO Ethanol UV–vis and CV 0.1 µM Gao et al. (2012)
GRP Cholesterol FTIR, ECL, and CV 4 µM Zhang et al. (2013a)
GO Thrombin UV–vis and ECL 1.3 × 10−13 M Jin et al. (2013)
GO Serum albumin UV–vis and fluorescence 2.25 µg/mL Ni et al. (2013)
GO Lysozyme EIS 0.38 µg/mL Erdem et al. (2014)
Single-layer GRP Protein QCM – Alava et al. (2013)
GRP SNP Fluorescence – Liu et al. (2011)
GRP nanosheets TNT SERS 10−11 M Liu and Chen (2013)
GRP Propranolol hydrochloride ECL 3.10−11 M Qi et al. (2011)
GRP Ammonia QCM 1 µg/mL Wua et al. (2013)
GRP Carcinoembryonic antigen CV and EIS 5 ng/mL Jin et al. (2014)
RGO Carbofuran and carbaryl XPS, CV, and DPV 4.2 and 7.5 µg/L Wang et al. (2014)
Electrochemically RGO Cadmium and lead ions AFM, EIS, SWV, and SV 0.5 and 0.8 µg/L Ping et al. (2014)
GO Salmonella CV and EIS 3 cfu/mL Ma et al. (2014)
GRP Vanillin LSV and DPV 20 nM Shang et al. (2014)

Note: Target molecules: H2O2, hydrogen peroxide; DA, dopamine; UA, uric acid; NSAID, nonsteroidal anti-inflammatory drug; SNP, single-­nucleotide poly-
morphism; Techniques: CV, cyclic voltammetry; EIS, electrochemical impedance spectroscopy; DPV, differential pulse voltammetry; EDX, energy
dispersive x-ray spectroscopy; FT-IR, Fourier transform-infrared spectroscopy; UV–vis, ultraviolet–visible spectroscopy; XRD, x-ray diffraction;
ATR-IR, attenuated total reflection-infrared spectroscopy; XPS, x-ray photoelectron spectroscopy; SWV, square wave voltammetry; SV, stripping
voltammetry; CA, chronoamperometry; SPR, surface plasmon resonance spectroscopy; ECL, electrogenerated chemiluminescence; QCM, quartz crys-
tal microbalance; SERS, surface-enhanced Raman scattering; CRET, chemiluminescence resonance energy transfer.

increased the sensitivity, and decreased the overpotentials for
the oxidation of l-cysteine. Consequently, the direct determi-
nation of free, reduced, and total l-cysteine in human urine
samples was done and that study (Ge et al. 2012) was success-
fully carried out without any separation techniques.
Jin et  al. developed a magnetic GO-based ECL aptasen-
sor for thrombin detection (Jin et al. 2013). In their study, the
iridium(III) (Ir[III]) complex was synthesized and applied to
develop this ECL biosensor.
A GRP and dsDNA composite material was prepared
and used for the determination of HRP at the surface of a
CILE by Sun et  al. It was presented that in the presence of
dsDNA–GRP, a biocomposite film on the electrode surface
could provide a specific microenvironment for HRP with its
direct electron transfer rate greatly enhanced on the electrode,
which could be attributed to the synergistic contributions of
the materials used (Sun et al. 2012d).
Lactate is an important analyte for clinical analysis, sports
medicine, and the food industry. In addition, it is a biomarker
for a variety of diagnostic purposes, such as heart failure
(Loforte et al. 2012), liver diseases (Zhou et al. 2012), meta-
bolic disorders (Tonini et  al. 2011), drug toxicity (Meethal
and Atwood 2012), mortality in ventilated infants (Boks et al.
2012), etc. Due to all these reasons, the detecting lactate has
a great importance. Labroo and Cui (2013) developed a flex-
ible GRP bionanosensor onto the polyester (PET) substrate for
lactate detection.
MCs are cyanotoxins and can be very toxic to plants, ani-
mals, and humans. Additionally, their hepatotoxicity may
cause serious damage to the liver; because of this reason,
the detection of MCs is very important. A GO-based biosen-
sor was developed by Shi et  al. for the MCs determination.
In their study, AuNPs induced GO fluorescence quenching,
and a reliable biosensor was developed by the fluorescence
Graphene-Based Biosensor Technologies
resonance energy transfer with 0.5 and 0.3 mg/L detection
limit observed for two variants of MC, MC-LR, and MC-RR,
respectively (Shi et al. 2012).
ST (5-hydroxytryptamine, 5-HT) is an important biomol-
ecule in physiological systems, playing a vital role in the reg-
ulation of mood, sleep, emesis, sexuality, and appetite. Low
levels of 5-HT are associated with several disorders, includ-
ing depression, anxiety, and migraines (Lin et al. 1998, Imeri
et al. 2000). The other study based on GRP modification was
performed by Kim et al. for ST determination. Various GRP
nanomaterials were used in their study to modified GCE such
as GO, RGO, and thiolated graphene oxide (THF). As a con-
clusion, the RGO-modified GCE exhibited the lowest detec-
tion limit, highest sensitivity, best selectivity, widest linear
range, fastest response time, and well-defined peak of ST. It
was also reported that the oxidation mechanism of ST demon-
strated an irreversible diffusion-controlled electrode process
(Kim et al. 2012).
A novel surface plasmon resonance (SPR) biosensor based
on GO was developed for the immunosensing determination
of transferring by Zhang et al. (2013b). Huang et al. reported a
“turn-on” fluorescent strategy for the direct detection of Cu2+
in solutions using molecular beacons (MBs) and GO (Huang
et  al. 2013b). In their sensing system, GO was used as an
efficient fluorescence quencher upon the adsorption of MBs,
which reduced the background signal and made the detection
method highly sensitive. GO also acted as a signal controller
through the release of short ssDNA fragments (cleaved MBs)
from its surface, achieving fluorescence generation with the
detection limit of the sensing strategy as 53.3 nM.
Erythromycin is a macrolide antibiotic that has an anti-
microbial spectrum similar to or slightly wider than that of
penicillin. An EC sensor was developed by Lian et al. In their
study, the double nanocomposite-modified electrode was
used for erythromycin detection. For preparing the modi-
fied electrode, first chitosan–platinum nanoparticles (CS–Pt
NPs) were modified onto the surface of the gold electrode.
After drying, graphene–gold nanoparticles (GR–AuNPs)
were added onto the CS–PtNPs-modified electrode (GR–
AuNPs/CS–PtNPs/gold electrode). After this, the electrode
was immersed into the solution containing erythromycin,
and 2-mercaptonicotinic acid as a template molecule. It was
reported that their sensor showed high selectivity, excellent
stability, and good reproducibility for the determination of
erythromycin, and it was successfully applied to the detec-
tion of erythromycin in real spiked samples in this study
(Lian et al. 2012).
GRP-based sensors were also used for the detection of
metal–drug interaction (Abdelhamid and Wu 2012), for the
detection of tumor markers (Han et al. 2012, Lin et al. 2013),
and were used as a modification material for ethanol biosen-
sor (Gao et al. 2013).
Ni et  al. investigated the interaction of GO, a medicinal
drug (10-hydroxy camptothecin [HCPT]), and bovine serum
albumin (BSA) with the aim of developing a method for the
analysis of serum albumin proteins. The selectivity of this
biosensor was also analyzed by using another three proteins,
99
lysozyme, pepsin, and trypsin. It was reported that the relative
fluorescence values were quite low in the cases of the lyso-
zyme and pepsin proteins. The relative fluorescence values for
BSA were comparatively high and the plot that was linear as a
function of the BSA analyte concentration was also reported.
It was concluded that GO-based fluorescence-enhanced bio-
sensors exhibited a satisfactory performance and the low
costs suggest a promising future in clinical diagnostics and
treatment (Ni et al. 2013).
GRP-based quartz crystal microbalance (QCM) assay
was performed by Alava et  al. and Concanavalin A pro-
tein was immobilized onto a self-assembled monolayer
of multivalent tripodal molecules on single-layer GRP.
It was reported that QCM showed that tripod-bound
Concanavalin A retains its affinity for polysaccharides
containing α-d-glucopyrannosyl groups as well as for the
α-d-mannopyranosyl groups. The QCM measurements
on unfunctionalized GRP indicate that the adsorption of
Concanavalin A onto GRP was accompanied by a near-
complete loss of these functions, suggesting that interac-
tions with the GRP surface induce deleterious structural
changes to the protein (Alava et al. 2013).
The other GRP-based study was performed to detect SNP
by using the fluorescent method. This study was based on
DNA ligase reaction and π-stacking between the GRP and the
nucleotide. The authors reported that this proposed assay is
providing a facile and sensitive protocol for measuring SNP,
as well as avoiding complex separation steps and displaying
high stability compared to normal platform-based principles
due to the intrinsic advantage of two-dimensional GRP (Liu
et al. 2011).
Liu and Chen investigated p-aminothiophenol (PATP)-
functionalized silver nanoparticles-supported graphene
nanosheets (Ag/GNs) for the ultratrace detection of 2,4,6-trin-
itrotoluene (TNT) by using surface-enhanced Raman
scattering (SERS). The results displayed that the PATP-
functionalized Ag/GNs material can be served as an excel-
lent SERS platform for TNT detection with a high sensitivity,
selectivity, and reproducibility (Liu and Chen 2013).
An ECL sensor for the determination of propranolol
hydrochloride was fabricated by employing tris(2,20-bipyri-
dyl)ruthenium(II) (Ru[bpy]32+) as an ECL signal producer and
GRP as a modified material. The ECL sensor was fabricated
by adsorbing Ru(bpy)32+ onto a mixture of GRP and Nafion.
The ECL intensity of Ru(bpy)32+ decreased in the presence of
propranolol hydrochloride. Under the optimized conditions,
the ECL intensity was linear with the concentration of pro-
pranolol hydrochloride with a detection limit of 3 × 10−11 M
(Qi et al. 2011).
Wua et al. reported the conductometric sensors based on
GRP/PANI nanocomposites, which were synthesized using
chemical oxidative polymerization for NH3 gas sensing. It
was found that the fabricated GRP/PANI sensor presented
higher sensitivity for NH3 gas than that of only PANI thin-
films gas sensor with a detection limit of GRP/PANI sensor
(ca. 1 ppm) lower than that of PANI (ca. 10 ppm) for NH3
(Wua et al. 2013).
100
8.3 CONCLUSION
GRP-based nanomaterials have received a great deal of atten-
tion recently for the development of advanced biosensors
due to their high conductivity and high specific surface area
resulting with the enhanced sensor response on biomonitoring
process. In recent years, GRP-based biosensor technologies
have been developed, and then applied for the detection of
important analytes.
ACKNOWLEDGMENT
A.E. would like to express her gratitude to the Turkish
Academy of Sciences (TUBA) as the associate member of
TUBA for its partial support.
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 9 Graphene-Based Laser Desorption/
Ionization Mass Spectrometry
for Bioanalytical Applications
Suresh Kumar Kailasa, Hui-Fen Wu, and Jigneshkumar V. Rohit

CONTENTS
Abstract...................................................................................................................................................................................... 105
9.1 Introduction...................................................................................................................................................................... 105
9.2 Physicochemical Properties and Morphological Structures of Graphene and Graphene Oxide...................................... 106
9.3 Graphene-Based LDI-MS Approaches............................................................................................................................. 109
9.3.1 Graphene-Assisted LDI-MS..................................................................................................................................110
9.3.2 Graphene- and Graphene Oxide-Assisted LDI-MS...............................................................................................112
9.3.3 Graphene Nanomaterials-Based MALDI-MS for Proteomics..............................................................................115
9.3.4 Graphene-Assisted MALDI IMS..........................................................................................................................117
9.4 Carbon Nanomaterials-Based LDI-MS.............................................................................................................................117
9.5 Conclusions and Future Prospects.................................................................................................................................... 120
Acknowledgments...................................................................................................................................................................... 120
References.................................................................................................................................................................................. 120

ABSTRACT building machines at the molecular scales far smaller than

The development of new nanomaterials has a significant influ-
ence on bioanalytical chemistry. The unique properties of
ordered graphene (G) have stimulated intense research inter-
ests in multidisciplinary science because of its unique band
structures, massless fermions, and ultrahigh carrier mobil-
ity. The G-based analytical tools can enhance the analytical
performance with excellent sensitivity and selectivity for the
detection of a variety of molecules. In this chapter, we pres-
ent the information on G and its applications in laser desorp-
tion/ionization mass spectrometry (LDI-MS) for analysis of
various chemical and biological molecules. We also provide
many examples from the last 5 years regarding the bioana-
lytical applications of G—graphene oxide (GO) and carbon—
based LDI-MS approaches for sensitive and selective analysis
of various molecules. Furthermore, we also demonstrate the
utility of G and carbon materials as molecular spacers and as
affinity probes to maintain the activity of the enzyme and to
concentrate the target species prior to their identification by
LDI-MS. Finally, the future perspective of G-based LDI-MS
approaches for biological applications is discussed.
9.1 INTRODUCTION
Nanotechnology is the study and creation process of func-
tional and useful materials at the dimensions between 1
and 100 nm (size), where unique phenomenon enables novel
applications. Nanoscience has received much attention by
a cell (Drexler, 1987, 1992). Generally, nanomaterials can
be referred as nanostructured materials, which possess at
least one dimension in the nanometer range with fascinating
properties (Burda et  al., 2005; Chaudhuri and Paria, 2012).
Nanomaterials are the cores of an emerging technological
revolution in analytical and bioanalytical research areas due
to their unique physicochemical properties and geometric fea-
tures (Iijima, 1991; Scida et al., 2011). Recently, a wide variety
of nanomaterials has been extensively studied to exploit their
unique physicochemical and optical properties that can be
of great utility in creating new recognition and in enhancing
the target signal intensities for sensitive and selective analy-
sis of chemical and biological species in complex matrices
(Saha et al., 2012). To support this, a wide variety of classes
of nanomaterials and nanocomposites have been synthesized,
characterized, and their applications are summarized in the
following review articles (Burda et  al., 2005; Huang et  al.,
2011; Chaudhuri and Paria, 2012; Chen et al., 2012; Zhu and
Dong, 2013). Among these nanomaterials, the carbon-based
nanomaterials exhibit unique structure endows with various
superior properties such as high electrical and thermal con-
ductivities, good transparency, great mechanical strength,
inherent flexibility, and high specific surface area (Messina
and Santangelo, 2006; Zhu and Dong, 2013) because carbon is
a unique element. It exhibits a variety of nanostructured mate-
rials such as fullerenes (zero-dimensional, 0D), conducting
and semiconducting carbon nanotubes (CNTs, one-dimen-
sional, 1D) and semimetallic graphenes (two-dimensional,
105
106
2D). Carbon-based nanomaterials are consisted from the
arrangements of carbon atoms with structural units on a nano-
meter scale in (at least) one direction. These carbon-based
nanostructured materials have unique/excellent physicochem-
ical properties, which can create new methods and improve-
ments in the fields of multidisciplinary sciences (Hiramatsu
and Hori, 2010).
Carbon shows difference morphological structures by the
structural modifications of carbon (allotropism). It has three
main allotropes such as diamond (sp hybridization), graphite
(sp2 hybridization), and carbyne (sp3 hybridization), and other
forms of carbon (amorphous carbon, phase diagram of carbon,
glass-like carbon, and carbon blacks). Based on the structural
arrangements of carbon atoms, the carbon-based nanomateri-
als are also classified as the following: (i) Fullerenes are also
identified as pure carbon and take the form of a hollow sphere,
ellipsoid, tube, or ring and its hybridization falls between
graphite (sp2) and diamond (sp3) due to the curvatures of the
surface (Haddon et al., 1993). These are 0D molecules with
formula Cn, where C60, C70, C76, C80, and C84, respectively. (ii)
Carbon nanotubes belong to the fullerene structural family
with cylindrical structures of sp2-hybridized carbon atoms. It
was observed that CNTs are closely related to graphite as their
structures can be conceptualized as a rolled-up monolayer of
graphites. The CNTs are classified into two types such as
single-walled carbon nanotube (SWCNT) and multiwalled
carbon nanotubes (MWCNTs). The SWCNT is formed by
only one layer structural attachments of carbon atoms. While
the MWCNTs can be formed by the multiple rolled layers of
graphite. (iii) Carbon nanofibers have the graphitic filamen-
tous structures, and they can be formed by the orientation of
graphite monolayer planes toward perpendicular to the fiber
axis (stacked form) or at an angle to the axis (herringbone
form). (iv) Graphenes are 2D carbon nanomaterials, which
can be produced by one or several monolayers of graphites.
(v) Carbon nanowalls or carbon nanosheets are formed by the
interactions of vertically aligned graphitic walls with 2D self-
supported networks. Owing to these properties afforded by
carbon-based nanomaterials, their physicochemical proper-
ties, structural alignment, unique morphological variations,
large surface-to-volume ratios, shape, and unusual target bind-
ing characteristics, these carbon-based nanomaterials exhibit
excellent capability for many applications in multidisciplinary
sciences. With the advantages of their unique properties (elec-
tronic, optical, mechanical, thermal, and electrochemical),
the carbon-based nanomaterials have received specific atten-
tion in bioanalytical method developments and technologi-
cal fields. Importantly, the carbon-based nanomaterials have
attracted tremendous interests in many analytical instruments,
which can markedly improve the sensitivity and specificity for
analyte detections. To date, great efforts have been devoted
to the preparation, characterization, and their applications
on the carbon-based nanomaterials in various research areas
including chemistry, physics, engineering, biology, environ-
mental, and medicine. The carbon-based nanomaterials inte-
grated analytical tools have been constituted a topic of huge
scientific interest and offered new opportunities to explore
Graphene Science Handbook
the distinct potential applications of carbon nanomaterials for
selective and sensitive detection of a wide variety of analytes.
With these advantages, the carbon nanomaterials have under-
gone a steady and rapid development and as a fast-growing
research field to solve problems in the nanobioanalytical
chemistry. As a result, various G-based nanomaterials have
been used to fabricate functionalized biosystems integrated
with various molecules for their applications in electroana-
lytical, chemical, and biosensors (Brownson and Banks 2010;
Chen et al., 2012; Jariwala et al., 2013). Owing to these unique
chemical and physical properties and the unique biocompat-
ibility, G-based nanomaterials have attracted much attention
in the multidisciplinary area including their synthetic routes
(top-down and bottom-up approaches), characterization, and
their applications in drug delivery, biosensors, fuel cell, elec-
tronic, and photonic devices. To enlighten the significance of
G-based nanomaterials, we have summarized the potential
reviews published on G-based nanomaterials preparations,
characterizations, and their applications in electronic devices,
analytical, and bioanalytical chemistry (Table 9.1). However,
to date, no book chapters and reviews have focused specifi-
cally on G-, GO-, and carbon nanomaterials-assisted LDI-MS
(laser desorption/ionization mass spectrometry) for the analy-
sis of biomolecules in various biological samples. Before dis-
cussing the applications of G-, GO-, and carbon nanomaterials
in LDI-MS for biomolecule analysis, the structural properties
of G and GO are introduced. This chapter is focused on G-
and carbon-based LDI-MS and their potential progress in the
field of analytical and bioanalytical chemistry. We explore the
potential and capability of carbon nanomaterials (G, GO, and
other carbon nanomaterials) integrated with matrix-assisted
laser desorption/ionization mass spectrometry (MALDI-MS)
as a bioanalytical device for proteomics. The main aim of this
chapter is to inspire researchers toward the applications of G-,
GO-, and nanocarbon materials as matrices, molecular spac-
ers, and affinity probes in LDI-MS for biomolecule analysis
in modern biology. Finally, we made a perspective view on the
development of nanocarbons-based LDI-MS for proteomics.
9.2 PHYSICOCHEMICAL PROPERTIES AND
MORPHOLOGICAL STRUCTURES OF
GRAPHENE AND GRAPHENE OXIDE
In recent years, several significant reviews have already been
discussed on the physicochemical, morphological structures,
and applications of G-based nanomaterials. Although it is out-
side the scope of the book chapter, it is worthy to emphasize
briefly the structures and properties of G-based nanomateri-
als. Graphene has been recognized as “the thinnest material
in our universe” (Geim and MacDonald, 2007). It has been
generating enormous excitement in multidisciplinary research
because of its fascinating physicochemical properties with
numerous promising applications in nanotechnology (Labroo
and Cui, 2013). It is a basic building block of 0D fullerene, 1D
CNTs, and 3D graphite. Graphene is a new 2D structure, con-
sists of a single-atom-thick sheet of sp2-hybridized carbons
arranged in a honeycomb structure. In G, carbon atoms are
Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications
TABLE 9.1
Published Review Articles on G-Based Nanomaterials Preparations and Their Applications
Reviewed G-Based
Nanomaterials
G and GO
G-based materials
Fabrication of G-modified
surface plasmon resonance
chips
Synthesis of hydrogenated G
G Structure, properties, top-down, and bottom-up
Biofunctionalization of G
and G-based nanomaterials
G G as a substrate: shaping molecules, shaped by
Fullerenes, carbon
nanotubes, G, and
composite materials
G Electrochemical applications and
Stable GO, highly reduced
GO, and G
G-based materials
Reduction of GO
GO and reduced GO
GO
G and GO
G-based materials
GO
G Structure, properties, synthesis
G-based materials
G and related materials
G and GO
107
Covered Topics Summarized Applications References
Synthesis of G and GO Biosensors, drug delivery, LDI-MS, Chung et al. (2013)
cell imaging
Nonconventional electrochemical and general – Salavagione (2014)
chemical approaches for G functionalization
through thiol–ene click reactions
Development of G-based surface plasmon Chemical sensing Szunerits et al. (2013)
resonance chips
Structure, theoretical studies, and – Pumera and Wong (2013)
characterization
– Edwards and Coleman (2013)
methods
Biofunctionalization with proteins, DNA G-based FRET biosensors for organic Wang et al. (2011)
and biomolecules
– Palermo (2013)
molecules, a 2D tunable polymer
Sample preparation and interesting catalytic Analytical applications Scida et al. (2011)
properties
Electrocatalysis of G, biosensing, Brownson and Banks (2010)
advancements of G enzymatic biofuel cells
Mechanical and electronic properties, – Compton and Nguyen (2010)
dispersions of G in aqueous and organic
solvents, electrically conductive, free-standing
G papers
Development of GN-based electrocatalysts for – Zhu et al. (2013)
oxygen reduction reaction in electrochemical
energy devices (fuel cells and batteries)
State-of-art status of the reduction of GO on – Pei and Cheng (2012)
both techniques and mechanisms
Typical chemical oxidation methods to produce – Mao et al. (2012)
GO from pure graphite, GO structural
modeling, and its reduction
Synthesis and structural characterization of – Dreyer et al. (2010)
GO, chemical reactivity, and functionalization
Synthesis, properties, and applications Field effect transistors, transparent Zhu et al. (2010)
conductive films, sensors, clean
energy devices
Synthesis, characterization, properties, and Electronic and photonic devices, clean Huang et al. (2011)
applications energy, and sensors
Preparation, functionalization, and Electrocatalysis, Chen et al. (2012)
electrochemical applications electrochemiluminescence,
electrochemical gas sensors,
biosensors
– Edwards et al. (2013)
Preparation methods, physical properties, – Navalon et al. (2014)
characterization techniques, functionalization
of G and GO, G and GO as carbon catalysts
for oxidation, acid–base reactions
Top-down, bottom-up approaches, Voltammetric and amperometric Ambrosi et al. (2014)
electrochemistry at G surfaces G-based sensors and biosensors, G in
energy systems
Synthesis of G, protein–G interactions, toxicity Drug delivery, biosensing, biomedical Mao et al. (2013)
evaluations of graphene and its derivatives imaging, stem cell technology, and
photothermal therapy
(Continued)
108
TABLE 9.1 (Continued)
Published Review Articles on G-Based Nanomaterials Preparations and Their Applications
Reviewed G-Based
Nanomaterials Covered Topics
G, GO, and reduced GO State-of-the-art assessment of G applications,
developments on G synthesis from foodstuffs
G Synthesis of G and heteroatom-doped G
electrocatalysts, structural characterization and
properties of G-supported nanoelectrocatalysts
G, GO G, fluorinated graphene, and GO
G Doping of G-based materials with main group
heteroatoms (s and p blocks)
bonded with two bonds, one is strongest bond (σ-bond, C–C)
in the material that exist in-plane and second one is π bond
that exist out-of-plane, which allows electrons delocalization
networks for the electron conduction of G and provides the
weak Van der Waals interactions among G layers. Graphene
exhibits remarkable properties that have acted as a wonder
material with significantly improved performance and novel
applications in multidisciplinary sciences (Shen et al., 2012).
Briefly, its charge carriers behave as massless relativistic par-
ticles or Dirac fermions with little scattering movements at
ambient conditions. This is due to overlapping between the
valence and conduction band at the Dirac point that can result
in a zero bandgap. It also exhibits a strong ambipolar electric
field effect by the charge carriers between electrons and holes
that lead to its high charge carrier concentrations (1013 cm−2)
and mobilities (~10,000 cm−2 s−1). It was noticed that G shows
unusual half-integer quantum Hall effect for both electron
and hole carriers by adjusting the chemical potential using
the electric field effect. Furthermore, G is a highly optical
transparency material with ~2.3% of absorption in visible
light. Apart from these, it shows exceptional and fascinating
properties including high specific surface area (2630 m2 g−1
compared to 10 m2 g−1 of graphite and 1315 m2 g−1 of nano-
tube), thermal conductivity, electronic conductivity (mobility
of charge carriers, 200,000 cm2 V−1 s−1), mechanical strength
(Young’s modulus, ~1100 Gpa), and intrinsic biocompatibility.
These distinctive properties make them as efficient materials
to spark interest in analytical and bioanalytical chemistry to
develop innovative approaches in modern biology (Chen et al.,
2011; Shen et al., 2012). Furthermore, the energy transfer in
perylene-functionalized G was investigated by a microscopic
view on the substrate–molecule interaction in the exemplary
hybrid material consisting of G functionalized with perylene
molecules (Malic et al., 2014). Based on the aforementioned
unique properties, it holds great promise in the fields of mul-
tidisciplinary research areas (Wang et  al., 2011; Chua and
Pumera, 2013) since its discovery by Novoselov’s group in
2004 (Novoselov et al., 2004). Although the concept of G has
been predicted more than half a century ago, in recent years,
a major focus of G-based research has been concentrated on
Graphene Science Handbook
Summarized Applications References
Use of G for food analyses, and Sundramoorthy and
G-based analytical methods in Gunasekaran (2014)
detection, which help to ascertain
quality and/or safety of foods
Applications of graphene-supported Liu et al. (2014a,b)
nanoelectrocatalysts in fuel cells
– Inagaki and Kang (2014)
Electronic, sensing, and energy Pumera (2014)
storage/generation devices
the development of analytical technologies such as nanoelec-
tronics (Xuan et al., 2008), composite materials (Fang et al.,
2010), catalysis (Qu et  al., 2010), and energy technology
(Stoller et al., 2008), and electrochemical and biosensors (Lu
et al., 2009; Chen et al., 2011; Huang et al., 2011). Dong et al.
described an eco-friendly method for preparation of G quan-
tum dots, GO, carbon quantum dots, and graphite nanocrystals
in coals (Dong et al., 2014). With recent advances in synthetic
routes, fluorinated graphene sheet was synthesized by chemi-
cal vapor deposition using CF4 plasma and studied its proper-
ties systematically via microscopic and spectroscopic probes
(Wang et al., 2014). Kang’s group described a straightforward
method for preparation of graphene transistors (Kang et al.,
2014). A novel procedure was developed for the preparation of
monodisperse graphene quantum disks with a homogeneous
size using pyridinium-assisted hydrothermal method and the
prepared G quantum disks used as probes for bioimaging of
HeLa cells (Chen et al., 2014).
Similarly, graphene oxide also deals with G research, and
it is essentially useful for the preparation of G by either chem-
ical or thermal reduction processes. It has a similar layered
structure to graphite, but the plane of carbon atoms in GO
is heavily decorated by oxygen-containing groups, which not
only expand the interlayer distance but also make the atomic-
thick layers hydrophilic. As a result, these oxidized layers
can be exfoliated in water under moderate ultrasonication. If
the exfoliated sheets contain only one or few layers of car-
bon atoms like G, these sheets are named as GO (Reprinted
with permission from Pei and Cheng, 2012, Copyright 2012,
Elsevier Publications). With respect to its structure, there are
several structural models described for the confirmation of
structural arrangements of carbon atoms and oxygen-con-
taining functional groups in GO (Chen et  al., 2012). It was
observed that the oxygen functional groups were present in
the form of hydroxyl and epoxy groups on the basal plane,
with smaller amounts of carboxy, carbonyl, phenol, lactone,
and quinone at the sheet edges (Li et  al., 2008). However,
there is an uncertainty still remains in the precise atomic
structure of GO (Chen et al., 2012). It was confirmed that the
electronic, mechanical, and electrochemical properties of GO
Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications 109

are strongly influenced by the oxygenated groups in GO that
can differentiate between GO and pristine graphene. The GO
was first synthesized in 1840 by Schafhaeutl (1840), but the
structure of GO is still indefinable today due to its nonstoi-
chiometry. Several papers have summarized the up-to-date
achievements of G and GO synthesis, characterization, and
applications (Allen et al., 2010; Dreyer et al., 2010; Schwierz,
2010; Jia et  al., 2011). These reports clearly illustrated that
the GO is formed by the breaking of sp2-hybridized structure
of the stacked graphene sheets that generates the defects that
manifest as clear wrinkles in the stack and increase the dis-
tance between adjacent sheets from 3.35 Å in graphite powder
to ~6.8 Å for GO powder (Compton and Nguyen, 2010). This
structural spacing varies significantly depending on the water
amount to intercalate within the stacked-sheet structure which
allows to reduce interaction between sheets for the delamina-
tion of GO into individual GO sheets. Similarly, the GO paper
exhibits intersheet spacing at 8.3 Å, which is near to that of
unexfoliated GO (6.8 Å). It was observed that the reduced
GO has shown higher conductivity (5.76 × 104 S m−1) than the
GO (10−8–10−5 S m−1) that shows the same order of magnitude
as that of graphite (8.4 × 104 S m−1) and it was two orders of
magnitude lower than the G (5 – 6.4 × 106 S m−1). Due to their
exotic and unique physicochemical properties, the largest rate
of growth in G-based nanomaterials has been occupied by the
interface of macro- and biomolecules and nanoscale objects
and have been attracting strong interest in modern biology
(Wang et  al., 2011). These fascinating properties of GO are
mainly due to its unique structural arrangements of carbons
such as small sp2-hybridized carbon domains surrounded by
sp3-hybridized carbon domains and hydrophilic nature by the
presence of oxygen-containing groups. It also shows hydro-
phobicity and large surface area of its nanosheet structure,
which allows to trap target species effectively and felicitates
to attaching the sample target more tightly. Table 9.2 summa-
rizes the structure and properties of G and GO.
With these advancements, G-based nanomaterials have
been exploited in a wide range of areas such as sensors, con-
ductors, capacitors, and engineering applications. A survey of
the recent literature testifies to ever-growing interest of G- and
carbon-based technologies in analytical, bioanalytical, and
biosciences (Dreyer et al., 2010; Chen et al., 2011, 2012). Since,
G- and carbon nanomaterials-based research area developed
at a truly relentless pace, more research papers are produced
with time (Chua and Pumera, 2013). Several review papers
have been reported on the synthesis, characterization, and
applications of G-, GO-, and carbon nanomaterials in the last
few years (Geim 2009; Bonaccorso et al., 2010; Chen et al.,
2011; Huang et  al., 2011; Scida et  al., 2011; Palermo, 2013;
Zhu and Dong, 2013). Despite the huge number of G-based
research articles available in the literature, the applications of
G-based nanomaterials in MALDI-MS are still in its infancy.
However, a strategic discussion is needed to cover the latest
progress, emerging trends, and opening opportunities in the
LDI-MS approaches (Chung et al., 2013).
9.3  GRAPHENE-BASED LDI-MS APPROACHES
In recent years, soft ionization technique namely MALDI-MS
has been applied to chemistry, biology, medicine, and physics
for accurate and sensitive analysis of a wide range of large
molecules, since its invention by Tanaka’s and Karas’s groups
in 1988 (Karas and Hillenkamp, 1988; Tanaka et al., 1988).
Later, a variety of nanomaterials such as ZnS NPs (nanopar-
ticles) (Kailasa et al., 2008), CdS NPs (Kailasa and Wu, 2011),
Mg(OH)2 NPs, Ag2Se NPs (Kailasa and Wu, 2010), Au NPs
(Kailasa and Wu, 2012a, b, c, d), QDs (Kailasa and Wu, 2012a,
b, c, d), HgTe QDs (Chiang et  al., 2010; Chen et  al., 2012),
BaTiO3 NPs (Kailasa and Wu, 2012a, b, c, d), Fe2O3 NPs (Lin
et al., 2009), and metal oxides (Watanabe et al., 2008) have
been integrated in MALDI-MS to reduce background signals
at low mass region and enhance the signal intensities of target
analytes. A major advancement of nanomaterials in LDI-MS
is the incorporation of photo absorbing media for the indirect
transfer of laser energy to analytes for their efficient ioniza-
tion with reduced background noise and the suppression of
molecular fragmentation. The progress and applications of
the above nanomaterials-assisted LDI-MS approaches have
been discussed in recent reviews (Zhu et al., 2009; Arakawa
and Kawasaki 2010; Chiang et al., 2011; Zhang et al., 2012).

TABLE 9.2
Structure and Properties of Graphene and Graphene Oxide
Properties G GO
Structure A single atomic plane of graphite, with sp2- GO consists of a single layer of graphite oxide and
hybridized carbon atoms (three σ-bonds and one consists of a hexagonal ring-based carbon network
π-bond) arranged in a hexagonal lattice and having both (largely) sp2-hybridized carbon atoms and
partially filled p-orbitals above and below the (partly) sp3-hybridized carbons bearing oxygen
plane of the sheet functional groups
High carrier mobility (cm2 V−1 s−1) 200,000 123
Mechanical stiffness 1,100 GPa 207.6 ± 23.4 GPa at 0.7 nm thickness
Thermal conductivity ~5,000 W m−1 K−1 3.91 W m−1 K−1
Specific surface area (m2 g−1) 2,630 320–920
Optical transmittance ~97.7% ~91.0%
Electrical conductivity ~64 mS cm−1 10−8–10−5 S m−1
110
Despite the fact that the applications of G-based nanomaterials
in mass spectrometry were discovered recently, their poten-
tial exploitations can be foreseen in LDI-MS for the analysis
of a wide variety of molecules. Therefore, in this section we
summarize the beauty and uses of G-based nanomaterials
as matrices for the analysis of small molecules by LDI-MS,
as enzymatic reactors for protein digestions and as affinity
probes for the enrichment of biomolecules prior to LDI-MS.
9.3.1 Graphene-Assisted LDI-MS
In recent years, G-based LDI-MS approaches have gained
extensive interests because of their easy sample preparation,
strong affinity toward target species, low-noise background
at low mass range, and high salt tolerance without the use
of an organic matrices. Importantly, the G-based nanoma-
terials show an excellent aqueous processability, amphiphi-
licity, surface functionalizability, and high absorptivity to
absorb and to transfer laser energy to analytes efficient ion-
ization. Nanomaterials-based LDI-MS was first invented by
Tanaka et al. in 1988. In this approach, cobalt NPs dispersed
in glycerols were used as the matrix media for laser absorp-
tion and transfer to the analytes for their ionization (Tanaka
et al., 1988) and collectively referred as surface-assisted laser
desorption/ionization mass spectrometry (SALDI-MS). After
this invention, a significant progress in the last several years to
develop nanomaterials-based LDI techniques without organic
matrices has been made. However, the carbon nanomaterials
are also promising and popular nanomaterials and have been
used as matrices in SALDI-MS. Sunner’s group first demon-
strated the potential use of graphite carbon-based SALDI-MS
for the analysis of peptides and proteins (Sunner et al., 1995).
Although carbon nanomaterials-based SALDI-MS work
started near about two decades ago, the use of G was greatly
excited and considered as a promising materials in LDI-MS
by the introduction of Wang’s group (Wang et al., 2010). The
major interest behind the utilization of G in LDI-MS is to
provide high desorption/ionization efficiency for polar and
nonpolar compounds. It also acts as a probe to trap analytes,
and it transfers energy to the analytes upon laser irradiation,
which allows their rapid and efficient ionization without the
interference of intrinsic matrix ions. The authors noted that
G-based LDI-MS eliminated the fragmentation of analytes
and provided good reproducibility. It is unquestionable that
G has electron-rich hydrophobic material with a high surface
and has opened new ways for the development of simple sam-
ple preparation approach to the more selective and sensitive
LDI-MS analysis. The authors found that the G exhibited dual
roles as the matrix and as the adsorbent for solid-phase extrac-
tion and LDI analysis of squalene at 0.2 μM. The G shows
high potentiality to act as the matrix and an adsorbent for the
sensitive detection of polar and nonpolar analytes by LDI-MS
with minimized sample preparations. The same group further
extended the application of G as a matrix and as an adsorbent
for the analysis of nonpolar compounds by LDI-MS (Wang
et  al., 2011). Interestingly, the signal intensities of nonpolar
compounds were greatly increased with increasing number
Graphene Science Handbook
of benzene rings in the polycyclic aromatic hydrocarbons.
This is due to the strong binding affinity of G surface with
the polycyclic aromatic hydrocarbons through π–π stack-
ing interactions. Furthermore, G serves as an adsorbent for
solid-phase extraction of coronene from river water and then
analyzed by G-assisted LDI-MS. As a result, the low detec-
tion limits at 10 –7 M were achieved; supporting that the G
nanosheet structure was featured with surface projections
that felicities efficient energy transfer to polycyclic aromatic
hydrocarbons through π–π stacking and strong hydrophobic
interactions between G surface and analytes. These interac-
tions allow to trap analytes efficiently, produced significant
field enhancements in their vicinity, leading to high desorp-
tion and ionization efficiency of analytes. To support these
assumptions, they tested various aromatic compounds and
observed that the signal intensities of analytes are propor-
tional to the number of benzene rings in analyte molecule,
benzene peak was not observed since it contains only one
aromatic ring. Therefore, G acted as selective LDI-MS probes
and matrices for the determination of polycyclic aromatic
hydrocarbons in real samples. Du’s and Li’s groups have taken
this idea to prepare layer-by-layer (LBL) fabrication of chemi-
cal-bonded G-coated fiber as solid support for the solid-phase
microextraction of polycyclic aromatic hydrocarbons prior to
their identification by gas chromatography–mass spectrom-
etry (Du and Li, 2011). This method allowed more than 150
replicate extractions without measurable loss of performance,
which provided good precision.
Similarly, negative ion LDI-MS was developed for the
exploration of G flakes as the good candidate for analysis of
small molecules (Cai et al., 2011). It was found that the pre-
pared graphene flakes were homogeneous with average flake
thickness of 8–10 nm (20–30 monolayers) and the average
particle (lateral) size of ~600 nm, which allows high miscible
and co-crystallization with analytes and avoids “hot-spots.”
In this approach, LDI-MS was performed in both positive and
negative ion modes by using α-cyano-4-hydroxycinnamic
acid and graphene flakes as the matrix for the peptides of Gly-
D-Phe, Gly-Gly-Leu, Tyr-Phe, Glu-Val-Phe, and Arg-Arg-
Pro-Tyr-Ile-Leu, respectively. In addition, a complete matrix
interference-free mass spectrum was produced by using G
flakes-based negative ion LDI-MS and the ions [M-H]− were
observed at m/z 221.23, 244.33, 327.42, 392.54, and 815.89
corresponding to the peptides of Gly-D-Phe, Gly-Gly-Leu,
Tyr-Phe, Glu-Val-Phe, and Arg-Arg-Pro-Tyr-Ile-Leu, respec-
tively. Using this approach, multiple ions were completely
eliminated, and only one characteristic ion ([M-H]−) was
observed for each peptide. It was interestingly observed that
the peak sensitivity was increased with the increasing number
of carbon chains from 12 to 20, supporting that the use of G
flakes as the new LDI material offers new analytical era for
the analysis of peptides, amino acids, fatty acids, nucleosides,
and nucleotides with minimized sample preparation, free
background noise, high salt tolerance, and shot-to-shot repro-
ducibility. This is attributed to its ultrahigh-energy mediator
(ability to transfer electron/energy to analytes) and strong
interactions with analytes (Wang et al., 2012).
Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications
Functionalization of G is necessary for achieving highly
efficient capture of the analyte from solution. Since, the modi-
fication of surface chemistry and creation of magnetism in
G layers is a new and powerful strategy that provides large
surface area (to maximize analyte adsorption) and high satu-
ration magnetization (efficient separation and preconcentra-
tion of NPs by a magnet) for selective and sensitive detection
of target species. With recent advances in nanotechnology,
Kawasaki’s group described a method for the synthesis of
G-coated cobalt (G-Co) NPs functionalized with benzylamine
groups (CoC–NH2 nanomagnets) and used as a multifunc-
tional probe (extraction and preconcentration) for the isola-
tion and identification of peptides and organic pollutants by
LDI-MS (Kawasaki et al., 2012). The surface-modified G-Co
nanomagnets were found to be of an average size of ~30 nm
with a specific surface area of 15 m2 g−1. The combination of
supramolecular graphene chemistry with Co NPs provides
very large surface areas and greater affinity that enhances ion
yields with reduced ion fragmentation, which exhibits excel-
lent magnetic properties for the isolation and preconcentra-
tion of target species with minimized sample pretreatments
at minimal volumes (Figure 9.1). To support this assumption,
surface modified G-Co nanomagnets greatly enhanced the
ion yield of angiotensin II than the bare G-Co nanomagnets
and also increased the signal-to-noise (S/N) ratio of target
species (47 for bare G-Co nanomagnets versus 313 for surface
modified G-Co nanomagnets). Since, the surface modified
graphene-coated cobalt-NH2 nanomagnets have the advan-
tages of a large high surface-to-volume ratio, and high surface
activity, all of which generate mass peaks with high intensity
and minimized ion fragmentation. The system is highly spe-
cific at pH 6 for the enrichment of polyfluorinated compounds
from aqueous solution followed by SALDI-MS, with a sensi-
tivity of ~0.1 ng L −1. They reported that the system was selec-
tive and sensitive toward the polyfluorinated compounds by
CoC–NH2
nanomagnets
Magnetic
separation
Dispersion
Sample solution
including analytes ( )
t=0s
1 cm
Magnetic separation
FIGURE 9.1  Dual role of functionalized graphene-coated cobalt nanoparticles as affinity probes and as the matrix for the analysis of small
molecules by SALDI-MS. (Reprinted with permission from Kawasaki, H. et al. 2012. Functionalized graphene-coated cobalt nanoparticles
for highly efficient surface-assisted laser desorption/ionization mass spectrometry analysis. Anal. Chem. 84:9268–9275. Copyright 2012
American Chemical Society.)
111
electrostatic attraction, hydrophobic and π–π stacking inter-
actions between benzylamino groups of G-Co nanomagnets
and analytes.
By covalent attachment of nano titania with graphene
surfaces, problems of selectivity and sensitivity can be over-
come. Tang’s group utilized the supramolecular chemistry to
functionalize G-nanosheets with nano titania that felicitates
to convert from hydrophobic nature to hydrophilic nature,
applied as selective affinity and enriching probes for the
phosphopeptides in cancer cells (HeLa cells) followed by
direct surface-enhanced laser desorption/ionization mass
spectrometry analysis (SELDI-MS) (Tang et  al., 2012). The
best extraction efficiency of phosphopeptides was observed
at pH 2 since the positively charged graphene–TiO2 hybrid
provides either selective extraction of the phosphopeptides or
selective rejection of interfering species by the protonation
of acidic peptides. At the same time, phosphopeptides get a
negative charge by the deprotonation of phosphate groups at
this pH, which allows selective binding with G–TiO2 hybrid.
The enriched phosphopeptides were eluted in basic condi-
tion through Lewis acid–base interaction between TiO2 and
phosphopeptides. During the laser irradiation, the efficient
charge and energy exchange was observed between G and
TiO2, which can promote the soft ionization of analytes and
offer a detection limit of attomole range. This method was
successfully applied to enrich and to detect phosphopep-
tides in cancer cells (HeLa cells) with high specificity (94%)
and identified 967 unique phosphopeptides with minimized
loading of extraction matrixes. Very recently, our group also
described the potential use of graphene as the matrix to study
the interactions of transition metals of Fe(II), Fe(III), Cu(II)
with a nonsteroidal anti-inflammatory drug (flufenamic acid)
by graphene-assisted laser desorption ionization mass spec-
trometry (GALDI-MS) (Abdelhamid and Wu, 2012). Metal–
flufenamic acid complexes were confirmed by UV–visible and
Solvent
Washing
Separation
Deposition of analyte-
Analyte-bound bound nanomagnets
nanomagnets on a MALDI plate
t = 20 s
10 nm
CoC–NH2 nanomagnets
112
fluorescence spectrometry, pH meter, and change in solution
conductivity. It was noticed that the metal complexation of
the drug is enhanced fluorescence signal near about 20 folds,
which is due to the charge transfer reaction or increase the
rigidity of drug. The formed complexes were effectively
observed by GALDI-MS, which involves strong π–π interac-
tions between G and complex. The system is highly specific
for the identification of metal–drug complexes, with a sen-
sitivity of 2.5 pM. The value of this approach was demon-
strated by detecting the interactions of metal–drug complex
with intact pathogenic bacteria (Pseudomonas aeruginosa,
Staphylococcus aureus). Furthermore, G was successfully
used as a new electrochemical biosensing platform for the
ultrasensitive detection of adenosine triphosphate by electron
transfer ability between G and ssDNA (single-stranded DNA)
(Wang et al., 2012). It was noticed that the strong π–π interac-
tions between adenosine triphosphate binding aptamer immo-
bilized on Au electrode and G that can lead to a large decrease
in the charge transfer resistance in the electrodes.
9.3.2 Graphene- and Graphene Oxide-
Assisted LDI-MS
Recently, one specific branch of G research deals with GO.
In addition to this, GO is also apparent as G and is shown
to possess excellent “electro-catalytic” activities and ana-
lytical applications toward the sensing of various molecules
(Compton and Nguyen, 2010). It has been extensively explored
to develop sensitive chemical and biosensors because of its
functionalizable surface, the larger surface area-to-volume
ratio, a larger number of active sites, and often also a higher
S/N ratio. Owing to these fascinating properties, graphene
oxide has been applied as electrodes for a wide range of appli-
cations in electrochemical sensors and electroanalysis (Chen
et al., 2012). It was found that GO surfaces exhibit more num-
ber of the carboxyl-rich structure. To support this assumption,
Wang and coworkers explored the marvelous application of
GO as intracellular monitoring and in situ molecular prob-
ing in living cells (Wang et al., 2010). The authors designed
an aptamer–carboxyfluorescein/GO-nanosheet nanocomplex
to investigate its ability for molecular probing in living cells.
Similar to this work, Jung et al. described the use of GO as a
photoluminescent probe for the sensitive and selective detec-
tion of rotavirus in living cells (Jung et al., 2010). The target
cell was captured by the rotavirus-specific antibody immobi-
lized on GO array, and the binding event was monitored by
observing the fluorescence quenching that results from fluo-
rescence resonance energy transfer (FRET) between GO and
Au NPs linked to antibodies.
The main difference between G and GO is only at func-
tional and hybridization at carbon atoms. The G consists only
trigonally bonded sp2 carbon atoms but in the case of GO,
consists a hexagonal ring-based carbon network having both
(largely) sp2-hybridized carbon atoms and (partly) sp3-hybrid-
ized carbons bearing oxygen functional groups (Chen et al.,
2012). Moreover, carbon atoms in GO are covalently bonded
(sp3 hybridization) with oxygen functional groups (such as
Graphene Science Handbook
hydroxyl, epoxy, and carboxy) that shows as oxidized regions.
Due to these structural changes and functional groups, the
original honeycomb-lattice structured G sheet is strongly dis-
turbed at the extended sp2 conjugated network. These changes
lead to a significant breakthrough in exploring G as the matrix
in SALDI-MS for the analysis of various molecules. Moreover,
the comparative studies between G and GO as matrices pro-
vide new and powerful SLADI-MS strategies that offer to
study the various target species with high sensitivity. To sup-
port this assumption, Loh’s group explored the distinctive
applications of G and GO as matrices for the rapid enrichment
of biomolecules and direct, label-free detection of DNA, and
proteins by LDI-MS (Loh et al., 2010). It was noticed that the
G exhibits hydrophobic nature and GO shows the hydrophilic
nature that is due to the presence of polycyclic aromatic hydro-
carbon of quasi-infinite size (G) and of oxidized functional
groups (GO). However, the solubility of G was remarkably
improved by the interaction of G with ssDNA via π–π inter-
actions, which leads to quenching the intensity of dye-labeled
ssDNA. Furthermore, G showed higher absorption capacity
(87 mg g−1) toward ssDNA than that of GO (30 mg g−1), which
is due to vanish of G-quadruplex and B-DNA configurations
of free-DNA by π–π binding interactions with G. In the case
of GO, the adsorption capacity is aided mainly by hydrogen
bonding or electrostatic interaction, since at neutral pH the
zeta potential of GO is −20 mV that creates weakly acidic
nature (COOH and OH groups), which enhances electro-
static repulsion between anionic GO and negatively charged
ssDNA. Interestingly, it was found that G showed a higher
binding capacity for cytochrome c than that of G. This is due
to hydrogen bonding and electrostatic interaction between GO
and cytochrome c. At the same time, the binding capacity of
G for cytochrome c is very low due to the reorientation of
cytochrome c to expose its hydrophobic moieties to bind with
G that result in its denaturization. These distinctive charac-
teristics of G and GO play a tremendous role to act as SELDI
probes for DNA and proteins analysis in LDI-MS with high
sensitivity. To test the efficiency of G as an extracting probe,
G was successfully used as a concentrating probe for selective
extraction of DNA in a mixture of cytochrome c and ssDNA
(5:1 ratio). The authors reported impressive lowest detect-
able concentrations are 1 fM for ssDNA with G and 100 fM
for cytochrome c with GO, respectively. During LDI-MS, G
shows extraordinary, a unique characteristic that allows to act
as an efficient matrix to desorb/ionize adsorbed target ana-
lytes through electron–phonon interactions. Since G shows
high thermal conductivity (4840–5300 W m−1 K−1), it permits
to acts as a thermal sink during the rapid thermalization of
laser-excited electrons. These distinctive physical and opti-
cal properties of G and GO allow to act as selective SELDI
probes for the rapid, label-free detection of target analytes in
proteomics and genomics.
The uses of G and GO as LDI probes are a new and pow-
erful material that offer to analyze a wide variety of target
analytes by mass spectrometry with high selectivity and sen-
sitivity. Zhang et al. have demonstrated the utility of G and
GO as matrices and as concentrating probes for the analysis
Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications
of long-chain fatty acids (Zhang et  al., 2011a), small mole-
cules from traditional Chinese medicine (TCM) herbs (Zhang
et al., 2011b), enzyme inhibitor (Zhang et al., 2011c), and tetra-
cycline residues (Zhang et al., 2012) by LDI-MS. The inherent
advantages and unique properties (energy adsorption, storage,
and transfer) of G and GO make them as promising materi-
als in LDI-MS for the efficient analysis of various analytes in
complex samples. These results showed that the use of both G
and GO as SELDI probes have the advantages of easy sample
preparation, high efficiency in analytes desorption/ionization,
enhanced sensitivity to free background noise, high salt tol-
erance, and shot-to-shot reproducibility, respectively. Briefly,
G and GO were used as matrices for the enrichment and
ionization of five long-chain fatty acids (n-dodecanoic acid
[C12], n-tetradecanoic acid [C14], n-hexadecanoic acid [C16],
n-octadecanoic acid [C18], and n-eicosanoic acid [C20]) by
SALDI-MS. It was observed that GO showed better perfor-
mance for the enrichment and ionization of long-chain fatty
acids than G. Because, GO has hydroxyl and epoxide func-
tional groups at basal planes, carbonyl and carboxyl groups
located at the sheet edges (He et  al., 1998), which creates
strong hydrophilic nature to felicitate an easy swell and well
dispersion in water (Szabo et al., 2005). Interestingly, the ion-
ization efficiency of fatty acids was increased with increas-
ing carbon chains in fatty acids by using GO as a SELDI
probe. The authors estimated the limit of detection values in
the range of 16–715 fmol for five fatty acids. The same group
demonstrated the utility of both G and GO as multifunctional
probes (as enrichment and as matrices) to preconcentrate
tetracyclines (tetracycline, oxytetracycline, demeclocycline,
and chlortetracycline) prior to their quantification in milk by
LDI-MS (Zhang et al., 2012). The mass peaks of four tetra-
cyclines were observed at m/z 444, 460, 464, and 478 corre-
sponded to tetracycline, oxytetracycline, demeclocycline, and
chlortetracycline, respectively. The preconcentrating mecha-
nism was involved in the hydrophobic interactions between
of G-based materials (electron-rich hydrophobic materials
with high surface areas) and tetracyclines. The same group
proposed a similar system for the enrichment and detec-
tion of medicinally important compounds (wogonin, ferulic
acid, and scutellarin) in TCM herbs (Angelica sinensis herb
and Scutellaria barbata D. Don herb) by G- and GO-based
LDI-MS (Zhang et al., 2011b). Using this approach, medically
important compounds, that is, ferulic acid (A. sinensis herb),
wogonin, and scutellaria (S. barbata D. Don herb) were suc-
cessfully detected ions at m/z 194, 284, and 462 with high
selectivity. The authors accurately identified the above com-
pounds and confirmed by MALDI-TOF-MS/MS using G and
GO as the matrices. In both systems, the ionization efficiency
was greatly enhanced in the presence of 0.1% trifluoroace-
tic acid through π–π interactions between analytes and GO,
which facilitate to detect the target analytes as low as 1.0 nM.
Acetylcholinesterase (AChE) plays a central role in vari-
ous biochemical pathways in human and animals. Numerous
methods have been reported for quantification of AChE activ-
ity and inhibition. To extend the potential applications of GO
in LDI-MS, Zhang et al. immobilized model enzyme AChE
113
onto 3-glycidoxypropyltrimethoxysilane (GLYMO)-modified
magnetic carbonaceous (MC) microspheres for the enhance-
ment of enzyme activity and its separation from substrate and
product (Zhang et al., 2011c). The MALDI-TOF-MS was used
for high throughput analysis of reduced substrate acetylcho-
line (ACh) and released product of choline by using GO as
the matrix. This method allowed to isolate the target analytes
with a magnet, which eliminates the sample pretreatment. The
isolated analytes were effectively quantified by MALDI-MS
using GO as the matrix.
Recently, GO has proved as the nanomaterials of choice for
the most nanomaterial-based optical and laser detection sys-
tems, owing to their unique properties, and active functional
groups for functionalization and the fact that they can be
used as marvelous candidates in molecule sensing. Since, the
organic framework on GO surfaces provides a highly stable
platform that can strongly capture target analytes at ultratrace
levels and transfer absorbed laser energy for their ioniza-
tion. For example, Tan’s group developed a dual platform for
the selective enrichment and efficient ionization of cocaine
and adenosine in mass spectrometry by using aptamer-con-
jugated GO as the matrix (Tan et  al., 2010). They immobi-
lized thiol functionalized cocaine and adenosine aptamers
on the surfaces of GO by activating carboxyl (−COOH)-rich
groups with the use of 1-ethyl-3-(3-dimethylaminopropyl)
carbodiimide/N-hydroxysuccinimide (EDC/NHS) chemistry
and by introducing a bifunctional poly(ethylene glycol) (PEG)
molecule (NH2-PEG-SH) as a spacer unit, which provides
stability in physiological media in biofluids. Their supramo-
lecular chemistry of surface modified GO consists amine
(–NH2) groups on one side that bind to the carboxyl groups
and thiol (–SH) groups can anchor to aptamers through disul-
fide bond formation (Figure 9.2). They attributed selective
extraction and enhanced ionization for cocaine and adenosine
in LDI-MS by using GO as a probe, which aids in π–π interac-
tions between analytes and GO. Because, physically adsorbed
cocaine aptamer–GO was used as a target for the prevention
of cocaine loading on GO by means of nonspecific interac-
tions (as is the case with π–π interactions) and upon target
capture, aptamer is released from the GO surface, which
yields significant improvement in extraction efficiency and a
significant increase in S/N ratio. The authors supramolecular
chemistry framework states that GO aptamers provide an effi-
cient platform for selective enrichment and signal enhance-
ment of target analytes by LDI-MS in complex media, which
would not be possible using either GO or aptamers alone.
The combination of GO/CNT has also been used as a
MALDI substrate for the efficient analysis of phospholipids by
LDI-MS. For example, Min et al. prepared GO-immobilized
substrates by immersing aminated glass coverslips or silicon
wafers in an aqueous suspension of GO (Min et al., 2010; Kim
and Min, 2012). The immobilization was based on the electro-
static interaction between negative charges of GO and positive
charges of substrates and used as a MALDI substrate for the
analysis of the different types of phospholipase (phospholi-
pase A2–PLA2, phospholipase C–PLC, and dipalmitoylphos-
phatidylcholine—DPPC) by LDI-MS. The PLC activity was
114 Graphene Science Handbook

O OH O
OH O OH O OH
OH 337 nm
HO
O N2 laser
O
OH
O
O
HO
O
OH HO OH
HO O
O

S
S
S S S
S
EDC S S
1 NHS O NH
O NH NH O
OH O NH
NH2-PEG-SH HO
O
O
OH
O
O
SH SH HN
SH SH O
OH HN O OH
HN O
O NH NH S
O O NH O NH S S
OH S
HO S S
O
O
OH
O
O
HN
O OH HN O OH
HN O SH

SH SH
2 er
ptam Aptamer
H S-a
PEG
Target

FIGURE 9.2  Scheme representation of GO functionalization with the aptamer and its uses as target capture for the analysis of biomol-
ecules by SALDI-MS. (Reprinted with permission from Gulbakan, B. et al. 2010. A dual platform for selective analyte enrichment and
ionization in mass spectrometry using aptamer-conjugated graphene oxide. J. Am. Chem. Soc. 132:17408–17410. Copyright 2010 American
Chemical Society.)

effectively measured with GO/CNT chip-based LDI-MS. The
peaks generated at m/z 591.4 ([M2+Na]+) and 607.4 ([M2+K]+)
corresponded to DPPC hydrolysis product of diacylglycerol
(DAG). These peaks are gradually increased with time while
those of DPPC ([M1+H]+, m/z 734.6; [M1+Na]+, m/z 756.5)
decreased. The GO/CNT substrate provided a better platform
for the catalytic reactions of PLC (the hydrolysis of glycero-
phosphate ester bonds of phospholipids to DAG and the phos-
phorylated headgroup). The PLA2 hydrolyzes the sn-2 acyl
ester linkage of phospholipids to free acids (M5) and 1-acyl-
2-lysophospholipids-lysophosphatidylcholine (LysoPC, M3)
and these products were directly observed by LDI-MS with-
out any sample preparations or posttreatments. The authors
observed the fascinating properties of GO/CNT proceed mul-
tiple enzymatic reactions in a single reaction mixture, and the
hydrolyzed products were successfully identified by LDI-MS.
The same group proposed a similar system for the analysis
of small molecules by LDI-MS using GO/MWCNT as the
matrix (Kim and Min, 2012). The authors prepared MWCNT-
NH2-GO layers by assembling MWCNT-NH2 groups (posi-
tive charges) on the surfaces of GO (negative charges) through
electrostatic interactions and then immobilized on glass cov-
erslips that results MWCNT-NH2/GO film (14.71–17.17 nm).
The fabricated MWCNT-NH2/GO film was promoted to
enhance the signal intensities of analytes without background
noises at the low mass region. The signal enhancements were
attributed to the laser energy absorption of MWCNT-NH2
(GO/MWCNT-NH2)n multilayers (wavelengths at 263 and
355 nm), which facilitate high desorption/ionization of ana-
lytes with reduced background noises at low mass region. In
this method, the analyte peaks were generated as protonated
ions and sodium and/or potassium adducts (cellobiose: m/z
365 [M+Na]+, Leu-enkephalin: m/z 576 [M+Na]+ and m/z 592
[M+K]+, glucose: m/z 203 [M+Na]+, lysine: m/z 169 [M+Na]+
and m/z 191 [M-H+2Na]+, leucine: m/z 154 [M+H]+ and m/z
175 [M+Na]+, and phenylalanine: m/z 188 [M+Na]+, m/z 204
[M+K]+, and m/z 210 [M-H+2Na]+). The limits of detection
ranging from 10 to 100 pM were achieved by using this sys-
tem. The authors reported the relatively high laser absorp-
tion and high desorption efficiency of GO/MWCNT-NH2
film was greatly increased by using MWCNT-NH2 (GO/
MWCNT-NH2)5 multilayer (n = 5), which lead to enhance LDI
efficiency to achieve low detection limits by providing ade-
quate laser energy absorption and transfer to analytes. The GO/
MWCNT-NH2 film offers significantly greater specific sur-
face areas for the lipids imaging in tissues sections in brain tis-
sue by imaging mass spectrometry (IMS) and detected several
mass peaks as [PC 34:1-N(CH3)3+K]+, [GC d18:0/24:0h+K]+,
Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications
and [GC d18:1/22:0h+Na]+, which corresponded to phosphati-
dylcholine (PC) and glycerophosphocholine (GC) derivatives,
respectively. Similarly, Deng and coworkers prepared mag-
netic-G and G/CNT composites via solvothermal procedure
and utilized as a novel matrix and absorbent for enrichment
and detection of small molecules (sucrose, curcumin, luteo-
loside, and histidine) by MALDI-MS (Deng et al., 2012). The
prepared composites have a 3-D open structure with magne-
tite NPs deposited on both CNTs and G, which enhanced the
mass signals and to permit efficient sample enrichment, sepa-
ration, and even recycling of the matrix. In order to explain
the unique nature of magnetic G/CNT composites, the authors
used several nanomaterials (magnetic G, magnetic CNTs, and
the mixture of magnetic G and magnetic CNTs) as the matrix
for the analysis of small molecules by MALDI-MS. They
reported that the signal intensities of analytes were greatly
increased by using magnetic G/CNT matrix than the other
three matrices. This is due to the strong interactions between
analytes and magnetic G/CNT nanocomposite, which allows
the efficient LDI process and the abundant electrons in the
π-conjugated system could be transferred to their ionization.
The combination of G and CNT 3-D open network showed
greater efficiency in analytes desorption/ionization process,
and higher peak intensities, thereby enabling analytes detec-
tion in complex samples. Zhang et al. prepared reduced GO
by spin-coating GO solution on SiO2 substrate, reduced with
hydrazine vapor and then used as a matrix in MALDI-MS for
the analysis of octachlorodibenzo-p-dioxin (OCDD) (Zhang
et al., 2010). The reduced GO contains π-conjugated networks,
which facilitate to adsorb analyte (OCDD) through π–π inter-
actions. The reduced GO-OCDD conjugated film showed high
affinity to absorb laser energy from the laser radiation, con-
duct heat, and transfer energy and charges (i.e., electrons) to
analytes for the desorption/ionization process. To compare the
efficiency of reduced GO, they analyzed OCDD by using vari-
ous matrices, including reduced GO powder, graphite powder,
activated carbon powder, SWCNTs, and silica particles and
found that reduced GO film showed higher sensitivity com-
pared to the other matrices.
9.3.3 Graphene Nanomaterials-Based
MALDI-MS for Proteomics
One of the most powerful and vital tools to date in proteomics
arises from the use of mass spectrometric-based approaches
for protein identification and quantification (Han et al., 2008).
A cornerstone of proteomics is the ability to identify proteins
and peptides in a complex mixture by sensitive mass spectrom-
etry. In a typical shotgun proteomics study, the identification of
digested proteins with high sequence coverage by mass spec-
trometry might be difficult due to long digestion time (18 h),
heterogeneity, tedious sample pretreatments, and difficult to
automate (Kailasa and Wu, 2012c). To solve these difficulties,
progress has been made on nanomaterials-based proteomics
including G-based materials for nanobiocatalytic enzyme
stabilization to improve trypsin stability, protein denaturing,
and enzyme columns as well as other digestion platforms on
115
chips or plates prior to their identification by MS (Kim et al.,
2010). Due to their unique and marvelous physicochemical
properties, G-based nanomaterials have been used as nano-
reactors for accelerating protein digestion by simply adsorb-
ing (immobilizing) trypsin and proteins into nanometer-scale
pores, which (compared with traditional methods) provides
larger surface areas for the immobilization of enzymes, allow-
ing effective enzyme loading and apparent enzyme activity
per unit mass or volume of immobilization host. For example,
Chen et  al. immobilized the trypsin in the LBL-coated GO
and chitosan on a piece of glass fiber to fabricate microchip
bioreactor for efficient proteolysis (Chen et al., 2011). The LBL
deposition driven by electrostatic forces can be enhanced sta-
bility of trypsin, favoring to the minimization of autolysis and
denaturation in the biocompatible LBL network of positively
charged chitosan and on the surfaces of GO coated glass fiber,
which offers a promising platform for highly efficient proteoly-
sis. The prepared trypsin-immobilized glass fiber was inserted
into the channel of a microchip to form a core-changeable
bioreactor. The authors illustrated the feasibility and perfor-
mance of unique bioreactor for the efficient tryptic digestion
of bovine serum albumin (BSA), myoglobin, cytochrome c,
and hemoglobin, respectively. The efficient digestion was
achieved within 10 s and then protein digests were identified
by MALDI-MS. The GO-based microchip bioreactor coupled
with MALDI-MS proved as a promising bioanalytical tool for
efficient protein digestion and peptide mapping with mini-
mized digestion time and sample pretreatments.
To further extend the applications of GO in proteolysis,
Yang’s and Wei’s groups modified the surfaces of GO with
polylysine (PL) and PEG–diglycolic acid (PEG) for immo-
bilization of trypsin via carbodiimide chemistry (Yang and
Wei, 2012). To enhance the immobilization capacity, the
authors functionalized both PL and PEG layers to minimize
the absorption of peptides and proteins onto the GO surface.
Since PL has high affinity to adsorb proteins through hydro-
gen bonding, hydrophobic, and electrostatic interactions, the
authors carried out PEG functionalization on GO surfaces after
PL coating, which serves as molecular spacers to minimize
the absorption of peptides and proteins onto GO surface to
enhance enzyme activity, and makes GO strongly hydrophilic
and easily dispersible in aqueous media. The trypsin immobi-
lized GO (423 ± 30 µg mg−1) was distributed in sample solu-
tion evenly on the MALDI plate, which helps in accelerating
on-plate digestion of protein. This system allows in situ mass
spectrometric measurements for the identification of digested
proteins without any additional procedure to remove trypsin-
linked GO. It was found that the efficiency of proteolysis was
greatly enhanced by microwave irradiation, which results in
rapid digestion of protein in trypsin-linked GO. The developed
system enables in situ mass spectrometric measurements of
digest proteins at 1.0 ng mL−1. Furthermore, Zhang’s group
recently developed a method for the preparation of magnetic
Fe3O4 nanoparticles-modified graphene oxide nanocomposites
(GO-CO-NH-Fe3O4) via covalent bond between the amino
groups of functionalized Fe3O4 and the carboxylic groups of
GO and used as a novel substrate for the immobilization of
116 Graphene Science Handbook

(a) COOH OH COOH OH O O

COOH C ON
OH OH O
(1) EDC/NHS
COOH O O
OH O OH O
O N
O
NH2

Trypsin (2) Fe3O4-NH2

COOH OH O HOOC HO O
NH NH
OH (3) Trypsin OH
NH NH
OH O OH O
O O
GFT GO-CO-NH-Fe3O4

(b)
MW radiation

Transfer to
Add GFT MW reactor

Peptides

Protein solution Protein solution Protein digestion

with GFT

Identified

m/z
Magnetic separation Transfer supernatant MALDI-TOF-MS

FIGURE 9.3  Schematic representation for (a) the preparation of GO-CO-NH-Fe3O4 nanocomposites and (b) their uses as microwave heat
absorber to accelerate protein digestion. (Reprinted with Anal. Methods, 4, Zhang, Y. et al., On-plate enrichment methods for MALDI-MS
analysis in proteomics, 2622–2631, Copyright 2012, with permission from Elsevier.)

trypsin (0.275 mg mg−1) through π–π stacking and hydrogen
bonding (Zhang et  al., 2012). Figure 9.3a shows the sche-
matic representation for the preparation of GO-CO-NH-Fe3O4
nanocomposites and their uses as microwave heat absorber to
accelerate protein digestion. The system acted as a multifunc-
tional probe (enzyme immobilization and excellent microwave
energy absorber) for the ultrafast proteolysis (15 s) prior to
their identification by electrospray ionization mass spectrom-
etry (Figure 9.3b). The authors demonstrated that compared
to the traditional protein digestion method, their system offers
advantages such as rapid digestion time, minimized sample
preparations, and detected totally 456 protein groups in rat
livers, thereby enabling lower detection limits. These sur-
faces readout methods enable applications to a broad range
of problems in chemistry and proteomics, including enzyme
assays, protein–protein interactions, and peptide screening.
These above-mentioned G-based proteolytic strategies are
successfully applied to rapid and high-throughput proteins
identifications (<15 s) by mass spectrometry with maximum
amino-acid sequence coverage, which obviates any inter-
ference coming from trypsin or enzyme. More recently, we
applied G-based materials as matrices and affinity probes for
sensing cancer cells (Manikandan et  al., 2014), organic and
inorganic molecules (Abdelhamid and Wu, 2014; Abdelhamid
et al., 2014), and their antimicrobial activity (Wu et al., 2014) by
MALDI-MS. These works show that G-based materials acted
as good energy mediator for laser absorption and transferring
absorbed laser energy to target analytes for efficient ioniza-
tion. Similarly, G-coated nanomaterials-based MALDI-MS
was applied as a biosensor tool for the differentiation of human
breast normal, cancer, and cancer stem cells (Manikandan
et  al., 2014). The antibacterial activities of G-coated SnO2
nanomaterials were investigated on P. aeruginosa and S.
aureus using optical density (OD600) and plate counting meth-
ods. It was observed that SnO2-G displayed a higher cytotox-
icity than G by 1–3 folds. The interactions between SnO2-G
Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications
nanomaterials and bacterial cells were evaluated by using
TEM (transmission electron microscopy), fluorescence spec-
troscopy, and MALDI-MS (Wu et  al., 2014). These results
confirmed that SnO2-G nanocomposites displayed strong
interactions toward the bacteria compared to G alone.
Further work on the enrichment of trace-level biomolecules
and cellular internalization pathways by G-based nanomateri-
als for proteomics and combined chemo- and gene therapy is
highly desired, to gain an enhanced therapeutic efficacy. Despite
its optical and physicochemical properties, Mao et al. studied
the mechanisms of cytotoxicity and antibacterial activity of G
materials (Mao et al., 2014). Similarly, Li’s group examined the
interaction of GO with lysozyme and its possible applications in
proteins separation (Li et al., 2014). It was found that lysozyme
showed higher affinity to adsorb on the surfaces of GO than the
BSA and human serum albumin, resulting a huge fluorescence
quenching effect of GO on lysozyme via electrostatic interac-
tions. To enhance the bioanalytical applications of G, Liu et al.
prepared thiol graphene-doped poly(ionic liquid [ViOcIm+Cl−])
boronate and used as an affinity monolithic material for cap-
turing of glycoproteins and their separation by capillary elec-
trophoresis (Liu et al., 2014a,b). This method was successfully
applied to specific capturing of low abundance glycoproteins
from egg white and human serum samples. To  explain the
excellent biocompatible nature of G quantum dots, Qu’s team
developed an antibacterial system based on the combination
of G quantum dots with low dose of common medical reagent
H2O2 (Qu et  al., 2014). It was observed that the antibacterial
performance of H2O2 was greatly improved in the presence of
G quantum dots due to the formation of hydroxide free radicals
from H2O2. The designed system exhibited a broad spectrum of
antibacterial activity against both Gram-negative (Escherichia
coli) and Gram-positive (S. aureus) bacteria.
9.3.4 Graphene-Assisted MALDI IMS
IMS is a booming field and is receiving a significant inter-
est in the mass spectrometric community to visualize the
spatial distribution of proteins, peptides, and drugs and their
metabolites in cells and tissues (Heeren et  al., 2009). Even
though traditional organic matrices provide better imaging
mass spectra for various analytes, these matrices may cause
inhomogeneous crystals (analyte/matrix), which facilitates
poor special resolution in imaging, thereby limiting its poten-
tial applications in biomedical research (Chiang et al., 2011).
With advances in synthetic methods has come the ability to
tailor the shape and surface chemistry of G, providing greater
control over the physical and chemical properties of G sur-
face, allowing homogeneous crystallization and providing
good spatial resolution for the analysis of target molecules in
IMS. For example, Kim et al. fabricated GO/MWCNT-based
films on solid substrates and used as a substrate for the detec-
tion of small molecules in tissues by IMS (Kim et al., 2011).
It was found that the centerline average surface roughness
of reduced GO film was also slightly increased to 1.914 nm
from 1.117 nm after π–π interaction-induced adsorption of
MWCNT. The GO-based film showed enhanced surface
117
roughness and higher surface area for the analyte adsorp-
tion, when it was combined with MWCNT-NH2, which facili-
tates to absorb UV light effectively and then convert into the
thermal energy for the efficient LDI. This method was suc-
cessfully applied to analyze small molecules (cellobiose, Leu-
enkephalin, glucose, lysine, d-mannitol, and phenylalanine),
offering analytes detection at 1 ng mL −1, without background
noise. Owing to the better performance of the fabricated film,
the authors decided to use reduced GO/MWCNT-NH2 sub-
strate to IMS of lipids in mouse brain tissue. The photonic
properties of the platform come from its unique optoelec-
tronic and chemical (hydrophobic nature) properties highly
ordered to provide special distribution and energy transfer in
the tissue sections, which produces a good resolved optical
image with enhanced signals at low mass reason in the imag-
ing mass spectra. The generated mass peaks were GC and
PC adducts with sodium and potassium ions, which provides
good distributions in mouse brain tissues (Figure 9.4).
Very recently, Qian et  al. prepared G sheets by chemi-
cal reduction of GO and studied the stability of G paper for
the matrix-free LDI-MS detection and imaging of invisible
stamped micro-patterns with increased detection limits toward
diverse molecules in tissues (Qian et al., 2012). The engineered
G paper can dramatically increase laser irradiation through a
pulsed-laser engineering process by forming densely packed
graphitic nanospheres (stable under 300 keV of an electron
beam) on the paper surface. Importantly, the engineered G
paper exhibited higher surface roughness and hydrophobic-
ity than the plain graphene paper. The authors highlight the
use of engineered G paper as a matrix in MS detection and
imaging of lipid molecule (N-[1-(2,3-dioleoyloxy)-propyl]-
N,N,N-trimethylammonium chloride) with free background
noise. This system enables from unwanted fragmentation and
laser energy loss, leading to ultrahigh ionization/detection
efficiency with an impressive detection limit (~fM). Table 9.3
provides an overview of G-based nanomaterials-assisted
MALDI-MS approaches reported in the literature.
9.4  CARBON NANOMATERIALS-BASED LDI-MS
Although the carbon-based LDI papers are beyond the scope
of this chapter, the purpose of this section is to highlight the
interesting affinity and energy mediator properties of carbon-
based nanomaterials that have the potential to be applied
for new analytical applications in the LDI-MS (Scida et  al.,
2011). One of the properties that arises when particle size
reaches the nanometer scale (and showing the interactions
with electromagnetic radiation) is referred as surface plasmon
resonance (SPR). This collective excitation of the electrons
on the particle’s surface depends on the surface chemistry,
size, and shape of the particle, which leads to trapping the
trace target analytes in the solution. Taking advantage of
such properties, Sunner’s group first demonstrated the use of
graphite dispersed in glycerol for peptide and protein analysis
by SALDI-MS (Sunner et al., 1995). Using their system, the
mass peaks were generated with good resolution by eliminat-
ing background noise at <500 Da. The same group described
118 Graphene Science Handbook

(a) Cerebral artes (b)

852 868
Overlaid
100 Accumulated spectra

844
Hippocampus
Thalamus

Intensity (%)

824
751
50

739

806
Hypathalamus
0
300 400 500 600 700 800 900 1000
m/z 806 m/z 868 m/z

868
100

852
Intensity (%)

824
50

844
751
739

806
0
(c) 300 400 500 600 700 800 900 1000
Assigned ion m/z m/z

844
[GC d18:0/24:0h+K]+ 868 100

824
Intensity (%)
[GC d18:0/24:0h+Na]+ 852

868
852
751

806
[GC d18:0/25:0h]+ 844 50

739
[GC d18:0/22:0h+Na]+ 824
[GC d18:1/22:0h+Na]+ 806 0
300 400 500 600 700 800 900 1000
[PC 36:1-N(CH3)3+Na]+ 751 m/z
[PC 34:1-N(CH3)3+K]+ 739

FIGURE 9.4  (a) Optical and mass images of a mouse brain tissue slice on a reduced GO/MWCNT-NH2 double-layer substrate. (b) Mass
spectra from designated regions in the brain tissue slice in (a). (c) Summary of the species identified in the mass spectra. The mass peaks
corresponding to (GC d18:0/24:0h+K)+ and (GC d18:1/22:0h+Na)+ were selected to reconstruct a total ion map. (Reprinted with permission
from Kim, Y. K. et al. 2011. Synergistic effect of graphene oxide/MWCNT films in laser desorption/ionization mass spectrometry of small
molecules and tissue imaging. ACS Nano 5:4550–4561. Copyright 2012 American Chemical Society.)

a method for the separation and detection of biomolecules by
thin-layer chromatography (TLC) coupled with SALDI-MS
using activated carbon particles as a solid support (Sunner
et al., 1998; Han and Sunner, 2000). The separated analytes
were well desorbed and ionized from the carbon particle in
TOF-MS, offering the detection limit of 25 ng for bradyki-
nin. Guo’s group used various types of carbon nanomateri-
als (CNTs and oxidized CNTs) as matrices for the analysis of
biomolecules by SALDI-MS (Guo et al., 2003, 2005; Ren and
Guo, 2005). The authors discuss the potential applications of
CNTs and oxidized CNTs as matrices for the small molecules
and biomolecules and observed that the oxidized CNTs pro-
vided well homogeneous crystals, offering the reproducibility
of peak intensities and between sample spots with reduced
background noise.
In addition, SALDI-MS approaches have been developed
by using several types of carbon nanomaterials including
SWMNTs (Nanjo et al., 2009), C70 fullerene (Montsko et al.,
2009), activated carbon surface (Guild et  al., 2010), pencil
(Langley et  al., 2007), pencil lead (Black et  al., 2006), oxi-
dized graphitized carbon black nanoparticles (Amini et  al.,
2009), graphite polymer film (Kawasaki et al., 2009), and dia-
mond nanocrystals (Kong et al., 2005a,b) as matrices for the
analysis of a wide variety molecules by SALDI-MS. In these
SALDI-MS approaches, carbon nanomaterials acted as affin-
ity probes to trap analytes and served as energy mediators for
the transfer of energy to analytes, which produced clean and
neat SALDI mass spectra with enhanced signal intensities.
These materials are more favorable for the phase transition/
destruction in SALDI substrate upon laser irradiation, which
is due to the weak bonding or interaction between the ana-
lytes and the substrates, resulting in efficient desorption of
analytes, which leads to greater sensitivity. Using these mate-
rials as matrices, “sweet spots’’ and high background noise
in the low-mass region are eliminated and detected a broad
range of analytes including small molecules, peptides, poly-
mers, drugs, steroids, DNA, and organic pollutants with high
sensitivity.
Regarding carbon nanomaterials, MWCNTs have attracted
more attention in LDI-MS not only due to their unique elec-
tronic properties but also due to the high surface area that
they offer when used as the matrix and affinity probes to
enhance the selectivity and sensitivity of MALDI-MS assays.
For example, Hsu and coworkers developed MWCNT-based
SALDI-MS method for the characterization of very long
chain fatty acids (eicosanoic acid [C20:0], docosanoic acid
[C22:0], tetracosanoic acid [C24:0], and hexacosanoic acid
[C26:0]) in serum (Hsu et al., 2010). The MWCNT acted as
an affinity probe for the enrichment of fatty acids signals in
the mass spectrum. They claimed that the MWCNT has the
advantage of a large surface-to-volume ratio, strong interac-
tion, and high surface activity, resulting in the fatty acids
TABLE 9.3
Overview of Graphene-Based Nanomaterials-Assisted MALDI-MS Approaches for Organic and Biomolecules Assays
Name of the Carbon Function of the Carbon
Nanomaterial Morphology Nanomaterial Analytes Sensitivity References
G Flake-like shape with Matrix and adsorbent Cholesterol, squalene, cyclophosphamide, cytosine β-d- 0.2 µM Wang et al. (2010)
crumpled silk waves arabinofuranoside, amino acids of Glu, His, and Trp, and polyamines
of spermine, spermidine, and putrescine
G Flake-like shape with Matrix and adsorbent Coronene, benzene, estrogen, nitronaphthalene, anthracene, chrysene, 0.1 µM Wang et al. (2011)
crumpled silk waves and benzo[α]pyrene
G Flake layer Matrix Peptides (Gly-d-Phe, Gly-Gly-Leu, Tyr-Phe,Glu-Val-Phe, Arg-Arg- 800 µM Cai et al. (2011)
Pro-Tyr-Ile-Leu), amino acids (l-glutamine, l-histidine,
l-phenylalanine, l-arginine, l-tryptophan), guanosine, uridine,
20-deoxyguanosine, adenosine 30,50-cyclic monophosphate sodium
salt, guanosine 20,30-cyclic monophosphate sodium salt
G-Co NPs – Matrix and affinity Angiotensin II, phenformin hydrochloride, N-propranolol hydrochloride, ~0.1 ng L−1 Kawasaki et al. (2012)
probes ranitidine hydrochloride, verapamil hydrochloride, acetylsalicylic acid,
ibuprofen, warfarin sodium, perfluorooctanesulfonate, perfluoro-
hexanesulfonate, pentachlorophenol, and bisphenol A
G–TiO2 platform Either float or sink Affinity probes and as Phosphoproteins and phosphopeptides in cancer cells (HeLa cells) Attomole Tang et al. (2012)
matrix
G Flake-like shape with Matrix Transition metals of Fe(II), Fe(III), Cu(II) with a nonsteroidal 2.0–2.5 pM Abdelhamid and Wu (2012)
crumpled silk waves anti-inflammatory drug (NSAID), flufenamic acid (FF)
G and GO Flakes Matrices DNA oligomer (ssDNA) and cytochrome c 1–100 fM Loh et al. (2010)
G and GO Sheets Matrices n-dodecanoic acid (C12), n-tetradecanoic acid (C14), n-hexadecanoic 16–715 fM Zhang et al. (2011a)
acid (C16), n-octadecanoic acid (C18), and n-eicosanoic acid (C20)
G and GO – Matrices Wogonin, ferulic acid, and scutellarin 1.0–5.0 nM Zhang et al. (2011b)
G and GO – Matrices Acetylcholine and choline 0.25–15.0 fM µL−1 Zhang et al. (2012)
G and GO – Matrices Tetracycline, oxytetracycline, demeclocycline, and chlortetracycline 2.0 nM Zhang et al. (2012)
Aptamer-conjugated GO – Affinity probe and matrix Cocaine and adenosine – Tan et al. (2010)
GO/CNT – Affinity probe and matrix PLA2, PLC, and DPPC – Min et al. (2010)
GO/MWCNT-NH2 Sheets Matrix Cellobiose, enkephaline, glucose, lysine, leucine, and phenylalanine, 10–100 pM Kim and Min (2012)
PC and GC
Reduced GO film – Matrix Octachlorodibenzo-p-dioxin 500 pg Zhang et al. (2012)
Magnetic G and CNT composites Sheets Matrix Sucrose, curcumin, luteoloside, and histidine – Deng et al. (2012)
GO – Microfluidic bioreactor BSA, myoglobin, cytochrome c, and hemoglobin 20.0 ng mL−1 Chen et al. (2012)
Graphene-Based Laser Desorption/Ionization Mass Spectrometry for Bioanalytical Applications

PL-PEG-GO – Biomicroreactor BSA, myoglobin, and cytochrome c 1.0 ng mL−1 Yang and Wei (2012)
GO-CONH-Fe3O4 – Biomicroreactor BSA, myoglobin, and cytochrome c 1.0 ng mL−1 Zhang et al. (2012)
Au nanohexagons on G sheets Sheets Affinity probe Human breast normal, cancer, and cancer stem cells – Manikandan et al. (2014)
G-coated SiO2 – Matrix Carbohydrates, spectinomycin, and tobramycin – Abdelhamid et al. (2014)
SnO2-coated G – Affinity probe P. aeruginosa and S. aureus – Wu et al. (2014)
G and GO Sheets Matrix Hg2+ pM Abdelhamid and Wu (2014)
GO/MWCNT-NH2 – Matrix Cellobiose, Leu-enkephalin, glucose, lysine, d-mannitol, and 1.0 ng mL−1 Kim et al. (2011)
phenylalanine
G-paper Sheets Matrix N-[1-(2,3-dioleoyloxy)-propyl]-N,N,N-trimethylammonium chloride ~fM Qian et al. (2012)
C-dots – Matrix Mefenamic acid 0.51 and 0.46 ng Gedda et al. (2014)
119
120
assay with greater sensitivity. The system is highly specific for
fatty acids in the serum, with sensitivity of 0.5–1.0 μg mL −1.
Recently, our group also described the utility of MWCNT
doped with Cd2+ as the matrix for the analysis of peptides
and proteins by MALDI-MS (Shrivas and Wu, 2010). The
MWCTN doped with Cd2+ served as multifunctional probes
(as the matrix and affinity probes) for peptides and micro-
wave-digested proteins. The enrichment was based on the
electrostatic interactions between peptides (negative charges)
and MWCNT (positive charges), whereby allowing effi-
cient preconcentration with minimized sample preparations.
Very recently, Soo et al. developed a method for the stream-
line identification of Mycobacterium tuberculosis complex
(MTBC) in broth culture media by using detonation nanodia-
monds (DNDs)-based MALDI-MS (Soo et al., 2012). It was
noticed that the DNDs (5 nm) captured the MTBC secretory
antigen without albumin interferences, which confirms that
the DNDs captured antigen is cell filtrate protein 10 (CFP-10).
The authors demonstrated the potentiality and applicability of
the method for routine identification of mycobacteria in 500
consecutive clinical specimens in the hospital. This method
showed good sensitivity, specificity, and enabled rapid iden-
tification of MTBC in clinical samples, with a low detection
limit (0.09 μg mL −1). Recently, our group developed carbon
dots (C-dots)-assisted LDI-MS method for the detection of
anti-inflammatory drug mefenamic acid (Gedda et al., 2014).
The C-dots exhibits outstanding properties to act as a matrix
for the generation of clean mass spectra with reduced back-
ground signals and fragmentation of mefenamic acid. This
method was successfully applied to detect mefenamic acid in
human serum samples. Although these approaches are very
promising and showed many advantages (rapidity, selectiv-
ity, and sensitivity) in MALDI-MS for various molecules
assays, one potential drawback, though, is the limited ability
of SALDI-MS to ionize large molecules (>5000 Da) in com-
parison with MALDI-MS.
9.5  CONCLUSIONS AND FUTURE PROSPECTS
The attractive physicochemical and optical properties of car-
bon-based nanomaterials (G, GO, and CNT) including strong
UV absorption, high planar surface (2630 m2 g−1), superlative
mechanical strength (Young’s modulus, ~1100 GPa), unparal-
leled thermal conductivity, and remarkable electronic proper-
ties, make them as efficient and good candidates to integrate
with various analytical instruments for ultrasensitive analy-
sis of a wide variety molecules. Knowledge of G chemistry
offers valuable insight into its reactivity and applications in
LDI-MS. As a result of the fascinating properties of G-based
nanomaterials, with respect to structures and surfaces that can
be modified, we believe that it offers important advantages
in MALDI-MS for nanoanalytical and bioanalytical applica-
tions, especially in the areas of environmental, drugs, and pro-
teomics. Such knowledge of G-based nanomaterials certainly
facilitates to be used as matrices, affinity probes, and biore-
actors in MALDI-MS for the analysis of peptides, proteins,
drugs, pollutants, and lipids at in situ and in vivo levels. These
Graphene Science Handbook
special characteristics of graphene-based nanomaterials serve
as excellent preenrichment materials and offer a powerful and
rapid technique for the detection of target analytes in vivo and
in situ levels. Furthermore, the unique structural features of
the engineered graphene-based nanomaterials offered high
performance of LDI-MS by providing improved electron
mobility on the substrate surface for better analyte ionization
without fragmentation and provided good special resolution
and homogeneous functional surface for the analysis of lipids
and metabolites by IMS in biological tissues. Compared to the
conventional enzymatic catalysis technologies applied to pro-
teomics studies by MALDI-MS, the use of G-based nanomate-
rials offers crucial advantages in enzymatic bioreactors. First,
they offer high surface area and absorbing characteristics,
which is critical for ensuring high catalytic performance in
bioreactors, enables novel nanoscale bioreactions, and accel-
erate proteolysis with reduced time from several hours to few
seconds. Additionally, G-based nanomaterial adsorbents offer
more adsorbent target analytes per unit mass than do conven-
tional materials, thereby enabling greater or faster trapping
of the target analytes from the complex samples. However,
the merging of G-based nanomaterials and MALDI-MS is in
its infancy; much work remains to be done in the field of gra-
phene-based nanomaterials assisted extraction tools coupled
with MALDI-MS. We believe that many promising results
about G-based MALDI-MS approaches could be generated in
the near future, which might open a new stage for the supra-
molecular chemistry on surfaces of G-based nanomaterials
and their applications in MALDI—and imaging—MS for the
monitoring of a variety of molecules in vitro and in vivo in
biological samples and in tissues.
ACKNOWLEDGMENTS
The authors thank Mr. Hani Abdelhamid (Department of
Chemistry, National Sun Yat-Sen University, Taiwan) and
Mr. Ganga Raju (Doctoral Degree in Marine Biotechnology,
National Sun Yat-Sen University, and Academia Sinica) for
their assistance in literature collection.
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 10 Richness of Graphene-Based Materials
in Biomimetic Applications
Bhaskar Garg and Yong-Chien Ling

CONTENTS
Abstract...................................................................................................................................................................................... 125
10.1 Introduction...................................................................................................................................................................... 125
10.2 Graphene-Based Enzyme Biomimetics............................................................................................................................ 128
10.3 Graphene-Based Artificial Photosynthesis........................................................................................................................131
10.4 Multiscale Biomimetic Graphene Films or Surfaces....................................................................................................... 133
10.5 Graphene-Based Biomimetic Sensors.............................................................................................................................. 136
10.6 Others............................................................................................................................................................................... 137
10.7 Conclusive Remarks and Future Directions..................................................................................................................... 139
Acknowledgments...................................................................................................................................................................... 139
References.................................................................................................................................................................................. 139

ABSTRACT commonly referred as “biomimetics” (which one means to

Nature is always the main source of all inspiration. During the
process of evolution, nature has created strong, sensitive, and
promising smart materials to realize structural construction
and functional integration. The unique and fantastic proper-
ties of natural materials have triggered enormous scientific
interest to fabricate carbonaceous materials such as graphene,
a two-dimensional single-layer carbon sheet with a hexagonal
packed lattice structure. Indeed, the last decade has witnessed
the certain merits and great advances of this wonder material
in a variety of scientific fields for both fundamental research
and practical applications. Given the enormous potential moti-
vated by its properties, graphene is now increasingly used as
a potent biomimetic material for wide technological applica-
tions. This chapter will provide a comprehensive overview of
the versatility of graphene and its counterparts as competent
biomimetic materials for artificial photosynthesis, enzyme
biomimetics, superhydrophobic films and surfaces, β-sheet
proteins, cellular membrane, mammalian skeletal muscle, as
well as cell sensors with remarkable performance.
10.1 INTRODUCTION
Nature is the greatest engineer and has always been the main
source of all inspiration. After evolution over a long time scale
(~3.8 Gyr), nature has evolved a myriad of creatures with
perfect structures, performance, and exceptional properties.
The understanding of the processes and functions found in
nature has indubitably provoked humans to imitate and pro-
duce smart, sensitive, and functional nanomaterials (NMs),
and nanodevices. Biologically inspired designs, adaptations
from nature, and attempts to incorporate such ideas into better
solutions for technological issues and sustainable living are
be synonymous with “biomimesis,” “biomimicry,” “bionics,”
or “biognosis”). It simply means mimicking nature or biol-
ogy. Biomimetics is derived from the Greek word biomime-
sis and was coined by Otto Schmitt, a polymath in the 1950s
(Schmitt 1969). Indeed, Schmitt’s doctoral work was centered
on the development of a physical device that could unequiv-
ocally mimic the electrical action of a nerve. Nevertheless,
the word “biomimetics” made its first public appearance in
1974 in Webster’s dictionary and is defined as “the study of
the formation, structure, or function of b­ iologically produced
­substances and materials (as enzymes or silk) and biological
mechanisms and processes (as protein ­synthesis or photosyn-
thesis) especially for the purpose of synthesizing similar prod-
ucts by artificial mechanisms which mimic natural ones.” In
light of the above-mentioned perspectives, it is obvious that the
field of biomimetics is highly interdisciplinary and provides
tremendous opportunities for biologists, physicists, chem-
ists, materialists, and engineers to come together and gather
round on a single platform. Over the past century, scientists
looked to nature for inspiration and have developed a variety
of devices and materials for the advancement of human life. A
large number of nature’s creatures including bacteria, plants,
insects, spiders, lizards, birds, s­eashells, land and aquatic
animals have been found with excellent properties of com-
mercial importance (Table 10.1). A few interesting and iconic
examples of biomimetics are discussed in the next paragraph.
The flagella of bacteria rotate at around 10,000 rpm (Jones
and Aizawa 1991) and have been used to design a biological
molecular machine. The stable wing designed by Ignaz and
Igo Etrich in 1904 was derived from the large-winged seed
of Alsomitra macrocarpa. Interestingly, the seed with its out-
growths functions as a flying wing and can glide smoothly
(Coineau and Kresling 1987). Similarly, taking into account
125
126
TABLE 10.1
Overview of Nature’s Prototypes and Their Selected Functions/Properties
Nature’s Prototypes Functions/Properties
Bacteria Biological molecular machine
Birds Aerodynamic lift
Insulation and camouflage
Plants and flowers Superhydrophobicity
Self-cleaning
Antireflective surfaces
Mechanical toughness
Aquatic objects Aerodynamic low friction drag
Hydrodynamic low friction drag
Flapping
Jetting
Insects Antireflective surfaces
Superhydrophobicity
Neutral circuits
Lizard Adhesion
Dynamic climbing and peeling
Spider Bumpy surface
Human brain Artificial intelligence
Molecular systems Self-assembly
Genetic optimization
the ground effect in birds, a microair vehicle has been devel-
oped with oscillating wings (Jones and Platzer 2002). The
observation that the leaves of the lotus are always clean
(waterproof surface, “lotus effect”) led to the development
of Lotusan, a paint for self-cleaning surfaces (Barthlott and
Neinhuis 1997). The secret behind this was in tiny micro-
and nanostructures having a special angle that can force the
water to turn into drops and wash all the dirt away. Similar
surface textures have been observed in other plants such as
Colocasia esculenta and in insect wings (Wagner et al. 1996)
that are known to be superhydrophobic and self-cleaning due
to hierarchical roughness (microbumps superimposed with
a nanostructure) and the presence of a hydrophobic coating
(Bhushan and Jung 2008; Koch et al. 2008, 2009). Insect eyes
(Bernhard et al. 1965), wings of insects (Stoddart et al. 2006),
and leaves of plants in the understory of tropical forests (Lee
1986) have been used to design antireflective surfaces on a
polythene sheet. Velcro (vel + cro = velvet + crochet, a small
hook) is an invention inspired by the hooked seeds of the
burdock plant (Velcro 1955). The orientation of cellulose in
the walls of wood cells results in the toughening of wood in
tension. This observation led to the discovery of the toughest
material (Gordon and Jeronimidis 1980) by making the use
of different orientations of glass fiber in a resin matrix. The
body shape of a penguin has extremely low drag and is used
to design low-drag dirigibles (Bannasch 1993). The natural
neutral circuits of insects have been used to design simple and
robust robotic control systems (Reeve and Webb 2001). An
understanding of the adhesive mechanism of gecko feet has
Graphene Science Handbook
References
Jones and Aizawa (1991)
Jones and Platzer (2002)
Barthlott and Neinhuis (1997)
Wagner et al. (1996)
Lee (1986)
Gordon and Jeronimidis (1980)
Bechert et al. (2000)
McHenry et al. (1995)
Bannasch (1993)
Tangorra et al. (2011)
Moslemi and Krueger (2011)
Stoddart et al. (2006)
Bhushan and Jung (2008)
Koch et al. (2008, 2009)
Reeve and Webb (2001)
Geim et al. (2003)
Cutkosky and Kim (2009)
Parker and Lawrence (2001)
Hecht-Nielsen (2005)
Russell and Norvig (2003)
Sarikaya and Tamerler (2009)
Drezner and Drezner (2005)
proved to be useful in the development of a dry adhesive tape
(Geim et  al. 2003). Another interesting example of biomi-
metics is camouflage (the varying combination of materials,
coloration, or illumination for concealment) and/or motion
camouflage (Anderson and McOwan 2003). The fins of fishes
have been used to design nektors in small submersibles and
thereby allow the vessels smooth movement in all six degrees.
An early example of the concept is the Twiddlefish (McHenry
et al. 1995). The vortices induced by ridges on shark skin can
cut down friction drag effectively. This observation is being
applied in the coating of pipes, on the hulls of sailing boats,
and also in an aircraft that can reduce friction drag by ~10%
(Bechert et  al. 2000). Besides shark skin, the divided wing
tip of birds such as the eagle and vulture having wings of
a low aspect ratio can significantly reduce tip drag (Tucker
1993), consequently being implemented in aircraft wings
and underwater propellers. Recent efforts have been focused
on flapping by fish and mantas (Tangorra et al. 2011) or jet-
ting by jellyfish and squid (Moslemi and Krueger 2011). The
replication of the dynamic climbing and peeling ability of
geckos has inspired scientists to develop the treads of wall-
climbing robots (Cutkosky and Kim 2009). The formation
of water droplets from damp air at the dew point is inspired
by the bumpy surface of the elytra of beetles (Parker and
Lawrence 2001). In molecular biomimetics, proteins are used
in the synthesis of hybrid, self-assembled, engineered func-
tional materials (Grunwald et al. 2009; Sarikaya and Tamerler
2009). Apart from these, information systems are also highly
inspired by nature. For example, evolutionary biology such as
Richness of Graphene-Based Materials in Biomimetic Applications 127

3D Biomimetics has spurred interest in highly organized bio-

Stack
Roll
0D
1D 2D
Wrap
FIGURE 10.1  Graphene: the basic building block for other carbon
allotropes, graphite (3D), fullerene (0D), and CNT (1D). (Reprinted
with permission from Wan, X., Huang, Y., and Chen, Y. 2012.
Focusing on energy and optoelectronic applications: A journey
for graphene and graphene oxide at large scale. Acc. Chem. Res.
45:598–607. Copyright 2012 American Chemical Society.)
inheritance, mutation, and selection is used in genetic opti-
mization algorithm techniques (Drezner and Drezner 2005);
while artificial intelligence (a term coined in 1956), neutral
network recognition, and classifier systems are inspired by the
human brain and nervous system (Russell and Norvig 2003;
Hecht-Nielsen 2005). In a nutshell, superhydrophobicity, self-
cleaning, self-healing, self-assembly, energy conversion and
conservation, controlled adhesion, antireflection, structural
coloration, composite materials (with high tensile strength),
fibers, honeycombs, thermal insulation, drag reduction, aero-
dynamic lift, robotics, camouflage, molecular-scale devices,
sensory-aid mechanisms, and pumping mechanisms are the
common examples in nature and represent a great source of
new and innovative ideas to resolve technological problems.
logical materials, in particular, from the molecular to the
nanoscale. The organization of NMs in a hierarchical manner
with intricate nanoarchitecture provides a significant impetus
in mimicking nature using nanofabrication techniques (Alberts
et al. 2008). Generally, a complex interplay between surface
structures, morphology, as well as physical and chemical prop-
erties results in multifunctional materials and ­surfaces. Among
such materials, the unique two-dimensional (2D) carbon mate-
rial, graphene, has revealed a cornucopia of both fundamen-
tal research and practical applications (Geim 2009). Indeed,
after the seminal work by Geim and Novoselov (Novoselov
et al. 2004), a single-atom-thick ­graphene has become a rap-
idly rising star on the horizon of material science (Geim and
Novoselov 2007; Castro Neto et al. 2009). In general, the hex-
agonal packed lattice structure of graphene could be consid-
ered as a potential building block of other graphitic materials
such as fullerenes (0D [zero dimensional]), carbon nanotubes
(1D [one dimensional]), and graphite (3D [three dimensional])
(Wan et  al. 2012; Figure  10.1). Nevertheless, compared to
its predecessors, graphene and/or its counterparts such as
graphite oxide, graphene oxide (GO), and reduced graphene
oxide (rGO) exhibit many exceptional properties (Table 10.2)
such as the quantum Hall effect (QHE) (Bolotin et al. 2009;
Guillemette et al. 2013), an ultrahigh-carrier mobility of about
200,000–250,000 cm2 V−1 s−1 (Bolotin et  al. 2008), large
theoretical specific surface area of 2630 m2 g−1 (Stoller et al.
2008), good optical transparency of ~97.7% (Nair et al. 2008),
a high Young’s modulus of ~1 TPa (Lee et al. 2008), excellent
thermal conductivity (3000–5000 W m−1 K−1) (Balandin et al.
2008), high electrical conductivity (Wu et al. 2009), flexibility
(Kim et al. 2009), high physicochemical stability (Girit et al.
2009), and biocompatibility (Chen et  al. 2008). Not surpris-
ingly, therefore, the last decade has ­witnessed the substantial
potential of graphene-based NMs in heterogeneous catalysis
(Garg and Ling 2013; Garg et al. 2014a,b), switching and infor-
mation storage applications (Chen et al. 2012), optoelectronic
applications (Wan et  al. 2012), energy conversion and stor-
age (Dai et al. 2012), molecular imaging (Garg et al. 2015a),

TABLE 10.2
Overview of Exceptional Properties of Graphene and Its Wide Technological Applications
Properties
(Fractional) QHE
Ultrahigh-carrier mobility
Large surface area
Good optical transparency
High Young’s modulus
Excellent thermal and
electrical conductivity and
good flexibility
High chemical–physical
stability
Biocompatibility
References Applications References
Bolotin et al. (2009) Heterogeneous catalysis Garg and Ling (2013)
Guillemette et al. (2013)
Bolotin et al. (2008) Optoelectronics Wan et al. (2012)
Stoller et al. (2008) Energy conversion and storage Dai et al. (2012)
Nair et al. (2008) Switching and information storage Chen et al. (2012)
Lee et al. (2008) Photocatalysis/photovoltaics Huang et al. (2012)
Balandin et al. (2008) Nanocomposites Kim et al. (2010)
Wu et al. (2009)
Kim et al. (2009)
Girit et al. (2009) Biosensors Guo et al. (2012)
Chen et al. (2008) Others Singh et al. (2011)
128 Graphene Science Handbook

photovoltaic devices, photocatalysis (Huang et al. 2012), and
other applications (Kim et  al. 2010; Singh et  al. 2011; Chua
and Pumera 2013). Despite this, the field of biomimetics is rel-
atively new within the framework of 2D graphene. Since the
focus of this chapter strongly lies on biomimetic applications
of graphene-based materials, the subject is categorized into
the following five sections:
• Graphene-based enzyme biomimetics
• Graphene-based artificial photosynthesis
• Multiscale biomimetic graphene films or surfaces
• Graphene-based biomimetic sensors
• Others
10.2  GRAPHENE-BASED ENZYME BIOMIMETICS
Natural enzymes such as peroxidases (PODs) are ubiquitous
in nature and have been widely studied owing to their excel-
lent properties including high catalytic activity and substrate
specificity under mild conditions. PODs are known to activate
hydrogen peroxide (H2O2) to perform a variety of chemical
reactions such as oxidation (Zhang and Dasgupta 1992) and
thus can be used as a diagnostic kit for H2O2 and glucose.
Nevertheless, the catalytic activity of these enzymes can be
easily affected by acidity, temperature, and inhibitors. In
addition, the limited stability of these enzymes due to dena-
turation and digestion, high costs of preparation, purifica-
tion, and storage also restricts their widespread applications.
Accordingly, in recent years, a great deal of attention has been
paid to the construction and discovery of a variety of enzyme
mimetics. In this context, the use of hemin (Wang et al. 2007),
hematin (Zhang and Dasgupta 1992), cyclodextrin (Liu et al.
1999), and porphyrin (Bonar-Law and Sanders 1995) as POD
mimetics is especially notable. Very recently, the discovery
of Fe3O4 nanoparticles having intrinsic POD-like activity, in
particular, horseradish peroxidase (HRP), a heme-containing
POD, opened the door for the development of nanoscale mate-
rials in the biochemical field (Gao et al. 2007). Indeed, owing
to their high stability, controlled preparation, tunable catalytic
activity, and flexibility in structural design at low cost, gra-
phene-based NMs offer great potential in enzyme mimetics
(Garg et al. 2015b) (Table 10.3).
In an elegant work, the carboxyl modified single-lay-
ered graphene oxide (GO–COOH), free from metallic
impurities, has been found to possess intrinsic POD-like
activity (Song et  al. 2010). In particular, the reaction of

TABLE 10.3
Summary of Graphene-Based NMs and Their Peroxidase Mimicking Properties
in the Presence of Hydrogen Peroxide (H2O2)
Oxidation
Graphene-Based NMs Substrate Product Applications References
GO a TMB b TMBDI c Colorimetric assay for glucose Song et al. (2010)
detection
GOa TMBb TMBDIc Voltammetric detection of H2O2 Sun et al. (2013)
GOa derived CNDsd MOe Degradation Generation of TiO2/CNDs Ming et al. (2012)
hybrid photocatalyst
GO-Fe3O4 composite TMBb TMBDIc Colorimetric assay for glucose Dong et al. (2012)
and H2O2 detection
CuPt nanorods–GO composite OPDf DAPg − Yang et al. (2012)
Hemin–graphene or Pyrogallol Purpurogallin − Xue et al. (2012)
FeTMPyPh–graphene
composites
FeTMPyPh–GO conjugates OPDf DAABi “Signal on” DNA biosensor Wang et al. (2013)
AuNPs–graphene hybrid TMBb, OPDf, Not specified Colorimetric biosensors Liu et al. (2012a)
and ABTSj
Cyt C–GSO3Hk OPD Not specified − Hua et al. (2012)
nanosheets

a Graphene oxide.
b 3,3′,5,5′-Tetramethylbenzidine.
c 3,3′,5,5′-Tetramethylbenzidine diimine.
d Carbon nanodots.
e Methyl orange.
f o-phenylenediamine.
g 2,3-Diaminophenazine.
h Iron(III)meso-tetrakis(N-methylpyridinium-4-yl)porphyrin.
i 2,2′Diamino azobenzene.
j 2,2′Azinobis(3-ethylbenzothiazoline-6-sulfonic acid.
k Cytochrome C-sulfonated graphene.
Richness of Graphene-Based Materials in Biomimetic Applications
OH
O OH
O OH
OH
OH
H3C CH3 HO
O H2N
H2N NH2
H 3C CH3
+ H2O2 + 2H+
SCHEME 10.1  Schematic representation of GO–COOH catalyzed conversion of TMB into TMBDI in the presence of H2O2.
3,3′,5,5′-tetramethylbenzidine (TMB) and H2O2 in the presence
of GO–COOH produced a blue color solution of 3,3′,5,5′-tetra-
methylbenzidine diimine (TMBDI), a diagnostic for POD-like
catalytic activity (Scheme 10.1). Further, the catalytic reaction
can be detected by simply monitoring TMB absorbance. It is
well known that the main product of glucose oxidase (GOx)-
catalyzed reaction is H2O2; therefore by combining the advan-
tage of GO–COOH (POD-like catalytic activity) and GOx, a
simple, cheap, selective, and sensitive colorimetric assay was
developed for glucose detection and successfully used in diluted
blood, buffer solution, and two commercial fruit juice samples.
Briefly, the mechanism of glucose detection can be understood
in two steps. First, using GOx, the oxidation of glucose to glu-
conic acid in buffer solution is achieved at pH 7.0 with simul-
taneous conversion of substrate oxygen to H2O2. In the second
step, H2O2 is reduced by GO–COOH in the presence of co-sub-
strate, TMB, at low pH (4.0) and thereby induces a blue color.
Using this method, glucose can be detected as low as 1 × 10−6
mol L−1 and in the linear range from 1 × 10−6 to 2 × 10−5 mol L−1
and thus is practically applicable to real glucose samples as
in healthy (~3–8 mM) and diabetic persons (9–40 mM). The
kinetic studies revealed that GO–COOH exhibits even higher
catalytic activity to TMB relative to HRP and the catalytic
reaction follows a ping-pong mechanism similar to HRP.
Recently, GO–COOH was used in a TMB-H2O2 system for
the sensitive voltammetric detection of H2O2 (Sun et al. 2013).
The generated product follows a second-order derivative linear
sweep voltammetric reduction peak at −0.93 V (vs. Ag/AgCl)
in the Britton–Robinson buffer. Under the optimized condi-
tions, the reduction peak current of the reaction product was
proportional to a H2O2 concentration in the linear range from
0.006 to 0.8 μmol L−1 with the detection limit of 1.0 nmol L−1.
This method is quite useful to determine the H2O2 content in
fresh milk with a satisfactory recovery from 94.3% to 103.2%,
indicating the accuracy of this method. Notably, as a peroxi-
dase mimic, GO–COOH has some inherent advantages such
as high stability, being inexpensive, high affinity to organic
substrates, high surface-to-volume ratio, and ease of synthesis,
which make it a promising NM in enzyme biomimetics.
In yet another work, highly crystalline, water-dispersible
carbon nanodots (CNDs) were synthesized from GO using
129
O
OH
O
OH
H3C CH3
O
+ +
NH2
H 3C CH3
+ 2H2O
pure water as the electrolyte. The as-prepared CNDs predom-
inantly had multilayer GO features with remarkable lumi-
nescence and photoluminescence properties and mimic the
POD function (Ming et al. 2012) in the degradation of methyl
orange (MO). Interestingly, upon mixing H2O2 with MO (buf-
fer, pH = 7.0) in the presence of CNDs, a moderate degrada-
tion of MO (23.6%, 160 min) was recognized. Nevertheless,
CNDs exhibited a better catalytic activity in the presence of
visible light and MO could be photo-decomposed completely
within 80 min. Following a hydrothermal route, the protocol
was further extended to fabricate a novel hybrid photocatalyst
(TiO2/CNDs) with excellent visible-light-driven photocata-
lytic activity. Dong et al. (2012) prepared GO-Fe3O4 magnetic
nanocomposites and demonstrated their intrinsic POD-like
activity by making use of TMB and H2O2. Kinetic studies
indicate that Fe3O4 magnetic NPs on GO sheets imparts desir-
able magnetic properties to GO and improves the catalytic
affinity of GO-Fe3O4 toward H2O2. The catalytic behavior
was in good agreement with Michaelis–Menten kinetics and
follows a typical ping-pong mechanism. Thus, the superpara-
magnetic GO-Fe3O4 nanocomposites offer a simple, sensitive,
and selective colorimetric assay for H2O2 and glucose in urine.
In other paradigm, by adopting a click chemistry, CuPt
nanorods with controlled size, uniformity, and aspect ratio
(AR = 1–11) were grafted onto GO surface (Yang et al. 2012)
and characterized by combinations of transmission electron
microscopy (TEM), Fourier transform infrared spectroscopy
(FT-IR), and x-ray photoelectron spectroscopy (XPS). The as-
prepared CuPt nanorods-grafted GO composites were used in
the oxidation of o-phenylenediamine (OPD) into correspond-
ing 2,3-diaminophenazine (DAP), generating a yellow solu-
tion of DAP in the aqueous phase. The UV–visible absorption
spectroscopy further revealed that without CuPt nanorods,
GO shows no catalytic activity. Notably, the CuPt nanorods-
GO with AR = 1 showed highest catalytic activity over others
(AR = 5, 11). The results clearly demonstrate that nonpolar
CuPt nanorods immobilized on GO can function as an effective
catalyst in OPD oxidation while GO can be used as a catalytic
nanorod support for organic transformation in aqueous phase.
It is well known that hemin, an iron-containing porphy-
rin and catalytic center for many proteins, can catalyze a
130
OH Hemin–graphene O
OH OH
OH conjugate or OH
2 Recently, the FeTMPyP–GO conjugates were synthesized
FeTMPyP–graphene
OH OH
Pyrogallol Purpurogallin
+ 3 H2O2 + CO2 + 5H2O
SCHEME 10.2  Schematic representation of hemin–graphene con-
jugate or FeTMPyP–graphene catalyzed conversion of pyrogallol
into purpurogallin in the presence of H2O2.
variety of oxidation reactions like PODs. However, its self-
destruction and molecular aggregation tendency in oxidizing
and aqueous media, respectively, is the major hurdle to use
it directly as an oxidation catalyst. Taking this into account,
Xue et  al. (2012) synthesized a hemin–graphene conjugate
to achieve desirable stability (Tris buffer, pH = 7.4) through
π–π stacking interactions. In parallel with this synthesis, the
group also immobilized an iron-porphyrin derivative, namely,
iron(III)meso-tetrakis(N-methylpyridinium-4-yl)porphy-
rin (FeTMPyP) on graphene. The spectroscopic studies
revealed that in the hemin–graphene conjugate, hemin retains
its catalytic active monomer form as in natural enzymes.
Furthermore, the significant blue shifts in the charge trans-
fer (CT) and Q bands clearly indicated the formation of an
axial ligation to the iron center of the hemin via cation–π
interactions between the iron centers and graphene. In the
presence of H2O2, the as-prepared hemin–graphene conju-
gate and FeTMPyP–graphene exhibited an almost similar
catalytic behavior in the biomimetic oxidation of pyrogallol
into purpurogallin (Scheme 10.2). In particular, the kinetic
studies demonstrated that the catalytic efficiencies of hemin–
graphene (Kcat/KM ~ 2 × 105) and FeTMPyP–graphene (Kcat/
KM ~ 5.7 × 105) conjugates are at least 100 times more than
that of free or dimeric hemin and nearly comparable to that of
the natural enzyme, HRP (Kcat/KM ~ 2 × 106). It is worthy to
note that graphene as a support prevents molecules from self-
dimerization, oxidative destruction, and provides relatively
Au
Au
Au Au
Au Au
TMBOX
TMB or ABTS
ABTSOX
SCHEME 10.3  Schematic illustration of a versatile and label-free colorimetric biosensing platform based on the tunable smart interface of
catalytic graphene/Au-NP hybrid. (Reprinted with permission from Liu, M. et al. 2012b. Interface engineering catalytic graphene for smart
colorimetric biosensing. ACS Nano 6:3142–3151. Copyright 2012 American Chemical Society.)
Graphene Science Handbook
large surface area which in turn results in the higher reaction
turnover rate and binding interactions.
by labeling with streptavidin following an amidation reaction
(Wang et al. 2013a). The as-prepared trace label exhibits high
POD activity toward OPD oxidation in the presence of H2O2.
By combing this porphyrin-based HRP mimic with a bioti-
nylated molecular beacon (MB), immobilized on a AuNPs-
single-walled carbon nanohorn (AuNPs-SWCNH) composite
modified glassy carbon electrode (GCE), a sensitive “signal
on” DNA biosensor is reported. Specifically, in the presence
of OPD and H2O2 in phosphate-buffered saline (PBS), the
FeTMPyP–streptavidin–GO modified GCE exhibited a sta-
ble differential pulse voltammetric (DPV) peak at −0.524 V
(peak current of −2.21 μA), which corresponds to the reduc-
tion of 2,2′-diamino azobenzene (DAAB), the oxidation prod-
uct of OPD. On the contrary, FeTMPyP-modified GCE gave
a very weak DPV peak (−0.10 μA), suggesting that the POD
activity generates from the integration of GO and FeTMPyP.
In this way, the porphyrin-based trace label is highly promis-
ing in mimicking natural enzymes.
In yet another work, a synergistic graphene-based catalyst
was engineered by the in situ growth of “naked” AuNPs on
graphene sheets (Liu et al. 2012a). The catalytic activity of the
AuNPs–graphene hybrid was confirmed when the oxidation
of three POD substrates, namely, TMB, OPD, and 2,2′-azino-
bis-(3-ethylbenzothiozoline-6-sulfonic acid) diammonium
salt (ABTS) in the presence of H2O2 gave different color
reactions similar to HRP. Importantly, the apparent catalytic
activity of as-prepared AuNPs–graphene hybrid could be
fine-tuned reversibly through interface passivation induced
by single-stranded DNA (ssDNA) due to π-stacking between
the nucleobases and AuNPs/graphene (Liu et al. 2012b). This
unique feature prevents the specific sites of POD substrates
from diffusing and binding to the surface of the catalyst and
thus provides a versatile protocol for designing graphene/
DNA-based label-free or m ­ odified c­olorimetric biosensors
(Scheme 10.3). What is more, such a reversible switching
ssDNA Insulin S1 nuclease
Richness of Graphene-Based Materials in Biomimetic Applications
interface can be considered as an ideal signal reporter with
low background signal due to the “Off-On” switching mode
during sensing and is applicable to a broad range of analytes.
Hua et al. (2012) used cytochrome C (cyt C), an electron
transfer protein in the respiratory chain, and intercalated it
between covalently modified sulfonated graphene (GSO3H)
nanosheets by means of electrostatic interactions. In a con-
fined environment, the GSO3H/cyt C assembly exhibited an
excellent POD catalytic activity (~8 times higher than that of
free cyt C) in the oxidation of OPD. It may be attributed to
the higher probability of the substrate to collide with cyt C.
This work sheds light on the fact that the property of proteins
in confined environments may differ significantly from their
free states and thus the native properties of proteins can be
fine-tuned using engineered nanostructures.
10.3 GRAPHENE-BASED ARTIFICIAL
PHOTOSYNTHESIS
Artificial photosynthesis, the biomimetic approach to convert-
ing sunlight’s energy directly into chemical fuels remains a
major challenge for this century. The main research area in arti-
ficial photosynthesis implies water splitting into protons (and
eventually hydrogen) and oxygen in the presence of photocata-
lysts having high reactivity and the capability to absorb a large
percentage of solar photons (Hammarstrom and Wasielewski
2011; Tachibana et al. 2012; Liu et al. 2013). On the other hand,
the light-driven reduction of CO2, replicating natural carbon
fixation is another studied process. As an integrated system
of nanostructures, graphene and/or its derivatives are success-
fully employed in both of the above-mentioned processes and
appropriately summarized in this section. Yadav et al. (2012)
designed a visible-light-driven chemically converted graphene
(CCG; acts as an electron acceptor) coupled multianthra-
quinone substituted porphyrin (MAQSP; acts as an electron
donor) photocatalyst for an efficient artificial photosynthetic
N N
Rh
ET +2e– +(H+ + 2e–)
ET
2+
N N
Rh
OH
Photocatalyst
2
TEOA
TEOA+
SCHEME 10.4  Graphene-based photocatalyst catalyzed artificial photosynthesis of formic acid from CO2 under visible light. (Reprinted
with permission from Yadav, R. K. et al. 2012. A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in produc-
tion of formic acid and CO2. J. Am. Chem. Soc. 134:11455–11461. Copyright 2012 American Chemical Society.)
131
production of f­ ormic acid from CO2. The working action of the
as-­prepared CCGCMAQSP photocatalyst begins with the tran-
sition of a photon between localized orbitals around MAQSP.
An organometallic rhodium complex receives the generated
electrons via graphene and gets reduced. The photocataly-
sis cycle thus reaches to a podium by abstraction of a proton,
subsequent transfer of a hydride and electrons to NAD+, and
­ultimately conversion of NAD+ to NADH (Scheme 10.4). In this
way, the rhodium complex functions as an electron mediator
between NAD+ and the photocatalyst. Finally, the enzyme for-
mate dehydrogenase converts CO2 (having NADH) into formic
acid (110.55 μmol in 2 h) and NAD+. These two catalytic cycles
work in synergy, leading to the photoregeneration of NADH
up to 45.54% with time linearity. This photocatalyst–enzyme
coupled system represents a benchmark example of the selec-
tive production of solar chemicals/fuels directly from CO2.
Water oxidation is a more complex chemical reaction
than carbon fixation. In nature, this reaction occurs via the
oxygen evolving complex by accumulating electrons in man-
ganese–calcium cluster within photosystem II (PS II). The
subsequent transfer of these electrons to water molecules
results in the production of molecular oxygen and protons or
hydrogen. In artificial photosynthesis, the similar task, lead-
ing to the continuous formation of solar fuels (H2 and O2) is
quite challenging (Umena et al. 2011) and relies on a tailored
­merging of water oxidation catalysis and NMs. In this milieu,
the graphene nanoplatform encourages bidimensional charge
carrier transport (Sun et  al. 2011) and can facilitate redox
surface events and catalysis to a significant extent. Recently,
dendron functionalized graphene nanosheets (d-G) with a
tailored distribution of polycationic, quaternized ammo-
nium pendants were designed to integrate the water oxidation
catalyst (WOC), tetra-ruthenium polyoxometalate {Ru4(μ-
O)4(μ-OH)2-(H2O)4[γ-SiW10O36]2}10− (Ru4POM), an inorganic
mimic of the natural photosynthetic Mn4 cluster (Quintana
et al. 2013; Scheme 10.5). Notably, as a multielectron WOC,
CO2 HCOOH
+H+ N N
Rh
H
NADH
NAD+
Formate
dehydrogenase
132 Graphene Science Handbook

Ru4POM
H3N
H3N
H2O, pH = 5, 16 h, rt
NH
NH3 NH Ru4POM@d-G
O O
HN
H
H
N O H N
N NH3
O
O Ru4POM
NH NH
O

N
Step B O NHBoc
N
N
H
(1) N
H2N
d-G
EDC, DMAP, HOBt NH
OH O OH O
O Step B
DMF anh, Ar, 48 h
NHBoc
N (2) HCl/dioxane, 12 h
N

Step A O
O H
(1) N
OH
Step A O
Paraformaldehyde, DMF, 72 h, 130 °C

(2) TFA/DMF, 12 h

SCHEME 10.5  Synthesis of graphene nanoplatform supporting Ru4POM. Reagents and conditions: Step A: (1) paraformaldehyde, N,N-
dimethylformamide (DMF), 72 h, 130°C; (2) trifluoroacetic acid/N,N-dimethylformamide, 12 h, room temperature. Step B: (1) dendron d, N-(3-
dimethylaminopropyl)-N′-ethylcarbodiimide, 4-(dimethylamino)pyridine, 1-hydroxybenzotriazole, anhydrous N,N-dimethylformamide,
48 h, room temperature, inert atmosphere. (Reprinted with permission from Quintana, M. et al. 2013. Knitting the catalytic pattern of artifi-
cial photosynthesis to a hybrid graphene nanotexture. ACS Nano 7:811–817. Copyright 2012 American Chemical Society.)

Ru4POM offers many advantages, such as exceptional robust-
ness, a diamond arrangement with four, oxo-bridged redox
metals similar to natural enzymes (Geletii et al. 2008), high
electron transfer rate, and redox-potential leveling effect.
Furthermore, the metal-oxo ­framework of Ru4POM serves as
a multisite H-bond acceptor and thus promotes supramolecu-
lar interaction with the ammonium functionalized graphene
environment. The as-prepared hybrid material displays oxy-
gen evolution at overpotential as low as 300 mV at neutral
pH with negligible loss of performance even after 4 h testing.
This multilayer electroactive asset enhances the turnover fre-
quency (TOF) by one order of magnitude with respect to the
isolated Ru4POM catalyst, and provides a definite upgrade of
the CNT material, having similar surface functionalization.
Zhang et  al. (2012a) used rGO as a promising alterna-
tive support for noble metals (cocatalysts) in photocatalytic
hydrogen production. Specifically, by appropriate use of
Cd(Ac)2 ⋅ 2H2O, Zn(Ac)2 ⋅ 2H2O, and Na2S precursors in the
presence of rGO, noble metal-free rGO-Zn xCd1−xS nano-
composites, in particular, rGO-Zn0.8Cd0.2S were prepared
via a coprecipitation-hydrothermal reduction strategy in an
eco-friendly manner. Under simulated solar irradiation, the
as-prepared rGO-Zn0.8Cd0.2S photocatalyst exhibited a high
H2 production rate of 1824 μmol h−1 g−1 at the rGO content
of 0.25 wt.% (GS0.25) and the apparent quantum efficiency
(QE) of 23.4% at 420 nm. Such high H2 production activity
of rGO-Zn0.8Cd0.2S (GS0.25) may be attributed to the rGO
which can function both as an electron collector and trans-
porter to lengthen the life of the charge carriers and thereby
improves the charge separation and photocatalytic activity.
Mechanistically, as the potential of graphene/graphene•− is
−0.08 V, it works as a cocatalyst for facile separation and
transfer of the photogenerated electron from conduction
band (CB) of Zn0.8Cd0.2S to the rGO. Consequently, water
splitting occurs and the hydrogen ion is reduced to hydrogen
molecules (Figure 10.2). Meanwhile, the holes in the valence
band (VB) of Zn0.8Cd0.2S are consumed by sacrificial agents.
Interestingly, the rGO-Zn0.8Cd0.2S nanocomposite exhibited
significantly improved photocatalytic hydrogen production by
450% relative to pristine Zn0.8Cd0.2S and better than that of
Pt-Zn0.8Cd0.2S under virtually identical experimental condi-
tions. Notably, in the presence of bare rGO or in the absence
Richness of Graphene-Based Materials in Biomimetic Applications 133

(a)
Zn0.8Cd0.2S NPs
properties (Table 10.4) in various research realms such as tis-
sue engineering, biomedical and device applications. Indeed,
–
H2O H2 within the graphene lattice, the carbon atoms are tightly
CB
–
CB S2–, SO32– packed into a 2D honeycomb-like structure which imparts
VB
+ flexibility and mechanical strength to single-layer graphene
– – OX
OX VB – (Lee et  al. 2008). However, the unique performance based
+
S2–, SO32– on such structures is rarely addressed. In general, the bioin-
spired honeycomb structures are reproducible through the
Reduced graphene oxide
(b) precise control of chemistry and (self)assembly processes. In
–2.0 an elegant work, Yin et  al. (2011) used the “breathe figure”
Reduced graphene oxide method for the assembly of graphene sheets into bioinspired
–1.0 honeycomb structures (Figure 10.3a). In a typical experiment,
– H2
CB by making the use of cationic surfactants of dimethyldiocta-
H2O Graphene/graphene––0.08 V decylammonium bromide (DODA.Br), GO was smoothly dis-
Potential vs. SHE (eV)

0 persed in organic phase (a prerequisite in using the “breathe

H+/H2 0.0 V
1.0
O2/H2O 1.23 V
2.0 S2–, SO32–
VB + ox
Zn0.8Cd0.2S
3.0
(pH = 0)
FIGURE 10.2  (a) Schematic illustration for the CT and separa-
tion in the RGO-Zn0.8Cd0.2S system; (b) proposed mechanism for
photocatalytic H2 production under simulated solar irradiation.
(Reprinted with permission from Zhang, J. et al. 2012a. Noble
metal-free reduced graphene oxide-ZnxCd1−xS nanocomposite with
enhanced solar photocatalytic H2-production performance. Nano
Lett. 12:4584–4589. Copyright 2012 American Chemical Society.)
of a photocatalyst, no appreciable hydrogen production was
detected, indicating that hydrogen production occurs only
by photocatalytic reaction of rGO-Zn0.8Cd0.2S. Furthermore,
contrarily to the metal sulfides, the rGO-Zn0.8Cd0.2S exhibits
exceptional stability and does not show any loss of activity
even after four consecutive cycles. The high stability of rGO-
Zn0.8Cd0.2S may be attributed to the close interaction between
rGO and Zn0.8Cd0.2S solid solution which ultimately prevents
the reduction of Cd+2 and Zn+2 by space separation of photo-
generated electrons and holes. Recently, a variety of visible-
light-driven photocatalysts were combined with graphene to
enhance water splitting activity (Ng et al. 2010; Jia et al. 2011;
Li et al. 2011; Xiang et al. 2011; Lv et al. 2012). These reports
certainly reflect the importance of graphene-based compos-
ites in photocatalytic hydrogen production and ultimately in
artificial photosynthesis.
10.4 MULTISCALE BIOMIMETIC
GRAPHENE FILMS OR SURFACES
In recent years, artificial or biomimetic graphene surfaces
having colorful appearance, stiffness, strength, toughness
(inspired by nacre and honeycombs), and adhesive superhy-
drophobicity (inspired by rose petals) have drawn considerable
research interest (Zhang et al. 2012b) due to their promising
figure” method [Lee et al. 2010] to mimic honeycomb struc-
ture). The as-prepared GO/DODA.Br chloroform solution
(1 mg mL−1) was cast onto glass substrate under a moist air-
flow (85% relative humidity). The ordered honeycomb films
were then obtained after subsequent removal of organic and
aqueous phase. The SEM images indicated that the average
size of the honeycomb holes was about 1.5 μm and the thick-
ness of the film was about 2.0 μm (Figure 10.3b). It should
be pointed out here that when the relative humidity was less
than 30%, no honeycomb structure formation was recognized.
Interestingly, when viewed with reflected light, honeycomb
films exhibited bright iridescent colors, which indicate a peri-
odic refractive index of variation throughout the thickness of
the film. Finally, the deoxidization of GO/DODA honeycomb
film in the presence of N2H4 vapor afforded a more conjugated,
reduced rGO/DODA honeycomb film which could be success-
fully used as anode materials leading to a high-performance
energy-storage device. Particularly, the experimental results
indicated that the honeycomb graphene electrode exhibits a
large and reversible capacity of up to 1600 and 1150 mA h g−1
after 50 cycles. Indubitably, such a simple, green, inexpensive,
and scalable fabrication process of honeycomb-inspired hier-
archical-structured graphene films would be quite promising
in catalysis, and rational design and engineering of graphene-
based microdevices. Besides the “breathe figure” method to
generate bright iridescent honeycomb graphene films, Wang
et  al. (2012) used a two-beam laser interference in order to
fabricate a periodic granting structure on a GO film. The as-
obtained graphene surfaces showed a beautiful iridescence
(due to light diffraction of grating) throughout the exposed
area. The formation of such a periodic grating structure with
an average period of 2 μm can be attributed to the removal
of oxygen-rich functionalities from the GO surface as well as
laser ablation. Interestingly, the period of grating on graphene
film can be fine-tuned in a wide wavelength range by simply
manipulating the laser processing parameters. In this regime,
when a relatively high laser power was employed, it resulted
in a superhydrophobic graphene surface with a high adhesion
force to a water droplet (CA ~ 157°), yet another facet of bio-
mimetic graphene, similar to the rose petal effect (CA ~ 152°).
Owing to its obvious advantages such as being clean, highly
efficient, time saving, and tunable, the laser route (intensity)
134 Graphene Science Handbook

TABLE 10.4
Summary of Graphene-Based NMs as Multiscale Biomimetic Films or Surfaces and Their Characteristic
Features or Functions
Nature’s
Graphene-Based NMs Objects Fabrication Methods Features/Functions References
GO/DODAa film Honeycomb Breath figure method Iridescent colors, porosity and energy Yin et al. (2011)
rGO/DODAa film storage device
GO or graphene Rose petal Two-beam laser Superhydrophobicity and iridescence Wang et al. (2013)
interference
Graphene Switching of dispersion Superhydrophobic to superhydrophilic Rafiee et al. (2010)
media and surface wettability
ultrasonication
rGOb Suction filtration Adhesion, reversible switching Zhang et al. (2011)
between superhydrophobicity and
superhydrophilicity
Graphene/PDMSc laminate Controlled relaxation of Superhydrophobicity, artificial muscle Zang et al. (2013)
pre-strains actuators
Chitosan/rGOb Nacre Vacuum filtration or Mechanical toughness, electrical Wang et al. (2010)
Composite film paper-making method conductivity, and thermal stability
Graphene/protein/cellulose Self-assembly of diblock Mechanical strength Laaksonen et al. (2011)
composite
HPGd/graphene Wet spinning method, Mechanical toughness, electrical Hu et al. (2012)
supramolecular fiber hydrogen bonding conductivity, stability, and corrosion
resistance
Graphene/polymer Cross-linking Mechanical toughness and electrical Cheng et al. (2013)
composite polymerization conductivity
GO + NaBF4 + borate ions Maize plant Co-filtration, annealing, Mechanical stiffness and strength An et al. (2011)
and borate-cross-linking
Graphene Cork Freeze casting method Superelasticity, ultralight weight, and Qiu et al. (2012)
mechanical strength

a Dimethyldioctadecylammonium bromide.
b Reduced graphene oxide.
c Polydimethylsiloxane.
d Hyperbranched polyglycerol.

is highly promising in controlling the surface wettability of
graphene substrates. Apart from two-beam laser interfer-
ence, the surface wettability of graphene could also be con-
trolled by simple switching of dispersion media, in particular,
from acetone to water, assisted by high-power ultrasonication
(Rafiee et al. 2010). In a typical experiment, graphene sheets
were dispersed in acetone, in water, as well as in their mix-
ture and deposited on an aluminum substrate. It was observed
that the average surface roughness of graphene, sonicated in
acetone (graphene-A), was larger than that sonicated in water
(graphene-W). Further, the surface wettability tests indicated
that CA of graphene-A was ~160° (superhydrophobic), while
that of graphene-W was 0° (superhydrophilic). With a different
ratio of acetone/water systems, it was quite possible to man-
age the surface wettability over a wide range (CAs from 0°
to 160°). Nevertheless, the irreversibility in switching between
superhydrophobic to superhydrophilic of this attractive proto-
col was quite questionable. Later on, this problem was sorted
out by Zhang et  al. (2011). In their work, by suction filtra-
tion of chemically rGO, graphene films having adhesive and
hydrophobic properties were produced with ease. Notably, a
reversible switch between hydrophobicity and hydrophilicity
could be explained as the periodic alteration of ultraviolet irra-
diation and air storage. Zang et al. (2013) reported that by har-
nessing the mechanical instabilities of graphene, adhered on a
biaxially prestretched p­ olymeric substrate like polydimethyl-
siloxane (PDMS) and by controlling the relaxation of the pre-
strains, graphene films can be crumpled into self-organized
hierarchical structures, a case of mimicking superhydrophobic
leaves. The crumpled graphene–polymer laminate could be
effectively used as a­ rtificial muscle actuators.
Inspired by the unique structure and mechanical properties
of nacre, a kind of “hard-shell” material, Wang et al. (2010) pre-
pared an electrically conductive and mechanically strong com-
posite film via the vacuum filtration/paper-making method of
chitosan (CTS) and rGO in aqueous solution. The as-obtained
CTS/rGO composite film containing 6 wt.% rGO exhibited high
tensile strength (δC = 206 ± 6 MPa), elongation (εb = 6.5 ± 0.6%),
and a Young’s modulus (6.3 ± 0.2 GPa) at break, which signifi-
cantly exceed those of nacre (δC = 140 – 170 MPa, εb = <1%).
Meanwhile, such nacre-like composite film exhibits a high con-
ductivity of 1.2 S m−1 and improved thermal stability. The high
Richness of Graphene-Based Materials in Biomimetic Applications 135

(a) Electrostatic
Oxidization interaction

Graphite DODA
Graphene oxide (GO)
GO/DODA
Humid gas

Pores
Water drop
Solvent evaporation Deoxidization
N2H4
Solution (GO/DODA)
substrate
C18H37 + CH3
Graphene Graphene oxide N
DODA C18H37 CH3
(b)
(iv)
(i) (iii)

1 2
CENTIMETERS
1 μm
(ii)
(v)

2 μm
10 μm 1 μm
Film
Cu foil

FIGURE 10.3  (a) Schematic illustration of synthetic procedure for honeycomb structured film using GO. (b) Configuration of the
­honeycomb structures: (i) photograph of the honeycomb film on the glass; (ii) photograph of the honeycomb-patterned film on the cop-
per foil; (iii, iv) SEM images of honeycomb-patterned film prepared from 1 mg mL −1 of the GO/DODA complex on the silicon wafer; (v)
cross-sectional SEM image of the honeycomb-patterned film on the copper foil. (Reprinted with permission from Yin, S. et al. Assembly
of graphene sheets into hierarchical structures for high-performance energy storage. ACS Nano 5:3831–3838. Copyright 2011 American
Chemical Society.)

mechanical as well as electrical properties of CTS/rGO com-
posite films are mainly due to the uniform dispersion of rGO
nanofillers in the polymer m­ atrices which results a compact lay-
ered structure. In another work on a nacre mimic, Laaksonen
et al. (2011) used an exfoliated graphene, genetically engineered
proteins, and native nanofibrillated cellulose for the prepara-
tion of biomimetic nanocomposites. The aligned co-assembly
of genetically engineered diblock (graphene-binding hydropho-
bin block and nanofibrillated cellulose-binding block) proteins
resulted in the formation of a final composite material with
tunable interconnectivity and properties. Specifically, the as-
prepared composite film with 1.25 wt.% of graphene (relative
to nanofibrillated cellulose) exhibited a superior tensile strength
(δC = ~278 MPa) over nacre. Such a high mechanical property of
a biomimetic nanocomposite can be r­ealized in the framework
of the bifunctionalization of proteins similar to those of the pearl
oyster Pinctada fucata, a natural nacre (Suzuki et al. 2009). Hu
et al. (2012) used an industrially viable wet spinning technology
in order to achieve the goal of continuous processing for nacre
mimics. In their work, hyperbranched polyglycerol (HPG) was
used as elastic glue and graphene as rigid platelets. The result-
ing macroscopic supramolecular fibers (mainly constructed by
H-bonding arrays) with “brick-and-motor” (B&M) structures
of alternating graphene sheets and HPG binders exhibited
good electrical conductivity, stability, corrosion resistance, and
eminent mechanical properties comparable or even superior to
nacre and bone. Interestingly, such artificial nacre fibers (ANFs)
upto tens of meters in length can continuously spun from their
concentrated liquid crystalline dope. Furthermore, the compo-
sitions of biomimetic fibers can be extended to other 2D col-
loids such as clay, layered double hydroxides (LDH), Al2O3, and
dendritic/linear polymers for advancing nanocomposites as well
as biomimics. This study clearly points out that H-bond forma-
tion is crucial for the self-assembly process which significantly
affects the fabrication of hierarchical structures as exemplified
with graphene nanoribbons in mimicking the secondary struc-
ture of β-sheet proteins of muscle tissues, ­amyloids, or spider
silk (Xu and Buehler 2009). Recently, ultratough artificial
nacre with high electrical conductivity was fabricated by the
conjugated cross-linking of long-chain polymers, made up of
10,12-­pentacosadiyn-1-ol monomers, and 2D GO sheets (Cheng
et al. 2013). The experimental results indicated that the tough-
ness of as-­prepared artificial nacre is ~2 times higher than that
of natural nacre attributable to the distinct inorganic–organic
136 Graphene Science Handbook

layered h­ ierarchical nano-/­microstructures and relatively low
content of organic ­polymers in the resultant composites.
In plants such as maize, borate plays a crucial role in rein-
forcing the intercellular structure via the cross-linking of the
polysaccharide, rhamnogalacturonan II. As a result, the cell
walls of the plants become stiffer and stronger for self-support.
Conversely, the presence of oxygen functionalities on both the
surfaces and edges of GO is quite beneficial for desired func-
tionalization via different chemical reactions. Taking these
facts into account, a simple co-filtration strategy combined
with low temperature annealing has been employed to mimic
higher-order plants (Blevins and Lukaszewski 1998).
The co-filtration of aqueous dispersion of GO and NaBF4
at low temperature annealing in the presence of borate ions as
the covalent cross-linking agent afforded borate-cross-linked
GO thin films with nearly 80% stiffness relative to untreated
graphene (An et al. 2011). The presence of even a trace quan-
tity of borate (0.0094%) in these films clearly indicates the
efficacy of borate ions for high stiffness. Qiu et al. (2012) real-
ized the problem of achieving high elasticity in a 3D graphene
network and accordingly developed ultralight, superelastic
graphene-based cellular cork-like monoliths by the so-called
“marriage of graphene chemistry with ice physics,” freeze
casting method. It is worthy to note that in wood or cork, cellu-
lose nanofibers in the cell walls are closely packed in a highly
ordered manner to maximize strength. Thus, by mimicking
the hierarchical structure of natural cork, the resulting mate-
rials could sustain their structural integrity under a load of
>50,000 times their own weight and could rapidly recover
from >80% compression. Such exceptional graphene-based
cellular material will pave the way for new types of flexible
devices in a self-supporting and 3D macroscopic form.
10.5  GRAPHENE-BASED BIOMIMETIC SENSORS
Over the last decade, the increasing understanding and
advancement of miniaturized chemosensors and chemodo-
simeters (Garg et al. 2014c; Garg and Ling 2015c) for sen-
sitive and selective detection of analytes have stimulated
material scientists to fabricate graphene-based smart biomi-
metic nanosensors in a variety of configurations. This section
covers the synthetic approaches and applications of biomi-
metic sensors (not relevant to enzyme mimetics, as already
discussed in the previous section), based on graphene and/
or its counterparts. Motivated by the biological importance
of nitric oxide (NO), Guo et  al. (2012) have developed an
arginylglycylaspartic acid (RGD) peptide functionalized gra-
phene live-cell electrochemical sensor for real-time detec-
tion of NO. In a typical experiment, GO was reduced to rGO
and functionalized by pyrenebutyric acid (PBA) via a direct
assembly approach through π–π interactions (Scheme 10.6).
The covalent attachment of RGD-peptide on the surface of

o
o

(a)
(b)
Pyrenebutyric acid Functionalization Assembly

Reduction

o
o Assembled graphene
film
Graphene oxide

Functionalized
graphene RGD-peptide
(c)
Drug covalent bonding

No
No
(d)

Cell growth

Live-cell assay RGD-peptide grafted

graphene film

SCHEME 10.6  Schematic illustration of preparation of the freestanding biomimetic film and its live-cell assay. (a) Chemical reduction of
GO and pyrenebutyric acid functionalization; (b) preparation of pyrenebutyric acid functionalized graphene film by filtration of the solution
of pyrenebutyric acid functionalized graphene; (c) fabrication of the biomimetic functional film by covalently bonding RGD-peptide on
the surface of the pyrenebutyric acid functionalized graphene film via EDC/NHS coupling; (d) the functional biofilm as cell adhesion and
­sensing matrix. (Reprinted with permission from Guo, C. X. et al. RGD-peptide functionalized graphene biomimetic live-cell sensor for
real-time detection of nitric oxide molecules. ACS Nano 6:6944–6951. Copyright 2012 American Chemical Society.)
Richness of Graphene-Based Materials in Biomimetic Applications
PBA-functionalized graphene afforded biomimetic graphene
film with a well-packed layered nanostructure. Notably, in
the film sensor, the RGD-peptide imparts desired biomimetic
properties for superior human cell attachment and growth
on the film surface for real-time detection of NO, released
(145–350 nM) from the attached cell under drug stimulations.
As expected, the film sensor exhibited good flexibility, sta-
bility, sensitivity, and selectivity toward real-time NO detec-
tion with an almost unchanged current response even after 15
repeated measurements, thus rendering it a powerful platform
to build next-generation biomedical devices. In yet another
work, Li et  al. (2013) presented a straightforward molecu-
lar imprinting technique (MIT) to fabricate a rGO modified
biomimetic electrochemical sensor for sensitive detection of
Sildenafil (Viagra®), an inhibitor of phosphodiesterase type 5
(PDE5), which is used for the treatment of erectile dysfunc-
tion in men. Typically, the rGO was first functionalized with
poly diallyldimethylammonium chloride (PDDA) and poly
sodium-p-styrenesulfonate (PSS) to afford the corresponding
PDDA-rGO and PSS-rGO, respectively. The stepwise electro-
static adsorption of PSS-rGO and PDDA-rGO through layer-
by-layer (LBL) self-assembly then produced the rGO modified
GCE. Finally, the constant electrochemical polymerization of
rGO-LBL modified GCE, dipped in a preassembled solution
of Sildenafil (template) and monomeric p-phenylenediamine
at 0.8 V for 500 s generated a rGO modified molecularly
imprinted electrochemical sensor (rGO-MIES); the template
could be removed by acid treatment with ease. Interestingly,
the as-prepared rGO-MIES exhibited ~6.2 nmol L −1 detec-
tion limit for Sildenafil in herbal sexual health products. In
addition, the recoveries for the spiked Sildenafil contents
were in the range of 92.34%–97.71% with the RSD of <2.31%.
Following the similar MIT, Wang et  al. (2013b) developed
a sensitive and selective biomimetic electrochemical sen-
sor, using functional monomers of OPD and 3-aminophenyl
boronic acid (ABA), graphene–Au nanoparticles (Gr–AuNPs)
modified GCE and 6-ferrocenylhexanethiol for detection of
bovine serum albumin (BSA), a template glycoprotein in the
assay. The quantification of BSA was monitored by detecting
the electrochemical oxidation signal of 6-ferrocenylhexaneth-
iol bonded onto the electrode. Under optimized conditions, a
good relationship between the response current and logarithm
of BSA concentration (1.0 × 10−11 to 1.0 × 10−5 g mL −1) was
detected with a detection limit of 7.5 × 10−12 g mL −1 (S/N = 3).
The fabricated MIP sensor exhibits a great validity and repro-
ducibility toward glycoprotein detection and is applicable in
practical analysis. It may be worthwhile to mention here that
the appropriate selection of template, functional monomers,
cross-linking monomers, polymerization initiator, and polym-
erization format are the key components that one should take
into consideration while designing MIPs for recognition
assays (Hayden et al. 2006).
Cell membranes play a key role for life as they are inter-
faces between cells and their surroundings. In addition to
their function as the structural components of cell mem-
branes, phospholipids are major elements of complex intra-
cellular signaling networks (Schultz 2010). As such, they
137
are potential candidates for biomimetic sensor develop-
ment in order to understand complex biological processes.
Taking into account the unique hydrophobicity of rGO, Liu
et  al. (2012c) developed a phospholipid–graphene assembly
through noncovalent hydrophobic interactions simply by mix-
ing the ­liposome and rGO suspension under sonication. The
as-prepared nanoassembly consisted of a bilayer of phospho-
lipids with an rGO sheet hosting in the hydrophobic interior,
thus represents a unique planar mimic of cellular membrane
(Figure 10.4a). Here, two seeming advantages are notable: on
the one hand, the phospholipid coating offers aqueous solubi-
lization with excellent biocompatibility; whereas on the other
hand, it retains the electronic conjugation within the graphene
sheets, manifested in a dark color change (Figure 10.4b).
Thus, it is understandable that the phospholipid–graphene
assembly exhibits a r­elatively higher absorption of energy in
the ­visible spectrum than GO and rGO and can be used as
an efficient energy acceptor (fluorescence resonant energy
­transfer; FRET) for biological assays. Accordingly, a nanoas-
sembly of phospholipid-coated graphene was prepared having
two phospholipid components, the dipalmitoyl-sn-glycero-
3-phosphochiline and a derivative of 1,2-dihexadecanoyl-sn-
glycero-3-phosphoethanolamine with a fluorescein label, for
activity assay of phospholipase D; an enzyme catalyzing the
hydrolysis of phosphatidylcholine into choline and phospha-
tidic acid. As depicted in Figure 10.4c, after incubation of the
nanoassembly with 1000 U L −1 phospholipase D, the reaction
mixture showed a very strong fluorescence signal at 514 nm
with a peak intensity and enhancement ratio of ~4370 and ~19,
respectively. This indicates that in the presence of active phos-
pholipase D, the phosphodiester bonds cleave and release the
fluorescein labels, and thus activate the fluorescence signals.
The control experiments, in the presence of phospholipase D
inhibitors, such as halopemide and ­ethylenediaminetetra ace-
tic acid (EDTA), further confirmed that the fluorescence acti-
vation is specific to phospholipase D activity. In this way, the
biomimetic sensor displays excellent robustness, simplicity, a
very low detection limit (0.010 U L −1) of phospholipase D, and
the intrinsic ability to real-time monitor the reaction kinetics.
10.6 OTHERS
This section will highlight some miscellaneous applications
as well as synthetic biomimetic approaches used for graphene
functionalization. Huang et al. (2011) presented a biomimetic
approach for fabricating a network structure of graphene oxide
nanoribbons (GONRs) on an electrode. Compared to other
procedures, the GONRs with MWCNTs as precursor could
function as nanowires similar to that of cellular pili produced
by some electrochemically active microbes, in particular,
Shewanella. A significant enhancement of the extracellular
electron transfer and thus in the power output was achieved
using electrochemical and microbial fuel cells which indicate
that GONRs could be a promising material for bio-electro-
chemical systems in the near future. Kaminska et  al. (2012)
used biomimetic dopamine (DA), a mussel-inspired adhesive
molecule and a neurotransmitter, for the simultaneous reduction
138 Graphene Science Handbook

(a)

Self-assembly
Phospholipase D

HO O O

HO O O
CH3
C OH +
O CH3 N CH3
O + O
N CH3 O CH3
O C OH CH3(CH2)13CH2 O O P O
CH3
CH3(CH2)14 C OCH2 O CH3(CH2)13CH2 O O–
CH3(CH2)14 C OCH O –OCH2CH2NH C NH
O
O CH2O P OCH2CH2NH C NH S
O S

(b) (c)

4000

Fluorescence intensity (a.u.)

3000

2000

1000
(i) (ii) (iii) (iv) (v)

0
510 520 530 540 550 560 570
Emission wavelength (nm)

FIGURE 10.4  (a) Structure of assembled monolayers of phospholipids on graphene surfaces and analytical principle for activity assay
of phospholipase D. (b) Photograph of suspensions for (i) liposome, (ii) GO, (iii) phospholipid-coated GO, (iv) rGO, and (v) phospholipid–­
graphene nanoassembly. (c) Fluorescence spectra obtained for phospholipid–graphene nanoassembly (solid line of lowest FL intensity),
phospholipid-coated GO suspension (dashed line below 1000 FL intensity), phospholipid–graphene nanoassembly plus 1000 U L −1 PLD
(solid line of maximum FL intensity), phospholipid-coated GO suspension plus 1000 U L −1 PLD (dashed line ~1000 FL intensity), phospho-
lipid–graphene nanoassembly plus 5% HSA (solid line of lower intensity), phospholipid–graphene nanoassembly plus 1000 U L −1 PLD in
the presence of 1 mg mL −1 inhibitor halopemide (solid line of 2nd highest intensity), phospholipid–graphene nanoassembly plus 1000 U L −1
PLD in the presence of inhibitors EDTA (1 mg mL −1), and 1 mg mL −1 halopemide (overlapped solid lines of lower intensities). (Reprinted
with permission from Liu, S.-J. et al. Phospholipid-graphene nanoassembly as a fluorescence biosensor for sensitive detection of phospholi-
pase D activity. Anal. Chem. 84:5944–5950. Copyright 2012 American Chemical Society.)

and noncovalent functionalization of GO under sonication at
room temperature. This simple and eco-friendly protocol was
further extended to prepare functional graphene/dopamine-N3
composite films using click chemistry. In a similar yet dif-
ferent biomimetic approach, biopolymer-functionalized GO
nanosheets have been reported through adhesive DA (Cheng
et  al. 2012). Specifically, the grafting of DA onto a heparin
backbone into corresponding DA-g-Hep, a precursor, was used
to prepare heparin-adhered GO (Hep-a-GO) and rGO (Hep-
a-rGO). The as-obtained (Hep-a-GO (rGO)) showed excel-
lent anticoagulant bioactivity and biocompatibility for human
blood cells and umbilical vein endothelial cells with ultralow
hemolysis ratio (<1.2%) and high cell viability. Another inter-
esting example of biocompatible polymer functionalized GO
was recently reported by Su-Xing et al. (2013). In their work,
biomimetic monomer 2-(methacryloyloxy) ethyl phosphoryl-
choline (MPC) was used to fabricate GO by reverse atom trans-
fer radical polymerization (RATRP) in alcoholic media. The
resulting GO-g-pMPC was then filled into the polyurethane
(PU) matrix to prepare PU/GO-g-pMPC nanocomposite films.
It was found that PU functionalized with zwitterionic brushes
(PU/GO-g-pMPC) exhibited improved resistance to nonspe-
cific protein adsorption and platelet adhesion. Apart from
biomimetic MPC, McHale et al. (2012) reported a biomimetic
segregation/templating approach to synthetic radical polym-
erization. In this regard, the reduced bimolecular termination
and controlled propagation along a defined number of tem-
plates afforded well-defined high-molecular-weight polymers.
Richness of Graphene-Based Materials in Biomimetic Applications
Ferritin (Fr) is a globular shell-like protein that is involved
in the biomineralization of iron oxide particles (Srivastava et al.
2007). By using Fr as a precursor, Wei et al. (2012) demonstrated
a facile biomimetic synthesis of FePt-NPs on the surface of GNs.
The as-synthesized FePt-NPs were found to have high solubility,
fluorescence, ferromagnetism, and electro-catalytic activity, and
might be useful as biosensors in cell imaging and drug delivery.
In another different work, Fan et al. (2013) used casein phospho-
peptides (CPPs) and carboxylated graphene (CGO) to prepare
CGO–CPPs biocomposites through amidation reaction. When
immersed in stimulated body fluid (1.5 × SBF) for different
periods, the CGO–CPPs scaffold mimicked the natural biomin-
eralization of bone due to the formation of hydroxyapatite (HA),
an important inorganic material found in the hard tissues of
bone and teeth. The composites are supposed to have potential
applications in the fields of biomedicine, bio-nanotechnology, as
well as in tissue engineering. Besides the experimental studies
­mentioned above, Rogers and Liu (2013) used ab initio simu-
lations and demonstrated that the electrochemical actuation of
highly ordered GO (asymmetrically unzipped C4O) can produce
high-performance quantum-mechanical responses, thus mim-
icking the behavior of mammalian skeletal muscle.
10.7 CONCLUSIVE REMARKS AND
FUTURE DIRECTIONS
As the building block of carbon materials of all dimensions,
graphene possesses many unique properties and physico-
chemistry. In this chapter, we have shed light on biomimetics,
a relatively new area of research for graphene-based NMs. By
mimicking natural enzymes, photosynthesis, and multiscale
natural structures, graphene and its derivatives have shown
their superiority over other NMs, holding great promise for
their future use in technological applications. Nevertheless,
the development of bioinspired graphene-based NMs, films,
surfaces, and/or their biomimetic applications is still in its
infancy and worthy of discussion here for future scientific
research and development. As discussed previously, graphene
derivatives are increasingly used as a potential HRP mimic;
however, mimics for enzymes such as transferase, ATPase,
aldolase, ribonuclease, and the extent of their potency as func-
tional models is still not available. Indeed, we can expect that
the combinations of Zn(II), Mg(II), Mn(II), Cu(I), and Cu(II)
ions and graphene may provide new insights into the struc-
tures, spectroscopic properties, and activities of metallopro-
tein active sites. Photocatalysis is yet another ­central goal of
artificial photosynthesis, which relies on a tailored merging
of the water oxidation catalysts/CO2 fixation and graphene-
based NMs. In this context, a fundamental understanding as
well as the fabrication of graphene NMs with well-designed
architectures, optimized charge cascading processes, charge
transport processes, insensitivity to oxygen, and high stabil-
ity over long terms remain significant c­ hallenges that can act
as a guide for the advancement of artificial photosynthesis.
Third, a variety of nature’s objects, to name a few, spider silk,
gecko feet, peacock feathers, and shark skin, are still avail-
able to fabricate multiscale structures with interesting and
139
diverse properties. It is therefore only a matter of patience and
effort to execute new biomimetic graphene structures. After
all, they are also patiently waiting to be discovered. Fourth,
the heteroatom doping (­nitrogen, boron) of graphene and its
derivatives should be widely investigated in an eco-friendly
manner. This strategy may be useful in the direct electro-
chemistry of enzymes and in the development of biomimetic
electrochemical sensors for bioanalysis and environmental
analysis. In general, diagnostics, healthcare, and security
topics; for instance, detecting illegal drugs is the main driv-
ing force behind biosensing. However, biomimetic sensing is
still a matter of research at the academic level rather than of
commercial development. Once established in those markets,
the applications in diagnostic areas would be more realistic.
It is anticipated that by mutual cooperation between biology,
chemistry, physics, material scientists, and engineer, graphene
may lead to new disciplines in the twenty-first century and
one can expect to see new and exciting biomimetics within the
framework of graphene-based NMs. As a final note—”there
are always good possibilities that today’s science fiction may
become the objects of tomorrow’s biomimetics.”
ACKNOWLEDGMENTS
The authors are thankful to the Ministry of Science and
Technology (NSC101-2113-M-007-006-MY3, MOST104-
2881-M-007-039, MOST104-2113-M-007-008-MY3) and
National Tsing Hua University (NTHU) (104N1807E1) of
Taiwan for financial support.
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Section II
Nanocomposites
 11 Graphene-Based Polymer
Nanocomposites
S. Chatterjee and B. T. T. Chu

CONTENTS
Abstract...................................................................................................................................................................................... 145
11.1 Nanocomposite................................................................................................................................................................. 145
11.2 Processing of Nanocomposites......................................................................................................................................... 146
11.2.1 Predispersion of Graphene Nanofillers................................................................................................................. 146
11.2.2 Dispersion of Nanofillers in the Polymer Matrix..................................................................................................147
11.2.2.1 Solution Mixing......................................................................................................................................147
11.2.2.2 Melt Mixing........................................................................................................................................... 148
11.2.2.3 In Situ Polymerization........................................................................................................................... 148
11.2.2.4 Covalent Bonding.................................................................................................................................. 149
11.2.2.5 Other Methods....................................................................................................................................... 150
11.3 Properties of Graphene-Based Nanocomposites.............................................................................................................. 150
11.3.1 Mechanical Reinforcement................................................................................................................................... 150
11.3.2 Electrical Conductivity......................................................................................................................................... 150
11.3.3 Thermal Properties............................................................................................................................................... 151
11.3.4 Other Properties.................................................................................................................................................... 152
11.4 Applications of Graphene-Based Nanocomposites.......................................................................................................... 152
11.5 Hybrid Composites with Graphene.................................................................................................................................. 154
11.5.1 Graphene–C60 Hybrid......................................................................................................................................... 154
11.5.2 Graphene–CNT Hybrid........................................................................................................................................ 154
11.5.3 Graphene–Graphene Nanoplatelet Hybrid........................................................................................................... 154
11.5.4 Properties of Hybrid Composites......................................................................................................................... 155
11.6 Toxicity............................................................................................................................................................................. 156
11.7 Conclusion........................................................................................................................................................................ 156
References.................................................................................................................................................................................. 156

ABSTRACT graphene sheets can form interconnected percolating pathways

Graphene, a unique material with a Young’s modulus of 1 TPa
and a strength of 130 GPa, coupled with high thermal conduc-
tivity and excellent electronic transport properties, is theoreti-
cally the best available reinforcing material today. This chapter
highlights various methods currently employed for the produc-
tion of graphene nanocomposites, for example, exfoliation in
water in the presence of soluble polymers, physical melt m­ ixing,
in situ polymerization, grafting, etc. Apart from single-layer
graphene, different forms of the material that are easily scal-
able for commercialization are in use. Dispersion of the fillers
is an important issue that needs to be addressed as it influences
the properties of the polymer composites. The most significant
part of the chapter is the discussion regarding the properties of
nanocomposites. Inclusion of a very small amount (0.1–2 vol%)
of graphene results in a large improvement in both modulus (up
to 900%) and strength (up to 100%) of a wide range of ther-
mosets, thermoplastics, and elastomers. Highly conductive
for enhanced ­electrical conductivity in matrices for as low as
0.1 vol% loading. Other important properties of the composites
include thermal conductivity, thermal stability, dimensional sta-
bility, and gas permeability. Such properties give rise to count-
less opportunities for novel applications for now and the future.
Hybrid composites utilizing two or more nanoparticles have
exhibited promising results and need further attention.
11.1 NANOCOMPOSITE
Nanocomposite is a class of multicomponent material in which
one of the phases is dispersed in another phase in the nanome-
ter range [1]. Conventional fillers in polymers have often been
used to reduce cost and/or improve material properties required
for particular applications. Ceramic fillers such as silica or alu-
mina are typically cost effective and increase the stiffness in
epoxy resins [2,3]. The drawback however is that the addition of
such rigid particles further reduces the ductility in the already

145
146 Graphene Science Handbook

brittle epoxy. Soft particles, such as rubber, on the other hand

can be used to toughen the epoxy matrix but they consequently TABLE 11.1
reduce the stiffness [2,4]. Polymer nanocomposites show sig- Conventional Synthesis Methods of Graphene Together
nificant improvements in properties at much lower loadings with Their Important Features and Their Current and
than polymer composites with conventional micron-scale fillers Prospective Applications
(e.g., carbon fibers or glass fibers). The reduction in weight can
Method Size Applications Comments
significantly affect their applications and processing, together
with a variety of new possibilities. The outstanding properties of CVS (on Ni, Cu, Thin films Touch screens, Moderate
Co) (≤75 cm) smart windows, scalability,
carbon nanotubes (CNTs), graphene nanoplatelets (GnPs) (few
flexible LCDs high cost,
layers of graphene), and graphene can be exploited by the inclu-
and OLEDs, high quality,
sion of such nanofillers into a matrix to form nanocomposites solar cells high process
[5]. The macroscopic properties of polymer nanocomposites temperature
are mainly dependent on thermodynamic factors such as the (>1000°C)
interfacial compatibility of polymer and filler phases, polarity Chemical Nanoflakes/ Polymer fillers, High scalability,
match between the filler surface and the polymer chains, etc. In reduction of powder battery low cost, low
addition, nanoscale dispersion and distribution of the filler also graphene oxide (mm to a electrodes, purity, high
depend on the size, shape, dispersion techniques and equipment, few μm) supercapacitors, defect density
time of mixing and applied shear, etc. [6]. For the complete uti- conductive inks
lization of the properties of nanofillers in the polymer matrix, and paints,
sensors
all the above parameters have to be taken into account while
Micromechanical Flakes Mainly research Small-scale
manufacturing the composite, and for its potential applications.
exfoliation (5–100 μm) purpose production,
high cost, high
11.2  PROCESSING OF NANOCOMPOSITES quality, uneven
films
The first step toward the effective manufacture of graphene Epitaxial growth Thin films Transistors, Low yield, high
nanocomposites is the availability of large quantities of gra- on SiC (>50 μm) circuits, cost, high
phene as the starting material. There are several methods interconnects, quality, high
employed for the synthesis of graphene, each having its own memory, process
merits and concerns. Based on the manufacturing method, the semiconductors temperature
application of the material also varies. Table 11.1 summarizes (1500°C), very
the different synthesis methods with potential applications for expensive
substrate
each type of graphene.
Liquid-phase Nanosheets Polymer fillers, High scalability,
exfoliation (mm to a transparent low yield,
11.2.1 Predispersion of Graphene Nanofillers few μm) electrodes, moderate
conductive quality, low
Strong van der Waals forces, interplaner π−π interactions, paints, sensors cost, impure
and high aspect ratio of the graphene sheets/platelets lead to Carbon nanotube Nanoribbons Interconnects, Moderate
physical entanglement, which makes it extremely ­challenging unzipping (few FETs, NEMs, scalability, high
to disperse these nanofillers in polymer matrices. They tend to microns) composites yield, high
aggregate together to form bundles or stacks, and in compos- quality,
ites, this can lead to a reduction of the load-carrying capabil- potentially low
ity between the reinforcing phase and the matrix [9]. Prior to cost
incorporation of fillers in the polymer matrix, it is essential to
Source: K. S. Sivudu and Y. Mahajan, Nanotech Insights, vol. 3, no. 2, 2012;
be able to fully deagglomerate these materials. G. Mittal et al. J. Ind. Eng. Chem., vol. 299, no. 8, pp. 906–931, 2014.
In this chapter, we will focus on the methods employed
for achieving better predispersion of nanofillers to be used as
additives in polymer matrices: charged nanoparticles (ZrO2) [12]. Surfactants have
assisted the dispersion process to some extent as
a. Utilizing the π−π-induced interactions. Nanofillers they debundle nanoparticles by steric or electrostatic
can be dispersed in solvents using the physical repulsions [13]. Techniques developed for CNTs
adsorption of π-aromatic compounds on the surface can be employed for graphene sheets to achieve
of the graphene sheets [10]. Such dispersions in sol- similar improvements in dispersion. Lomeda et  al.
vents can be consequently utilized for s­ olution mix- functionalized chemically converted graphene with
ing with polymers to make the composites. large amounts of varying aryl addends, allowing the
b. Making other noncovalent-induced dispersions (van nanosheets to be solubilized in organic solvents [14].
der Waals, physical adsorption), by wrapping with c. Making covalent bonded side wall functionalization/
surfactants and polymers [10,11] or by the use of oxidation-induced dispersions.
Graphene-Based Polymer Nanocomposites
Boukhvalov et  al. [15] summarizes the main motiva-
tions for studying the different chemical functionalization
paths of graphene as (i) modification of electronic proper-
ties via opening the energy gap in the electron spectrum of
single- and bilayer graphene; (ii) potential use of graphene
for hydrogen storage; (iii) decoration of various defects in
graphene; (iv) a way to make graphene magnetic for poten-
tial use in spintronics; (v) a search for ways to produce
“cheap graphene” by chemical reduction of graphite oxide
and manipulation of its electronic and mechanical proper-
ties; (vi) the functionalization of graphene edges in graphene
nanoribbons and their protection; and (vii) oxidation and
cracking of graphene as tools to create graphene nanostruc-
tures of a given shape.
Different forms of covalent functionalization are more
widely used due to stronger modifications of physical and
electronic structures. The chemical modification of nano-
filler walls by forming a covalent bond with substituents on
the walls can greatly increase the dispersibility of the modi-
fied graphene. Computational methods have been employed
to understand the various possibilities for the chemical func-
tionalization of graphene. Hydrogen on graphene is an area
of active interest and different configurations of one-side
hydrogenation have been studied and it is concluded that
configurations when hydrogen atoms are bonded with differ-
ent sublattices (Figure 11.1) are the most stable [15,16]. The
(a)
(b)
(c)
FIGURE 11.1  A schematic representation of chemical bonds in
(a) pure graphene (dashed lines correspond to delocalized double
bands), (b) graphene with single chemisorbed hydrogen atom (white
circle; the black circle corresponds to unpaired electron at the ­broken
bond, it distributes in the sublattice shown in dark gray), (c) ­graphene
with chemisorbed pair of hydrogen atoms (nonequivalent sublattices
are shown in different shades). (From D. W. Boukhvalov and M. I.
Katsnelson, J.  Phys. Condens. Matter, vol. 21, no. 34, p. 344205,
2009. With permission.)
147
structural alteration can take place at the end of the sheets
and/or on the surface. Surface functionalization causes rehy-
bridization of one or more sp2 carbon atoms of the carbon
network into the sp3 configuration accompanied by simulta-
neous loss of electronic conjugation. Kuila et al. discusses the
four ­primary methods of covalent modification of graphene,
namely, nucleophilic substitution, electrophilic addition,
condensation, and addition [17]. Alkyl amine-modified gra-
phene, as shown in Figure 11.2, is commonly used as fillers in
­polymer nanocomposites due to their improved dispersion and
hydrophilicity that helps in bonding to the polymer matrix.
11.2.2 Dispersion of Nanofillers in
the Polymer Matrix
11.2.2.1  Solution Mixing
This is a very efficient and comparatively easy-to-process
method for the manufacture of nanocomposites; however, it
is crucial to have a good compatibility of the polymer and
the filler with the solvent. The method usually consists of
three steps: dispersion of the filler in a suitable solvent typ-
ically using ultrasonication, incorporation of the polymer,
and removal of the solvent by distillation or evaporation
[18,19]. During the solution mixing process, the polymer
coats the graphene sheets, and when the solvent is evapo-
rated, the graphene sheets are uniformly dispersed in the
polymer matrix. Owing to the oxygen functional groups,
graphene oxide (GO) can be directly mixed with water-
soluble polymers such as polyvinyl alcohol (PVA) by this
method as carried out by Zhao et  al. [20]. Field emission
scanning electron microscopy (FESEM) images of such
composites are used to show that most of the GO sheets
are fully exfoliated and clearly well dispersed in the PVA
matrix, while few do restack together. X-ray diffraction
observations of composites also confirmed the molecular-
level dispersion of GO in the PVA matrix corroborating the
processing method. This method has also been efficiently
used in preparing polyvinyl fluoride (PVF) [21], polyeth-
ylene (PE) [22,23], poly(methylmethacrylate) (PMMA)
[24], poly(ethylmethacrylate) (PEMA) [25], and polyure-
thane (PU) [26]-based nanocomposites. As discussed ear-
lier, chemical functionalization can improve the solubility
and interaction of GO with polymers. Stankovich prepared
graphene–polystyrene (PS) composites with significantly
enhanced electrical conductivity [27]. He used a stable dis-
persion of phenyl isocyanate-treated graphite oxide mate-
rials, prepared by ultrasonic exfoliation to which PS was
added and dissolved by stirring. Reduction of the dispersed
nanoparticles was carried out with dimethylhydrazine
in the solution. Various types of polar polymers such as
PMMA, poly(acrylic acid) PAA, polyacrylonitrile (PAN),
and PS have been successfully mixed with functionalized
GO (f-GO) [23,28] or polymer-grafted GO [29] using a
solution mixing technique [30]. However, in situ thermal
reduction of GO proves to be extremely challenging since
the majority of polymers cannot stand the high temperature
necessary for the reduction.
148 Graphene Science Handbook

O
HOOC
O
(a) HOOC
O OH
COOH
O
HO
Oxidation COOH OH OH

Sonication COOH
O OH COOH
O O GO
HO O

Graphite HOOC COOH

O
– 3–(CH2)16–CH2–
R–CH HO COOH OH

RNH2
(b)
NHR NHR OH
(c) OH HOOC
NHR NHR
OH
HOOC
OH OH OH
NHR NHR
COOH
NHR OH NHR HO NHR
HO
Reduction COOH OH OH

COOH
RHN OH
NHR NHR OH OH COOH
HO NHR NHR HO OH NHR OH NHR

HOOC COOH

NHR OH NHR
HO HO COOH OH
RNH-G
RNH-GO

FIGURE 11.2  A simple route for the preparation of functionalized graphene sheets from graphite: (a) Oxidation of natural flake ­g raphite
to graphite oxide, followed by ultrasonication; (b) an aqueous GO dispersion is treated with alkylamine to obtain amine-modi-
fied GO (RNH-GO); (c) RNH-GO is reduced using hydrazine to produce amine-modified graphene (RNH-G). (From J. R. Lomeda et al.,
J. Am. Chem. Soc., vol. 130, no. 48, pp. 16201–16206, 2008. With permission; Reprinted from Prog. Mater. Sci., vol. 57, T. Kuila et al.,
Chemical functionalization of graphene and its applications, pp. 1061–1105, Copyright 2012, with permission from Elsevier.)

11.2.2.2  Melt Mixing
This method involves high shear mixing of polymer melt with
the nanofillers and is mostly applied for thermoplastic poly-
mers at elevated temperatures. Physical mixing using extrud-
ers, kneaders, etc. is performed where the temperature of the
melt governs the viscosity. The advantages of melt mixing are
that it is an economical option and larger quantities can be pro-
cessed. This process is free from solvents and does not involve
the presence or removal of any other material in the system.
This method becomes significantly less effective in dispersing
higher amounts of nanofillers in the polymer matrix due to the
increase in viscosity of the composites [31], making the pro-
cess cumbersome. High shear mixing can result in buckling,
rolling, and also breaking of graphene sheets during mixing,
resulting in reduced aspect ratios, which may adversely affect
the properties of the composites [32]. Kim  et  al. [23] have
investigated the effect of blending methods on the properties
of graphene–PE nanocomposites. As shown in Figure  11.3,
the PE graphene composites fabricated using solution m ­ ixing
show isolated, single graphene sheets whereas the melt-
blended samples appear ­predominantly phase separated with
larger agglomerates.
However, in contrast, Bao et  al. [33] reported a suc-
cessful preparation of graphene–poly(lactic acid) (PLA)
nanocomposites by melt blending with improved prop-
­
erties. They adopted a master-batch strategy to disperse
graphene into PLA by melt blending. The graphene was
well ­d ispersed and the obtained nanocomposites present
markedly improved crystallinity, rate of crystallization,
mechanical properties, electrical conductivity, and fire
resistance [30].
11.2.2.3  In Situ Polymerization
In this case, nanofillers are added to the polymerizable mas-
ter solution and physically mixed or sonicated, followed by
polymerization of the matrix. Wang et  al. fabricated gra-
phene nanosheet (GNS) functionalized PU, as shown in
Figure 11.4 [34]. Graphite oxide powders synthesized from
graphite by Hummers’ method was chemically reduced
and the aqueous GO nanosheet was dispersed by hydrazine
to generate a GNS suspension. Finally, in situ polyconden-
sation of 4,4′-diphenylmethane diisocyanate (MDI) and
poly(tetramethylene ether) glycol (PTMG) was carried out in
the presence of graphene sheets.
Graphene-Based Polymer Nanocomposites 149

(a) (b) Researchers [27] have prepared PS–graphene composites

0.5 μm 200 nm
(c) (d)
0.5 μm 200 nm
FIGURE 11.3  TEM images of 1.0 wt% TRG/PE prepared by
(a,b) solvent mixing (c,d) melt blending. (Reprinted from Polymer
(Guildf)., vol. 52, H. Kim et al., Graphene/polyethylene nano-
composites: Effect of polyethylene functionalization and blend-
ing methods, pp. 1837–1846, Copyright 2011; Graphene, vol. 1,
D. Galpaya et al., Recent advances in fabrication and characteriza-
tion of graphene-polymer nanocomposites, pp. 30–49, Copyright
2012, with permission from Elsevier.)
using complete exfoliation of graphite and molecular-level
dispersion of individual, chemically modified graphene sheets
within polymer hosts. In situ polymerization has been used to
produce noncovalent composites of a number of polymers, for
example, poly(ethylene) [35], PMMA [36], and poly(pyrrole)
[37,38].
11.2.2.4  Covalent Bonding
In this approach, typically, a surface functional group is
attached to the graphene wall and is subsequently used to
covalently bond with polymers forming composites. It has
been demonstrated that for the grafting-from approach [39],
atom transfer radical polymerization (ATRP) initiators are
covalently attached to the alcohols present across the graphene
surfaces. Similar ATRP-based methods used for ­ making
polymer-grated platelets when used in solution ­mixing with
the polymer matrix results in well-dispersed nanocomposites
with enhanced properties. Grafting-to is another approach for
covalently attaching polymers to graphene surfaces, for exam-
ple, grafting of azide-terminated PS chains to the surface of
alkyne-functionalized GO platelets [40]. Between grafting-to
and grafting-from reactions, the grafting-to approach may
lower the grafting density of chains to the platelet surface,
which may affect the dispersion of these polymer-grafted

O OH
O HO OH
O
O
OH N2H4 • H2O
NaNO3, 98%H2SO4
O O OH
KMnO4 100°C
O
O HO O O OH

NCO
OCN CH2 NH HN
O OH O O
HO OH O O O OH

OH MDI O
OH
O OH 70°C, 2h O O N
H
HO OH O O NCO
O NCO
N O N
H H
NCO

PTMG, EG
80°C, 8 h

FIGURE 11.4  Synthesis of polyurethane-functionalized graphene nanosheets. (X. Wang et al., In situ polymerization of graphene
nanosheets and polyurethane with enhanced mechanical and thermal properties, J. Mater. Chem., vol. 21, no. 12, p. 4222, 2011. Reproduced
by permission of The Royal Society of Chemistry.)
150 Graphene Science Handbook

platelets for further mixing into a polymer matrix [41]. It is adhesion, flexibility, and ­environmental stability. The foremost
interesting to note that sometimes covalent bonding between advantage of this technique is that these organized layered
the polymer and the matrix occurs automatically during the assemblies can provide a route to precisely engineer the gra-
processing of composites, for example, for an epoxy matrix phene–polymer interface and control the distribution and con-
composite, curing with an amine hardener may result in the tent of the graphene component on a molecular level.
incorporation of graphene sheets directly in the cross-linked
network as discussed in the literature [42].
11.3 PROPERTIES OF GRAPHENE-
11.2.2.5  Other Methods BASED NANOCOMPOSITES
Besides the fabrication methods for nanocomposites discussed
11.3.1 Mechanical Reinforcement
above (and summarized in Table 11.2), there are several other
unconventional methods being tried out by researchers. Some Graphene has been ushered into the world of materials with
of them are novel techniques while some are modifications of the crown for being the strongest material tested to date; the
the more established routes. It has been reported that emul- in-plane elastic modulus of pristine, defect-free graphene is
sion polymerizations can be carried out in aqueous suspen- approximately 1.1 TPa. The discovery of graphene led to the
sions of GO platelets [43,44], suggesting a general approach for belief that if such a high-strength material can be incorpo-
­dispersion of chemically modified graphene platelets with latex- rated in small amounts in commonly used matrices, it can
based polymers [45]. A reduction of an aqueous ­suspension of bring about significant changes in mechanical properties. The
GO platelets with hydrazine results in the extraction of the extent of the improvement is related to many factors such as
hydrophobic RGO platelets into an organic layer (containing the the reinforcement phase concentration and the distribution
dissolved polymer) and the formation of a homogeneously dis- in the host matrix, interface bonding, and the reinforcement
persed nanocomposite [46]. As discussed in detail by Hu et al. phase aspect ratio [30].
[47], layer-by-layer (LbL) assembly is another e­ fficient fabrica- Table 11.3 shows a comprehensive list of improvements
tion approach for the development of ultrastrong and robust thin achieved in the mechanical properties for graphene-reinforced
films, membranes, and coatings with high strength, controlled nanocomposites. As expected, we can observe a large variation
in properties based on the polymer used, the form of graphene
(also functionalization), dispersion techniques, and quantity
TABLE 11.2 of filler used among many other factors. Although pristine
graphene has the highest theoretical strength, it is very chal-
Summary of Most Common Techniques Employed for
lenging to achieve good dispersion in polymer ­matrices due to
Polymer Nanocomposites Manufacture restacking as well as its low wettability, resulting in decreased
Method Name Technique Comments mechanical properties of reinforced nanocomposites. Rather,
Solution mixing Predispersion in Efficient technique if GO, which also boasts of excellent mechanical properties (i.e.,
solvent, the polymer and the the Young’s modulus of monolayer of GO is 207.6 ± 23.4 GPa
incorporation of graphene sheets are [62]), is commonly used to improve the mechanical properties
polymer, removal of compatible with the of graphene–polymer composites. GO exhibits more options
solvent solvent for functionalization, which facilitates dispersion and conse-
Melt mixing High shear mixing at Mostly used for
quently strong interfacial interaction and load transfer from
elevated thermoplastic
the host polymers to the GO [53].
temperature using polymers, can result
extruder, kneader, or in poor dispersion, no
similar tools other material added 11.3.2 Electrical Conductivity
ore removed from the
composite The most commonly used polymers are insulators and it is
In situ polymerization Nanofillers added to Often used with of prime importance if a material with enhanced mechanical
polymerizable functionalized properties and high electrical conductivity can be brought to
solution followed by nanofillers, good the market. Graphene has remarkable electrical and thermal
mixing and dispersion conductivity and a very small amount of filler can bring about
polymerization percolation in an insulating matrix. The conductive nanofill-
reaction ers form a pathway in the polymer matrix for electrical perco-
Covalent bonding Surface Possible to achieve
lation. Stankovich reported a bottom-up chemical approach of
functionalized well dispersed
tuning the properties of graphene sheets that provides a path
groups are attached composites with
to the polymer enhanced properties
for a broad new class of graphene-based materials and their
chains, either use in a variety of applications [27]. He combined graphene
grafting-to or with PS to exhibit a percolation threshold of 0.1 vol% for
grafting-from room-temperature electrical conductivity, and at only 1 vol%,
method is used the composite achieved a conductivity of ~0.1 Sm−1, making
several electrical applications possible [27].
Graphene-Based Polymer Nanocomposites 151

TABLE 11.3
Mechanical Properties of Graphene-Based Polymer Nanocomposites
% Increase Compared to Neat Polymer
Fabrication Tensile Elastic Fracture Fracture Toughness
Matrix Filler Loading Process Strength Modulus Energy (G1c) (K1c) Reference
Epoxy f-GP c 0.489 b In situ ~−22.6 ~26.7 ~296 ~55.3 [48]
f-GPc 1.5a In situ ~7.7 ~55 [49]
TRGOd 0.1a In situ 20 25 [30]
f-GPc 4.0a In situ −15 21.6 200 100 [50]
GPe 4.0a In situ −23 7.4 104.3 50 [50]
TRGOd 0.1a In situ 40 31 126 53 [51]
f-GPc 1.0a In situ 30 50 Negligible [52]
TRGOd 0.125a In situ ~45 ~50 115 65 [53]
GNRf 0.3a In situ 22 30 Marginally increased [54]
GO 0.1a In situ 12 ~4 29 28 [55]
GPe 1.0a In situ 0.9 22.6 [56]
GO 1.0a Sol. blend ~0.5 ~3.6 [22]
TRGOd 1.0a Sol. blend −8.9 [23]
CRGOg 3.0a Melt blend 77 87 [57]
PU f-GPc 0.5a Melt blend ~49.1 [26]
Sol. blend ~98.4
In situ ~14.7
PVA CRGOg 1.8b Sol. blend 150 ~940 [20]
f-CRGOh 3.0 Sol. blend 177 86 235 [58]
PVAc GO 0.07a Sol. blend ~38.7 ~−9.35 [59]
f-GOi ~55.30 ~−11.7
PP CRGOg 1.0 Melt blend 75 74 [60]
PMMA GO 2.0a In situ 15.0 29.9 [61]
CRGOg −1.9 35.8

Source: D. Galpaya et al. Graphene, vol. 1, pp. 30–49, 2012. With permission.
a wt%.

b vol%.

c Functionalized graphene.

d Thermally reduced GO.

e Graphene.

f Graphene nanoribbons.

g Chemically reduced GO.

h Functionalized CRGO.

i Functionalized GO.

Figure 11.5 shows the DC surface resistance of thermo-
plastic polyurethane (TPU) containing graphite and thermally
reduced graphene (TRG). Both graphite and TRG effectively
increased electrical conductivity (reduced resistance), but they
differ greatly in the onset concentration for electrical percola-
tion (>2.7 vol% for untreated graphite versus <0.5 vol% for
TRG) [26].
11.3.3 Thermal Properties
Pristine graphene is highly thermally conductive; at room
temperature, the thermal conductivity has been measured to
exceed 3000 W/m K when suspended [71,72] and approxi-
mately 600 W/m K when supported on a SiO2 substrate [73].
Similar to the case for electrical conductivity, graphene in its
different forms is able to increase the thermal conductivity in
polymer composites by the formation of a conductive network
in the matrix. Efficient heat propagation in graphene sheets is
mainly due to the acoustic phonons; a uniform dispersion and
network of sheets in the polymer matrix may contribute to
the steady increase in thermal conductivity in the composites.
Covalent bonding between the matrix and fillers can reduce
phonon scattering at the matrix–filler interface, promoting
higher composite thermal conductivity [41]. However, the
effectiveness of thermal resistance containing contact resis-
tance between exfoliated graphite nanoplatelets (EGNPs) and
interfacial thermal resistance between the EGNPs and the
matrix should be considered [74,75]. As seen in Figure 11.6a,
thermal conductivity increases steadily with the incorpora-
tion of the EGNPs. At 2.0 wt% EGNP loading, an increment
152 Graphene Science Handbook

1012 11.3.4 Other Properties

Graphite, melt
1011 The coefficient of thermal expansion (CTE) is of crucial
1010 1012 importance in the manufacturing of composite parts, and
graphene with its negative CTE can be used to harness this

Resistance (Ω)
109 1010
Surface resistance (Ω)

108
107
106
105
104
103
TRG, solvent
102
101
0.000 0.005
FIGURE 11.5  DC surface resistance of melt-blended graphite–
thermoplastic polyurethane (TPU) composites (closed symbols, also
in inset) and melt-blended, solution-mixed, and in situ polymer-
ized TRGO–TPU composites (open symbols). (Reprinted with per-
mission from H. Kim, Y. Miura, and C. W. Macosko, Graphene/
polyurethane nanocomposites for improved gas barrier and elec-
trical conductivity, Chem. Mater., vol. 22, no. 11, pp. 3441–3450.
Copyright 2010 American Chemical Society.)
of 36% is observed as compared to pristine epoxy. It has been
shown in a previous work (Figure 11.6b) that GnP of size
25 μm performs better showing significant improvement of
85% compared to pristine epoxy while for 5 μm GnP-filled
composites, the improvement is 36% at 2.0 wt% loading. The
size of the graphene platelet plays a significant role in fabri-
cating the pathway for thermal conductivity. Similar increase
in thermal conductivity in the epoxy matrix with the incorpo-
ration of graphite nanoplatelets and graphene is reported in
the literature [76,77] making such composite materials attrac-
tive for thermal interfaces. Table  11.4 ­presents a summary
of electrical and thermal conductivity of graphene–polymer
nanocomposites studied by different groups.
108
106
property as well [79]. It has been demonstrated that the CTE
104 Graphite, melt of a GO–epoxy composite can be lowered by about 32% for
102 temperatures below the Tg of the matrix at 5 wt% loading [77].
0.00 0.05 0.10 0.15
TRG, Filler volume fraction GnPs have been reported to decrease the CTE of polypro-
in situ polym pylene (PP) in two directions instead of one when aligned in
TRG, melt the matrix [80]. When it comes to thermal stability (defined
as loss in mass measured using thermogravimetric methods),
there are a number of reports to show increased thermal stabil-
ity in polymers with the addition of GnPs and other graphene
0.010 0.015 0.020 0.025 0.030 fillers [59,81–83]. Polymer composites with greater thermal
Filler volume fraction stability can be used for high-temperature applications, which
were dominated by ceramic or metals and can also be used for
manufacturing flame-retardant materials.
Graphene-based nanocomposites have demonstrated
improved gas barrier properties. Kim et  al. [26] reported
that exfoliated carbon sheets can act as diffusion barriers in
polymeric membranes since N2 permeation is remarkably
­
reduced. A network of nanoplatelets efficiently inhibits the
pathway for the diffusion of gas molecules, causing decreased
permeability. It is possible to change the gas barrier properties
with the orientation and aspect ratio of the two-dimensional
(2D) fillers in the matrix [79]. Nanocomposites have the capa-
bility to alter the glass transition temperature of the matrix;
it has been reported that thermally expanded graphite oxide
and PAN show a large shift in Tg of 40°C at only 0.05 wt%
nanofiller loading [84].
11.4 APPLICATIONS OF GRAPHENE-
BASED NANOCOMPOSITES
The wide range of properties that we discussed so far holds the
potential for several applications of graphene-based polymer
composites. The energy sector has being conducting ongoing

(a) 0.52 (b)

0.70
Thermal conductivity (W/mK)

5 μm
Thermal conductivity (W/mK)

0.50
0.65 25 μm
0.48
0.60
0.46
0.55
0.44
0.42 0.50

0.40 0.45

0.38 0.40
0.36 0.35
0 0.1 0.5 1 2 0 0.1 0.5 1 2
EGNP loadings (wt%) GnP loadings (wt%)

FIGURE 11.6  Thermal conductivity of (a) EGNP composites with varying nanofiller content. (From S. Chatterjee et al., Chem. Phys.
Lett., vol. 531, no. 0, pp. 6–10, 2012.) (b) GnP composites of two different sizes of nanofillers with varying content. (Reprinted from Carbon
N. Y., vol. 50, S. Chatterjee et al., Size and synergy effects of nanofiller hybrids including graphene nanoplatelets and carbon nanotubes in
mechanical properties of epoxy composites, pp. 5380–5386, Copyright 2012, with permission from Elsevier.)
Graphene-Based Polymer Nanocomposites 153

TABLE 11.4
Electrical and Thermal Properties of Graphene–Polymer Nanocomposites
Electrical Properties Thermal Properties
Surface
Resistancea
(Ω)/Electrical % Increase Thermal
Fabrication Percolation Conductivityb in Thermal Conductivity
Matrix Filler Loading Process Threshold (Sm−1) Conductivity (W/mK) Reference
Epoxy f-GPc 1.5a In situ ~25 [48]
f-GPc In situ 0.244b [63]
CRGOd In situ 0.52b [64]
Graphene 1.0a In situ 23.8 [56]
PMMA CRGOd In situ 0.62b [65]
f-GOe In situ 0.26b 2.47 × 10−5 b [66]
PE TRGOf Solution blend 0.16b [24]
TRGOf 1.0a Solution blend 2 × 108 a [23]
Graphene In situ 3.8b [67]
PU f-GPc 0.5 Melt blend >0.5b [26]
Solution blend <0.3b
In situ >0.5b
PVA f-CRGOg 3.0a Solution blend 0.37b 0.9 × 10−2 b [58]
PVDF TRGOf Solution blend 4.5a [21]
TRGOf Solution blend 0.016b [68]
PBT Graphene 0.5 Solution blend 760 [69]
1.0 50
PANI CRGOd 10.0a Solution blend 8.38 × 10−4 a [70]
11.92 × 102 b

Source: D. Galpaya et al. Graphene, vol. 1, pp. 30–49, 2012. With permission.
a wt%.

b vol%.

c Functionalized graphene.

d Chemically reduced GO.

e Functionalized GO.

f Thermally reduced GO.

g Functionalized chemically reduced GO.

research to improve the performances of energy-storing devices,
for example, Li ion batteries that are widely used from commer-
cial products to more recently in aircraft due to their high energy
density, fast charge/discharge rate, and durable performance.
Su et  al. efficiently fabricated graphene–Fe3O4 nanocompos-
ites with superior electrochemical properties from GO through
a facile, effective, and scalable hydrothermal method. These
nanocomposites exhibit remarkable lithium storage property,
including highly reversible capacity, good cycle performance,
and good rate capability, which make them promising anode
material for high-performance batteries [85]. Similarly, Yao
et  al. processed SnO2–graphene nanocomposites with three-
dimensional (3D) architecture by an in situ chemical reduction
method, resulting in enhanced properties for Li ion cells [86].
The high electrical conductivity of graphene-based nanocom-
posites has facilitated their application as field-effect transistors
(FETs) [87] and solar cells (and other photovoltaic applications)
[88]. Using poly(3-hexylthiophene) (P3HT) blended with gra-
phene as the active layer in bulk heterojunction (BHJ), polymer
photovoltaic cells result in enhanced quenching of the photolu-
minescence of the P3HT, indicating a strong electron/energy
transfer from the  P3HT to the graphene [89]. Photovoltaics
and optoelectronics take advantage of the fact that monolay-
ers of graphene are about 98% transparent but still have high
electrical conductivity [41]. Enormous effort is being put into
improving the efficiency of such devices, especially in the field
of organic solar cells where currently power conversion of up to
1% can be achieved with graphene nanocomposites. Graphene
nanocomposites are promising for supercapacitor applications;
the presence of graphene in a network of polyaniline changes
the composite structure, and can be utilized for high-powered
supercapacitor applications for portable devices [90]. It has
been reported that polyvinylidene difluoride (PVDF)–TRG
nanocomposites exhibit negative temperature coefficient [18].
This result can be attributed to contact resistance predominat-
ing over tunneling resistance due to the large aspect ratio of
graphene sheets. This property can be successfully exploited in
the manufacture of thermal sensors.
154
Multifunctional polymer nanocomposites are being fab-
ricated that can respond to external stimuli, for example,
­temperature, electric field, light, and pH among many others.
Nanocomposites have exhibited repeated-infrared actuation
performance. Graphene nanocomposites improve the ther-
mal stability of polymer matrices creating a pathway for their
application as a flame-retardant material. GO–polycarbonate
composites demonstrated diminished flammability as the
amount of GO was increased; the total heat release and peak
heat release rate decreased while the char yield increased [91].
Mechanical reinforcement as discussed before provides
us with extremely lightweight nanocomposites, which can be
efficiently used in the aerospace and automotive sectors for
improving fuel efficiency. Thin films containing nanoparticles
are lightweight and can be utilized in a variety of applications
such as membranes in areas ranging from the petrochemical
to biomedical industries. The platelet morphology of gra-
phene and superior gas barrier properties make it possible to
fabricate membranes with enhanced permittivity and selec-
tivity [18]. Poly(N-vinylcarbazole)–graphene ­nanocomposite
­solution and thin film have been fabricated that exhibit anti-
microbial and biocompatible properties, which can potentially
be used for diverse biomedical applications where bactericidal
properties coupled with low cytotoxicity to mammalian cells
is of crucial importance [92].
11.5  HYBRID COMPOSITES WITH GRAPHENE
Hybrid composites have lately attracted the attention of
researchers with different mixtures being tried out, for exam-
ple, multiwalled CNT with carbon black [93], few-layer gra-
phene with single-walled CNT and nanodiamonds [94], and
multiwalled carbon nanotube (MWCNT) with GnP [56]. The
synergistic effect brought about by these combinations is
yet to be completely understood. Improvements in mechani-
cal properties and thermal conductivity have been reported
but the ratio of the nanofiller mixture is an important f­actor
governing the reinforcing capabilities of the composites
­ 11.5.3 Graphene–Graphene Nanoplatelet Hybrid
[56,94]. Kumar et al. [95] suggested that by bringing together
two nanofillers like CNT and GnP, a cosupporting network
of both fillers like a hybrid net structure is formed, in which
the platelet geometry shields the tube-like fillers from frac-
ture and damage during processing while still allowing full
dispersion of both during high-power sonication, thus causing
improved properties. Shin et  al. reported ultra-tough fibers
containing CNT–reduced GO flake mixture. This is attributed
to the formation of an interconnected network of partially
aligned nanofillers during solution spinning [96].
11.5.1 Graphene–C60 Hybrid
C60 (fullerene), the zero-dimensional (0D) carbon nanomate-
rial, exhibits novel properties and chemical reactivity making
it an attractive candidate for hybrid composite manufacture
together with graphene. Graphene–fullerene hybrids can be
prepared through covalent bonding methods as described by
Chen et al. [107,108]. A facile preparation of a graphene–C60
Graphene Science Handbook
hybrid material via a simple coupling reaction between GO and
pyrrolidine fullerenes resulting in enhanced nonlinear optical
performance in the nanosecond regime was carried out.
11.5.2 Graphene–CNT Hybrid
CNTs are widely used as one-dimensional (1D) reinforcing
additives in polymer composites. It is interesting to note that
CNTs form hybrid nanocomposites with 2D graphene in dif-
ferent topological formations for maximum synergistic effects.
Zhang et  al. classify the CNT–graphene hybrids into three
categories as shown in Figure 11.7, namely, CNTs adsorbed
horizontally onto the graphene surface, CNTs adsorbed per-
pendicular to the graphene surface, and CNT wrapped with
graphene [97]. The most common form of this hybrid is CNTs
adsorbed horizontally on to the graphene surface forming a
doubly reinforced network of graphene–CNT in the matrix.
In CNTs adsorbed perpendicular to the GNS surface, pos-
sible reasons for the formation of this type of hybrid structure
can be considered as a single interaction point between the
GNS and CNT, namely, CNTs are connected with the GNS by
the catalyst nanoparticles in CVD growth. In CNT wrapped
with GNS, the formation of the wrapping type depends on the
interaction types between CNTs and GNS as well as the ini-
tial ratios between them [104]. Besides these methods, several
other techniques can also be employed for producing hybrids
with specific tunable properties. For example, Xie [49]
reported that divalent metal ions can be used to coordinate
the oxidized MWCNTs and GO by the oxygen-containing
functional groups in a solution-based route. This method is
promising for the development of transparent electrode mate-
rials with high flexibility and strength that can be used for
nanoscale biosensors and catalyst-loaded reactors.
Table 11.5 presents a summary of different graphene–CNT
hybrids that have been studied in the literature using GO,
GNS, and GnP.
Different forms of 2D graphene can be used in combination to
form hybrid composites with improved dispersion and proper-
ties (Figure 11.8). Tian et al. [52] used aqueous GO to effec-
tively disperse GnP in suspension for facile wet-processing
into nanocomposites of GnP embedded in GO. The resulting
nanocomposite is lightweight with mechanical fl ­ exibility at
high loadings of GnP. The nanocomposites have improved
thermal transport properties comparable to conductive metals
such as aluminum and copper.
Type 1 Type 2 Type 3
FIGURE 11.7  Classification of graphene and CNT hybrids. (From
C. Zhang and T. Liu, Chinese Sci. Bull., vol. 57, no. 23, pp. 3010–
3021, 2012. With permission.)
Graphene-Based Polymer Nanocomposites 155

TABLE 11.5
Hybridization Modification of Graphene with CNTs in Solvents
Dispersion Weight Ratio
Graphene CNT Interaction Architecture Solvent (G:CNT) Reference
GO SWNT van der Waals interaction Type 1 Water – [97]
GO MWCNT π−π stacking Type 1 Water >3 [98]
GO SWNT – – Water 0.5 [99]
GO SWNT π−π stacking Type 3 Water 2.5 [100]
GO MWCNT π−π stacking Type 1 Water >2 [100]
GO NH2-MWCNT Covalent bonding Type 3 Water 40 [101]
GO salt SWNT van der Waals interaction Type 1 Water 0.5–5 [102]
GNS SWNT – Type 1 Hydrazine 0.2 [103]
GNS MWCNT CVD growth Type 2 – – [104]
GNS A-MWCNT π−π stacking Type 1 Water 1 [97]
GNS A-MWCNT Ion-coordinated interaction Type 1 Water <0.25 [105]
GnP SWNT – – – 3 [106]
Chitosan (CS)-grafted GNS MWCNT van der Waals interaction Type 1 Water 1 [97]

Source: C. Zhang and T. Liu, Chinese Sci. Bull., vol. 57, no. 23, pp. 3010–3021, 2012. With permission.

11.5.4 Properties of Hybrid Composites

(a)
200 nm
(b)
50 nm
FIGURE 11.8  TEM images of G–CNT (1:1) hybrids at (a) low
and (b) high magnifications. (C. Zhang et al., Facile preparation of
water-dispersible graphene sheets stabilized by acid-treated multi-
walled carbon nanotubes and their poly(vinyl alcohol) composites,
J. Mater. Chem., vol. 22, no. 6, p. 2427, 2012. Reproduced by per-
mission of The Royal Society of Chemistry.)
The motivation behind preparation of hybrid composites is
to be able to completely disperse the two nanofillers with
mutual assistance and consequently achieve improvements
in the properties beyond the limits of a single nanofiller.
Different hybridization techniques and proportions of the
components play a crucial role in the properties of the com-
posites. In our previous work with a hybrid composite of car-
boxylated CNT and GnP, the carboxyl groups on the CNTs
are expected to form an integrated mesh with the graphene
platelets and this connected network of nanofillers should
increase the tensile properties of the epoxy composites
[78]. A synergistic effect was observed for flexural modu-
lus measurements where the composites with CNT:GnP
ratio of 9:1 showed the highest increase of 17% compared
to an increase of 9% and 5% with pristine CNT and GnP,
respectively, as shown in Figure 11.9. The flexural modu-
lus for the CNT:GnP ratio of 5:1 was also observed to be
higher than that of composites with pure CNT and GnP. This
increase indicates an improved load transfer mechanism
from the matrix to the nanofillers when stress is applied. As
proposed by Yang et al. [14], the CNTs seem to have effec-
tively reduced the π–π stacking and agglomeration in GnPs
and together they produce better reinforcement. High aspect
ratio of CNTs facilitate the reinforcement mechanism; how-
ever, with the inclusion of small amounts of GnP, the surface
area increases significantly, encouraging better linkage with
the polymer matrix. Thus, the CNT:GnP ratio of 9:1 comes
across as the most appropriate combination of nanofillers for
mechanical improvements.
Sun et  al. [41] prepared PVA hybrid fibers with single-
wall nanotubes (SWNTs), GO, and graphene as additives. As
expected, mixing SWNTs and GO improves the dispersion of
both the fillers in the polymer matrix and leads to the syner-
getic enhancement of the strength of the fibers. There was also
156
3.2
3.1
Flexural modulus (GPa)
3.0
2.9
2.8
2.7
2.6
0.0
Pure CNT GnP 1:9 9:1 1:5 5:1 1:3 3:1
Ratio (CNT:GnP)
FIGURE 11.9  Flexural modulus of composites with varying ratios
of CNT and GnP mixtures together with pure epoxy, 100% CNT,
and 100% GnP at nanofiller concentration of 0.5 wt%. (Reprinted
from Carbon N. Y., vol. 50, S. Chatterjee et al., Size and synergy
effects of nanofiller hybrids including graphene nanoplatelets and
carbon nanotubes in mechanical properties of epoxy composites,
pp. 5380–5386, Copyright 2012, with permission from Elsevier.)
improvement in the electrical conductivity of the fibers by mix-
ing SWNTs and GO together at a ratio of 2:1. It was possible to
design fibers with tunable toughness by mixing SWNTs with
graphene in different ratios. Zhang et al. [48] prepared PVA com-
posites containing GNS–MWCNT hybrids as shown in Figure
11.8, by a water casting method bringing about a homogeneous
dispersion and synergistic interaction of the two kinds of nano-
fillers. The tensile strength and the Young’s modulus of the PVA
nanocomposite filled with only 0.6 wt% G–CNT hybrids are
significantly improved by about 77% and 65%, respectively.
Hybrid composites can prove to be exceptional in terms of
thermal and electrical conductivity, which is based on a con-
ductive percolating network. Two different nanofillers together
help to bridge gaps and significantly improve conductivity.
Yu et al. [50] reported that a synergistic effect in the thermal
conductivity enhancement of epoxy composites was achieved
by combining SWNT with GnP fillers. The combination of
the flexible SWNTs with GnPs leads to a decrease in thermal
interface resistance along the (2D–1D) hybrid filler network
due to the extended area of the SWNT–GnP junctions.
To be able to completely exploit the full potential of
graphene-based hybrid nanocomposites, it is important to
­ carbon nanotubes reinforced polyamide 6 via in situ polym-
maximize the interactions between them, which are benefi-
cial for efficient load transfer among the fillers and the poly-
mer matrix. The nanostructured hybrids have the potential for
stronger interfacial interaction with the matrix than what is
achieved with graphene or nanotubes alone.
11.6 TOXICITY
An important issue to be taken into account is nanosafety;
nanotoxicology itself is a vast field of research. So far, it is
not clear what adverse effects carbon nanofillers are likely to
have on living cells. It is reported that toxicity is shape and
Graphene Science Handbook
composition dependent [110], the overall toxicity of graphene
is supposed to be lower than CNTs. However, it is interesting
to note that the toxicity of graphene is inverse to its concen-
tration [111], with graphene exhibiting a higher toxicity than
CNTs at low concentrations [111]. Researchers have investi-
gated that on abrasion nanocomposites release freestanding
nanoparticles, which can cause health hazards [112]. Extreme
caution and safety measures are to be observed when ­handling
nanoparticles both in the laboratory and in an industrial setup.
Nanocomposites for commercial applications should be tested
for long-term wear and tear, taking into account the possible
release of toxic nanoparticles.
11.7 CONCLUSION
Currently, with more than 10,000 publications in 2013, the field
of nanocomposites is growing rapidly. There are endless pos-
sibilities for a large number of future studies. It is important to
be able to disperse individual graphene sheets in the polymer
matrices to be able to completely exploit their strength. The
processing routes should be optimized to inhibit reagglom-
erations of dispersed phases. Further chemical modification/
functionalization techniques can be explored to ensure better
interaction with the polymer matrix. The nanofiller content in
the matrices used are very low; in the range of 0.1–2 wt%, it
would be interesting to be able to synthesize composites with
higher nanofiller loadings as micromechanical models predict
vast improvements given the potential of individual nanofill-
ers. The mechanism of the “nano” effect in the polymers is not
yet well understood using existing micromechanical models.
Further morphological study will be carried out to be able to
selectively tune the structure of the composites with the incor-
poration of nanofillers, which will in turn positively influence
the properties. It should be possible to be able to manufacture
materials with specific applications in terms of either mechan-
ical strength or conductivity. Graphene-based nanocomposites
is the material to look forward to in the near future.
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 12 Preparation of Cellulose/Graphene
Nanocomposites
Nguyen Dang Luong and Jukka Seppälä

CONTENTS
Abstract.......................................................................................................................................................................................161
12.1 Introduction.......................................................................................................................................................................161
12.1.1 Cellulose................................................................................................................................................................161
12.1.1.1 Cellulose Solution.................................................................................................................................. 162
12.1.1.2 Nanofibrillated Cellulose Suspension.................................................................................................... 162
12.1.1.3 Bacterial Cellulose................................................................................................................................. 162
12.1.2 Graphene............................................................................................................................................................... 163
12.2 Preparation of Cellulose/Graphene Nanocomposites....................................................................................................... 163
12.2.1 NFC-Based Cellulose/Graphene Composites....................................................................................................... 164
12.2.2 Cellulose Solution-Based Cellulose/Graphene Composites................................................................................. 167
12.2.3 Other Cellulose-Based Cellulose/Graphene Composites..................................................................................... 168
12.3 Properties of Cellulose/Graphene Nanocomposites and Their Potential Applications.................................................... 169
12.3.1 Mechanical Properties.......................................................................................................................................... 169
12.3.2 Electrical Conductivity..........................................................................................................................................170
12.3.3 Interaction of GO and Cellulose by Rheology Study............................................................................................171
12.3.4 Thermal Properties................................................................................................................................................171
12.3.5 Cellulose/Graphene Composite for Supercapacitors and Lithium-Sulfur Batteries............................................. 172
12.4 Summary and Concluding Remarks................................................................................................................................. 172
References...................................................................................................................................................................................173

ABSTRACT component of the primary cell wall in plants with content

Significant advances have been made on development of
cellulose/graphene composites in the last few years, dem-
onstrating various potential applications. The incorporation
of graphene-based materials into cellulose has been carried
out mostly with cellulose solutions or cellulose suspensions.
The proposed applications include electrical conductor, anti-
static coating, biomimetic composites, and in energy conver-
sion and storage devices such as lithium sulphur batteries and
supercapacitors.
12.1 INTRODUCTION
12.1.1 Cellulose
Cellulose is probably the most abundant organic polymer on
Earth and it is considered as an almost inexhaustible source
for environmentally friendly and biocompatible products.
Biosphere production of cellulose is estimated to be around
90 × 109 metric tons per annum [1]. It is renewable, biode-
gradable and can be transformed to various useful materi-
als. It has been considered as a promising material to replace
petrochemical derived compounds in many uses, such as fab-
rication of films and fibers. Cellulose is the main structural
being up to 47%. It can also be produced by bacteria, which is
called bacterial cellulose (BC) or microbial cellulose.
Cellulose is a linear polymer whose each monomer unit
comprises two anhydroglucose rings ((C6H10O5)n; n = 10000–
15000, where n is varied depending on cellulose source)
joined via a β-1,4 glycosidic linkage (C-O-C) at the C1 and
C4 positions (Figure 12.1) [1,2]. Each glucose unit in cellu-
lose chain is rotated 180° with respect to its neighbor. One
cellulose chain has a reducing hemiacetal group at the C1
position and the other end has an alcoholic hydroxyl group at
the C4 position. In nature, cellulose chains are held strongly
together side-by-side by inter- and intra-hydrogen bonds
between hydroxyl groups on the glucose and oxygen atoms
on the same or on a neighbor chain, which forms cellulose
microfibrils of 15–50 nm in diameter and several microns in
length. This network of strong intra- and inter-chain hydro-
gen bonding makes cellulose a relatively stable polymer and
gives the cellulose fibrils high axial stiffness. These fibrils
constitute the main reinforcement phase for trees and plants.
However, the strong hydrogen bonding prevents cellulose
from being melted below its degradation temperature and
soluble in most common solvents. Various solvent systems
such as viscose method, Lyocell [3], and ionic liquids (ILs)

161
162
(a) 6
OH
OH
4 5 O
OH
2 O
OH
3 1 O cal lateral dimension of 5–20 nm and length of several tens
OH
n
OH
(b)
H H
O OH O high-pressure homogenizers which delaminate cell walls of
HO
O
O O
HO O
O
OH O HO
H H H early 1980s. This mechanical disintegration can be achieved
O OH O
HO
O O
O
O
O O
HO O cal disintegration can be facilitated either by acid hydrolysis
OH O HO
H [7] or enzymatic hydrolysis [8] which resulted in improved
FIGURE 12.1  (a) Chemical structure of cellulose chain and (b)
Inter- and intra-molecular hydrogen bonds in cellulose.
[4] have been developed to fabricate films, fibers, and plastics.
However, utilization of these solvents for cellulose dissolu-
tion has many problems which are either toxic or expensive
chemicals. For example, viscose process uses sodium disul-
fide which is a toxic chemical and whose by-products can
be harmful/dangerous to the environment. Whereas, ILs are
expensive, and in Lyocell process, the N-methylmorpholine
N-oxide (NMMO) solvent is flammable. To solve the men-
tioned problems, nanofibrillated cellulose (NFC) suspension
can be a good choice in some areas, for instance, food indus-
try and composite reinforcements. NFC is a cellulose mate-
rial whose nanosized-cellulose fibrils are stably suspended in
water, which was first introduced in the early 1980s [5]. These
processable celluloses, which have been used to prepare vari-
ous cellulose/graphene composites, are going to be discussed
in the following subsections.
12.1.1.1  Cellulose Solution
For more than 100 years, few tens of solvent systems have
been found to dissolve cellulose. However, there are only a
few of them that are commercialized successfully, including
CS2/NaOH (Visco rayon production) and NMMO (Lyocell
production). Recently, the discovery of ILs has opened up a
new way for cellulose dissolution and functionalization [4].
Many ILs have been considered as “green solvents” owing to
its non-toxic property. They are considered as powerful sol-
vents for cellulose dissolution. For example, a 25 wt% cel-
lulose solution has been successfully prepared using an IL
containing 1-butyl-3-methylimidazolium cations ([C4mim]+)
[4]. The regenerated cellulose after dissolving in ILs has
shown lower onset temperature decomposition and gives a
higher char yield in thermal analysis. The cellulose solutions
in ILs can be used as dispersing media for graphene, and sub-
sequently fabricated cellulose/graphene composites.
Graphene Science Handbook
12.1.1.2  Nanofibrillated Cellulose Suspension
NFC, which is also called microfibrillated cellulose, is a
O material composed of nanosized-cellulose fibrils with typi-
of nm to several microns. It is produced in form of suspen-
sion wherein low concentrations of cellulose nanofibrils are
suspended in water. NFC is usually called as nanocellulose
for simplicity. NFC suspension is produced from wood using
O the fibers and liberate nanosized fibrils. Extraction of nanocel-
O
lulose by direct mechanical disintegration of wood pulp was
OH
first reported by Herrick et al. [6] and Turbak et al. [5] in the
without chemical or enzymatic pretreatment, which, however,
requires a significant energy input. Meanwhile, mechani-
OH
product homogeneity and reduced energy consumption. Acid
hydrolysis usually lowers the molecular weight, resulting in
cellulose material with short fibrous structure and reduced
reinforcement ability. Contrarily, enzymatic treatment in
combination with mechanical shearing and high-pressure
homogenization is environmentally friendly process and the
obtained nanocellulose shows higher aspect ratio and stronger
gel network of cellulose fibers. Other chemical pretreatments
that should be mentioned here are carboxymethylation [9] and
TEMPO-mediated oxidation [10]. Specially, after the treat-
ment of cellulose in a controlled TEMPO-mediated oxidation,
the oxidized cellulose can be easily disintegrated into indi-
vidual microfibrils through a simple mechanical treatment.
Since then, significant advances have been made in utiliza-
tion of nanocellulose in various fields including food indus-
try, biotechnology, and composite materials. NFC has been
commercialized successfully by several companies, such as
Daicel (Japan), Rettenmaier (Germany), Innventia (Sweden),
and UPM-Kymmene Corporation (Finland). NFC can be used
to fabricate film or paper upon eliminating the water by vac-
uum filtration or casting.
12.1.1.3  Bacterial Cellulose
Some bacteria, such as Acetobacter xylinum are capable
of synthesizing cellulose containing ultra-long nanofibers
through a polymerization process in which glucose molecules
are converted into β-1,4-glucan chains. In static culture condi-
tion, bacteria can produce a thick gel or pellicle of cellulose
with interesting mechanical properties in wet state [11]. BC has
shown an excellent biocompatibility and therefore has found
a number of applications in paper, textile, and biomaterial in
cosmetics and medicine [12]. Moreover, this kind of cellulose
usually possesses higher crystallinity (up to 84%–89%) and
longer fibrous structure than those of plant-based cellulose,
which results in BC’s higher mechanical properties [13]. In
addition, BC contains no lignin and hemicelluloses and thus
no chemical treatment is needed to eliminate these chemi-
cals as in the case for plant cellulose. It is worth mentioning
that the BC has a very high wet mechanical strength, how-
ever, once it is dried, it is very brittle. Thus, several flexible
Preparation of Cellulose/Graphene Nanocomposites
polymers such as poly (vinyl alcohol) have been blended into
BC to increase the flexibility in dried state [14].
Cellulose itself has very strong mechanical properties; for
example, the theoretical Young’s modulus along the chain axis
of perfect native cellulose crystal has been calculated to be
167.5 GPa, which is higher than that of steel and similar to that
of Kevlar [15]. Moreover, there are many other characteristics
cellulose, such as transparency, biocompatibility, and chemical
reactivity of the hydroxyl functionality on large surface area of
nanostructured cellulose that make it a widely used material.
Cellulose in various forms including cellulose solutions, NFC
suspensions, bacterial cellulose, pulp, and filter papers has been
used for fabrication of cellulose/graphene nanocomposite mate-
rials. The reported cellulose/graphene composites have been uti-
lized in different applications, such as supercapacitor, antistatic
coating, conductor, and high-performance polymer composites.
12.1.2 Graphene
Graphene is one-atom thick layer of sp2-bonded carbon atoms
packed tightly into a two-dimensional (2D) honeycomb lat-
tice. It is the basic structural element of all other graphitic car-
bons. It can be wrapped up into 0 D fullerenes, stacked into
3D, and rolled into 1D carbon nanotubes (CNTs) [16]. Many
physical properties of graphene measured in experiments are
higher than those of any other materials. Table 12.1 presents
several important physical and mechanical properties of gra-
phene. These outstanding values make graphene very attrac-
tive materials for various applications ranging from electronic
devices to polymer composite applications.
Graphene, especially chemically functionalized graphene
material, has shown a great potential use in polymer com-
posites in which many properties of polymer can be signifi-
cantly improved, even with very small amount of graphene
loading [20]. Graphene can be produced through several ways
including bottom-up approach (chemical vapor deposition,
arc-discharge, epitaxial growth on silicon carbide, chemical
conversion, reduction of copper oxide, and unzipping CNTs)
and top-down (separation/exfoliation of graphite or graph-
ite derivatives such as graphite oxide, and graphite fluoride)
[21]. Currently, the most promising methods for large-scale
production of graphene material are based on graphite oxide,
which is obtained via the oxidation of graphite. Graphite
oxide can be easily exfoliated into graphene oxide (GO),
TABLE 12.1
Mechanical and Physical Properties of Graphene
Properties Values References
Mechanical properties [17]
  Tensile strength 0.5–1 Tpa
  Elastic modules 130 Gpa
Resistivity 10−6 Ω cm [18]
Electron mobility 2 × 105 cm2 V−1 s−1 [18]
Thermal conductivity 5000 W m−1 K−1 [19]
163
which is a single layer of graphite oxide, in water or organic
solvents with the assistance of sonication or mechanical stir-
ring. It should be addressed that graphite has an annual global
production of over 1.1 million tons and a relatively cheap price
in the order of 825 $/ton [21]. Thus production of graphene
from oxidized graphite could be an interesting and economi-
cal approach.
Despite the recent discovery of graphene in 2004 and
its growing interest for broad range of applications, graph-
ite oxide was first prepared over 150 years ago [23]. Later,
different modifications on production of graphite oxide were
reported by Staudenmaier [24] and Hummers [25]. In these
methods, graphite is oxidized using strong oxidants such as
KMnO4, KClO3, and NaNO3 that are dissolved in nitric acid
or sulfuric acid or their mixture. These methods usually pro-
duce oxidized graphite with an approximate C/O/H atomic
ratio of 2/1/0.8, which, however, depends strongly on the
reaction condition and graphite source. The precise chemical
structure of graphite oxide has been the subject of theoretical
and experimental studies over the years. The Lerf-Klinowski
model is probably the most widely accepted description of
graphite oxide structure (Figure 12.2), wherein the hydroxyl
and epoxy groups are found on the basal planes and car-
boxylic acid groups are located in the edges. Recent studies
have shown the presence of other functional groups of 5- and
6-membered lactols on the periphery of the graphitic plate-
lets and esters of tertiary alcohols on the surface [26,27]. On
account of the recently significant progress in polymer com-
posites using GO as graphene source, this chapter will focus
primarily on cellulose/graphene composites whose graphene
fillers are based on GO. Some other graphene-based filler for
cellulose composites such as graphene nanoplatelet (GNP)
and exfoliated graphite will also be presented.
12.2 PREPARATION OF CELLULOSE/
GRAPHENE NANOCOMPOSITES
The preparation of cellulose/graphene composites has been
recently obtained a significant progress in the field of polymer
nanocomposites, thanks to many advantages. First, cellulose is
abundantly available everywhere and many of its processable
forms such as NFC suspensions and cellulose solutions are
industrially available. Second, the utilization of graphite oxide
in the cellulose/graphene composites as the main graphene
precursor is highly promising because it can be large-scale
synthesized from graphite, an inexpensive commercial prod-
uct. Third, dispersing GO in cellulose media is facile due to the
fact that GO is readily dispersible in aqueous media. Finally,
cellulose and GO have strong interactions via hydrogen bonds
which are formed between polar hydroxyl groups in cellulose
and oxygen functionalities in GO. However, a main drawback
of using GO is that the reduced graphene oxide (RGO) has
lower electrical conductivity than pristine graphene.
Several processing techniques have been adopted for fabri-
cating cellulose/graphene composites with the idea of achiev-
ing uniform distribution of graphene and cellulose phases.
A common method to prepare cellulose/graphene composites
164
HOOC
HOOC
HOOC
HOOC
= —OH
FIGURE 12.2  Chemical structure of GO by Lerf-Klinowski model presenting the various oxygen functionalities on GO sheet. (Reprinted
with permission from Lerf, A. et  al. Structure of graphite oxide GO revisited. J. Phys. Chem. B 102(23):4477–4482. Copyright 2012
American Chemical Society.)
is based on GO. For example, GO is readily dispersible in
NFC suspension and many cellulose solutions in which GO
can be in situ reduced to conductive graphene consequently.
Another approach is that GO is first thermally or chemically
reduced to graphene and then it is dispersed in processable
cellulose. Chemical reduction of GO can be done by reduc-
ing agents such as hydrazine and ammonia [28]. Thermal
treatment of solid cellulose/GO composites is also an effec-
tive way to restore the sp2 structure of conductive graphene.
Thermal treatment is carried out via heating the solid film
containing GO at elevated temperature of several hundred
°C [29]; however, in this heating process, the volatile prod-
ucts may be released and trapped inside the composite films.
A combination of chemical reduction and thermal treatment
may be used to increase the electrical conductivity of the
composite. However, it has shown that most cellulose com-
posites filled with GO had improved mechanical properties
but usually they are electrically insulating. For the benefits
of readers and researchers, most of the studies available on
­cellulose/graphene composites are summarized in Tables 12.2
through 12.4. The different kinds of cellulose and graphene
materials which can be used in preparation of cellulose/gra-
phene composites are represented by Scheme 12.1.
12.2.1 NFC-Based Cellulose/Graphene Composites
There have been recently a few studies on combining NFC
and graphene to make cellulose/graphene composites, which
are carried out at Aalto University and VTT Research Center
in Finland. The NFC used by these research groups is pre-
pared by combining enzymatic hydrolysis treatment and
mechanical homogenization [8]. It should be addressed that
UPM-Kymmene Corporation (Finland) has successfully com-
mercialized this type of NFC. This developed method produces
highly entangled cellulose nanofibrils with high aspect ratio
of around 20–30 nm in diameters and several micrometers in
Graphene Science Handbook
COOH
COOH
COOH
COOH
COOH
= —O—
length. These graphene-containing cellulose composites have
shown a very high mechanical properties, which is due to the
synergistic effect of NFC and graphene (see Table 12.2).
Graphite oxide is commonly produced via Hummers’
method or its modifications in which a mixture of H2SO4,
KMnO4, and NaNO3 is used for the oxidization of natural
graphite [25]. Graphite oxide is then readily exfoliated in
water to form a stable suspension of individual and heav-
ily oxygenated GO sheets. Those sheets contain epoxy and
hydroxyl groups on the basal planes and carbonyl and car-
boxyl groups at the edges. The oxygen functionalities make
GO hydrophilic and create electrostatic repulsion and steric
hindrance to prevent the reaggregation of exfoliated GO in
water [20]. Aksay and his co-authors reported that thermal
treatment of graphite oxide at high temperature with high
heating rate could exfoliate graphite oxide into single layer
functionalized graphene which is electrically conductive [34].
In an attempt to form covalent bonding between NFC and
GO, our group has tried to introduce amine groups on NFC in
aqueous media using click chemistry. The amine functional-
ized NFC is called aminated NFC or ANFC [35]. The amine
groups in ANFC are supposed to react with epoxide func-
tionalities on GO basal planes via epoxide opening reaction
in which GO dispersion is mixed with ANFC suspension at
70°C in the presence of ammonia (pH is around 10). It was
seen that GO was uniformly dispersed in NFC suspension.
GO in this mixture was then chemically reduced by hydrazine
to form a conductive chemically RGO. Usually, the change in
the color of GO dispersion from yellow to black may be used
as an indicator of GO being reduced to graphene. In this reac-
tion, before adding hydrazine to the mixture, they added a
small amount of ammonia to adjust the pH to 10. The ammo-
nia molecules bound to RGO sheets and prevented them from
agglomeration. As a result, various stable ANFC/RGO sus-
pensions with RGO contents ranging between 0.1 to 10 wt%
were fabricated. These stable suspensions were then filtered
Preparation of Cellulose/Graphene Nanocomposites 165

TABLE 12.2
Cellulose/Graphene Nanocomposites Based on Nanofibrilated Cellulose
Composition of Potential
Composite Fabrication Process Mechanical Properties Other Properties Applications References
NFC/RGO GO exfoliated in water; adding Tensile strength (MPa) Electrical Electric conductor; [30]
(0.3–10 wt%) GO dispersion into NFC 0 wt%: 194 conductivity: Li-S batteries;
suspension; reduction of GO by 0.3 wt% RGO: 232 0.3 wt% RGO: antistatic coating;
hydrazine at 95°C for 2 h; 5 wt% RGO: 273 4.79 × 10−4 S m−1 composite
vacuum filtration of NFC/RGO Young’s modulus (GPa) 10 wt% RGO:
mixture; drying 0 wt%: 5.8 71.8 S m−1
0.3 wt% RGO: 6.4
NFC/diblock Natural graphite was exfoliated 1.25 wt% functionalized N/A Biomimetic [31]
protein-modified by tip sonicator in the presence graphene: composites
graphene of NFC and diblock protein Tensile strength (Mpa): 278
HFBI-DCBD; the mixture is Young’s modulus (GPa): 20.2
vacuum filtered; drying 65°C Toughness (kJ m−2) of 57.9
overnight
NFC/exfoliated Natural graphite is exfoliated by 1.25 wt% multilayer graphene: N/A Environmentally [32]
graphite tip sonicator in NFC; vacuum Tensile strength (Mpa): 351 green composite
filtration; drying Young’s modulus (GPa): 16.9
Work of fracture (MJ m−3): 22.3
Cellulose nanofiber/ GO exfoliated in water; CNF was N/A Capacitance: Solid-state flexible [33]
graphene prepared by TEMPO oxidation 207 F g−1 supercapacitor
(CNF/RGO) (CNF); preparation of CNF/ (PVA-H2SO4 gel
RGO hydrogel (GO was reduced electrolyte)
by vitamin C); CNF/RGO
aerogel was obtained from CNF/
RGO hydrogel after washing and
supercritical CO2 drying

to make ANFC/RGO conductive composite papers as shown
in Figure 12.3. Additionally, it was observed that after reduc-
tion of GO by hydrazine, the RGO remains dispersed in the
mixture for months. The fabricated ANFC/RGO composite
papers are very flexible and bendable.
Laaksonen et  al. [31] developed another way to prepare
multilayer graphene platelets and subsequently fabricate NFC/
graphene composite. In the study, natural graphite was exfoli-
ated while being dispersed in NFC suspension in the presence
of a diblock protein named HFBI-DCBD. The HFBI-DCBD
protein plays two roles wherein HFBI side of this protein is
capable of binding to NFC fibrils whereas the DCBD can
bind to graphene platelets. Thanks to this compatibilization,
no sedimentation was observed in the NFC/HFBI-DCBD/
multilayer graphene suspension, which is not the case when
diblock proteins were not used. The NFC/graphene compos-
ite was then fabricated via filtration and drying of the NFC/
exfoliated graphite/protein mixture. Moreover, in the dried
NFC/graphene composite paper, the aggregation of multilayer
graphene was observed when protein was not added to the sys-
tem, whereas in the composite incorporated with the protein,
no aggregation has been observed. However, in a simpler pro-
cedure, Malho et  al. [32] shows that graphite can be exfoli-
ated successfully in NFC suspension to create a stable NFC/
multilayer graphene suspension if the amount of mixture is
small enough. No additional stabilizer or surfactant was used.
The author stressed that the power of sonication power needed
to be controlled so that the NFC fibrils would not be broken
down, which will decrease the mechanical properties. NFC/
multilayer graphene composite papers with uniform dispersion
of graphene sheets and improved mechanical properties were
also prepared through vacuum filtration step. SEM (scanning
electron microscope) image taken at the cross-sectional sur-
face of a NFC/multilayer graphene composite paper having 50
wt% of graphene content was provided to show uniform distri-
bution of graphene sheets in NFC matrix (Figure 12.4).
Other nanocellulose can also be used to fabricate graphene
composite, for example, TEMPO-oxidized nanocellulose.
Recently, Gao et  al. [33] reported a preparation of porous
nanocellulose/graphene composite aerogel by supercritical
CO2 drying a TEMPO-oxidized cellulose/RGO hydrogel. In
general, fabrication of cellulose/graphene composites based
on NFC suspension is simple because no toxic or expensive
solvent for cellulose is used. Furthermore, it does not require
the regeneration step as in the case where cellulose solutions
are used. Thus, it is expected that cellulose/graphene com-
posites will continue to be developed using this methodol-
ogy. It should also be mentioned that the stable NFC/GO,
NFC/RGO, and NFC/exfoliated graphite mixture in dried
or suspension states may be used as reinforcements to fab-
ricate other polymer composites with improved mechanical,
thermal, and electrical properties.
166 Graphene Science Handbook

TABLE 12.3
Cellulose/Graphene Nanocomposites Based on Cellulose Solutions
Composition of Potential
Composite Fabrication Process Mechanical Properties Other Properties Applications References
BC/GO and BC/ • BC/GO composite: GO exfoliated in Tensile strength (MPa) Electrical conductivity: Composite [40]
RGO water; BC is dissolved in NaOH 0 wt% GO: 198 1 wt% RGO: 1.1 × 10−4 S m−1
solution; mixing GO dispersion and 1 wt% GO: 230
BC solution; vacuum filtration; drying 5 wt% GO: 242
• BC/RGO composite: BC/GO Young modulus (GPa)
suspension is prepared; reduction of 0 wt% GO: 1.5
GO by hydrazine (RGO); vacuum 1 wt% GO: 1.8
filtration of the mixture; drying 5 wt% GO: 1.7
Cellulose/GO GO exfoliated in NMMO; cellulose powder Tensile strength (Mpa) • Thermal stability (TGA): Composite [29]
is dissolved in NMMO/GO; casting the 0 wt% GO: 73.1 carbonaceous residue at
mixture; regeneration of the cellulose in 1 wt% GO: 84.2 0.25 wt% GO is
water bath for 4 days; drying; annealing at 5 wt% GO: 97.8 24.5 wt% while at 0% is
250°C for 30 min Young’s modulus (GPa) 20.5 wt%
0 wt% GO: 4.5 • Electrical conductivity:
1 wt% GO: 4.7 5 wt% GO with
5 wt% GO: 5.5 annealing: 10−4 S m−1
Cellulose/GO • GO exfoliated in cellulose solvent Young’s modulus: N/A Aerogel [41]
(NaOH/thiourea/H2O:9.5:4.5:86 wt%; 58.1 MPa (90%
storing at −10°C for 8 h) improved)
• Cellulose powder was added and Compression strength:
stirred at 3000 rpm for 5 min at 1.13 MPa (30%
ambient temperature improved)
• The mixture was store at ambient
temperature for 30 min for gelation/
solvent exchange and washing with
water/free-drying
Cellulose/graphite GO exfoliated in water; adding NaOH and Tensile strength (Mpa) • Thermal stability (TGA): Composite [39]
oxide urea; adding cellulose powder; freezing 2.5 wt% GO: 54.6 0 wt% GO: Ti = 210°C,
(0–7.5 wt%) and thawing; casting; regeneration of 7.5 wt% GO: 83.1 Tmax = 316°C, Tf = 366°C
cellulose in 5 wt% H2SO4 and then water; Young’s modulus (GPa) 7.5 wt% GO: Ti = 231°C,
drying 0 wt% GO: 1.19 Tmax = 340°C, Tf = 391°C
2.5 wt% GO: 1.28 • Water contact angle:
7.5 wt% GO: 1.91 0 wt% GO: 12.9°
7.5 wt% GO: 51.5°
Cellulose/ Cellulose powder dissolved in [Emim]Cl at 3 wt% graphene: • Thermal stability Composite [42]
graphene 80°C for 4 h; adding GNP and sonicating; Tensile strength: 34% • RC: T10 = 106.5,
nanoplatelet mixing; casting; regenerating in water higher T20 = 294.5, T80 = 434.5
(RC/GNP) bath; washing; drying Young’s modulus is 56% RC/GNP (5 wt%):
higher T10 = 275, T20 = 314.5,
T80 = 454.7
• Water contact angle:
RC/GNP (5 wt%) 57.12°
Cellulose/RGO GO exfoliated in water; adding [Bmim]Cl N/A • Electrical conductivity: Tissue [28]
(24 wt%) and sonicating; evaporating water; adding 24 wt% RGO: 3.2 S m−1 engineering
cellulose solution in [Bmim]Cl and • Water contact angle: scaffold
ammonia; heating to 80°C for 12 h Neat RGO paper: 81.6°
(RGO); precipitating cellulose/RGO by Cellulose/RGO
water; collecting by filtration; dispersing composite: 49.2°
in NaOH/thiourea aqueous solution; • Good biocompatibility
sonicating and collecting by
centrifugation; washing with DI water;
drying; vacuum filtration
Preparation of Cellulose/Graphene Nanocomposites 167

TABLE 12.4
Cellulose/Graphene Nanocomposites for Supercapacitors
Composition of Mechanical Potential
Composite Fabrication Process Properties Other Properties Applications References

Filter paper/TEGO GO exfoliated and reduced via thermal 7.5 wt%: • Electrical resistivity: 6 Ω cm Supercapacitor [44]
expansion, additionally reduced with Tensile strength • Capacitance 120 F g−1
hydrogen, and dispersed in NMP (TEGO); (MPa): 8.68 (in H2SO4-PVA gel electrolyte)
the incorporating TEGO into filter paper
via vacuum filtration; drying at 100°C
Cellulose pulp/ GO exfoliated and reduced by thermal 3.2 wt% RGO: • Electrical conductivity: Supercapacitor [52]
TEGO treatment at 1000°C in Ar for 1 h (TEGO); Tensile strength 11.6 S m−1
dispersing the TEGO in water/SDS (Mpa): 2.3 • Capacitance: 252 F g−1 (in
solution; adding cellulose pulp dispersion; Young’s modulus organic electrolyte, LiPF6)
mixing and vacuum filtrating the mixture; (GPa): 0.19
drying
Cotton cloth/RGO GO exfoliated by bath sonication; GO N/A • Electrical resistance: 225 Ω Supercapacitor [45]
dispersion was painted onto cotton fabric • Capacitance: 81.7 F g−1 (in
using brush-coating technique; drying at aqueous electrolyte, 6 M
150°C; annealing at 300°C for 2 h in Ar. KOH)
Xerox paper/ Drawing with a graphite pencil on Xerox N/A • Sheet resistance: 223 Ω ◻−1 Supercapacitor [57]
graphite rod paper; fabricating electrodes for • Capacitance:
supercapacitors based on the developed 23.1 F g−1 (aqueous electrolyte,
material. 1M H2SO4)
NFC/RGO Freeze-dried NFC/RGO was used as host N/A • Capacity over 1200 mAhg−1 Li-S batteries [30,58]
(30, 50, and matrix for sulfur to prepared electrode in for the best sample
70 wt%) the batteries.

Graphene make hydrogen bonds with both cellulose and GO, good dis-
Graphene oxide persion of GO in the cellulose solution is readily obtained.
Graphene nanoplatelets The cellulose/GO composite was then prepared through
Exfoliated graphite
1. Mixing casting-regeneration-drying process. Thermal treatment of
Cellulose/graphene
composites the cellulose/GO composite film at 250°C was carried out to
2. Chemical improve the material’s electrical conductivity. Han et al. [39]
Cellulose reduction, thermal
Nanocellulose treatment, or both used a mixture of 6 wt% of NaOH and 4 wt% of urea in water
Cellulose solutions as a solvent for cellulose dissolution. Here, graphite oxide was
Pulp
first exfoliated in water before adding NaOH/urea mixture
and cellulose. Casting, regenerating, and drying were subse-
SCHEME 12.1 Demonstrates the preparation of the quently carried out to fabricate cellulose/GO composite films
cellulose/graphene composites using different sources of from the developed cellulose/graphene/solvent mixture.
­graphene and cellulose materials. Room-temperature ILs have been recently used as a good
solvent for cellulose dissolution. The ILs offer many strong
12.2.2 Cellulose Solution-Based Cellulose/ points, such as good chemical and thermal stability, low flam-
mability, and no volatile chemicals emitted into the atmo-
Graphene Composites
sphere due to the liquids’ non-measurable vapor pressure.
Many cellulose/graphene composites have been prepared Mahmuodian et  al. [42] used 1-ethyl-3-methylimidazolium
wherein cellulose solutions were used as dispersing media for acetate ([Emim]Ac) as solvent to prepare cellulose solution
graphene fillers (Table 12.3). The combinations of graphene using microcrystalline cellulose powder. A dispersion of
and cellulose have been successfully carried out in a variety graphene nanoplatelets (GNPs) in the same solvent was pre-
of solvents, such as NMMO, ILs, and NaOH-urea system. pared, and then mixed with the above cellulose solution. The
It should be noted that the cellulose-solvent systems have obtained cellulose/GNPs solution was casted, regenerated,
been used to prepare cellulose/CNT composites [36–38]. In and dried to fabricate cellulose/graphene composite film with
a study by Kim et al. [29], graphite oxide was first exfoliated improved gas barrier properties. In a more complicated pro-
in NMMO which was also the solvent for cellulose. Cellulose cedure that was developed by Wang et al. [43], GO dispersion
powder was then dissolved in the NMMO/GO system. It has in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) was
been reported that NMMO is an excellent dispersing agent mixed with cellulose solution in the same solvent. The mix-
for GO and a good solvent for cellulose. Because NMMO can ture was regenerated, ground, and washed away from [Bmim]
168 Graphene Science Handbook

(a) (b) 0.3 wt% 1 wt% NFC

5 wt% 10 wt% A-NFC

GO A-NFC/RGO
suspension suspension
(10 wt% of RGO)

FIGURE 12.3  (a) Optical pictures of GO and ANFC/RGO suspensions. (b) Optical pictures of NFC, ANFC, and ANFC/RGO com-
posite papers containing 0.3, 1, 5, and 10 wt% of RGO loadings. (Luong, N. D. et al. 2011. Graphene/cellulose nanocomposite paper
with high electrical and mechanical performances. J. Mater. Chem. 21:13991–13998. Reproduced by permission of The Royal Society
of Chemistry.)

(a) (b)

5 μm 5 μm

FIGURE 12.4  (a) Cross-sectional SEM image of a pure NFC-nanopaper film. (b) Cross-sectional SEM image of graphene/NFC nano-
composite with 50 wt% graphene multilayers. (Reprinted with permission from Malho, J.-M et  al. Facile method for stiff, tough, and
strong nanocomposites by direct exfoliation of multilayered graphene into native nanocellulose matrix. Biomacromolecules 13:1093–1099.
Copyright 2012 American Chemical Society.)

Cl by centrifugation. The dried powder was redissolved in the
IL and the solution was casted and regenerated for cellulose/
GO composite films.
12.2.3 Other Cellulose-Based Cellulose/
Graphene Composites
Cellulose/graphene composites which have been fabricated
using other celluloses such as cellulose pulp, cotton cellulose,
and filter cellulose paper are discussed in this section. Weng
et  al. [44] prepared a porous cellulose/graphene composite
where graphene nanosheets (GNSs) cover cellulose fibers of
a cellulose filter paper, forming a conductive interwoven net-
work. In this procedure, GNSs, produced by thermal expansion
and hydrogen reduction of graphite oxide, were incorporated
into the cellulose macroporous texture of via filtration of GNS
suspension through a filter paper. The cellulose fiber surfaces
and the voids of the filter paper were then fully covered and
filled by these GNSs. The GNSs are bound to cellulose fibers
via electrostatic interaction. The good adhesion was seen
when the composite was bended and no detachment was
observed. This graphene-containing composite structure was
used to fabricate supercapacitor electrodes exhibiting high
capacitance and good capacitance stability.
Cotton cloth is a flexible and porous type of fabric which
has a hierarchical network made of natural cotton fibers with
abundant hydroxyl groups. Owing to the advantages of these
cellulose materials, interesting porous cellulose/graphene
composites have been developed in which GO dispersion was
used as ink to pain on the cotton cloth with a brush. Brush-
coating and drying steps were repeated to increase the amount
of GO content absorbed, through which the GO-coating cotton
Preparation of Cellulose/Graphene Nanocomposites
cloth was then transformed into a conductive fabric with the
help of the annealing at 300°C for 2 h in argon atmosphere
[45]. The mentioned porous cellulose/graphene composites
have been used in supercapacitor electrodes (see Section
12.3.4) showing good capacitance and performance stability.
In another study, hydrophilic cotton cloth surface was coated
with graphene to make a superhydrophobic and electroconduc-
tive textile [46]. The incorporation of GO in cotton cloth was
carried out by immersing the cellulose cotton cloth in GO dis-
persion which was followed by drying. The immersing/drying
was repeated to increase the amount of GO in the composite.
The GO was reduced to graphene using ascorbic acid. The
surface of cotton/GO composite was additionally coated with
polymethyltrichlorosilane through in situ polymerization of
methyltrichlorosilane to increase the hydrophobicity and adhe-
sion between graphene and cotton. Improved hydrophobicity
of cellulose/graphene composites have also reported for some
other cellulose/graphene systems. For example, a cellulose/
graphene composite showed higher contact angle on addition
of graphene nanoplatelets [42]. It is showed that an addition of
5 wt% of graphene nanoplatelets increases the water contact
angle to 57.12° from 38.3° for neat cellulose [42]. The improve-
ment in hydrophobicity was reported for cellulose composite
incorporated with GO by Han et al. [39] in which water contact
angle was measured to be 51.5° for the cellulose/GO while the
neat cellulose showed a contact angle of only 12.9°.
12.3 PROPERTIES OF CELLULOSE/
GRAPHENE NANOCOMPOSITES AND
THEIR POTENTIAL APPLICATIONS
Combinations of graphene and various forms of cellulose
have created many interesting properties for the cellulose/gra-
phene composites. Among them, mechanical, thermal, elec-
trical, and rheological enhancements are the most prominent
characteristics. These properties and potential applications
are presented in Tables 12.2 through 12.4.
12.3.1 Mechanical Properties
The excellent stiffness (1 TPa) and tensile strength (130 GPa)
of graphene, make it an interesting reinforcement for strength-
ening and stiffening of polymer matrixes [47]. The mechani-
cal properties of polymer composites depend mostly on how
well they are dispersed and how strong interaction between the
graphene and cellulose is. That explains why reinforcement
additives that have strong interaction with the polymer matrix
are widely used to enhance mechanical properties of poly-
mer materials. The uniform dispersion is to maintain uniform
properties throughout the composite. The interfacial bonding
is responsible for effective loading transfer from the matrix to
the reinforcement which is commonly the stronger and stiffer
phase in the composite. Thus, molecular-level dispersion of
individual graphene sheets in cellulose and/or strong binding
between them, especially through covalent bonding, could sig-
nificantly improve the mechanical performances of cellulose/
graphene nanocomposites. In cellulose/graphene composites,
169
strong hydrogen bonding between oxygen-functionalized gra-
phene and cellulose would allow excellent loading transfer
leading to the enhancement in mechanical properties.
As a two-dimensional material, graphene has a large sur-
face area, high aspect ratio and wrinkled surface structure,
which allow more contacts between cellulose and graphene
sheets. Many studies in this area have proved clearly that the
incorporation of graphene usually increases not only Young’s
modulus but also the ultimate tensile strength. It has been
shown that these enhancements in mechanical properties of
graphene-incorporated materials are more significant com-
pared with those of CNTs incorporated materials like the
case of epoxy/graphene and epoxy/SWCNT composites [48].
Rafiee et al. reported that graphene-containing epoxy shows
higher tensile strength, elastic modulus, fracture toughness,
and fracture energy than the SWCNT-containing composite
at 0.1 wt% of filler loading. The higher mechanical properties
are explained by stronger interfacial bonding between poly-
mer and graphene, which is due to the high aspect ratio and
wrinkled surface structure of graphene sheets.
In our study [30], we have shown that the incorporating GO
into ANFC followed by chemical reduction of GO produces
ANFC/RGO composite paper with dramatic improvement in
both tensile strength and Young’s modulus and, interestingly,
without any lose in strain at break [30]. For example, at 0.3 wt%
of graphene loading, the composite gained a tensile strength of
232 MPa, which was much higher than the value of 198 MPa
of neat NFC paper. Remarkably, when graphene content was
up to 5 wt%, tensile strength was around 273 MPa, which is
1.4 fold higher than that of neat cellulose paper. Malho et al.
[32] also studied the NFC/graphene composite and showed
the improvement in mechanical properties by tensile test. The
composite paper with 1.25 wt% of graphene shows a superior
combination of stiffness, toughness, and strength, which are
increased by 50%, 18%, and 22%, respectively.
Significant enhancements in mechanical properties have
been observed in NFC/graphene composite paper in which
diblock protein was used as a binding agent between NFC and
graphene phases. Measured via tensile testing, Young’s modu-
lus (YM), ultimate tensile strength (UTS) and work of fracture
(WOF) of the composites are improved significantly [31]. The
binding capability of bifunctional HFBI-DCBD protein in NFC/
graphene nanocomposites was more effective than that of the
wild-type HFBI. The composite containing HFBI-DCBD pro-
teins and 1.25 wt% of graphene possesses YM, UTS, and WOF
of 20.2 GPa, 278 MPa, and 57.9 kJ m−2, respectively, whereas
the composite containing HFBI has much lower mechanical
properties with YM of 12.2 GPa and UTS of 73 MPa. It should
be noted that the NFC/graphene composites mentioned earlier
have mechanical properties that do not follow the common rule
of mixture for composites, but demonstrates a synergetic per-
formance at optimum composition instead.
Wang et  al. discussed the differences in morphology
between two cellulose/graphene composites made with the
help of two solvents, which are NaOH-H2O and IL [43]. The
use of NaOH-H2O solvent in the preparation led to formation
of a porous cellulose composite, while the use of IL created a
170 Graphene Science Handbook

material with high density and homogeneous structure of the
graphene-containing cellulose film. Owing to this reason, opti-
mal GO loading content in the composite for mechanical rein-
forcement was very different in these two cases which were
0.5 and 4 wt% for the cellulose regenerated in NaOH-H2O
and IL, respectively [43]. Zhang et  al. reported a cellulose/
GO composite aerogel with improved mechanical properties.
The composite aerogel containing 0.1 wt% of GO gained com-
pression strength and Young’s modulus by about 30 and 90%
compared to those of neat cellulose aerogels, respectively [41].
These enhancements were due to strong interaction between
GO and cellulose which was explained by rheology data. Han
et al. [39] discussed the improvement of storage modulus (E′)
of BC composite with the addition of GO in DMA measure-
ment. Significant result was that the incorporation of GO in
BC not only increased the E’ at normal temperature (25°C) but
also at high temperature condition (up to 180°C).
12.3.2 Electrical Conductivity
The incorporation of an electric phase into a cellulose paper
can make the material electrically conductive, which may be
applicable in various fields, for example, antistatic packages,
electromagnetic shielding, electrodes, and sensors. Many
kinds of conductive carbon-based fillers have been used to
make cellulose paper conductive, such as carbon black, carbon
fibers, CNTs, and graphenes. For example, dispersing CNTs
into cellulose papers or imprinting them as conductive lay-
ers has generated conductive cellulose/CNTs composites with
good performance when used in supercapacitor and interfer-
ence shielding applications [49–51]. However, agglomerated
CNTs are difficult to disperse due to their Van der Waals
forces, so it requires a large amount of CNTs to introduce
electric connection into the cellulose paper at the sacrifice
of the paper’s mechanical properties. In contrary, functional-
ized graphene such as GO can be easily dispersed in cellulose
matrix. It should also be addressed that graphene sheets have
a very large surface area and high aspect ratio, which makes
the particle-particle connection in graphene sheets stronger
than that in CNTs. For example, the electrically conductive
cellulose/graphene composite papers made in our group pos-
sess a low percolation threshold value for electrical conductiv-
ity of around 0.3 wt% of graphene loading [30].
GO is insulating or has very low electrical conductivity
depending on its oxidation level, which depends on the oxi-
dation condition. Chemical reduction or thermal treatment
of GO or combination of both are effective in restoring the
conjugated graphitic structure and subsequently increase the
electrical conductivity of the reduced GO-incorporated mate-
rials. The effectiveness of the reduction reaction can be evalu-
ated by x-ray photoelectron spectroscopy (XPS) which is used
to collect information about chemical composition of the sam-
ple’s surfaces. For example, XPS analysis was conducted for
ANFC/RGO composite paper shown in Figure 12.5 [30]. After

(a) × 101 (b) × 102 (c) × 103

40
N1s HiRes XPS C1s HiRes XPS O1s HiRes XPS

160

160
32

140

120
24
Intensity (cps)

RGO/A-NFC
120

80 16
GO/A-NFC
100

A-NFC paper 40
80 8
O-C-O

GO paper
C-O

C-C

60
412 408 404 400 396 296 292 288 284 280 540 536 532 528
Binding energy (eV)

FIGURE 12.5  (a) N1s, (b) C1s, and (c) O1s XPS results for GO, ANFC, ANFC/GO and its reduced form ANFC/RGO composite papers
using 50/50 weight ratio of ANFC/GO composition. (Luong, N. D. et al. 2011. Graphene/cellulose nanocomposite paper with high electrical
and mechanical performances. J. Mater. Chem. 21:13991–13998. Reproduced by permission of The Royal Society of Chemistry.)
Preparation of Cellulose/Graphene Nanocomposites
chemical reduction with hydrazine, the C1s band of ANFC/
RGO composite with 50/50 ratio shows a much stronger C-C
signal compared to that of the ANFC/GO. Meanwhile, the
C-O peak, which is the main feature of ANFC/GO com-
posite, is clearly reduced. Indirect evidence of GO being
reduced to graphene in cellulose composite is the increase in
electrical conductivity of the cellulose/graphene composite
compared to that of the composite containing non-reduced
GO. At around 0.3 wt% of RGO content, the ANFC/RGO
composite paper possess a low percolation threshold and
electrical conductivity of 5 × 10−4 S m−1, which is well above
the antistatic value. In NFC/exfoliated graphite compos-
ites developed by Laaksonen et al. and Malho et al. [31,32],
however, electrical conductivity of the composites was not
reported.
In another study, an electrical conductivity of 3.2 S m−1
was found a flexible cellulose/RGO composite containing 24
wt% of RGO [28]. Meanwhile, Kang et  al. [52] studied the
electrical conductivity of cellulose/graphene prepared from
pulp and thermally reduced graphene oxide (TEGO). They
obtained a high conductivity of 11.6 S m−1 for the composite
containing 3.2 wt% TEGO, which is much higher than that of
a cellulose/CNT composite with a very high CNT content of
35 wt%.
12.3.3 Interaction of GO and Cellulose
by Rheology Study
Rheology analysis helps to provide information of how well
the dispersion of a component in the mixture is and how
the components interact with each other. The information is
used to predict the processability and properties of materi-
als. For example, incorporation of an additive that has strong
interaction with the matrix may result in the improvement of
mechanical properties of the composite. Till now, there have
been several studies on the rheological properties of cellulose/
GO mixture, which could provide information on possible
interactions between them.
Zhang et al. [41] studied the interaction between GO and
cellulose in a cellulose/GO solution which was created via
dispersing GO in cellulose solution in a NaOH/thiourea/water
solvent system. They observed that the addition of GO sheets
to cellulose solution could lead to the gelation of cellulose
solution, revealing the existence of strong physical interac-
tion between GO and cellulose chains. With an addition of 0.1
wt% of GO into 10 wt% cellulose solution in NaOH/thiourea/
water solvent, the mixture became gel after 20 min compared
to 1h taken for the neat cellulose solution to gel (Figure 12.6).
Differential scanning calorimetry analysis shows that the
sol–gel transition temperature of the mixture containing 0.1
wt% GO was almost 20°C lower than the cellulose solution.
Rheological measurement for the gelation process at 50°C
and the sol–gel transition shows that the storage modulus (G′)
and loss modulus (G″) are significantly larger than the neat
cellulose solution. These values may indicate stronger inter-
molecular interaction and more entanglement of cellulose
chains in the system containing GO sheets.
171
(a) (b)
FIGURE 12.6  Digital pictures of gelation process of cellulose/GO
dispersion (black) and cellulose solution (white) standing at room
temperature for 20 min (a) and for 1 h (b). (Reprinted with permis-
sion from Zhang, J. et al. Graphene-oxide-sheet-induced gelation of
cellulose and promoted mechanical properties of composite aero-
gels. J. Phys. Chem. C 116:8063–8068. Copyright 2012 American
Chemical Society.)
Rheology measurement has been applied for cellulose/GO
mixture with cellulose being dissolved in NMMO [29]. In this
study, the interaction between cellulose and GO was stud-
ied using a Brookfield viscosity and dynamic viscometer. It
clearly shows that by the addition of GO in cellulose solution,
the viscosity increases significantly even at low loading of
0.25 wt% of GO. In addition, the dynamic rheological prop-
erties demonstrate that the storage modulus (G′) is increased
more than the loss modulus (G″) when GO was added, which
also reflect an increase in elasticity. Besides, the Newtonian
plateau region in complex viscosity (η*) decreases as the GO
content increases, and this behavior may indicate that the
large-scale polymer relaxations in the dope are restrained by
the hydrogen bonds between cellulose and GO sheets [29].
However, till now there has been no study on rheology of
NFC/graphene suspension. It is believed that the rheology
characteristic is very useful parameter in fabricating NFC/
graphene nanostructured materials including films, papers,
and porous forms.
12.3.4 Thermal Properties
Thermal stability of cellulose materials has been improved
by the incorporation of graphene fillers. Thermal gravimet-
ric analysis (TGA) has been used to characterize the thermal
stability of cellulose/graphene composites by comparing the
thermal degradation temperature at different weight losses.
For example, T10 (temperature at 10% weight loss) of cellu-
lose was 106.5°C, while it increased to around 270°C for the
composite containing 1, 3, and 5 wt% of graphene contents.
T20 (temperature at 20% weight loss) increased about 20°C for
the composite containing 5 wt% of graphene as seen, when
the TGA analysis was conducted in oxygen environment with
heating rate of 10°C/min. Furthermore, it is also recognized
that with the incorporation of graphene, the char content of
the composite (at 650°C) is higher than that of neat cellulose
[42]. Improvements in thermal properties are also observed
when GO was incorporated into cellulose as reported by Han
et al. [39]. The composite shows improved thermal stability
172
compared with the neat cellulose film. Thermal properties
were analyzed in air demonstrated that the initial decomposi-
tion temperature (Tid) and maximum decomposition tempera-
ture (Tmax) of the neat cellulose were increased from 210°C
and 316°C to 231°C and 340°C for the composite with 3
wt% of GO, respectively. The enhancement in properties is
explained by the good compatibility between the two com-
ponents, which were supported by SEM and FTIR (fourier
transform infrared spectroscopy) studies. Furthermore, the
good compatibility is believed to be due to hydrogen bonding
interaction between the components. In contrary, Wang et al.
[43] observed a lower thermal decomposition temperature at
large weight loss of GO-containing cellulose composite when
compared to that of the neat cellulose.
12.3.5 Cellulose/Graphene Composite for
Supercapacitors and Lithium-Sulfur Batteries
Among various energy storage systems, supercapacitor finds
many attractive applications in consumer ordinary and future
flexible and transparent electronic device, thanks to its higher
power energy density, fast rate of charge-discharge, long-term
operation stability, and safety [45]. The introduction of super-
capacitors based on cellulose/carbonaceous composite gives
the opportunity for novel applications such as flexible and
transparent electronics. Carbonaceous materials such as CNTs
and activated carbon have been used for supercapacitor elec-
trodes. A supercapacitor based on a CNT-incorporating paper
showed excellent performance with a specific capacitance of
200 F g−1 and a specific energy of 30–47 Wh kg−1 (only CNT
mass is considered in these calculated values) [49]. Pushparaj
et  al. [53] fabricated a mechanically flexible energy storage
device, in which the electrodes were made of nanoporous cel-
lulose paper with aligned CNTs. A supercapacitor based on
this cellulose/CNT composite gained specific capacitances
of 36 F g−1 and 22 F g−1 when it was operated with potassium
hydroxide solution and room-temperature IL as electrolytes,
respectively.
Recently, graphene has been considered as a good candi-
date for this type of application because of its high electron
mobility, chemical and thermal stability, large surface area,
and excellent electrochemical performance over a wide range
of voltage scan rates [54]. It has been reported that the intrinsic
capacitance of graphene was 21 µF cm−2, which is the highest
value among carbon-based materials [55]. Xu et al. [56] dis-
cussed the use of graphene and GO as the electrode materials
for supercapacitors and surprisingly found that GO could be a
better choice than graphene. Capacitance values of 189 F g−1
and 165 F g−1 have been obtained for supercapacitors based
on graphene and GO, respectively. The higher capacitance of
GO-based supercapacitor was explained due to an additional
pseudo-capacitance effect of attached oxygen functionalities
on the basal planes. The incorporation of various graphene
forms such as chemically reduced GO and thermally reduced
GO into cellulose porous materials resulted in high capacitive
materials for supercapacitors [44,45,52]. The porous cellulose
Graphene Science Handbook
materials can be cotton cloth [45], filter paper [44] and pulp
[52]. However, till now there has been no report on utilization
of cellulose/GO composite as electrode in supercapacitor.
In an attempt to fabricate supercapacitor based on cellu-
lose/graphene composite, Weng et  al. [44] used a cellulose/
graphene composite which is prepared by an incorporation of
RGO sheets into cellulose filter paper. The developed super-
capacitor possess a high capacitance per geometric area of
81 mF cm−2, which is equivalent to a capacitance of 120 F g−1
for graphene. In addition to its high capacitance, the perfor-
mance retained almost 99% after 5000 cycles. In another
work, the authors used a cellulose/graphene composite fab-
ricated from pulp and TEGO to prepare electrodes in super-
capacitor, a very impressive capacitance of 252 F g−1 has been
obtained [52]. Liu et  al. [45] reported a smaller capacitance
of 81.7 F g−1 for RGO-containing cotton fabric, which was
measured in aqueous electrolyte. However, it was noted that
the capacitance was decreased to around 40 F g−1 when scan
rate in the test was 100 m V s−1. It could be of great inter-
est if there is any study that compares capacitance of RGO-
incorporating and TEGO-incorporating celluloses when they
are used in supercapacitor. Recently, Gao et al. [33] fabricated
a solid-state flexible capacitor based on cellulose nanofiber
(CNF)-RGO aerogel. This supercapacitor exhibited a very
good capacitance of 207 F g−1 in PVA-H2SO4 gel electrolyte.
In a simple approach, Zheng et al. [57] demonstrated that
drawing a graphite pencil on a xerox paper resulting in a con-
ductive cellulose/multilayer graphene composite paper, which
can be used as electrodes in supercapacitor. Although, graph-
ite was not exfoliated to graphene sheets, a good capacitance
of 12 F g−1 was measured for the supercapacitor based on this
composite. In addition, after 15 000 cycles of testing, almost
90% of capacitance was remained.
The high capacitance and excellent performance stability
of cellulose/graphene composite-based supercapacitor were
possibly due to the combination of macroporous texture and
high strength of cellulose paper and the good electrical con-
ductivity and electroactivity of GNSs. It should be addressed
that these graphene-based electrodes are flexible and thus it
may be used to developed bendable electronic devices. The
utilization of cellulose/graphene composite in supercapacitor
is summarized in Table 12.4.
Additionally, to the use in supercapacitors, cellulose/­
graphene has been used in lithium-sulfur (Li-S) batteries
as demonstrated by us [58,59]. In this study, NFC/graphene
porous structure has been used effectively as host matrix for
sulfur impregnation in (Li-S) batteries. It has been shown that
the use of NFC/graphene as host matrix for sulfur prevents the
opening of graphene sheets and thus lowering the diffusion of
lithium polysulfides into the electrolyte during battery opera-
tion. As a result, it enables a long cycle life.
12.4  SUMMARY AND CONCLUDING REMARKS
The advances in development of cellulose/graphene nanocom-
posites have implied a great potential applications of the mate-
rials in several fields, such as antistatic coatings, eco-friendly
Preparation of Cellulose/Graphene Nanocomposites
composites, electric conductors, and supercapacitors. Graphene
materials have proved to be great nanofillers in cellulose com-
posites. Graphene’s rough and winkled surface can interlock
well with the surrounding matrix and thus improving the load
transfer. Furthermore, its large surface area helps to increase
the contact with the matrix. Most of the studies so far have been
relied on GO as the main graphene source, which is probably
due to the readily dispersible capability of GO in processing
media. Additionally, thanks to its oxygen rich functionalities
(hydroxyl, epoxy, and carboxyl groups), it can therefore form
strong adhesion with the cellulose matrix through hydrogen
bonding. This strong bonding enables significant enhance-
ments in mechanical properties, which is a critical issue in
high-performance polymer composites. Another advance is the
use of the cellulose/graphene composite to fabricate electrodes
in supercapacitors, which have been shown to be promising
devices for flexible electronics. It should be strongly addressed
that, unlike CNTs, GO does not need any stabilizer when it
used in preparation of cellulose/graphene composites.
However, it is clear that there are other advantages of gra-
phene materials that have not been yet investigated and charac-
terized. High thermal conductivity and very low and negative
coefficient of thermal expansion of graphene can make cellu-
lose/graphene composites useful in thermal management. The
lubricating property of graphene should be researched for cel-
lulose/graphene composites. Flammability of cellulose/gra-
phene composites is also needed to be determined. Cellulose/
graphene composites may be used as biomaterials such as
tissue engineering scaffolds [28]. Transparent and conductive
cellulose/graphene film could be made if TEMPO-oxidized
nanocellulose is used as in the case with CNT [60]. Last, but
not least, stable cellulose/graphene suspension could have
potential to be used as conductive ink.
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 13 Straightforward Routes for the
Preparation of Graphene-Based
Polymer Nanocomposites
Giulio Malucelli and Alberto Mariani

CONTENTS
Abstract.......................................................................................................................................................................................175
13.1 Methods for Obtaining Exfoliated Graphene from Graphite: An Overview....................................................................176
13.2 ​Polymer–Graphene Nanocomposites............................................................................................................................... 180
13.2.1 Graphene Nanocomposites Using Thermoplastic Matrices................................................................................. 180
13.2.1.1 Polyethylene: Graphene Nanocomposites........................................................................................... 180
13.2.1.2 Polypropylene–Graphene Nanocomposites......................................................................................... 182
13.2.1.3 ​Polycarbonate–Graphene Nanocomposites......................................................................................... 182
13.2.1.4 Poly(Vinyl Acetate)–Graphene Nanocomposites................................................................................ 182
13.2.1.5 Poly(Vinyl Alcohol)–Graphene Nanocomposites............................................................................... 182
13.2.1.6 Polystyrene–Graphene Nanocomposites............................................................................................. 183
13.2.1.7 ​Poly(Lactic Acid)–Graphene Nanocomposites................................................................................... 183
13.2.1.8 ​Polyurethane–Graphene Nanocomposites.......................................................................................... 183
13.2.1.9 Poly(Etherimide)–Graphene Nanocomposites.................................................................................... 183
13.2.1.10 Liquid Crystalline Polymer–Graphene Nanocomposites.................................................................... 183
13.2.1.11 Polyaniline–Graphene Nanocomposites............................................................................................. 184
13.2.1.12 Polypyrrole–Graphene Nanocomposites............................................................................................. 184
13.2.1.13 Poly(Ethylenedioxythiophene)–Graphene Nanocomposites............................................................... 184
13.2.1.14 Poly(Ethylene Terephthalate)–Graphene Nanocomposites................................................................. 184
13.2.1.15 Chitosan–Graphene Nanocomposites................................................................................................. 185
13.2.2 ​Graphene Nanocomposites Using Thermosetting Matrices................................................................................. 185
13.2.2.1 Epoxy–Graphene Nanocomposites..................................................................................................... 185
13.2.2.2 Hydrogel–Graphene Nanocomposites................................................................................................. 186
13.2.2.3 Polyacrylate–Graphene Nanocomposites............................................................................................ 187
13.2.2.4 ​PUR–Graphene Nanocomposites........................................................................................................ 187
13.2.2.5 ​Elastomers–Graphene Nanocomposites.............................................................................................. 187
13.3 ​Conclusions....................................................................................................................................................................... 187
References.................................................................................................................................................................................. 187

ABSTRACT obtained through direct sonication, milling, or thermal expan-

This chapter is aimed at reviewing the state of the art related
to the preparation of polymer nanocomposites having tun-
able graphene loadings and summarizing their main distinct
features. The current open literature describes several types
of so-called “graphene,” which differ in the processes used
to obtain it, namely: expansion, exfoliation, functionaliza-
tion, oxidation, oxidation/reduction, etc. Thus, very often it
becomes quite difficult to discriminate among the different
“graphene products” and to avoid any misunderstanding:
indeed, as an example, the use of reduced graphene oxide
instead of “graphene” can influence the overall final prop-
erties of the polymer material, to which the nanofiller is
added, in a very different way with respect to the “graphene”
sion. Among the up-to-date methods exploited for obtaining
and utilizing this nanofiller in nanocomposite fabrication, the
direct sonication from colloidal suspensions of graphite and
the use of graphene nanoplatelets (GNP) (defined as graphene
mono- or few layers, possibly bearing some functional groups
attached to the carbon structure) are the most convenient in
terms of cost and simplicity; they differ as far as the purity
and the presence of process-induced defects are concerned.
The former method involves a simple protocol based on low-
energy consumption and high volume production and allows
obtaining graphene substantially without any defect. In addi-
tion, such a nanofiller, obtained by direct exfoliation (i.e.,
without any chemical oxidation and subsequent reduction) in
175
176
suitable common solvents, surfactants, or monomers to even-
tually polymerize, can be used for the preparation of both
thermoplastic and thermoset polymer nanocomposites. GNP
can be obtained by exploiting different exfoliation processes
(i.e., milling, sonication, thermal expansion, etc.), usually in
the presence of chemically reactive compounds that are used
for the functionalization of the nanofiller. Nowadays, they
represent the most used type of “graphene” existing in the
market. However, it will be shown that, despite their avail-
ability, they should be used with caution in that they can
hardly be considered “real graphene,” because of the number
of defects induced by the fabrication process still remaining
in the structure.
The first part of the chapter summarizes the main meth-
ods for obtaining graphene, showing the advantages and
drawbacks. In the second part, the morphology, as well as
the thermal, physico-mechanical, electrical, and rheological
peculiarities of the obtained nanocomposite materials based
either on graphene from direct sonication of colloidal suspen-
sions of graphite or GNP are reviewed in detail.
13.1 METHODS FOR OBTAINING
EXFOLIATED GRAPHENE FROM
GRAPHITE: AN OVERVIEW
The use of graphite has been especially and largely used in
many artistic applications and for writing for a long time.
However, its structure was revealed in detail only during the
last century by means of x-ray crystallography.1
Graphite is characterized by a crystalline structure derived
by the ordered stacking of a large number of carbon layers
having a thickness of one atom (ca. 0.35 nm), each of them
being called graphene.2,3
Any graphene sheet is a large macromolecule constituted
of sp2-hybridized carbon atoms organized in a planar honey-
comb structure made of condensed six-term aromatic rings.
Although several theoretical studies carried out on gra-
phene suggested that this material could not exist in this form
but must be aggregated as graphite,4,5 this assumption was
disproved in recent years: in particular, the most important
work in this respect was published in 2004 by Novoselov and
Geim, who obtained single graphene layers by micromechan-
ical cleavage of graphite, using common scotch tape.6 This
finding resulted in a huge amount of papers devoted to gra-
phene and its applications that were published immediately
after. The importance of such a discovery was adequately rec-
ognized in 2010 when Novoselov and Geim were awarded the
Nobel Prize in physics.
Graphene was found to exhibit unusual electronic proper-
ties and seemed to be an ideal material in many advanced
fields.3 Indeed, it is one of the strongest materials ever discov-
ered: its outstanding properties include high values of Young’s
modulus (~1100 GPa), fracture strength (125 GPa),7 thermal
conductivity (~5000 W m−1 K−1),8 mobility of charge carriers
(200,000 cm2 V−1 s−1),9 and specific surface area (calculated
value: 2630 m2 g−1),10 plus fascinating transport phenomena
such as the quantum Hall effect.11
Graphene Science Handbook
Apart from the preparation of polymer nanocompos-
ites, which will be discussed in detail below, graphene and
chemically modified graphene are promising candidates as
components for energy-storage materials,10 “paper-like” mate-
rials,12,13 liquid crystal devices,14 and mechanical resonators.15
For these reasons, in recent years, several different meth-
ods for graphene production have been proposed. Some of the
most commonly used are summarized in Table 13.1 and will
be discussed in the following.
One of the most used synthetic strategies to obtain gra-
phene exploits graphite as a starting material. Graphite is
oxidized to graphite oxide, which can easily exfoliate to give
graphene oxide (GO) layers; these are eventually reduced to a
somehow definable “graphene,” although it should be prefera-
ble to name it “reduced graphene oxide (RGO),” as it still con-
tains a number of oxidized groups. Indeed, even if it is only
partially oxidized, several exciting properties of graphene are
fairly destroyed.
The first paper on the obtaining of graphite oxide dates
back to the nineteenth century when Brodie reported on the
oxidation of graphite by KClO3 in fuming HNO3.16
More recently, an analogous approach has been developed
by Hummers17 who proposed the oxidation of graphite with
NaNO3 and KMnO4 in concentrated H2SO4, and the subse-
quent removal of the excess of KMnO4. This is still the most
used method nowadays.
All the aforementioned approaches involve the oxidation
of graphite in the presence of strong acids. The oxidation
extent can be tuned by varying the reaction conditions and the
type of graphite used as starting material.
Although thorough research studies have been performed
in order to assess the chemical structure of graphite oxide, a
definitive conclusion has not been reached yet. However, it has
been established that many of the carbon atoms are linked to
hydroxyl groups or participate in epoxy groups, thus bearing a
sp3 hybridization. Furthermore, carboxylic and carbonyl groups
are present on the edges of the layers.18–21 Owing to the pres-
ence of these groups, graphite oxide is characterized by a strong
hydrophilic character, which favors the intercalation of polar
solvents among its layers. In particular, the interlayer distance
varies from 6 to 12 Å depending on the relative humidity.22
Such a high degree of hydrophilicity has been exploited
for the exfoliation of graphite oxide in aqueous media to give
the so-called “graphene oxide,” as a result of sonication treat-
ments23 or mechanical stirring.24
Li et al. found that the process is favored by the electro-
static repulsion among the sheets of GO, which are negatively
charged when dispersed in water, and that give rise to sta-
ble suspensions.25 In addition, graphite oxide can be exfoli-
ated in polar organic solvents such as dimethylformamide,
N-methylpyrrolidone (NMP), ethylene glycol, and tetrahydro-
furane (THF).26
Thermal exfoliation is another method to separate the lay-
ers of graphite: it is usually carried out at about 1000°C for
a short time, usually less than 1 min. A description of the
structural changes for graphite particles of ca. 45 μm occur-
ring at this temperature was reported by Schniepp et  al.27
Straightforward Routes for the Preparation of Graphene-Based Polymer Nanocomposites 177

TABLE 13.1
Methods Used for Producing “Graphene”: An Overview
Starting Carbon Final “Graphene”
Source Form Method References
Graphite Graphite oxide Oxidation of graphite by KClO3 in fuming HNO3 [16]
Graphite Graphite oxide Oxidation of graphite with NaNO3 and KMnO4 in concentrated [17]
H2SO4, and subsequent removal of the excess of KMnO4
Graphite oxide Graphene oxide Sonication treatments in aqueous media [23]
Graphite oxide Graphene oxide Mechanical stirring in aqueous media [24,25,29]
Graphite oxide Graphene oxide Exfoliation in polar organic solvents such as [26]
dimethylformamide, NMP, ethylene glycol, and THF
Graphite Graphene layers Thermal exfoliation [27]
Graphene oxide Graphene Reduction with dimethylhydrazine, hydrazine, hydroquinone, [30–35]
and sodium boron hydride
Graphene oxide Monolayer graphene Heat treatment (at 500°C for 2 days) in Ar/H2 flow [36]
Highly oriented Graphene Treatment with potassium to give KC8 that is exposed to [38–40]
pyrolytic graphite isoprene vapors at temperatures beyond 500°C. Polymerization
of isoprene in between the layers of graphite, exfoliation of
this latter to graphene, and final removal of the polymer
Graphite Negatively charged Exfoliation in NMP [41]
graphene sheets
Graphite Partially oxidized Chemical vapor deposition [42]
graphene sheets
Graphite Multilayer graphene Mild milling in a stirred mill in the presence of a surfactant [43]
sheets (sodium dodecyl sulfate)
Graphite Graphene monolayers Low-power ultrasonication in liquid media (cyclopentanone) [48]
without surfactants
Graphite Graphene monolayers Ultrasound treatment in imidazolium-based ILs [50]
Graphite Graphene nanosheets Electrochemical synthesis assisted by imidazolium-based ILs [52]
Graphite Graphene nanosheets Exfoliation and stabilization in 1-butyl-3-methylimidazolium [53]
hexafluorophosphate
Graphite Graphene nanosheets Sonication in HMIH [50]
Graphite Graphene nanosheets Sonication in NMP [50]
Graphite Graphene nanosheets Sonication in different monomeric liquid systems (tetraethylene [55–59]
glycoldiacrylate, N-vinylcaprolactam, diisocyanate, and diols,
organosilanes)

More specifically, it was found that thermal treatment of GO
after being dried with air spray yielded a high concentration
of monolayer graphene (up to 80%).28
The aqueous dispersions of graphite oxide are then ultra-
sonicated to give GO sheets that, after removal of the non-
exfoliated flakes by centrifugation, turn out to be stable for
months.29 As mentioned above, after graphite oxide exfolia-
tion, GO can be reduced by using various chemical agents,
including dimethylhydrazine,30 hydrazine,31–33 hydroqui-
none,34 and sodium boron hydride.35
Furthermore, a heat treatment (at 500°C for 2 days) in
Ar/H2 flow was found to be effective for the obtaining of
­monolayer graphene.36
Obviously, the goal of any reduction method is to produce
a material that is similar to the pristine graphene obtainable
by direct exfoliation of graphite. Although numerous efforts
have been made, all of the above methods significantly fail
and the material resulting from GO reduction still contains
defects that alter, even drastically, the structure of the carbon
plane. As a consequence, the resulting properties are also
­substantially different.
This means that it is necessary to cautiously consider the
materials derived from the above methods as “graphene”: as
already mentioned, it should be highlighted that the material
resulting by the reduction of GO should not be called gra-
phene but only “RGO.” Indeed, the residual oxygen content
after the reduction process is very high: more specifically,
x-ray photoelectron spectroscopy (XPS) analyses37 measured
a C/O atomic ratio around 10.
Furthermore, when hydrazine is exploited as a reduc-
ing agent (this is the most commonly used approach), a sig-
nificant amount of nitrogen is also incorporated in the RGO
(C/N ≈ 16.1 as assessed by elemental analysis), presumably
because of the reaction of hydrazine with the carbonyl groups
of GO.23,31
Alternatively, the exfoliation process can be achieved by
using graphite intercalation compounds. In particular, highly
oriented pyrolytic graphite was treated with potassium to give
178
a compound with formula KC8 and then exposed to isoprene
vapors at temperatures beyond 500°C.38–40 Isoprene turned
out to polymerize into the galleries in between the layers of
graphite, hence giving rise to its exfoliation. Polyisoprene
was then removed, thus obtaining graphene. It is notewor-
thy that this process was reported before the publication of
the work by Novoselov and Geim that was awarded with the
Nobel Prize.6 Furthermore, although the above works by
Shioyama and coworkers were not cited in their paper, Valles
et al. later reported an analogous approach for the obtaining
of negatively charged graphene sheets in solutions of NMP.41
The authors claimed that no traces of N (owing to NMP) or K
were found after washing. However, the presence of oxygen,
assessed by XPS analyses, was not taken into consideration in
the main paper.
Chemical vapor deposition (CVD) is one of the most effi-
cient techniques for producing large-area films of contiguous
graphene. In CVD, a metal substrate such as copper is placed
in an oven and heated under vacuum to about 1000°C. The
heat anneals the copper, increasing its domain size. Hydrogen
catalyzes a reaction between the hydrocarbon and the metal
substrate surface, causing carbon atoms to deposit on the
metal surface by chemical adsorption.
Although the discussion of this method is far beyond the
scope of this chapter, it should be underlined that in this case
also, partially oxidized graphene, instead of pure graphene, is
finally obtained.42
The direct exfoliation of graphite in suitable liquid media
represents one of the low-cost methods that allow the obtain-
ing of pure graphene. This approach, first proposed by Knieke
et  al. in 2010, does not involve any chemical manipulation
and the resulting graphene does not contain oxygen atoms.43
On the basis that stirred media milling is known as a scalable
technique for the production of highly concentrated nanopar-
ticle suspensions, sodium dodecyl sulfate (SDS) has been used
as surfactant in aqueous solution to disperse graphite particles
(with an average size of 4 μm and a density of about 2.3 g/
cm3). The graphite particles were stressed under mild mill-
ing conditions in a stirred media mill; wear resistant commer-
cially available yttria-stabilized zirconia milling beads with
diameters of 50 and 100 μm were used as grinding media.
During the milling process, SDS molecules are absorbed on
the graphite surface, thus resulting in high surface charge and
strong repulsive forces. In such a way, exfoliation can take
place and possible agglomeration and restacking is success-
fully prevented. As a consequence, the formation of multi-
layer graphene sheets occurs. SDS stabilizes the exfoliated
layers and allows water to wet the nonpolar graphite surface.
Furthermore, an SDS concentration exceeding 5.5 mmol/L
can be utilized in the grinding experiments, since in this con-
dition the graphite surface is completely covered by the sur-
factant. Thus, the formation of micelles that may influence the
stability of the suspension is avoided.
During the mechanical process, graphite particles
undergo strong compressive and shear forces that lead to the
delamination of thin graphite layers having an aspect ratio
that depends on the process parameters. This is possible
Graphene Science Handbook
because of the anisotropy in the bond forces inside the
graphite crystals. Namely, the weak van der Waals forces
between the graphene sheets have to be overcome by the
shear forces applied. At the same time, attention is paid to
the compressive forces, which cannot be too large in order
to reduce the possibility of in-plane fracture, hence leading
to a significant reduction of the lateral size of the result-
ing graphene sheets. In other words, the milling conditions
must be effective but also mild enough in order to ensure
that shear becomes the main stressing mechanism. On the
other hand, the acting shear forces must be strong enough
to overcome the weak van der Waals forces between the
graphene sheets. At the same time, compressive forces are
reduced so that no fracture in the plane occurs. The obtained
graphene suspensions were found to be highly stable toward
agglomeration and sedimentation, because of the absorption
of the SDS molecules on graphite and graphene, which leads
to the creation of a large negative charge on the particle sur-
face. After centrifugation, which is necessary to remove the
non-exfoliated graphite (EFG) particles, and spin coating
of the suspensions, these latter were washed with deionized
water and analyzed by atomic force microscopy (AFM).
However, it should be underlined here that, as also assessed
by Hernandez et al.44 AFM overestimates the height of the
sheets because of both (i) the presence of a number of solvent/
surfactant layers among those of graphene and (ii) the reag-
gregation resulting from the deposition process. In particu-
lar, as it will be discussed later on, this latter phenomenon
should be avoided when polymer–graphene nanocomposites
are prepared, thus suggesting that the direct use of graphene
dispersed into the monomer to eventually polymerize should
represent the recommended protocol.
Raman spectroscopy is a powerful analytical technique
to determine the exact number of graphene layers. Indeed,
graphitic materials can be characterized by a D-band (at ca.
1350 cm−1), a G-band (at about 1580 cm−1), and a 2D-band
(around 2700 cm−1). The symmetry as well as the full-width
at half-maximum of the 2D peak can be used to discriminate
between monolayer, bilayer, or multilayer graphene sheets.
More specifically, monolayer graphene is characterized by
a symmetric 2D peak; at variance, the 2D peak present in
the graphite spectrum is characterized by the presence of a
shoulder.45–47 As a consequence, the results of Raman spec-
troscopy allowed the confirming of the presence of mono- and
bilayer graphene as main components together with a number
of multilayer structures. Furthermore, the existence of rela-
tively high intensity D- and 2D-bands indicated the presence
of an increased number of defects originated by the smaller
lateral dimensions of the flakes. However, by performing XPS
analyses on the initial and the delaminated powder (the latter
being stressed for 5 h in the stirred media mill), the possible
presence of oxidized carbon forms was excluded; therefore,
apart from the increased disorder due to the larger fraction
of edges, no other defects in the carbon structure result from
this method. The authors also claimed that the contribution of
the edges to the disorder can be reduced by simply choosing
graphite flakes having a larger width; this means that even
Straightforward Routes for the Preparation of Graphene-Based Polymer Nanocomposites
larger sheets may be produced by choosing larger feed par-
ticles and optimized stress conditions.
A similar, but even easier approach, was proposed first by
Hernandez et al.48 who exploited the stabilizing effect of a liquid
medium to exfoliate graphite by using a low-power ultrasonic
bath without the need of any surfactant. This is possible when
the solvent–graphene interaction is strong enough to balance
the interlayer attractive forces. This process appears to involve
only weak van der Waals-type bonding, specifically disper-
sion, dipolar, and hydrogen-bonding interactions. The presence
of graphene monolayers was assessed by electron diffraction
and transmission electron microscopy (TEM). In particular,
approximately 25% of monolayers were found, together with
the majority of flakes containing less than five sheets.
To rationalize and predict the solubility behavior of gra-
phene in various liquid media, further studies aimed at find-
ing solvents characterized by the Hansen and Hildebrand
parameters matching those of graphene were carried out by
the same group.49 In particular, the dispersibility of graphene
in 40 different solvents was assessed. The actual graphene
obtained was checked by TEM analysis. Among the solvents
used, cyclopentanone was found to be the most effective;
indeed, in this liquid, a graphene concentration as high as
8.5 ± 1.2 μg/mL was measured. However, it should be noticed
that the above graphene concentration is quite low as com-
pared to that recently achieved. As a matter of fact, in this
work, the authors themselves stated that all the dispersions
were prepared without optimizing the process parameters.
Although it might be questionable since the kinetics factors
are not considered, in their opinion, such an optimization pro-
cess should affect all the liquid media in the same way. Hence,
the concentrations could increase but still retain their relative
order. TEM analysis was used for the statistical determination
of the number of layers constituting any resulting flake. In
this respect, it was found that NMP is more effective than the
other chosen solvents, including cyclopentanone. Indeed, the
mean number of graphene layers in NMP is 2.5, whereas in
cyclopentanone it rises up to 4.8.
As mentioned before, it is worth noticing that AFM was
not used to measure flake thickness. As a matter of fact, such
a technique was found to be non-reliable when graphene
was obtained from its dispersions in highly boiling solvents,
because of its tendency to aggregate during deposition onto
surfaces, and due to the presence of molecules of liquid that
remain inside the graphene layers, thus rendering a quantita-
tive analysis impossible.
In 2011, Nuvoli et  al. reported on the effective use of
an ionic liquid (IL) as a dispersing medium to be used for
direct graphite exfoliation by ultrasound treatment, without
any chemical manipulation.50 The use of ILs originates from
some previous published works. In particular, Fukushima
et  al. observed that imidazolium-based ILs can be success-
fully used as solvents for untangling carbon nanotubes.51 It
was assumed that this process involves interactions between π
electrons of the nanotube and the positive charge of the imid-
azolium ring. In 2008, Liu et al. reported the preparation of
graphene nanosheets by electrochemical synthesis assisted by
179
imidazolium ILs.52 In 2010, Zhou et al. reported on the use
of the IL 1-butyl-3-methylimidazolium hexafluorophosphate
as a solvent to disperse graphene, stabilized with a polymer-
ized IL.53 It is worthy to note that in these latter two works,
ILs were exploited as media for the chemical synthesis and/or
modification of graphene or graphite, respectively.
Nuvoli et al. found that a graphene concentration as high
as 5.33 mg/mL is reachable by using a simple protocol con-
sisting in dispersing 5 wt.% graphite in 1-hexyl-3-methyl-
imidazolium hexafluorophosphate (HMIH) and sonicating it
at room temperature for 24 h in a common low-power ultra-
sound bath.50 It is also remarkable that, when the sonication
was applied for just 30 min, that is, the same time used by
Hernandez et  al. in the work discussed above,49 a graphene
concentration in HMIH equal to 11 μg/mL was found, which
is about 30% higher with respect to the best one reported
(8.5 ± 1.2 μg/mL) by Hernandez et al. in cyclopentanone.
Graphene dispersion in NMP was used by the same group
to dissolve N-isopropylacrylamide and to obtain the corre-
sponding stimuli-responsive nanocomposite hydrogel after
washing with distilled water.54
However, all the above-described liquid media are inert
solvents, in which the formation of pure graphene may occur;
at variance, they are not directly exploitable in the solvent-
free methods for the obtaining of polymer materials. To
address this issue, the method was applied by the same group
also to a number of monomeric liquid systems in order to
prepare graphene-based polymer nanocomposites by direct
graphite sonication in the same monomers. Namely, the fol-
lowing monomers were used: tetraethylene glycoldiacry-
late,55,56 N-vinylcaprolactam,57 diisocyanate and diols,58 and
organosilanes.59 It should be underlined that in most of the
above systems very high graphene concentrations were found.
In particular, tetraethylene glycoldiacrylate, with a graphene
content of 9.45 mg/mL, turned out to be the best dissolving
system found. Furthermore, these dispersions were stable for
months.
Thus, the advantages of the overall method for the polymer
nanocomposite production can be summarized as follows:
1. It is extremely cheap and simple.
2. Graphene is obtained from common graphite by
simply dissolving and sonicating it in a common
ultrasound bath.
3. It is one of the few methods allowing the obtaining
of pure graphene in that no residual oxidized carbons
are present, with obvious consequences on the prop-
erties of the resulting material.
4. Graphene is obtained into the monomer medium,
thus allowing for its direct polymerization; this
avoids any graphene recovering process in the solid
state and prevents its possible restacking to graphite
flakes.
5. At variance to milling, which is a technique that may
induce the polymerization of the liquid monomers
during the exfoliation process, the use of ultrasound,
which is a milder treatment, prevents this drawback.
180
On the basis of what discussed above, the pros and cons of
the type of “graphene” to be used should be properly weighed
by considering: the properties to be imparted to the final
material, its cost, the time taken to produce it, the possibility
of restacking to graphite when the chosen “graphene” is dis-
solved in a medium that is different from that in which it is
made available on the market, etc.
13.2 ​POLYMER–GRAPHENE NANOCOMPOSITES
As previously mentioned, several papers dealing with the
preparation and characterization of graphene-containing
nanocomposites, where graphene is used in form of nanoplate-
lets or is obtained as mono or few layers by direct sonication
from colloidal suspensions of graphite, have been reported in
the literature so far. As schematized in Figure 13.1, graphene
nanoplatelets (GNP) or nanosheets can be obtained from
graphite, which is subjected to exfoliation in the presence
of either chemically reactive compounds (that are used for
the functionalization of the nanofiller) or nonreactive media
(that are responsible for the exfoliation process only); to this
aim, different exfoliation techniques such as milling, sonica-
tion, and thermal expansion, can be successfully exploited.
Nowadays, GNP represent the most used type of graphene
available in the market.
Although graphene nanocomposites refer to both thermo-
plastic and thermoset matrices, the number of papers involving
thermoplastics is still prevalent. In the following, a detailed
overview of the different graphene nanocomposite systems is
presented and the special features (i.e., thermal, mechanical,
rheological, and electrical properties) of the obtained systems
are highlighted.
Graphite
Milling
Sonication
Exfoliation
Thermal expansion
In chemically reactive In nonreactive media
compounds
Graphene nanoplatelets/
Nanosheets (GNP)
FIGURE 13.1  ​Obtaining of GNP.
Graphene Science Handbook
13.2.1 Graphene Nanocomposites Using
Thermoplastic Matrices
Table 13.2 lists the types of graphene nanocomposites based
on thermoplastic matrices, as well as the main features of the
obtained materials.
13.2.1.1  Polyethylene: Graphene Nanocomposites
Jiang and Drzal used exfoliated GNP for preparing high-
density polyethylene (HDPE)-based nanocomposites through
the melt extrusion and injection molding process.60 GNP were
previously treated and coated with low molecular weight par-
affin wax, aiming to improve their dispersion within the poly-
olefin and to lower the percolation threshold, thus enhancing
the electrical conductivity of the obtained nanocomposites.
This latter was found to significantly increase in the pres-
ence of 5 vol.% of wax-coated GNP: indeed, a decrease of
more than five orders of magnitude of the in-plane resistiv-
ity was assessed for the nanocomposite containing 5 vol.% of
wax-coated GNP, as compared to the same nanocomposite
where GNP nanoplatelets were not treated with wax (i.e., a
non-conductive system). As a consequence of the good disper-
sion of the nanofiller within the HDPE matrix, the percola-
tion threshold turned out to decrease below 5 vol.% from the
previous 10–15 vol.% GNP loading. In addition, the prepared
systems showed enhanced flexural properties with respect to
the pure HDPE matrix: more specifically, the nanocompos-
ites containing 5 vol.% of wax-coated GNP exhibited 12%
flexural strength increase, as well as a 20% flexural modulus
improvement, hence further confirming the enhanced GNP
dispersion within the polyolefin.
Pursuing this research, quite recently, the same group
investigated the crystallization behavior and the electrical and
thermal conductivity of GNP-reinforced HDPE nanocompos-
ites, fabricated by a novel compounding method (solid state
ball milling [SSBM]) followed by injection molding.61 This
technique allowed the significant reduction of the percolation
threshold of HDPE/GNP nanocomposites (from ca. 10–15
down to 5 vol.%). The exfoliated GNP, when added at low
concentration to HDPE, were found to act as good nucleating
agents, considerably increasing the crystallization tempera-
ture and the degree of crystallinity of the polymer. At vari-
ance, the crystallization process of the polyolefin was delayed
at high GNP loadings, owing to the close proximity of GNP.
In addition, the presence of the nanofiller improved both the
thermal stability (as assessed by thermogravimetric analyses)
and the through-plane thermal conductivity of the polymer,
which was described by means of the Agari model.62
Very recently, Fim et  al. prepared polyethylene/graphene
nanocomposites by in situ polymerization of ethylene in the
presence of graphene nanosheets and investigated the ther-
mal stability, electrical conductivity, and the mechanical and
dynamic-mechanical behavior of the final material.63 It was
found that the presence of graphene nanosheets (5.4 wt.%) was
responsible for a significant increase of the onset d­ egradation
temperature by 30°C with respect to the pure polyethylene
matrix. Furthermore, impedance measurements evidenced
Straightforward Routes for the Preparation of Graphene-Based Polymer Nanocomposites 181

TABLE 13.2
Graphene/Thermoplastic Nanocomposites
Type of Graphene Polymer Matrix Processing Highlights References
Graphene HDPE Melt extrusion and • Increase of electrical conductivity [60]
nanoplatelets injection molding • Increase of flexural strength
Graphene HDPE Solid state ball milling • Increase of thermal stability [61,62]
nanoplatelets • Increase of the crystallization temperature and of
the degree of crystallinity of the polymer
• Increase of the through-plane thermal
conductivity
Graphene PE In situ polymerization of • Increase of tensile strength and storage modulus [63]
nanosheets ethylene • Increase of the onset degradation temperature
• Low critical percolation threshold
Graphene PP Melt compounding • Increase of the crystallization temperature, [64]
nanoplatelets crystallization rate, and degree of crystallinity
Graphene PP In situ polymerization • Significant increase of the crystallization [65]
nanoplatelets (using metallocene temperature
catalysts)
Graphene PC Supercritical CO2 • Increase of thermal and thermo-oxidative stability [66]
nanoplatelets dissolution one-step • Decrease of water uptake and oxygen transfer
batch foaming process rate
Graphene Poly(propylene carbonate) Solution blending • Increase of mechanical properties [67]
nanoplatelets • Increase of thermal stability
Graphene PVAc Solution blending • Decrease of wettability [68]
nanoplatelets • Shear strength increase in veneer lap joints
Exfoliated graphite PVA nanofibers Spinning • Increase of the thermal stability of the nanofibers [69]
• Increase of their degree of crystallinity
Graphene sheets PS Rapid thermal expansion • Increase of thermal stability [70]
of expandable graphite • Increase of electrical conductivity
Graphene PLA Ultrasound sonication • Increase of elastic modulus and tensile strength [72]
nanoplatelets • Increase of the barrier properties (N2 and O2)
Graphene layers PUR Ultrasound sonication • Increase of the mechanical properties [58]
and nanoribbons • Lubricant effect
Graphene PUR Melt mixing • Formation of small crystals [73]
nanoplatelets • Welding processes become easier
Graphene PEI Melt extrusion, • Outstanding mechanical properties (using SSBM) [74]
nanoplatelets ultrasonication, SSBM, • Significant decrease of the percolation threshold
and their combinations (using SSBM)
• Further mechanical enhancements by combining
the extrusion with the SSBM method
Graphene LCP Thermal exfoliation of • Increase of mechanical properties [75]
nanoplatelets acid-intercalated graphite • Increase of the electrical conductivity
Graphene PANI Aqueous in situ chemical • Fabrication of ammonia sensors having high [77,78]
nanoplatelets oxidative polymerization sensitivity and consistent linearity
of the monomer • High specific capacitance and good cyclic
stability (weight ratio of aniline to graphene fixed
at 1:2)
Graphene PANI Aqueous in situ chemical • Enhanced thermal stability [79]
nanoplatelets oxidative polymerization • Increase of electrical conductivity
of the monomer
Graphene PANI derivatives Chemical oxidative • High specific capacitances and small relaxation [80]
nanoplatelets polymerization time constants
Graphene PANI Chemical oxidative • High specific capacitance [81]
nanoplatelets polymerization
Graphene Polypyrrole In situ oxidative • Suitability for the fabrication of supercapacitors [82]
nanoplatelets polymerization method • High cyclic stability
using ammonium
persulfate as oxidant
(Continued)
182
TABLE 13.2 (Continued)
Graphene/Thermoplastic Nanocomposites
Type of Graphene Polymer Matrix Processing
Graphene Polypyrrole nanofibers In situ polymerization
nanoplatelets reaction
Graphene Poly(ethylenedioxythiophene) Oxidative polymerization
nanoplatelets of ethylene
dioxythiophene
Graphene PET Melt mixing
nanoplatelets
Graphene Chitosan Cryomilling of graphene
nanoplatelets powder and then
ultrasonication in
distilled water
the presence of a critical percolation threshold for a concentra-
tion of nanosheets equal to 8.4 wt.% (3.8 vol.%) which, at the
same time, promoted a slight increase in the tensile strength,
as well as a significant increase of the storage modulus of the
nanocomposites, as compared with the unfilled polymer.
13.2.1.2  Polypropylene–Graphene Nanocomposites
Very recently, Ferreira et  al.64 prepared graphene/polypro-
pylene nanocomposites exploiting a melt compounding pro-
cess in a co-rotating twin-screw intermeshing extruder and
investigated their crystallization behavior through differential
scanning calorimetry (DSC) measurements. It was found that
the GNP strongly modified the non-isothermal crystalliza-
tion behavior of the polyolefin: more specifically, a significant
increase of the crystallization temperature, crystallization
rate, and degree of crystallinity was observed. The use of the
Avrami kinetic model under isothermal conditions allowed
demonstrating that the nanofiller acts as an effective nucleat-
ing agent, favoring the crystallization kinetics and modifying
the structure of the polymer crystallites.
Milani et  al. synthesized graphene/polypropylene nano-
composites by in situ polymerization at 40°C, using metal-
locene catalysts. To this aim, two different graphene sources
were considered and the morphology and thermal features of
the corresponding nanocomposites were compared.65 It was
found that the obtained nanocomposites did not show signifi-
cant variations in molecular weight, melting point, and degree
of crystallinity with respect to the pure polymer matrix syn-
thesized in the same conditions; at variance, they exhibited a
significant increase of the crystallization temperature.
13.2.1.3 ​Polycarbonate–Graphene Nanocomposites
Gedler et al.66 evaluated the thermal stability of polycarbon-
ate/graphene foams, prepared by using a supercritical CO2
dissolution one-step batch foaming process on 0.5 wt.%
polycarbonate pellets obtained via melt compounding. The
foamed nanocomposites showed a remarkable thermal and
thermo-oxidative stability as compared to the pure matrix:
Graphene Science Handbook
Highlights References
• Increase of charge transformation and the ion [83]
transportation
• High electrical conductivity, low internal
resistance, and good electrochemical properties
• Suitability for the fabrication of supercapacitors [84]
• Strong nucleation effect exerted by the nanofiller [85]
• Increase of mechanical properties [86]
this finding was explained on the basis of a combination
of heat-transfer reduction exerted by the insulating foamed
structure and the presence of the GNP, which through the cre-
ation of a physical barrier, delayed the escape of volatile prod-
ucts, generated during the thermal decomposition.
Very recently, Lee et al. prepared poly(propylene carbon-
ate)/EFG nanocomposite films containing different EFG
amounts, through a solution blending method. EFG was pre-
viously obtained by a thermal treatment of graphite at 1050°C
and a subsequent ultrasonication.67 The obtained nanocom-
posites containing 2 wt.% EFG showed enhanced mechani-
cal properties (~50% increase of their tensile strength), an
improved thermal stability (the degradation onset was raised
by 30°C with respect to the pure polymer matrix), as well as
a significant decrease of both water uptake (from 10.6% pure
polymer to 3.3% nanocomposite containing 2 wt.% EFG) and
oxygen transfer rate (−33%).
13.2.1.4 Poly(Vinyl Acetate)–Graphene
Nanocomposites
Very recently, Pinto et  al.68 succeeded in dispersing GNP
directly into a poly(vinyl acetate) latex, without using addi-
tional surfactants or dispersants and achieving the formation
of stable dispersions. The presence of the nanofiller was found
to increase the viscosity of the latex, as well as its pseudo-
plastic behavior. Furthermore, upon incorporation of 0.1 wt.%
hydrophobic GNP, a significant increase (ca. 13°) of the equi-
librium contact angle with water was assessed; at variance,
at higher concentration, reaggregation phenomena occurred.
Besides, the addition of very small amounts of the nanofiller
(up to 0.3 wt.%) turned out to be responsible for a 50% shear
strength increase in veneer lap joints.
13.2.1.5 Poly(Vinyl Alcohol)–Graphene
Nanocomposites
Very recently, Das et al. used pristine graphene (i.e., graphene
directly exfoliated from graphite without covalent functional-
ization) for preparing poly(vinyl alcohol)-based nanocomposite
Straightforward Routes for the Preparation of Graphene-Based Polymer Nanocomposites
fibers, starting from an aqueous dispersion of polyvinylpyr-
rolidone-stabilized graphene and poly(vinyl alcohol).69 Very
homogenous nanofiller dispersions within the fibers were
obtained, as assessed by high resolution TEM and rheology
measurements (for these latter, the storage modulus of the
polymer was found to increase by ca. 205%). Furthermore,
the presence of graphene increased the thermal stability of the
nanofibers (by 15°C), as well as their degree of crystallinity
(from 23%, for the neat polymer matrix, to 37%, for the nano-
composite containing 0.5 wt.% graphene), thus showing that
the nanofiller behaves as an effective nucleating agent.
13.2.1.6  Polystyrene–Graphene Nanocomposites
Patole et al. succeeded in synthesizing polystyrene nanopar-
ticle-functionalized graphene sheets (FGS) by exploiting an
ultrasonically initiated water-based in situ microemulsion
polymerization.70 Graphene was obtained by a rapid thermal
expansion of a commercially available expandable graphite,
performed at high temperature (from 700°C to 1000°C, for
2 min). The proposed method allowed producing polysty-
rene nanoparticle-FGS at a large scale, which showed mutual
compatibility, enhanced thermal stability, and gave rise to
lightweight conductive polystyrene films (3 wt.% graphene
provided antistatic features to the obtained nanocomposite
thin films).
Pursuing this research, the same group investigated the
synthesis and properties of self-assembled graphene/carbon
nanotube/polymer hybrid systems by ultrasonically initiated
water-based in situ microemulsion polymerization.71 An inter-
connected nanocomposite network was obtained, where the
large GNP provided most of the total surface area, and the
carbon nanotubes acted as connection wires, thus resulting in
the formation of an effective electrical conductive system hav-
ing enhanced thermal and mechanical features as compared
to neat polystyrene films.
13.2.1.7 ​Poly(Lactic Acid)–Graphene Nanocomposites
Pinto et al. incorporated GNP (nanofiller concentration rang-
ing from 0.2 to 1 wt.%) into a poly(lactic acid) matrix, using
ultrasound sonication.72 A significant improvement of the
mechanical properties (in particular of the elastic modulus
and tensile strength) of the obtained nanocomposite films was
assessed; more specifically, it was found that the best mechan-
ical performance was achieved in the presence of 0.4 wt.%
nanofiller. In addition, the barrier properties toward oxy-
gen or nitrogen diffusion turned out to be very significantly
improved by using this nanofiller concentration: indeed, the
permeabilities to oxygen and nitrogen showed a decrease
from 3.76 × 10−18 and 1.10 × 10−18 m2 s−1 Pa−1 to 1.20 × 10−18
and 0.250 × 10−18 m2 s−1 Pa−1, respectively.
13.2.1.8 ​Polyurethane–Graphene Nanocomposites
Scognamillo et  al. succeeded in synthesizing thermoplastic
graphene–polyurethane (PUR) nanocomposites through the
polymerization of 1,4-butanediol with 1,6-hexane diisocyanate
(HDI) or isophorone diisocyanate (IPDI), in which the nano-
filler was previously exfoliated by a simple ultrasonication
183
process.58 High concentrations of exfoliated graphene were
achieved (i.e., up to 1.14 and 0.80 mg/mL for IPDI- and HDI-
based PURs, respectively). The thermal (DSC) and rheological
characterizations performed on the obtained nanocomposites
clearly indicated that their Tg values, as well as their rheologi-
cal features, strongly depend on the type of PUR and on the
nanofiller concentration as well: more specifically, graphene
substantially acted as a lubricant for the HDI-based system,
whereas it behaved as a reinforcing agent in the case of the
IPDI-based polymer matrix. Finally, the exfoliation process
of the nanofiller allowed achieving the formation of graphene
nanoribbons, regardless of the formation of GNP.
Very recently, Landa et al. investigated the differences in
the isothermal crystallization of two nanocomposites filled
with multiwalled carbon nanotubes (MWCNTs) or GNP,
using a hot melt adhesive PUR as the thermoplastic matrix.73
Both the nanofillers were incorporated in PUR by exploit-
ing a melt mixing method in a Haake Mini-Lab twin-screw
extruder. Unlike PUR/MWCNT nanocomposites, the rheo-
logical percolation was not reached for PUR/graphene nano-
composites. Furthermore, by analyzing the elastic modulus
versus time plots, it was found that the crystallization pro-
cess is more hastened by MWCNTs than by graphene, which
favored the welding process of the corresponding adhesives.
Finally, from a morphological point of view, correlative AFM
images confirmed that crystals in neat PUR are bigger than
those in PUR/graphene (>PUR/MWCNT): this behavior was
ascribed to the poorer dispersion of graphene in the PUR
matrix, as compared to MWCNT.
13.2.1.9  Poly(Etherimide)–Graphene Nanocomposites
Wu et  al. studied the effect of different processing meth-
ods (melt extrusion, precoating, i.e., using ultrasonication
of the nanofiller in acetone, SSBM and their combinations)
for preparing poly(ethereimide)–graphene nanocomposites.74
The effectiveness of the dispersion of the nanofiller within
the polymer matrix was assessed through SEM and TEM
observations, flexural tests, and measurements of the elec-
trical resistivity. As compared to the other two processing
methods, SSBM turned out to ensure outstanding mechani-
cal properties, as well as a significant decrease of the per-
colation threshold (2 wt.%, as compared to 10 wt.% for the
melt-extruded products). These findings were ascribed to the
ability of GNP to create a continuous and adherent coating
on the surface of the polymer powder. Although the precoat-
ing method allowed achieving a similar percolation threshold,
the corresponding obtained nanocomposites were found to
exhibit lower mechanical features with respect to their coun-
terparts prepared with the SSBM approach. In addition, fur-
ther mechanical enhancements were found by combining the
extrusion with the SSBM method.
13.2.1.10 Liquid Crystalline Polymer–
Graphene Nanocomposites
Biswas et  al. prepared poly[(benzoyl-1,4-phenylene)-co-(1,3-
phenylene)]–graphene (obtained from thermal exfoliation of
acid-intercalated graphite) nanocomposites and evaluated their
184 Graphene Science Handbook

mechanical and electrical features.75 The highly aromatic liq- supercapacitor sheets.81 In particular, a specific capacitance
uid crystalline copolymer turned out to be responsible for the of 136.8 F/g was achieved in the presence of just 0.02 g/mL
good dispersion of the nanofiller; furthermore, the presence of of the nanofiller, thus indicating a significant enhancement
GNP allowed achieving 25 or even 55% increase of modulus of the energy and power capabilities of the capacitor.
when 1 or 5 vol.% GNP were, respectively, added to the liquid
crystalline polymer (LCP) matrix. In addition, the presence of 13.2.1.12  Polypyrrole–Graphene Nanocomposites
this latter nanofiller loading enhanced the electrical conductiv- Sahoo et  al. prepared polypyrrole–GNP nanocomposites,
ity of the nanocomposite, achieving 4.5 × 10−4 S/cm. where the nanofiller was eventually previously functional-
ized with amine groups.82 To this aim, an in situ oxidative
13.2.1.11  Polyaniline–Graphene Nanocomposites polymerization method using ammonium persulfate as
Similarly to polypyrrole and polythiophene, ­ polyaniline oxidant was exploited and the obtained nanocomposites
exhibits distinct features such as high sensitivity, fast response, were compared with those prepared without modifying the
low cost, and operation at room temperature, which justify nanofiller. Although the capacitance value of the untreated
its use in the fabrication of chemical sensors.76 Very recently, ­graphene-based materials was found to be slightly higher with
Wu et al. synthesized graphene–polyaniline doped with hydro- respect to the amine-modified counterpart (240 vs. 220 F/g,
chloric acid, exploiting an aqueous in situ chemical oxidative respectively), this latter exhibited a higher cyclic stability.
polymerization of the monomer.77 The obtained nanocompos- However, the electrical features of the prepared nanocompos-
ites were used for fabricating ammonia sensors: indeed, they ites clearly demonstrated their suitability for the fabrication
showed a higher sensitivity with respect to the pure polymer of supercapacitors.
matrix, maintaining a consistent linearity over an extended Very recently, the same research group succeeded in pre-
range of concentrations (in between 1 and 6400 ppm): these paring graphene–polypyrrole nanofiber composites, suitable
findings were ascribed to the high level of dispersion of the for the fabrication of supercapacitors, exploiting an in situ
nanofiller within the polymer, which may increase the surface- sodium alginate-assisted polymerization.83 The incorporation
to-volume ratios, thus enhancing the sensitivity. The detection of graphene during the polymerization reaction turned out to
limit of the obtained nanocomposites for ammonia was found improve the charge transformation and the ion transportation
to be one order of magnitude lower with respect to the unfilled throughout the material as well, thus leading to high electrical
polymer (i.e., 1 vs. 10 ppm, respectively). conductivity, low internal resistance, and better electrochemi-
Gomez et  al. prepared highly conductive polyaniline–­ cal properties as compared with the unfilled matrix. More
graphene nanocomposites, suitable for fabricating effective specifically, 1.45 S/cm electrical conductivity was achieved at
high powered supercapacitors for portable devices.78 The room temperature for the synthesized nanocomposites, which
presence of the nanofiller gave rise to a penetrating network- also exhibited nonlinear current–voltage features and a spe-
like structure, which showed a high specific capacitance and cific capacitance of 466 F/g (at 10 mv/s scan rate).
good cyclic stability when the weight ratio of aniline to gra-
phene was fixed at 1:2. 13.2.1.13 Poly(Ethylenedioxythiophene)–
Sahoo et al. surface-modified graphene by grafting amine Graphene Nanocomposites
groups to the basal carbon atoms of the nanofiller and used Alvi et  al. prepared GNP–poly(ethylenedioxythiophene)
this product for preparing nanocomposites with polyani- conducting polymer nanocomposites as electrode materials
line.79 The obtained nanocomposites showed enhanced ther- for supercapacitor applications.84 The nanocomposites were
mal stability and electrical conductivity with respect to the synthesized by oxidative polymerization of ethylene dioxy-
unmodified graphene–polyaniline systems: more specifically, thiophene in the presence of ammonium peroxydisulfate and
the highest electrical conductivity reached was 8.12 S/cm iron(III) chloride (the ethylene dioxythiophene:graphene ratio
(vs. 6.05 S/cm, as measured for the unmodified graphene–­ was fixed at 1:1). Their electrochemical charge/discharge fea-
polyaniline nanocomposites). tures were studied in different electrolytic media; at 0.01 A/g
Very recently, Basnayaka et  al. investigated the effect of current ranges, the maximum capacitance was about 374 F/g,
different polyaniline derivatives (i.e., polyaniline, poly(o- which is quite close to the value estimated by cyclic voltam-
anisidine) and poly(o-toluidine)) on the electrical behavior metry (304 F/g).
of graphene-containing nanocomposites obtained through
chemical oxidative polymerization reaction of the correspond- 13.2.1.14 Poly(Ethylene Terephthalate)–
ing monomers (i.e., aniline, o-anisidine, or o-­toluidine).80 Graphene Nanocomposites
High specific capacitances and small relaxation time con- Very recently, Aoyama et  al. compared the morphology of
stants were found for all the systems investigated: among poly(ethylene terephthalate)-based nanocomposites filled with
them, the highest specific capacitance (425 F/g) was measured graphene or MWCNTs, exploiting a melt mixing approach.85
for graphene–poly(o-toluidine) nanocomposite, owing to the Melt rheology and TEM measurements were exploited for
excellent electron donating features of this polymer matrix, in obtaining aspect ratio and interparticle distance of graphene in
combination with the conductivity exhibited by the nanofiller. the nanocomposites, respectively. It was found that the inter-
Very recently, Liu et  al. prepared polyaniline–graphene particle distance of the nanocomposites containing graphene
nanocomposite materials for the fabrication of flexible was much smaller than that determined in the counterparts
Straightforward Routes for the Preparation of Graphene-Based Polymer Nanocomposites
reinforced with multiwall carbon nanotubes. Non-isothermal
crystallization experiments showed that the nucleation
effect of graphene was stronger than that of MWCNTs. This
behavior was ascribed to the confinement effect exerted by
graphene, which suppressed the crystal growth rate of the
polyester, leading to the formation of smaller crystals with
higher perfection.
13.2.1.15  Chitosan–Graphene Nanocomposites
Chitosan, the second most abundant natural biopolymer on
earth, shows significant limitations as far as its mechanical
features are considered. For this reason, very recently, Lee
et al. tried to improve the mechanical properties of this bio-
polymer by preparing nanocomposites reinforced with GNP.86
To this aim, cryomilled graphene powder was subjected to
ultrasonication in distilled water and added to acetic acid and
chitosan, thus obtaining thin nanocomposite films by ther-
mally treating the prepared liquid dispersions under vacuum
(graphene loading: 1 wt.%). The nanocomposite films showed
enhanced mechanical features as compared to raw graphene/
chitosan counterparts: as an example, the elastic modulus of
the latter was 33% lower with respect to the systems contain-
ing the cryomilled nanofiller.
13.2.2 ​Graphene Nanocomposites Using
Thermosetting Matrices
Table 13.3 lists the types of graphene nanocomposites based
on thermosets, as well as the main features of the obtained
materials.
13.2.2.1  Epoxy–Graphene Nanocomposites
In a recent work, Wajid et  al. exploited two different meth-
ods, that is, freeze dry/mixing and solution processing for
preparing high-strength conductive pristine graphene/epoxy
composites.87 As far as the latter method is concerned, nano-
filler dispersions in dimethylformamide, which also ensured
a good compatibility with the epoxy resin, were prepared by
tip sonication for 60 min. Freeze-drying was used to obtain
polymer-stabilized graphene dispersions in water, over a
­ the other hand, under these conditions, the reinforcing action
period of 48 h; these dispersions were then mixed with the
epoxy resin by mechanical stirring and sonication and finally
cured under the same conditions as those adopted for the solu-
tion processing method. Although both methods turned out
to give rise to nanocomposites exhibiting improved thermal
stability, as well as enhanced mechanical and electrical fea-
tures, freeze-drying allowed the obtaining of better overall
performances as compared to the solution processing method.
In particular, the nanocomposites showed a very low electri-
cal percolation threshold (0.088 vol.%), as well as a significant
increase of elastic modulus and mechanical strength (+37 and
+38%, respectively; the used graphene content in the nano-
composites was set at 0.46 vol.%).
Very recently, Monti et  al.88 used two different solvent-
assisted processing methods for preparing graphene–epoxy
nanocomposites. These two methods differ from each other
because, in one case, the epoxy monomer was added to a
185
GNPs–THF suspension, which was added to the epoxy mono-
mer after the solvent removal. In the second method, the hard-
ener was mixed with a GNP–tetrahydrofuran suspension and the
epoxy monomer was added after the evaporation of the solvent.
Both approaches allowed the obtaining of a good dispersion of
the nanofiller, although the dispersion was slightly better using
the second method. As assessed by electrical and dielectric
measurements, the electrical percolation threshold was achieved
at reasonably low graphene loadings (i.e., within 1 and 2 wt.%).
Shokrieh et  al. carried out nanoindentation and nano-
scratch tests on graphene/epoxy-based vinyl ester nanocom-
posites; the nanofiller was previously dispersed in the liquid
resin by means of mechanical stirring and ultrasonication.89 In
the presence of 0.05 wt.% nanofiller, both elastic modulus and
hardness increased; in addition, GNP turned out to enhance
the wear resistance of the nanocomposites with respect to the
unfilled counterparts.
Recently, Prolongo et  al. prepared GNP/epoxy nanocom-
posites, using a high shear toroidal mixer.90 To this aim, sev-
eral GNP having different thickness and lateral dimensions
were used. A significant nanofiller concentration gradient was
found from the top to the bottom in the nanocomposites rein-
forced with large nanoplatelets owing to a natural deposition
by gravity. This phenomenon was not encountered when the
GNP size decreased. At variance, the incorporation of small
nanoplatelets into the epoxy matrix led to agglomeration phe-
nomena, giving rise to stacked nanofiller morphologies. From
an overall point of view, the addition of GNP promoted an
increase of the glass transition temperature, as well as of the
stiffness and thermal stability of the obtained nanocompos-
ites, as compared to the neat epoxy resin. These enhance-
ments were found to depend on the dimensions (i.e., surface
area and thickness) of the used nanofillers.
Very recently, Shadlou et al. investigated the effect of the
strain rate on the mechanical response of GNP-reinforced
epoxy nanocomposites having different nanofiller contents,
under tensile and compressive loading conditions.91 The yield
strength and Young’s modulus of both the neat epoxy and
nanocomposites were found to increase at high strain rates; on
of the nanofiller decreased.
In addition, the presence of GNP led to a transition, which
was found more severe under the compressive loading state,
from ductile to brittle in the mechanical response of the epoxy
system. Finally, the plastic flow behavior in the nanocompos-
ites was assessed and found different from that of the neat
epoxy: indeed, unlike the nanocomposites, this latter showed
stress softening after the yielding point.
Liu et al. investigated the effect of graphene nanosheets on
the morphology, thermal stability, and flame retardancy of an
epoxy resin.92 The partial exfoliation of graphene nanosheets
into the epoxy resin was achieved by using an ultrasonication
treatment. The nanofiller was found to change the decom-
position pathway of the epoxy resin at high temperature, to
improve its thermal stability, and to promote the formation of
char residue. In addition, the flame retardant features of the
epoxy system were enhanced in the presence of the graphene
186 Graphene Science Handbook

TABLE 13.3
Graphene/Thermosets Nanocomposites
Type of Graphene Polymer Matrix
Graphene nanoplatelets Epoxy resin
Graphene nanoplatelets Epoxy resin
Graphene nanoplatelets Epoxy-based vinyl ester resin
Graphene nanoplatelets Epoxy resin
Graphene nanoplatelets Epoxy resin
Graphene nanosheets Epoxy resin
Graphene nanolayers Poly(N-isopropylacrylamide)
hydrogels
Graphene nanolayers Poly(N-vinylcaprolactam)
hydrogels
Graphene nanolayers Poly(tetraethyleneglycol
diacrylate)
Graphene nanolayers Tetraethyleneglycoldiacrylate/
bisphenol A glycerolate
dimethacrylate copolymers
Graphene nanosheets PUR
Graphene layers and PUR
nanoribbons
Graphene nanoplatelets Styrene–butadiene rubber
Processing Highlights References
Freeze dry/mixing and • Increase of thermal stability [87]
solution processing • Increase of mechanical properties
• Increase of electrical features
Solvent-assisted • Low electrical percolation threshold [88]
processing methods
Mechanical stirring and • Increase of elastic modulus and hardness increased [89]
ultrasonication • Increase of wear resistance
Shear toroidal mixing • Increase of the glass transition temperature [90]
• Increase of the stiffness
• Enhanced thermal stability
Solvent-assisted • Increase of the yield strength and elastic modulus [91]
processing method • Disappearance of stress softening after the
yielding point
Ultrasonication • Enhanced thermal stability [92]
• Increased fire retardant properties
Ultrasonication • Enhanced swelling ratio [54]
• Increase of the storage modulus and of the
complex viscosity up to a concentration threshold
Ultrasonication and • Enhanced swelling ratio [57]
frontal polymerization • Lubrication effect of the nanofiller
Ultrasonication • Enhanced glass transition temperatures [55]
• Increase of the flexural and storage moduli
Ultrasonication • Increase hardness and elastic modulus [56]
Physical blending/ • Increase of shape memory properties [94]
in situ polymerization • Enhanced mechanical features
Ultrasound sonication • Increase of the mechanical properties [58]
• Lubricant effect
Solution mixing process • Low percolation threshold of electrical conductivity [95]
• Increased thermal conductivity
• Enhanced mechanical properties

nanosheets: indeed, a significant increase of the limiting oxy-
gen index and the inhibition of the dripping phenomena of the
epoxy resin during flammability tests were achieved.
To investigate the thermal and mechanical properties of gra-
phene/epoxy nanocomposites using molecular dynamics (MD)
simulation, Shiu and Tsai considered three different types of
graphene (graphene flakes, intercalated graphene, and interca-
lated GO).93 The mechanical properties of the graphene/epoxy
nanocomposites, including Young’s modulus, glass transition
temperature, and coefficient of thermal expansion, were thor-
oughly studied. In addition, the effect of graphene on the den-
sity distribution of the epoxy polymer in the nanocomposites
was also examined. In particular, the local density in the vicin-
ity of the graphene nanofillers was found to be relatively high,
and then progressively decreased to the bulk value in regions
far away from the interface. In addition, the nanocomposites
with intercalated graphene showed a higher Young’s modulus,
and glass transition temperature, and lower thermal expansion
coefficient than those containing graphene flakes. This behav-
ior was ascribed to intercalated graphene that can lead to a
high amount of high-density polymer in the nanocomposites,
and thus enhance their overall properties.
13.2.2.2  Hydrogel–Graphene Nanocomposites
Alzari et al. exploited the frontal polymerization on sonicated
graphene dispersions in NMP for synthesizing graphene–
poly(N-isopropylacrylamide) nanocomposite hydrogels, reach-
ing a high nanofiller concentration (i.e., 2.21 mg/mL).54 The
swelling ratio of the obtained nanocomposites was significantly
enhanced by the presence of the graphene layers, even at very
low concentrations. Furthermore, the nanofiller was able to
increase the storage modulus and the complex viscosity of the
obtained products, as assessed by rheological measurements.
However, at high concentration (i.e., 0.13 wt.%), graphene was
found to exert a lubrication effect, lowering the rheological
parameters and nearly approaching the pseudoplastic behav-
ior of the neat hydrogel. It is noteworthy that actual polymer
nanocomposites, characterized by a good graphene disper-
sion, were possible thanks to the use of the frontal polymer-
ization technique. Indeed, analogous samples polymerized by
Straightforward Routes for the Preparation of Graphene-Based Polymer Nanocomposites
classical methods (prolonged heating at relatively low tem-
perature) were characterized by graphene reaggregation to
graphite. This is owing to the very fast monomer-to-polymer
conversion typically occurring during the frontal polymeriza-
tion, which “froze” graphene in a metastable, exfoliated state.
Pursuing this research, the same group synthesized ther-
moresponsive graphene–poly(N-vinylcaprolactam) nanocom-
posite hydrogels; the chosen frontal polymerization approach
allowed the obtaining of nanocomposite systems with one of
the highest pristine nanofiller loading reported so far in the
literature (i.e., 5 mg/mL).57 Similarly to graphene–poly(N-
isopropylacrylamide) nanocomposite hydrogels,54 the pres-
ence of the nanofiller turned out to significantly increase the
swelling ratio of the obtained systems (from 1700 unfilled
hydrogel to 3260% for the nanocomposite containing 1 wt.%
of the nanofiller) and to exert a lubricating effect, irrespec-
tive of the employed graphene concentration, as evaluated by
rheological tests.
13.2.2.3  Polyacrylate–Graphene Nanocomposites
Alzari et al. succeeded in preparing poly(tetraethyleneglycol
diacrylate)—graphene nanocomposites by sonicating graph-
ite flakes into the corresponding monomer and subsequently
thermally curing the obtained dispersions.55 Although the
achieved graphene loading was as high as 9.45 mg/mL, the
nanofiller could significantly enhance the glass transition
temperature values, as well as the mechanical properties (i.e.,
flexural and storage moduli) of the polyacrylate matrix up to a
threshold concentration (i.e., 4.67 mg/mL), beyond which the
nanofiller acted as a lubricating agent, hence approaching the
thermal and mechanical behavior of the unfilled polymer.
The addition of exfoliated graphene layers to acrylic
monomers to eventually polymerize turned out to be very
effective also for preparing nanocomposites with potential
use for biomedical applications that require compression
strength and hardness performance as well.56 To this aim, high
­graphene-loaded dispersions (up to 6 mg/mL) were obtained
by simply sonicating graphite flakes in tetraethyleneglycoldi-
acrylate monomer and used in copolymerization reactions with
bisphenol A glycerolate dimethacrylate. Owing to the strong
reinforcing effect provided by the nanofiller, the obtained
nanocomposites showed 14% hardness and 33% elastic modu-
lus increase with respect to the neat copolymer matrix.
13.2.2.4 ​PUR–Graphene Nanocomposites
Recently, Han and Chun succeeded in preparing PUR
nanocomposites with surface-functionalized, nano-­ layered
graphene sheets, exploiting a covalent incorporation of
the nanofiller.94 To this aim, partially reduced graphene
nanosheets or surface-functionalized graphene with diazo-
nium salts carrying phenethyl alcohol groups were physi-
cally blended or covalently bonded with an amorphous PUR,
obtaining a cross-linked structure. The obtained nanocom-
posites were found to exhibit larger shape memory properties
(i.e., up to 98% shape fixity, 94% shape recovery ratio after
four cycles, and very low hysteresis loss at an extremely low
loading of 0.5%), as well as higher mechanical, thermal, and
187
dynamic-mechanical properties, with respect to the reduced
graphene/PUR composites: this behavior was ascribed to
fine dispersion-induced hydrogen interactions taking place in
between graphene sheets and polymer chains.
13.2.2.5 ​Elastomers–Graphene Nanocomposites
Recently, Araby et  al. investigated the electric and thermal
behavior of elastomers (styrene–butadiene rubber) added
to GNP, exploiting a solution mixing process.95 A percola-
tion threshold of electrical conductivity was observed in the
presence of 5.3 vol.% of GNP; furthermore, thermal conduc-
tivity of the elastomer was found to increase three times at
24 vol.% nanofiller concentration. Outstanding enhancements
of the mechanical properties (mechanical strength, Young’s
modulus, and tear strength) were also achieved at 16.7 vol.%
nanofiller. The comparison of solution mixing with melt com-
pounding, where the same starting materials were used, dem-
onstrated that the former is more effective in promoting the
reinforcing effect of GNP, since it provides more interlayer
spacing for elastomer molecules intercalating and retains the
high aspect ratio of the nanofiller, thus leading to the forma-
tion of a filler–filler network at a lower volume fraction.
13.3 ​CONCLUSIONS
This chapter has clearly shown that it is possible to exploit
graphene, either in the form of nanoplatelets or as mono/
few layers obtained by direct sonication of colloidal suspen-
sions of graphite, for preparing nanocomposite materials, in
which the nanofiller is able to strongly affect the final ther-
mal, rheological, mechanical, and electrical properties of the
polymer matrix. The description of the different methods for
exfoliation of the nanofiller currently used has demonstrated
that both the direct sonication from colloidal suspensions of
graphite and the use of GNP are the most convenient ones
as far as the cost and simplicity of procedure are considered.
However, they exhibit significant differences in regard to the
purity and the occurrence of process-induced defects in the
final exfoliated nanofiller. Finally, the possibility of preparing
either thermoplastic- or thermosetting-based graphene nano-
composites with enhanced features even at very low nanofiller
content has been plainly assessed.
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 14 Solar Cells and Ultracapacitors
Polymer Devices with Graphene

Agnieszka Iwan, Bronislaw Szubzda, and Andrzej Sikora

CONTENTS
Abstract.......................................................................................................................................................................................191
14.1 Introduction.......................................................................................................................................................................191
14.2 G as a Material for Polymer Solar Cells........................................................................................................................... 192
14.2.1 G for Transparent Conductive Electrodes in Polymer Solar Cells....................................................................... 193
14.2.1.1 G as an Anode........................................................................................................................................ 193
14.2.1.2 G as a Cathode....................................................................................................................................... 195
14.2.2 G for Interface Layer in Polymer Solar Cells....................................................................................................... 195
14.2.2.1 Functionalized G as an Interface Layer................................................................................................. 196
14.2.3 G for Acceptor in Polymer Solar Cells................................................................................................................. 197
14.2.3.1 Functionalized G as an Acceptor........................................................................................................... 198
14.3 G as the Material for UCs................................................................................................................................................. 199
14.3.1 G-Based Electric Double-Layer Capacitors......................................................................................................... 199
14.3.2 G-Based Electrochemical Capacitors with Pseudo-Capacitance......................................................................... 200
14.3.2.1 Electro-Conducting Polymers................................................................................................................ 200
14.3.2.2 Metal Oxides.......................................................................................................................................... 200
14.4 AFM Study of Polymer Devices with G........................................................................................................................... 201
14.4.1 Polymer Solar Cells with G.................................................................................................................................. 202
14.4.2 UCs with G........................................................................................................................................................... 203
14.5 Conclusion and Outlook................................................................................................................................................... 203
References.................................................................................................................................................................................. 204

ABSTRACT
Graphene (G) exhibits a considerable number of new optical
and electronic effects that have not been observed in other
materials such as zero-band-gap semiconductivity with a high
carrier mobility, high optical transparency, and high tensile
strength. Various chemical synthetic methods are used to
obtain G for basic studies and industrial applications. In this
chapter, we discuss two different kinds of polymer devices
with G or graphene oxide such as: (i) solar cells and (ii) ultra-
capacitors. With respect to all analyzed devices, we propose
to analyze G based on three aspects: (1) as the addition to
polymer, (2) as transparent conductive electrodes, and (3) as
interface layers. This chapter is closed by examples of atomic
force microscopy analytes of properties of G-based materi-
als for energy conversion and storage in polymer solar cells
and ultracapacitors. We analyzed the results of investigations
described in articles published from 2007 to 2014 because
there were essentially no papers dedicated to this subject
before 2007. The selection of referenced papers is subjective,
and our primary objective is to emphasize the new and impor-
tant trends in various polymer devices with G.
14.1 ​INTRODUCTION
Graphene (G) is a material which thanks to its structure shows
a lot of absolutely unique properties. Therefore, it constitutes a
raw material that can potentially contribute to completely rev-
olutionary changes in materials engineering, in particular, in
technologies connected with electronic and electroenergetic
engineering. The range of particular features, which G shows,
includes a list of properties, which is continuously comple-
mented with new properties: electrical, thermal, magnetic,
optical, chemical, and mechanical ones. It is widely described
in the scientific and popular literature (e.g., References 1–5).
We can observe a significant interest in G among experts in
the domains in which its practical use is expected.
Many of these unique properties suggest employing G
in power engineering—a strategically important domain in
today’s world. After many years of dominance, the world is
quickly running out of sources of conventional energy, which
results in ecological, technological, and social problems that
are difficult to assess. A new trend in the energy industry is
expected to increase the use of new energy sources which
are less dangerous for the environment. Clean and renewable

191
192
TABLE 14.1
Methods Synthesis of G
Top Down Bottom Up
Mechanical exfoliation Epitaxial growth on different substrates
Chemical oxidation Chemical vapor deposition
Exfoliation Arc discharging methods
energy sources are becoming more and more important and
their share in the general energy balance must grow all the
time. A solution to the problem of energy storage needs to be
found.
Currently, G or graphene oxide (GO) is tested as the addi-
tion to polymer, as transparent conductive electrodes, and
as separate layers in different devices such as light-emitting
diodes, field effect transistors, organic photovoltaic devices
(OPV), fuel cells, or ultracapacitors (UCs) (e.g., References
6–10). In our work G (or GO) is analyzed in such polymer
devices as solar cells and UCs. In this chapter, we would like
to discuss the advantages and disadvantages of polymer solar
cells and UCs that incorporate G.
Considering the parameters of constructed polymer devices
with G, it should be stressed that the methods of G prepara-
tion strongly influence the performances of the devices (e.g.,
[6–10]). Generally, two methods of G synthesis are known: (1)
top down and (2) bottom up [9–11]. Details of both methods
of G synthesis are summarized in Table 14.1.
The chemical vapor deposition (CVD) method of G films
preparation is much more attractive for efficient organic pho-
tovoltaics owing to their superior electrical and surface prop-
erties compared to rGO.
It is known that G exhibited such advantages as high car-
rier mobility and better mechanical flexibility than indium tin
oxide (ITO) electrodes. At the present time the best value of
the sheet resistance of G is 30 Ω/◻ (with optical transmittance
90% for G multilayers) and is comparable with the sheet resis-
tance of often used ITO electrodes in organic photovoltaics
(Rs = 10 Ω/◻, Tr = 85%). However, the G plates obtained up
to date are characterized with sheet resistance of the order of
a few hundred Ω/◻, which is insufficient at a transparency of
~80%. On the other hand, the resistance of G is 1 × 10 −8 Ωm
and is three time of magnitude higher than the resistance of
ITO (2.4 × 10 −5 Ωm) and is moreover, comparable with the
resistance of Cu and Ag. The good way to receive better val-
ues of resistance is to dope or functionalize G with different
organic and inorganic compounds [9,12].
14.2 ​G AS A MATERIAL FOR POLYMER
SOLAR CELLS
The development of organic photovoltaics (called also poly-
mer photovoltaics) at the current time includes: (1) synthesis
of new polymers and small-molecular compounds for active
layers, (2) modification of the architecture of the solar cell,
and (3) improvement of processing methods of solar cell
Graphene Science Handbook
construction (e.g., [13–21]). The synthesis of new materials
with different structures such as polymers, oligomers, den-
drimers, pigments, dyes, and liquid crystals for photovoltaic
applications required careful purification to obtain optimum
efficiency and stability [22].
As a donor (D) polymer, widely investigated in polymeric
photovoltaics, poly(3-hexylthiophene) (P3HT) is applied
[13–21]. It is the excitation of the pi-orbit electron in P3HT
that gives the PV (photovoltaic) effect [23]. However, vari-
ous polymers such as donor or donor-acceptor are synthe-
sized and their application is tried in polymer solar cells.
For example, a device based on poly[4,8-bis-substituded-
benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl-alt-4-substituded-
thieno[3,4-b]thiophene-2,6-diyl] (PBDTTT) and PC70BM
possesses a value of power conversion efficiency (PCE)
of about 7.4% [24]. As an acceptor, mainly [6,6]-phenyl-
C61-butyric acid methyl ester (PCBM) and [6,6]-phenyl-
C70-butyric acid methyl ester (PC70BM) possessing a high
hole mobility are tested (e.g., [13–23]). The chemical struc-
tures of some polymers applied in organic photovoltaics
along with the chemical structure of the typical acceptor
(PCBM) are presented in Figure 14.1.
On the other hand, considering the architecture of poly-
mer solar cells bulk heterojunction (BHJ) devices [25] with
architecture such as tandem [26], inverted [27,28], and elastic
[29–31] polymer solar cells are constructed and investigated.
The BHJ structure helps to increase the exciton separation,
but charge mobility and collection efficiency are affected
[13–22]. A typical current density–voltage curve of an organic
solar cell along with the photovoltaic parameters (FF: fill fac-
tor, η (PCE): power conversion efficiency) and architecture of
BHJ devices are presented in Figure 14.2.
The general mechanism in organic photovoltaic cells
leading to the generation and collection of charge carriers in
organics includes such processes as: (1) photon absorption, (2)
generation of excitons, (3) exciton diffusion, (4) exciton disso-
ciation (hole–electron separation), (5) carrier transport toward
the electrodes, and (6) charge collection at the respective elec-
trodes (e.g., [6,13–22]).
The molecular structure of the donor and acceptor applied
along with the architecture of constructed devices and con-
ditions (air atmosphere, oxygen, water, temperature, and
stability) influences the parameters of polymer solar cells.
Presently, the main problem with organic solar cells is the sta-
bility of the devices, which without encapsulation have very
short lifetime (from few minutes to a few days). Apart from
oxygen and water, the stability of organic solar cells nega-
tively influence the direct contact of the Al electrode with the
active layer and the presence of the hygroscopic PEDOT:PSS
layer, which adsorb the moisture from the atmosphere and
consequently increase the resistance of ITO [15].
Polymer solar cells containing G or GO based mainly on
P3HT are investigated in three aspects: (1) as transparent
conductive electrodes (anode or cathode), (2) interface layer,
and (3) as the addition (acceptor) to donor or donor-acceptor
material in BHJ organic photovoltaic cells as is schematically
presented in Table 14.2.
Polymer Devices with Graphene 193

O O H17C8
CH3 C C8H17
H3C CH3 N
F O
C6H13 O S O O
O
H S S
C C S
S S n S S
n
n n
P3HT H O O PBDTTPD
O PBDTTT-3
MDMO-PPV
CH3
S S S
N N N N N N

S S S
R R
N S
n n
H25C12 n = 1-4, R: H, Br APFO-3
PTPTB H17C8 C8H17

C4H9 S
C4H9 N N

C2H5 C2H5
OC12H25 S
N N S
S n
N
PCDTBT
S S CH
S n H17C8 C8H17
N N
OC12H25 S
P

OCH3
C

PCBM

FIGURE 14.1  Chemical structure of some typical polymers used in organic solar cells along with the chemical structure of PCBM applied
as an acceptor.

14.2.1 ​G for Transparent Conductive
Electrodes in Polymer Solar Cells
Presently, transparent electrode ITO is used to construct solar
cells. The disadvantages of ITO such as limited resources,
cost, brittleness, and chemical stability resulted in new mate-
rials being investigated for application as transparent elec-
trodes in devices. G has a transparency of about 98% per
monolayer, high electron mobility and chemical stability, and
flexibility, and can be applied in transparent electrode appli-
cations [9,12]. G can be applied as a replacement for ITO
(anode) or and Al (cathode) for the transparent electrodes of
polymer solar cells [6–8].
14.2.1.1 ​G as an Anode
For polymer solar cells with G used as an anode, the PCE value
was found to be in the range 0.1%–2.58% [6–8,32–34,40–48].
G, GO, or doped G was applied as an anode on the glass or
flexible substrate [6–8,32–34,40–48]. G was obtained as an
anode by the modified Hummers’ method or by the CVD
method [6–8]. The best performances exhibited polymer solar
cells with G obtained via the CVD method. The architecture
of the investigated polymer solar cells with G as an anode
was usually such as G/PEDOT:PSS/P3HT:PCBM/Al in some
cases before the aluminum electrode LiF or Ca or TiO2 (few
nanometers thick) was applied as a buffer layer [6–8,32,40–
44]. The presence of a thick buffer layer, for example, LiF
in organic solar cell enlarges Voc and acts as a block layer
to prevent the reaction between the Al electrode with active
layer [15].
As an example, the best performance (PCE = 2.58% and
FF = 48%) was exhibited by solar cells with the architec-
ture glass/G/PEDOT:PSS/P3HT:PCBM/Ca/Al [32]. G was
obtained by layer-by-layer (LbL) molecular doping with
194 Graphene Science Handbook

O
I/mA Under illumination N N O
Al
O
P3HT:PCBM N
PEDOT:PSS
ITO O
In dark N T N
Substrate PBASE
U/V
FIGURE 14.3  Chemical structure of the organic compounds T
VOC*ISC*FF VMPP VOC and PBASE used to modify G applied in solar cells as an anode.
ηe =
Pin
Impp*Vmpp
FF =
Isc*Voc
with G was lower than for solar cells with ITO applied as an
IMPP anode (PCE = 3.80%) [43].
Another example of applied modified G in polymer solar
ISC cells was presented by Wang et al. [42]. G modified by pyrene
butanoic acid succidymidyl ester (PBASE) used in the device
with architecture G–PBASE/PEDOT:PSS/P3HT:PCBM/LiF/
FIGURE 14.2  Typical current density–voltage curve of an organic
solar cell along with the photovoltaic parameters and architecture
Al exhibited PCE at 1.71%, however, compared to the device
of BHJ device. ISC, the short circuit current; VOC, the open circuit with ITO, this value is low (PCE = 3.10%) [42]. On the other
voltage; IMPP, the current at maximum power point (MPP); VMPP, the hand, devices with lack of PBASE exhibited very low value of
voltage at maximum power point; FF, fill factor, and η (or PCE) PCE at 0.21%. This behavior can be explained by the fact that
power conversion efficiency. The photovoltaic devices are tested the work function of G obtained by CVD method was 4.2 eV,
under an air mass 1.5 G illumination at 1000 W m−2. whereas for G–PBASE it was 4.7 eV [42]. The chemical struc-
ture of T and PBASE is presented in Figure 14.3.
tetracyanoquinodimethane (T) process on G. The authors 14.2.1.1.1 ​G as a Flexible Anode
[32] investigated the influence of G layers on the photovoltaic G owing to its high specific surface area and mechanical
parameters of the constructed devices. The best result was flexibility is probably a good example to be applied as a flex-
obtained for the anode structure with two T layers (G/T/G/ ible electrode material [33,34,45–48]. In a few papers, G was
T/G) [32]. applied as an anode on flexible substrates such as poly(ethylene
Choe et al. [43] investigated the influence of a TiOx layer terephthalate) (PET) or poly(vinylidene fluoride-co-trifluo-
on the performance of BHJ solar cells with a transparent roethylene) (P-(VDF-TrFE)) [6,33,34,48]. Devices with the
multilayer G anode prepared by the CVD method (glass/G/ architecture PET/G/PEDOT:PSS/P3HT:PCBM/Ca(or TiO2)/
PEDOT:PSS/P3HT:PCBM/TiOx/Al) [43]. The enhance- Al were investigated [33,34]. The best photovoltaic parameters
ment of the PCE in the devices with a TiOx layer was evi- (PCE = 2.54% and FF = 55.9%) were found for the device with
dent (PCE = 2.60%, PCE for device with lack of TiOx layer a G electrode doped with HNO3 obtained by the CVD method
1.34%) [43]. The TiOx layer functions as an optical spacer and [34]. However, the device with G with lack of HNO3 exhibited a
hole blocking layer and for these reasons, it retains holes in lower PCE value at 1.77%. It is interesting that the authors [34]
the p-type material and allows electrons to be transferred to compared the influence of the glass and flexible substrate on
the n-type material [6]. However, the performance of devices the performance of organic solar cells with G. For the devices
with a G–HNO3 electrode, the same PCE value was found [34].
Interesting work concerning applied GO on the flexible
TABLE 14.2 substrate as an anode was done by Yin et al. [33], however, the
Role (Place) of G or GO in BHJ Polymer Solar Cells best PCE value was quite low (PCE = 0.78%). GO in this case
was obtained by the modified Hummers’ method. The device
Architecture of Polymer Solar Cell Role of G Ref.
with the architecture PET/GO/PEDOT:PSS/P3HT:PCBM/
Glass/G/PEDOT:PSS/P3HT:PCBM/Ca/Al Transparent [32] TiO2/Al was analyzed in detail considering the thickness of
anode GO layers [33]. TiO2 in the device was applied as a hole block-
PET/G/PEDOT:PSS/P3HT:PCBM/Ca/Al Transparent [33,34]
ing layer. The best performance was obtained for the 16 and
flexible anode
21 nm thickness of the layers, which is also caused by the
Glass/ITO/ZnO/P3HT:PCBM/ Transparent [35]
PEDOT:PSS/G cathode
fact that the transmittance was not so low (T = 65% and 55%,
Glass/ITO/GO/PBDTTPD:PCBM/ZnO/ Interface layer [36]
respectively) as in the case of 4 and 10 nm thickness of the
LiF/Al layers (T = 88% and 78%, respectively) [33].
Glass/ITO/TiOx/PCDTBT:PCBM/GO/Al Interface layer [37] Arco et  al. [47] and Park et  al. [46] investigated flexible
Glass/ITO/PEDOT:PSS/P3HT:G:MDMO- Acceptor [38] organic solar cells with G as an anode and found PCE in the
PPV/LiF/Al range 1.18%–1.51%.
Glass/ITO/PEDOT:PSS/GO–P3HT/C60/Al Addition [39] Kim et al. [48] improved the performance and long-term
stability of G-based polymer solar cells using electrostatically
Polymer Devices with Graphene
TABLE 14.3
Some Examples of PCE Values for Polymer Solar Cells
with G as an Anode
Architecture of Polymer Solar Cell PCE (%)
Glass/G/PEDOT:PSS/P3HT:PCBM/Ca/Al 2.58
Glass/G/PEDOT:PSS/P3HT:PCBM/TiOx/Al 2.60*
Glass/G/PEDOT:PSS/P3HT:PCBM/Al 1.34
G–PBASE/PEDOT:PSS/P3HT:PCBM/LiF/Al 1.71**
G/PEDOT:PSS/P3HT:PCBM/LiF/Al 0.21
Flexible Anode
PET/G/PEDOT:PSS/P3HT:PCBM/Ca 2.54
(or TiO2)/Al
PET/GO/PEDOT:PSS/P3HT:PCBM/TiO2/Al 0.78
P(VDF-TrFE)/G/PEDOT:PSS/P3HT:PCBM/ 2.07***
Ca/Al
Note: With ITO PCE equal to 3.80%*, 3.10%**, and 2.86%***.
doped G films via a ferroelectric polymer (P(VDF-TrFE)). A
device with the architecture P(VDF-TrFE)/G/PEDOT:PSS/
P3HT:PCBM/Ca/Al was analyzed in detail considering the
number of G layers and the influence of voltage applied to
polarize the ferroelectric film [48]. The best PCE value equal
to 2.07% was found for the polarized device with five G lay-
ers (for the unpolarized device, the PCE value was lower at
1.68%). Unfortunately, the device with ITO as an anode (lack
of G layers) exhibited a higher PCE value = 2.86% [48].
The PCE values for polymer solar cells with G as an anode
are summarized in Table 14.3.
14.2.1.2 ​G as a Cathode
The polymer solar cell devices with G applied as a cathode
exhibited a PCE from 0.30% to 2.70% [6–8,35,45,49–51].
Organic solar cells with G applied as a cathode are investi-
gated as semitransparent devices and in the most cases are
illuminated from both sides (anode or cathode) [6–8,35,45,49–
51]. For these devices as an anode, ITO, Ag, or Au are tested
[6–8,45,49,50]. Good performance was exhibited by the semi-
transparent inverted solar cells with the architecture ITO/
ZnO/P3HT:PCBM/GO/G (PCE 1.88% and 2.04% for 10 and
8 layers of G, respectively, for shining from the G side, and
2.50% (2.40%) for shining from the ITO side) [51]. G in this
case was obtained by the CVD method [51]. For the reference
device ITO/ZnO/P3HT:PCBM/GO/Ag with a silver cathode,
the highest PCE value was detected (PCE = 3.30%) [51].
A solar cell with the architecture ITO/ZnO/P3HT:PCBM/
PEDOT:PSS/G (or Au–G) was illuminated from the ITO and
G side. The best PV parameters were obtained for the 410 nm
thickness of ITO, G, and graphene doped with Au. The work
function of G was about 5 eV, whereas for ITO it was 4.8 eV
[35]. The PCE of a device with G and Au–G (illuminated from
the G side) was found to be 1.40% and 1.98% respectively,
whereas for the device illuminated from the ITO side it was
1.95% [35]. Liu et al. [35] showed that devices with G doped
195
by Au (obtained by the CVD method) exhibited the highest
PCE value . Moreover, the position of the G layer doped with
Au strongly influence the performance of the devices. The
best PCE values were found for organic solar cells with Au–G
layer close to the anode [35]. The device with the architecture
Ref.
G/Au–G/PEDOT:PSS/P3HT:PCBM/G has a PCE of 2.70%,
[32]
whereas device ITO/Au–G/PEDOT:PSS/P3HT:PCBM/G has
[43]
a PCE of 2.22% [35].
[43]
[42]
The device with the architecture Au/MoO3/P3HT/ZnO/
[42]
PEDOT PEG(PC) or RG-1200/G [49] possesses a low PCE
value of about 0.3%–0.5%. In this case, P3HT and PbS were
used as a photoactive materials. It is very interesting that the
[34] change of P3HT by PbS quantum dots drastically increase the
PCE value to 4.2% [49]. Devices with ITO PbS as a cath-
[33] ode exhibited PCE at 5.1%, whereas solar cells with ITO and
[48]
P3HT possess PCE of 0.4% [49]. ZnO nanowires were grown
on PEDOT:PEG(PC) (poly(3,4-ethylenedioxythiophene)-
block-poly(ethylene glycol) doped with perchlorate, PC) or
sulfonated poly(thiophene-3-[2-(2-methoxyethoxy)-ethoxy]-
2,5-diyl (abbreviated RG-1200) by a hydrothermal method
[49]. The work function of G was 4.3 eV, whereas for Au it
was 5.1 eV [49].
An Al–TiO2 composite was applied to modified single
layer G toward application in BHJ solar cells [50]. The device
with the architecture Ag/MoO3/P3HT:PCBM/Al–TiO2/G
was investigated. The work function of G decreased from
4.6 to 4.1 eV via the G electrode modified with the Al–TiO2.
For the device with Al–TiO2/G applied as a cathode, PCE
was found at 1.59%, whereas it was higher for the cathode
grid/G/Al–TiO2 (PCE = 2.58%). The highest PCE value was
found for the reference device with the ITO/Al–TiO2 cathode
(PCE = 3.45%) [50].
In conclusion, G can theoretically be applied in polymer
solar cells as an electrode (one or both electrodes), however, in
practice, it is still not good enough to be used instead of ITO.
To realize the successful application of G as an electrode in
polymer solar cells, G should be prepared in the form of thin
films with large area, almost no defects, and intact surface
[7]. For these reasons only, G prepared by the CVD method
promises to be used with success in polymer solar cells and
increase performance in the devices [7,45]. Presently, the rela-
tively low PCE values for organic solar cells with G applied as
electrodes are caused by the relatively high sheet resistance of
G film and some wrinkles in the grown G [7,45]. Therefore,
it is important to improve the CVD growth processing condi-
tions of G layer toward efficient organic BHJ solar cells.
The PCE values for polymer solar cells with G as cathode
are summarized in Table 14.4.
14.2.2 ​G for Interface Layer in Polymer Solar Cells
The highest PCE values were achieved among devices where
G was used as an interface layer (PCE from 0.22% to 8.21%)
compared to solar cells where G was used as an electrode or
as an additive to the polymer [6–8,36,37,52–62]. The influ-
ence of the GO interlayer position on PCE values of polymer
solar cells is investigated [54].
196
TABLE 14.4
Some Examples of PCE Values for Polymer Solar
Cells with G as a Cathode
Architecture of Polymer Solar Cell PCE (%)
ITO/ZnO/P3HT:PCBM/GO/G 2.04*
ITO/ZnO/P3HT:PCBM/GO/G 2.40a
ITO/ZnO/P3HT:PCBM/ 1.40 (1.98)*
PEDOT:PSS/G (or Au–G)
ITO/ZnO/P3HT:PCBM/ 1.95**
PEDOT:PSS/G (or Au–G)
G/Au–G/PEDOT:PSS/P3HT:PCBM/G 2.70***
Au/MoO3/P3HT/ZnO/PEDOT 0.3–0.5
PEG(PC) or RG-1200/G
Ag/MoO3/P3HT:PCBM/Al–TiO2/G 1.59b
a With Ag PCE = 3.30%.
b Cathode grid/G/Al–TiO2 PCE = 2.58%.
*Illuminated from G side; **illuminated from ITO side; ***with
ITO PCE = 2.22%.
As a hole transporting layer (HTL), commonly PEDOT:PSS
is applied in organic solar cells (e.g., [13–22]). However,
PEDOT:PSS has a problem with acidity and hygroscopicity,
which decrease the solar cell performance and shorten its
life [7]. Organic solar cells still have problems with stability
[36]. For this reason, GO is proposed to be applied as a HTL
in organic solar cells. The device with the architecture ITO/
GO/PBDTTPD:PCBM (1:4)/ZnO/LiF/Al has a PCE equal to
5.50% [36]. Chemical structure of copolymer PBDTTPD is
presented in Figure 14.1. When instead of GO reduced GO
(r-GO) (or PEDOT:PSS) was used, the PCE was lower and was
found to be at about 4.6% [36] in both cases. Structural dif-
ferences between GO and r-GO are presented in Figure 14.4.
A similar PCE value equal to 5.33% was obtained by
Sharma et al. [60] for the device with the architecture ITO/
rGO–TiO2/P:PC70BM/Al. Devices without the interfacial
layer or only with the TiO2 layer exhibited lower PCE values
PCE (3.26% and 4.18%, respectively) than devices with the
rGO–TiO2 interlayer. The chemical structure of polymer P is
presented in Figure 14.1.
Yusoff et  al. [37] investigated devices with the architec-
ture ITO/TiOx/PCDTBT:PCBM (1:4)/GO/Al considering
the thickness of the GO layer. The chemical structure of
PCDTBT is presented in Figure 14.1. Device with lack of the
GO layer exhibited a PCE value of about 1.49%, whereas for
organic solar cells with a GO layer of thickness 20–40 nm,
PCE was found in the range 4.21%–4.63% [37]. This device
possesses good stability over 2160 h of storage. The efficiency
was reduced only about 3.67% (PCE = 4.46%).
Polymer solar cell devices with GO applied as an interface
layer with the architecture ITO/GO/NiOx/P3HT:PCBM/LiF/
Al (PCE 3.48%) [55], ITO/r-GO/P3HT:PCBM/Ca/Al (PCE
3.70%) [56], ITO/GO/P3HT:PCBM/Al (PCE 3.5%) [57],
ITO/r-GO/P3HT:PCBM/LiF/Al with r-GO obtained by spray
process at 400°C (PCE 3.71%) [59], and ITO/PEDOT:PSS/
PCDTBT:PCBM/GO–Cs–Al/GO/MoO3/PCDTBT:PCBM/
Graphene Science Handbook
Ca/Al (tandem device, PCE 3.91%) [62] exhibited a simi-
lar PCE value almost independent of the architecture of the
device. In Reference 57, it was shown that a change in the GO
layer by PEDOT:PSS one, does not influence the increase in
the performance of the solar cell (PCE 3.6%). In the device
Ref.
ITO/GO/NiOx/P3HT:PCBM/LiF/Al, NiOx was applied as the
[51]
additional HTL layer which leads to planarization of the GO
[51]
layer and increase in the photovoltaic parameters [55].
[35]
Iwan et al. [54] tested OPV with the GO obtained by modi-
[35] fied the Hummers’ method considering the position of the GO
layer in device. Three different configurations such as ITO/
[35] PEDOT:PSS/P3HT:PCBM/GO/Al, ITO/GO/P3HT:PCBM/
[49] PEDOT:PSS/Al, and ITO/GO/P3HT:PCBM/GO/Al were
investigated. The device with the GO layer placed close to
[50] the Al cathode (ITO/PEDOT:PSS/P3HT:PCBM/GO/Al)
showed better photovoltaic parameters in comparison with
other kinds of devices with the GO interlayer investigated in
Reference 54, giving a PCE of 0.47%. However, the device
with lack of the GO layer ITO/PEDOT:PSS/P3HT:PCBM/Al
gives the highest PCE value of 1.38% from the all investi-
gated devices in Reference 54. The interesting fact is that the
reference device ITO/PEDOT:PSS/P3HT:PCBM/Al [54] with
the not annealed P3HT:PCBM active layer showed the pho-
tovoltaic parameters (FF of 0.21% and PCE of 0.57%) simi-
lar to the photovoltaic parameters of the device with the GO
interlayer placed close to the Al cathode, ITO/PEDOT:PSS/
P3HT:PCBM/GO/Al (FF of 0.30% and PCE of 0.47%) [54].
The devices comprising the GO interlayer on the ITO (instead
of PEDOT:PSS), or on the ITO and before Al, showed very
low photovoltaic performance (PCE~0.004%) [54].
The highest PCE value equal to 8.21% was found by Yu
et al. [61] for the device with a modified PEDOT:PSS layer.
The device with the architecture ITO/PEDOT:C-GO (pH = 9)
composite layers/PTB7:PC70BM/Al exhibited a higher
PCE value than the device with PEDOT:GO interlayer with
pH = 3 (PCE 7.48%). The device with PEDOT:PSS applied
as a HTL exhibited the lowest value of PCE = 7.04% [61].
PTB7 is poly[[4,8-bis[(2-ethylhexyl)oxy]-benzo[1,2-b:4,5-b’]
dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]
thieno[3,4-b]thiophenediyl]].
14.2.2.1 ​Functionalized G as an Interface Layer
Zheng et  al. [53] proposed modified GO by Mo6+ cation by
the low-temperature solution method with different amounts
of ammonium heptamolybdate (Mo-precursor) added into the
GO solution. The amount of Mo-precursor strongly influences
the performance of organic solar cells with the configuration
ITO/GO/P3HT:PCBM/Al [53]. The highest PCE value of 2.61%
was found for the device with 0.10 g of Mo-precursor and was
identical with the PCE value of the device ITO/PEDOT:PSS/
P3HT:PCBM/Al with lack of the GO HTL layer [53]. The device
ITO/P3HT:PCBM/Al exhibited a low PCE value of about 0.19%
[53]. It was found that the improvement of performance of solar
cells was owing to Mo cation in the GO layer rather than the
molybdenum oxide crystal in the GO/MoO3 composition [53].
Changing the periphery groups –COOH in GO to –COOCs
(see Figure 14.4) [12,63] could improve the performance of
Polymer Devices with Graphene 197

HO O HO O HO HO
HO HO HO O O HO
C C C C
C O C O
OH OH
C C
OH O OSO3H OSO3H O
HO
O HO C O OH
O C
OSO3H O
OH
OH
HO C HO C C
O OH C C O
GO O C
HO O HO O HO O
GO–OSO3H
HO O HO O
HO HO HO
C C
C O CsOOC CsOOC
CsOOC
OH COOCs
C
O COOCs
HO OH
CsOOC
O
OH
HO C COOCs
O OH C CsOOC
HO O COOCs COOCs
r-GO
GO–COOCs
H13C6

S CH2OH
OOC CH2
H13C6 n

H13C6
HOH2C CH2
S n
O
COO
O CH2 CH2OH
S
n
COO
HO
H13C6
H13C6
COO
C O CH2 S CH2OH
HOH2C CH2O O n
S
n

FIGURE 14.4  Chemical structure of GO, r-GO, GO–OSO3H, GO–COOCs, and GO–P3HT.

solar cell devices via change in the work function of GO.
GO–Cs applied as an electron extraction layer in the BHJ
devices ITO/GO/P3HT:PCBM/GO–Cs/Al and ITO/GO–Cs/
P3HT:PCBM/GO/Al give a PCE as high as 3.67% [63].
Sulfonated GO (GO–OSO3H) (see Figure 14.4) applied as
a hole extraction layer (HEL) in the polymer solar cell with
the configuration ITO/GO–OSO3H/P3HT:PCBM/Ca/Al
gives a PCE value in the range 4.23%–4.37% depending on
the thickness of the HEL (2–6 nm) [64]. Devices with the non-
functionalized GO layer exhibited a lower PCE value (2.66%–
3.04%). The device possessing PEDOT:PSS layer exhibited a
similar PCE value as the device with the GO–OSO3H layer
with 2 nm thickness (4.39% and 4.37%, respectively) [64].
The PCE values for polymer solar cells with G as an inter-
face layer are summarized in Table 14.5.
14.2.3 ​G for Acceptor in Polymer Solar Cells
In organic photovoltaics, major effort is being made to synthe-
size new acceptors (e.g., References 65,66). Compounds such
as perylene diimide, polymers with fullerene in the main or
side chain, polyimides, and fullerenes (C60, C70) were tried
for application as acceptors in organic solar cells. However,
currently the best performance is exhibited by devices with
PCBM (e.g., [6,13–22]). Theoretically, G has significant poten-
tial to be used as an acceptor for OPV owing to its very good
electron transport properties and very high carrier mobility,
however, this is still very far from application from the practi-
cal point of view [6–8].
In polymer solar cells with G used as an addition to the
active layer, the PCE value was found to be in the range
198 Graphene Science Handbook

TABLE 14.5 S O
Some Examples of PCE Values for Polymer Solar Cells C N H2N C
PITC HO
with G as an Interface Layer ANI BA
Architecture of Polymer Solar Cell PCE (%) Ref. C60

ITO/GO/PBDTTPD:PCBM (1:4)/ZnO/LiF/Al 5.50* [36] O

ITO/rGO/PBDTTPD:PCBM (1:4)/ZnO/LiF/Al 4.60 [36] C8H17
N
ITO/rGO–TiO2/P:PC70BM/Al 5.33** [60]
ITO/TiOx/PCDTBT:PCBM (1:4)/GO/Al 4.63*** [37] O
ITO/GO/NiOx/P3HT:PCBM/LiF/Al 3.48 [55] O
ITO/r-GO/P3HT:PCBM/Ca/Al 3.70 [56]
ITO/GO/P3HT:PCBM/Al 3.5 [57] N
C8H17
ITO/r-GO/P3HT:PCBM/LiF/Al 3.71 [59]
O PDI
ITO/PEDOT:PSS/P3HT:PCBM/GO/Al 0.47**** [54]
ITO/PEDOT:C-GO (pH = 9) composite layers/ 8.21a [61]
FIGURE 14.5  Chemical structure of the organic compounds used
PTB7:PC70BM/Al
to modify G applied in solar cells as an acceptor.
ITO/PEDOT:PSS/PCDTBT: PCBM/GO–Cs 3.91 [62]
–Al/​GO/MoO3/PCDTBT:PCBM/Ca/Al
ITO/GO with Mo/P3HT:PCBM/Al 2.61b [53]
GO functionalized chemically with CH2OH-terminated
ITO/GO/P3HT:PCBM/GO–Cs/Al 3.67 [63]
P3HT was applied in an organic solar cell with the architec-
ITO/GO–Cs/P3HT:PCBM/GO/Al 3.67 [63] ture ITO/PEDOT:PSS/GO–P3HT/C60/Al [39]. The presence
ITO/GO–OSO3H/P3HT:PCBM/Ca/Al 4.37c [64] of GO–P3HT (see Figure 14.4) as hole transporting material
in the active layer in the device caused a three-fold enhance-
a With PEDOT:PSS: PCE = 7.04%. ment of efficiency in comparison with the solar cell with lack
b 0.19%. of GO (0.61% and 0.20%, respectively) [39]. Good band-gap
c 3.04%.
matching between the chemically bonded P3HT and GO
*With PEDOT:PSS: PCE = 4.60%; **without rGO–TiO2: PCE = 3.26%; enhances charge transport and consequently increases the
***without GO: PCE = 1.49%; ****1.38%.
performance of the organic solar cell [12].
Fullerene C60 functionalized G for efficient BHJ organic
0.002%–1.5% [6–8,38,52,67,68]. The highest PCE value solar cells with the configuration ITO/PEDOT:PSS/P3HT:G–
(1.5%) was observed for the device architecture ITO/ C60/Al exhibited the PCE at about 1.22% and was higher
PEDOT:PSS/P3HT:G:MDMO-PPV (10:1:1.5)/LiF/Al [38]. than for the device with lack of G possessing an active layer
The chemical structure of MDMO-PPV is presented in Figure P3HT:C60 (PCE 0.47%) [71]. In this case, functionalized G
14.1. For the device with the active layer with lack of MDMO- was used as an electron transporting material in the active
PPV the PCE value was lower (1.05%) [38]. Instead MDMO- layer of the photovoltaic solar cell [12].
PPV by P3OT (poly(3-octylthiophene) in the device ITO/ Graphene quantum dots (GQDs) functionalized with ani-
PEDOT:PSS/P3HT:G:P3OT (10:1:1)/LiF/Al caused a small line (ANI) were used in the active layer of the device ITO/
decrease in the PCE value from 1.33% to 1.12% [38]. PEDOT:PSS/P3HT:ANI-GQDs/LiF/Al [72]. The highest PCE
value was found for the device with 1 wt.% of ANI-GQDs
14.2.3.1 ​Functionalized G as an Acceptor to P3HT (PCE 1.14%). Similar efficiency was found by Ye
With a view to increase the performance of organic solar cells et al. [68] for the device with the active layer P3HT:BCFG-F
with G applied as an acceptor, a few works were dedicated to (10 wt.% of BCFG-F), where G was functionalized with ben-
the functionalization of G or GO [12,39,67–72]. zoic acid. The chemical structure of the organic compounds
Liu et  al. [69] functionalized GO with a phenyl isocya- applied to functionalize GO applied as an acceptor in polymer
nate (GO–PI) toward organic photovoltaics. The device ITO/ solar cells is presented in Figure 14.5.
PEDOT:PSS/P3HT:GO–PI/LiF/Al exhibited a PCE value of The PCE values for polymer solar cells with G as an accep-
about 1.1% [69]. A similar PCE value of 1.02% was found for tor are summarized in Table 14.6.
the device ITO/PEDOT:PSS/P3HT:GO–PITC/Al possessing Further development in such areas as the (i) controlled
GO functionalized with phenyl isothiocyanate in the active synthesis of G, (ii) large scale of G synthesis, (iii) different
layer (PITC, see Figure 14.5) [67]. structures of G including layer number, size, defects, and edge
The organic solar cell with G N,N-dioctyl-3,4,9,10- group, and (iv) improvement of the sheet resistance for the
perylenedicarboximide hybrid wire (G–PDI, see Figure transparent electrode application are required [9,12] for the
14.5) was investigated by Wang et al. [70]. The device ITO/ continued success of G or GO in polymer solar cells. For the
PEDOT:PSS/P3HT:G–PDI/LiF/Al with G–PDI hybrid wire CVD synthesis of G, more attention to their scalability and
(P3HT:G–PDI 1:0.5) exhibited a higher PCE value (1.04%) defect controls are key [9,12]. G electrode resistance is still
than the device with G–PDI mixture (P3HT:G–PDI 1:10, PCE about one order of magnitude higher in sheet resistance than
0.002%) [70]. ITO. Theoretical results showed that G can give the same as
Polymer Devices with Graphene 199

1000
TABLE 14.6
Fuel cells
Some Examples of PCE Values for Polymer Solar 100

Energy density (Wh/kg)

Cells with G as an Acceptor Batteries
10
Architecture of Polymer Solar Cell PCE (%) Ref.
1 Ultracapacitors
ITO/PEDOT:PSS/P3HT:G:MDMO-PPV 1.5 [38]
(10:1:1.5)/LiF/Al
ITO/PEDOT:PSS/P3HT:G:P3OT (10:1:1)/ 1.12 [38] 0.1
Capacitors
LiF/Al
ITO/PEDOT:PSS/P3HT:GO–PI/LiF/Al 1.10 [69]
0.001 0.01 0.1 1 10 100 1000
ITO/PEDOT:PSS/P3HT:GO–PITC/Al 1.02 [67]
ITO/PEDOT:PSS/P3HT:G–PDI/LiF/Al 1.04 [70] Power density (kW/kg)
ITO/PEDOT:PSS/GO–P3HT/C60/Al 0.61* [39]
ITO/PEDOT:PSS/P3HT:G–C60/Al 1.22** [71] FIGURE 14.7  Ragone plot. Areas of application of energy storage
ITO/PEDOT:PSS/P3HT:ANI-GQDs/LiF/Al 1.14 [72] devices.

*Lack of GO: PCE = 0.20%; **lack of G: PCE = 0.47%.

layer. On the other hand, high areas of monolayers constitute a
valuable property in producing non-organic composites, which
PCE (%) Polymer solar cells with graphene as: gives the possibility of the scattering and stabilizing of metal
9 oxide (MeO) nano-particles (NPs) resulting in a wider range
8 8.2 of capacitor capacitance by pseudo-Faraday and Faraday pro-
7 cesses. This gives the opportunity to use the materials in UCs
6
5
[73]. Similarly, the structure of oxidized G is conducive to the
4 improvement of the electrochemical efficiency of composites
3 containing conducting polymers. Moreover, the mechanical
2.6 2.7
2 properties of G are very valuable in these composites and they
1 1.5
also extend its performance by constructional significance.
0
For each of these promising applications, a particularly valu-
Anode Cathode Interface Acceptor
layer able property is very high electrical conductivity.

FIGURE 14.6  Comparison of maximum PCE values of polymer
solar cells with G.
ITO sheet resistance with a similar or even higher transmit-
tance [9,12]. The CVD method is a key to improving this, and
in our point of view, is the best way to synthesize G toward
application in polymer solar cells. The comparison of maxi-
mum PCE values of polymer solar cells with G is schemati-
cally presented in Figure 14.6.
14.3  G AS THE MATERIAL FOR UCs
Modern technological society demands the use and storage
of energy on a large scale. In this regard, the development of
high-performance UCs constitutes the focus of current scien-
tific research. Benefits of using UCs for energy storage are
presented by the Ragone plot (Figure 14.7). It shows how the
use of these devices will expand the area of advanced energy
storage.
G, owing to its desirable properties, has attracted attention
for UCs applications. A high surface area as well as a layer
structure, and a possibility of influencing interlayer distances
constitute very promising properties which are particularly
useful in designing the electrochemical capacitor electrodes
of EDLC (electrical double-layer capacitor) double electrical
14.3.1 ​G-Based Electric Double-Layer Capacitors
Recent research relevant to the subject of UCs is strictly con-
nected with the extraordinary advantages of G as the mate-
rial for electrode preparation. An UC with G-based electrodes
was found to exhibit specific energy density of 85.6 Wh kg−1
at room temperature and 136 Wh kg−1 at 80°C, measured at
the current density of 1 A g−1. These energy density values
are comparable to that of a Ni metal hydride battery, but the
UC can be charged or discharged in seconds or minutes [74].
Partially reduced graphite oxide (GOpr) prepared from natural
as well as synthetic graphite was used as the electrode mate-
rial for UCs in 1 M Et4NBF4 in acetonitrile electrolyte. The
graphite layer distance varied between 0.46 and 0.33 nm. The
initial specific capacitance of all samples was negligibly small
around the open circuit potential. During the first potential
cycle, however, electrochemical activation resulted in specific
capacitance of up to 220 F g−1 for samples with a G layer dis-
tance of 0.44 nm. The potential for anodic and cathodic elec-
trochemical activation was found to be a function of the GO
layer distance [75]. Microporous carbon containing graphene
(G-MC) was prepared by a one step activation-free method of
graphite oxide GO/PVDF film, where PVDF is polyvinylidene
fluoride. From the charge/discharge results, the electrochemi-
cal performance of G-MC was higher (311 F g−1) than that of
MC prepared with PVDF alone (249 F g−1). It was suggested
200
that well-balanced mezo- and microporous features of G-MC
allow feasible ion transfer during charge/discharge, leading
to the maximizing of the charge accumulation. The addi-
tion of G could provide a combination effect between excel-
lent conducting G and the high microporous features of MC
[76]. Using chemical activation of exfoliated graphite oxide,
porous carbon was synthesized with Brunauer–Emmett–
Teller surface area of up to 3100 m2 g−1, high electrical con-
ductivity, and a low oxygen and hydrogen content. With neat
ethylmethyl imidazolium bis (trifluoromethylsulfonyl) imide
(EMIM TFSI) as an electrolyte, the measured gravimetric
capacitance at current density of 0.7 A g−1 is 200 F g−1, with an
equivalent series resistance of 8.6 Ω [77]. Other authors have
noticed that we can significantly enhance the electrochemi-
cal capacitive performances of graphene sheet (GS)-based
composites by stacking one-dimensional carbon nanotubes
(CNTs) between the sheets. Inserting the proper quantity of
CNTs as nano-spacers can effectively impede the stacking of
GSs and enlarge the space between the sheets, leading to the
achievement of a highly porous nanostructure. The specific
capacitance of composite G–CNTs GS–CNT was 326 F g−1
at 20 mV s−1 much higher than the same G material (83 F g−1).
The energy and power densities of G–CNTs are, respectively,
21.7 Wh kg−1 and 78.3 kW kg−1. A hierarchical G–CNT archi-
tecture provides remarkable effects on enhancing the capaci-
tive performance of composites. Therefore, the GS–CNT
composites are promising carbon materials for UCs [78].
14.3.2 ​G-Based Electrochemical Capacitors
with Pseudo-Capacitance
According to the literature, G symmetric electrochemical
capacitors can obtain the capacity of a double layer 100–
200 F g−1 in water and organic electrolytes [79–81]. On the
other hand, higher capacities (200–550 F g−1) are noticed
when the G material is connected with pseudo-capacitive
materials (conducting polymers or metal oxides) [82–84]. In
research laboratories, there are two dominant general strate-
gies of preparing new materials on the basis of G to be applied
in the systems connected with energy: in situ and mixing with
the use conducting polymers or metal oxides [85]. UCs based
on the redox pseudo-capacitance with Faraday-active materi-
als are increasingly popular.
14.3.2.1  Electro-Conducting Polymers
Many researches indicate that electrical conducting polymers
(ECPs) are proper materials for such applications [86]. The
kinetics of the electrochemical charge–discharge is relatively
fast, the charge being stored throughout the volume of the
material, and they can be produced easily at low cost [87].
The materials in their pristine state have an energy gap around
1–3 eV. It is possible to close that gap by doping or ordering
the polymer structure.
There are a numerous reports in the literature on p-doped
heterocyclic polymers. Either polypyrolle (PPY) or polyani-
line (PANI) can be used individually as electrode materials
of symmetric UCs. Both polymers are p-doped ECPs, have a
Graphene Science Handbook
similar glass-transition temperature (above 220°C) and a high
degradation temperature (PANI 250°C and PPY 1000°C).
Those polymers can also exist together as part of a mixed
copolymer with polyacetylene (melanin). There are possi-
bilities to connect the polyaniline and polypyrolle into one
material to strengthen their properties: better conductivity
and greater power capability. Polyaniline can exhibit a charge
density of 140 mAh g−1, which is slightly lower than the one
obtained with expensive metal oxides, but much higher than
the one given by carbon devices that often deliver less than
15 mAh g−1. Carbon-symmetric UC devices achieve a specific
power of 3–4 kW kg−1 and specific energy of 3–5 Wh kg−1,
whereas a PANI-based UC presents twice lower power at
2 kW kg−1 but double the specific energy (10 Wh kg−1). PANI
has a high specific capacitance of 400–500 F g−1 (acidic
medium) and is environmentally stable [88]. Polypyrrole has
a high capacitance per unit volume 400–500 F cm−3. PPY and
PANI are typically doped with single-charged anions such
as Cl−, ClO4−, and SO3−, so they can be modified together.
Polypyrolle would build a strong matrix and polyaniline
would interact as an interpolymer network or exist as a dif-
ferent layer. For conductivity improvement and energy gap
closing, G platelets can be added. Such a filler will modify
electrical or mechanical properties and is more compat-
ible with ECPs than CNTs. G exhibits extraordinary elec-
tronic transport property and high electro-activity resulting
in enhanced voltammetric response. Moreover, the electro-
chemical properties of G can be effectively modified by inte-
gration with other functional nanomaterials. When compared
with CNTs, G shows advantages of high conductivity, ease
of function, and the abundance of inexpensive source mate-
rial. Therefore, it is highly desirable to explore G–polyaniline
hybrid materials [89,90].
Moreover, it has been proved that among conducting
polymers, the most stable poly(3,4-ethylenedioxytiophene)
(PEDOT) is found to be appropriate for applications in energy
storage devices like electrochemical capacitors or asymmetric
systems with a lithium anode [91]. PEDOT combined with poly-
electrolyte allows minimizing ionic transport to the cation sorp-
tion/desorption process. Reduction of ionic streams is desired
for fast transport being the key phenomenon during the charg-
ing/discharging processes. The increase of specific capacitance
can be obtained by combining polymer with redox-active spe-
cies like metal hexacyanoferrate or cobaltite. Recently, a new
technology has been proposed for the formation of organic/
inorganic electrode films based on hydrodynamic electrochem-
ical deposition. Such films were successfully tested in electro-
chemical symmetric and asymmetric electrochemical devices
showing efficient cyclability [92].
14.3.2.2 ​Metal Oxides
A composite of graphene oxide supported by needle-like
MnO2 nanocrystals (GO-MnO2 nanocomposites) was fabri-
cated through a simple soft chemical route in a water–iso-
propyl alcohol system. Interestingly, it was found that the
electrochemical performance of the as-prepared nanocompos-
ites could be enhanced by the chemical interaction between
Polymer Devices with Graphene
GO and MnO2. This method provides a facile and straight-
forward approach to the deposition of MnO2 NPs onto GO
sheets and may be readily extended to the preparation of other
classes of hybrids based on GO sheets for technological appli-
cations [83]. A facile approach to the synthesis of nanocom-
posites was also developed with Fe3O4 NPs attached to the
rGO sheets by a solvothermal process, which combines the
growth of Fe3O4 NPs and the reduction of GOs in one single
step. These Fe3O4/rGO nanocomposites were further used to
fabricate thin film UC electrodes by using a spray deposition
technique. It was found that the Fe3O4/rGO nanocomposites
showed much higher specific capacitances than that of either
pure rGO or pure Fe3O4 NPs [93].
Along with the work aimed at obtaining a composite
metal oxide (RuO2, TiO2, and Fe3O4) NPs, there is a reported
method which combines reduction GO to rGO with the
growth of Fe3O4. Synthesized Fe3O4/rGO nanocomposites
were further used to fabricate thin film UC electrodes by
using a spray deposition technique. Nanocomposites showed
much higher capacitances than pure rGO or pure Fe3O4 NPs.
Electrochemical characterization of the Fe3O4/rGO nanocom-
posites with different Fe3O4:rGO weight ratios showed the
highest specific capacitance of 480 F g−1 at a discharge cur-
rent density of 5 A g−1 with the corresponding energy density
of 67 Wh kg−1 and the power density of 5506 W kg−1. These
Fe3O4/rGO nanocomposites also showed stable cycling per-
formance without any decrease in specific capacitance after
1000 charge/discharge cycles [93].
Among transition metal oxides, RuO2 has been widely
explored and confirmed to be the prominent candidate for
electrochemical capacitor electrodes as a result of its stable
and reversible charge–discharge property and large pseudoca-
pacitance. Coating RuO2 onto G or/and CNTs templates might
therefore result in materials with even higher capacity [94].
Structural and chemical properties of G allow achieving
sophisticated spatial structures such as an example compos-
ite of three-dimensional (3D) G with metal oxide nanowires.
Using a hydrothermal procedure, cobalt oxide (Co3O4) nanow-
ires were in situ synthesized on 3D G foam grown by CVD.
The 3D G/Co3O4 composite was used as the monolithic free-
standing electrode for UC application and for the enzymeless
electrochemical detection of glucose. The authors demon-
strated that it is capable of delivering high specific capaci-
tance of about 1100 F g−1 at the current density of 10 A g−1
with excellent cycling stability [95].
Research using the very promising properties of G syn-
ergy with conducting polymers (polyaniline PANI) have also
been also performed. Electrochemical performance of as-
prepared graphene (HEG), functionalized graphene (f-HEG),
RuO2-f-HEG, TiO2-f-HEG, Fe3O4-f-HEG, and PANI-f-HEG
nanocomposites is examined using cyclic voltammetry and
galvanostatic charge–discharge techniques for UC applica-
tions. The maximum specific capacitance of 80, 125, 265,
60, 180, and 375 F g−1 for HEG, f-HEG, RuO2-f-HEG, TiO2-f-
HEG, Fe3O4-f-HEG, and PANI-f-HEG nanocomposites,
respectively, was obtained with 1 M H2SO4 as the electrolyte
at the voltage sweep rate of 10 mV s−1 [96]. Composite films
201
of chemically converted graphene (CCG) and polyaniline
nanofibers (PANI-NFs) were prepared by vacuous filtration
of the mixed dispersions of both components. The composite
film has a layered structure, and PANI-NFs are sandwiched
between CCG layers. The conductivity of the composite film
containing 44% CCG (5.5 × 102 S m−1) is about 10 times
higher than of a PANI-NF film. UC devices based on this con-
ductive flexible composite film showed large electrochemical
capacitance (210 F g−1) at a discharge rate of 0.3 A g−1. They
also exhibited improved electrochemical stability and rate
performances [97].
The experimental approach that maximized the pseudo-
capacitive contribution from redox-active manganese oxide
(MnOx) and polypyrrole (PPy), as well as the electrochemical
double-layer capacitive EDLC characteristic from graphene
(GR) sheets is presented in Reference 98. Long cyclic mea-
surements indicated that the high specific capacitance (up to
320 F g−1), of the obtained ternary nanocomposite film could
retain 93% of its initial value over 1000 charge/discharge cycles.
Among a variety of nanostructured carbon materials,
G has received rapidly growing attention for use in UCs in
recent years. Thanks to its two dimensional structure, made
of mono-layered or multilayered graphitic nanosheets, G car-
ries exceptional electrical and thermal conductivities, ultra-
or mechanical properties, and a very large specific surface.
G can also be conveniently fabricated and functionalized,
exfoliated G nanosheets derived from natural graphite can
be produced on a large scale at low cost. These G nanosheets
with the average thickness of 3–5 nm typically consist of a
few G monolayers and have demonstrated attractive physi-
cal and chemical behaviors as a new family of carbon nano-
materials for use in electrochemical energy conversion and
storage. The resulting specific capacitance depends highly
on the fabrication process of G nanosheets. For instance, it
is crucial to avoid the aggregation of G nanosheets in order
to maintain the high specific surface area [99]. New tech-
niques and processes are still desired in order to achieve the
ultrahigh specific surface area and extraordinary properties
of functionalizing of G.
14.4 AFM STUDY OF POLYMER
DEVICES WITH G
AFM is one of the diagnostic methods allowing the imaging of
morphological, mechanical, electrical, magnetic, thermal, and
optical properties of the surface at micrometer and nanometer
scale. Considering the dimensions of usually investigated G
samples, AFM measurements can provide particularly valu-
able information in terms of the variety of acquired data. The
investigation can be focused on the material itself, as well as
on G-based devices [100–102]. This method is very popular
among scientists despite the fact that one has to perform the
measurements carefully as certain limitations of this tech-
nique may be a source of misinterpretation [103]. One should
be aware that industrial applications of AFM may, however,
suffer low throughput due to the measurement principles
as well as limited dimensions measurement accuracy when
202
(a)
Z(nm)
250.0
0.0
0.0
10.0
20.0
30.0
40.0
X(µm) 50.0
FIGURE 14.8  Topography of the G-based quantum Hall effect observation device with color representation of the electrical potential pres-
ence while the device was biased with 1 μA current, acquired with KPFM technique (a). The topography of the GO obtained with modified
Hummers method (b).
rough substrates are used [104]. The examples of the AFM
measurement results are presented in Figure 14.8.
A number of papers have been published lately in the area
of research aimed at the improvement of the properties of PV
modules [54,59,71,105–110] and supercapacitors [111–119]
using G-based materials. If the used material creates G flakes
on the surface, the AFM measurements have often been
focused on the determination of the lateral size and thickness
of the created layers [111,114]. The measured thickness of
the G monolayer was in the range of 0.3–0.5 nm [54,113,118]
(Kuila et al. prepared SPEEK-modified G), however, mostly
the 0.7–1.25 nm range was reported [113,114,115,117,119]
which referred to the influence of the oxygen atoms bonded
to the surface of G (GO). Jeon et al. [59] presented the rela-
tion between the spraying temperature of the GO on an ITO/
glass substrate and the thickness of obtained GO monolay-
ers. Obtained results varied from 1.18 to 0.79 nm, whereas
the spraying temperature increased from 100°C to 400°C
and the oxygen groups were removed more efficiently. Using
such an approach, the HTL was developed, providing better
performance of the PV module for higher spraying tempera-
ture. Also, the roughness of created surfaces was determined
[54,71,107,108]. Both basic tip-sample force interaction meth-
ods have been used: contact [109,110] and intermittent contact
[54,105–107,110,114,115,117–119]. One can distinguish three
mainly used substrates utilized for the experiments: mica
[110,114,117], glass, ITO/glass, quartz [54,71,105,107,108],
and silicon/silicon dioxide [106,109,111–113]. As electrical
properties of developed materials and structures were a major
issue, electrical properties of G layers have also been imaged
using Kelvin probe force microscopy (KPFM) [106,107] and
conductive probe AFM [109].
14.4.1 ​Polymer Solar Cells with G
Two major objects of experiments may be distinguished
among the papers concerning photovoltaic application:
Graphene Science Handbook
Z range: 367.8 nm
15.0
60.0 (b)
50.0 200
40.0
Y(µm)
30.0 100
7.50
µm
20.0
0
10.0
0
0.0
0 7.50 15.0
60.0
µm
complex structures [54,71,105,107] and materials planned to
be used in the structures [106,108,109,111], although in some
cases, the investigated issues overlap and combine. Chuchmala
et al. [54] analyzed the roughness of the GO layer using the
modified Hummers’ method, utilized as the interlayer in
various combinations of PEDOT:PSS/P3HT:PCBM devices,
where ITO on glass and Al were used as the electrodes. It
was assumed that the complexity of the GO layer, in terms of
the size of flakes and contact area as well as surface rough-
ness, can determine the way in which the light is reflected and
absorbed, due to the active surface area. Similar structures
have been investigated by Yu et  al. [71]. ITO on glass and
Al were used as the electrodes and the active layer was C60-
:P3HT, C60 –G:P3HT, C60/G mixture:P3HT in order to find the
solution with the highest PCE. PEDOT:PSS was applied as the
hole transporting layer. It was concluded that the high rough-
ness (Ra = 9.7 nm for C60/G mixture:P3HT) may cause bad
electrical contact and result in the low efficiency: η = 0.44%
against Ra = 5.9 nm and η = 1.22% for C60-G:P3HT. With
regard to the specific optical properties of G, its utilization as
transparent electrodes was investigated by Park et al. [108]. In
order to solve the issue of the HTL incompatibility between
G and the often utilized PEDOT:PSS, a molybdenum trioxide
layer was tested instead of PEDOT:PSS. The surface complex-
ity versus MoO3 thickness was verified. Also, AFM studies
of the influence of various methods of poly(methyl methacry-
late) (PMMA) removal from G on the morphological proper-
ties were carried out. As the low pressure CVD method of
G was used, the impact of obtained thickness on the surface
roughness was also verified. Liu et al. presented an approach
of the development of the hybrid graphene inclusion complex
(HGIC) [110], which may be useful in electrodes fabrication
with the obtained 3D network structure of the hydrogel, which
exhibits sol–gel transition at elevated temperature. AFM stud-
ies of the morphology at certain process stages have been
performed in order to observe the transition of flat G flakes
into complex structures. In terms of utilization of the CVD
Polymer Devices with Graphene
deposited G layer as the electrode, the modification of its sur-
face potential by the immersing in AuCl3 solution was pre-
sented by Shi et al. [106]. KPFM was used in order to observe
locally changing surface potential owing to the presence of
Au particles, formed during the spontaneous reduction of
metal ions. The obtained range of surface potential modifica-
tion was 0.5 eV. Such a procedure allowed the increase of the
PCE of developed photovoltaic devices up to 40 times more
(η = 0.08%) than in case of the device without doping. The
KPFM technique was also used by Tong et al. [107] for inves-
tigation of the work function of the G intermediate layer with
metal oxide (MoO3), which was used in a tandem solar cell.
As the thickness of MoO3 increased, the work function of G
rose up to 6.28 eV. On the other hand, Boutchich et al. [109]
presented various methods of the reduction of GO into G. The
chemical approaches (hydrazine, UV photocatalyst) and bio-
logical (a microorganism extracted from a river in the Aichi
prefecture in Japan) were tested. As one of the benchmarking
tools, the conductive probe AFM was used, in order to deter-
mine the local resistance of G flakes. The best results were
obtained by using hydrazine (10–30 kΩ), however, the micro-
organism allowed to acquire the promising value of 1 MΩ,
whereas the UV photocatalyst provided only 1–3 GΩ.
14.4.2 ​UCs with G
One of the major challenges in UC materials development, is
design of electrodes, which should provide certain properties
such as mechanical stability, long-cycle life as well as large
specific capacitance. In order to obtain the desired solution,
carbon materials were extensively employed as being prom-
ising for UC electrodes. Gao et  al. [114] presented a solu-
tion based on a special partially rGO nanosheet/polyaniline
nanowafer (GNS/PANI) hybrid. Performed AFM analysis
allowed the verification of the thickness of GO flakes. By the
integration of the GO and PANI nanowafer, the improvement
of electrical properties (329.5 F g−1 at 5 mV s−1) as well as a
promising long-cycle life have been achieved . Also, Luo et al.
[116] described the utilization of the PANI and GO composite.
The morphology analysis before cyclic potential scanning and
after 500 cycles allowed the observation of the changes into a
more uniform surface. No detachment of PANI particles from
the GO surface was observed after long-term cycling. In the
experimental work of Gao et  al. [112], the asymmetric UC
based on G hydrogel and nanostructured MnO2 was investi-
gated. AFM study of the GO flakes confirms the quality of
the Hummers’ method. The developed asymmetric UC con-
taining MnO2 nanoplates and G hydrogel which created 3D
structures exhibited energy density of 23.2 Wh kg−1. In terms
of morphological verification of the obtained modification of
GO, Kuila et al. [113] used the AFM technique as well. By
utilizing sulfonation of poly(ether-ether-ketone) (SPEEK), the
GO developed by Hummers’ method was modified to SPEEK-
modified graphene (SPG). The observed increase of the flakes
thickness from 0.84 to 1.34 nm was due to the adsorption of
SPEEK on the surface of G. Zhang et al. [117] presented an
environment-friendly approach of reduction GO obtained
203
with the modified Hummers’ method to graphene nanosheets
(GG). The observed reduction of the thickness from 1.037 to
0.76 nm confirmed the accuracy of the process. The specific
capacitance of the obtained material was determined to be
238 F g−1 at the current density of 0.1 A g−1 in 1 M H2SO4
electrolyte. Moreover, it remained at 97% of the initial value
at the current density of 2 A g−1 after 1000 cycles. The AFM
observation of the thickness of Co–Al LDH-NS/GO bilayers
stack as the function of the bilayers’ quantity was described by
Dong et al. [115], where LDH-NS is a layered double hydrox-
ide nanosheet. Such a prepared film allowed the obtaining of
the specific capacitance and area capacitance 1204 F g−1 and
90 F m−2, respectively. In addition, it was possible to deposit
such a film on the PET surface in order to develop a flexible
energy storage device. Xiong et al. [119] presented the utiliza-
tion of the multilayer film of the sulfonated reduced graphene
oxide (SRGO) prepared by electrostatic LbL adsorption as
the electrodes. The specific capacitance of cross-linked films
with nine bilayers was measured to be 150.4 F g−1 in 1.0 M
Na2SO4 under the scanning rate of 10 mV s−1. Because of the
cross-linked structure, this electrode material exhibited supe-
rior cyclic stability with a 97% capacitance retention even
after 10,000 charge−discharge cycles.
14.5 ​CONCLUSION AND OUTLOOK
Following the award of the Nobel Prize in Physics 2010 to A.
Geim and K. Novoselov for Graphene—The Perfect Atomic
Lattice a huge number of scientists have begun to use modi-
fied G in various applications such as optoelectronic devices,
electrode materials, UCs, sensors, biomedical, and catalyti-
cal applications [120]. However, perspectives of the practical
applications of G and its commercialization require large-
scale, good quality, low cost, and eco-friendly synthetic tech-
niques. Two main issues particularly concern solar cells and
UCs applications: How to improve the electrical and mechan-
ical properties of G?
In this review, we have demonstrated that G has interest-
ing mechanical, optical, and electrical properties that can be
exploited for solar cells and UCs. With regard to polymer
solar cells, the highest PCE value for a BHJ device (lack of
G) was observed to be approximately 12%, whereas the maxi-
mum PCE value for polymer solar cells with G applied as an
interface layer was found to be 8.21%. In our point of view, a
good method for improving the efficiency (PCE) in polymer
solar cells is the use of chemically modified G (or GO) as a
separate interlayer or as electrodes.
This chapter also demonstrates how the use of G in UCs can
improve the properties of these devices and increase the pos-
sibility of their use in modern energy techniques. Properties of
this material allow the use of G in all types of UCs, both based
on the principle of electrical double layer, and pseudocapaci-
tance. This opens up new possibilities for the application of G
to build advanced energy storage devices. For dynamic and
promising research progress [85,104], further market-aimed
investigations should enable the commercial applications of G
as described above in many others materials and devices.
204
It was shown, that AFM was utilized efficiently in the
determination of the properties of G/GO as the component of
the process as well as the structures working in photovoltaic
modules or supercapacitors. Owing to the unique diagnostic
abilities of AFM, the morphological, mechanical, and elec-
trical properties have been investigated and correlated with
other measurement results.
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Section III
Electrical/Sensor Devices
 15 Current Status and Future Trends
Graphene-Based Sensors

Goutam Koley, Amol Singh, and Ahsan Uddin

CONTENTS
Abstract.......................................................................................................................................................................................211
15.1 Introduction.......................................................................................................................................................................211
15.2 Graphene Sensors............................................................................................................................................................. 212
15.2.1 Graphene Creation................................................................................................................................................ 212
15.2.1.1 Mechanical Exfoliation and Ultrasonication......................................................................................... 212
15.2.1.2 Thermal Annealing................................................................................................................................ 213
15.2.1.3 Chemical Vapor Deposition................................................................................................................... 213
15.2.2 Fabrication of Graphene Sensors...........................................................................................................................214
15.2.3 Physical Sensors................................................................................................................................................... 215
15.2.3.1 Graphene Resonators..............................................................................................................................216
15.2.3.2 Magnetic Field Sensors...........................................................................................................................218
15.2.3.3 Graphene IR and THz Sensor.................................................................................................................219
15.2.3.4 Pressure Sensor.......................................................................................................................................219
15.2.4 Chemical and Biological Sensors......................................................................................................................... 220
15.3 Multidimensional and Selective Sensing.......................................................................................................................... 222
15.3.1 Multidimensional Sensing Approach................................................................................................................... 222
15.3.2 Tuning Sensitivity and Selectivity........................................................................................................................ 223
15.4 Correlation between Sensing and Material Properties..................................................................................................... 225
15.5 Future Trends.................................................................................................................................................................... 226
15.5.1 Graphene Heterostructure Sensors....................................................................................................................... 226
15.5.2 Other 2D Material-Based Sensors........................................................................................................................ 229
15.6 Summary.......................................................................................................................................................................... 230
Acknowledgments...................................................................................................................................................................... 230
References.................................................................................................................................................................................. 230

ABSTRACT of carrier transport theories will be discussed. The formation

Although discovered only recently in 2004, graphene has
already established itself as an outstanding material for sens-
ing applications due to its excellent properties that include a
two-dimensional structure with unsaturated bonds, high car-
rier mobility, extraordinary mechanical strength, chemical
inertness, and low thermal and 1/f noise. In this chapter, we
will perform a review of graphene as a material for devel-
oping physical, chemical, and biological sensors, and discuss
the correlation between its various sensing applications and
fascinating material properties. The dependence of sensing
properties of graphene on the substrate on which it is grown
or transferred will be discussed in addition to other possible
means of modulating its sensitivity to various analytes. The
importance of surface work function measurements on gra-
phene to reveal its material properties will be highlighted,
and correlation between conductance and surface work func-
tion changes caused by molecular adsorption on graphene
films, and their quantitative modeling within the framework
of technologically significant heterostructures between gra-
phene, various semiconducting thin films, and other emerging
two-dimensional materials, and their applications in realizing
physical or chemical sensors, will be included as a part of
future trends.
15.1 INTRODUCTION
Graphene, a two-dimensional (2D) allotrope of sp2-bonded
carbon atoms, has drawn huge research interests since its
discovery in 2004 due to its extraordinary material prop-
erties including remarkably high charge carrier mobility
of 200,000 cm 2/V/s [1], very high thermal conductivity
[2], and mechanical strength [3], as well as high degree of
chemical inertness at room temperature [4]. The 2D nature
of graphene coupled with its unsaturated C–C (sp2) bonding
makes it highly suitable for sensing applications. The 2D
nature makes it essentially a surface (Figure 15.1), enabling
211
212
FIGURE 15.1  (a) Schematic representation of single planner hexa-
gon consisting of six C atoms connected to each other by sp2 bond-
ing with C–C bond length of 1.42 Å. (b) Periodic repetition of the
hexagonal unit resulting in 2D honeycomb structure of graphene.
analyte molecules to adsorb very efficiently and produce the
maximum change in its physical properties. On the other
hand, the presence of unsaturated sp2 bond makes it sen-
sitive to a large variety of analytes that can adsorb on its
surface and exchange charge with it or modify its surface
properties. These exceptional material properties have led
to the demonstration of graphene-based sensors that are
capable of detecting down to a single-analyte molecule
(Table 15.1) [5].
In spite of these highly promising aspects of graphene for
sensor development, it still suffers from a lack of selectivity in
detecting molecules. In addition, it does not have a bandgap,
nor changes its resistance appreciably under strain, which
makes its potential applications in optoelectronic devices and
nanoelectromechanical systems (NEMS) rather challenging.
The lack of bandgap in graphene also results in low turn-
off ratio in graphene transistors, which makes it unattractive
for use in integrated circuits. Thus, research activities have
recently started to focus on other 2D materials beyond gra-
phene, and the heterojunctions of these materials as well as
other traditional semiconductors with graphene, for applica-
tions where graphene by itself is deemed unsuitable.
In this chapter, we will discuss the scope, applications,
and limitations of graphene for developing physical, chemi-
cal, and biological sensors. We will first discuss the synthesis
and processing of graphene to realize graphene-based sen-
sor devices in Section 15.2 along with their various sensing
Graphene Science Handbook
TABLE 15.1
Electronic and Material Properties of Single-Layer
Graphene
Mobility 65 × 104 [6]–106 cm2/V/s [7]
Thermal conductivity (4.84 ± 0.44) × 103 to
(5.3 ± 0.48) × 103 W/mK [2]
Young’s modulus 1.0 [3] to (2.4 ± 0.4) TPa [8]
Breaking strength 42 N/m [3]
Breaking strain 25% [3]
Normalized noise spectral density 10−9 to 10−7 Hz−1 [9]
(at f = 10 Hz)
Noise amplitude (μm scale devices) ~10−9 to 10−7 [9]
Source: Reprinted with permission from Singh, A.K. et al.: Electrically tun-
able molecular doping of graphene, Applied Physics Letters, 102
(4), pp. 043101–043105. Copyright 2013, American Institute of
Physics.
applications. In Section 15.3, we will discuss the various
approaches to perform selective detection of analytes using
graphene. The sensing properties of graphene have been
found to correlate strongly with its material properties, espe-
cially defect density, which will be the subject of our discus-
sion in Section 15.4. In Section 15.5, we will focus on the
future trends in sensor development utilizing graphene and
other 2D materials, especially considering the heterojunction
formation between graphene and traditional semiconductor
thin films.
15.2  GRAPHENE SENSORS
15.2.1 Graphene Creation
Before sensors based on graphene can be fabricated, high-
quality graphene (preferably monolayer) need to be produced.
There are three common techniques for producing graphene,
which are discussed below.
15.2.1.1  Mechanical Exfoliation and Ultrasonication
In the very beginning, graphene sheets were obtained by
mechanical cleavage or exfoliation of graphite, which consists
of loosely bonded parallel layers of graphene [10]. This tech-
nique, which is often referred to as the “scotch-tape method,”
can result in 2D graphene of high structural and electronic
quality, with dimensions in the range of several tens to hun-
dreds of microns. Though delicate and time consuming, this
is the only technique that can guarantee production of defect-
free graphene without any contamination. Thus, it is very well
suited for basic research and proof-of-concept device demon-
stration, which only requires a small size of graphene with
typical dimensions on the order of tens of microns. Instead
of exfoliating graphite (typically highly oriented pyrolytic
graphite) manually, it is also possible to automate the process
by using methodologies such as ultrasonic cleavage [11]. This
method leads to stable suspensions of submicron graphene
Graphene-Based Sensors
TABLE 15.2
Different Graphene Growth Methodologies and Relevant Attributes
Graphene Type Growth Method
Exfoliated • Exfoliation [10]
• Ultrasonication [11]
• Intercalation [12]
Epitaxial SiC is heated to ~1600°C
for growth [13]
Chemical vapor Growth on Cu foil/film
deposition (CVD) with CH4 and H2 in Ar
~1000°C [14]
Source: Reprinted with permission from Singh, A.K.et al.: Electrically tunable molecular doping of graphene, Applied Physics Letters, 102
(4), pp. 043101–043105. Copyright 2013, American Institute of Physics.
crystallites, which can then be used to make polycrystalline
films and composite materials [11,12]. Conceptually similar
is the ultrasonic cleavage of chemically “loosened” graphite
where atomic planes are partially detached first by intercala-
tion making the sonication method more efficient [12]. The
ultrasonication method allows production of larger area gra-
phene, although controllability of the process and the struc-
tural integrity of graphene are still challenges that need to be
addressed (Table 15.2).
15.2.1.2  Thermal Annealing
Another popular method for producing large area gra-
phene of high quality is through thermal annealing of SiC
wafers [13,15,16]. This method, which takes advantage of
well-established SiC epitaxy, involves heating 6-H or 4-H
polytype of SiC in the temperature range of 1200–1600°C
in ultrahigh vacuum (UHV) of 1 × 10 −10 Torr for several
minutes. At this high temperature, Si leaves the SiC surface
owing to its higher vapor pressure than carbon. The remain-
ing C-rich surface then rearranges itself on the hexagonal
lattice of SiC to form single- to few-layer graphene on both
Si- and C-terminated faces of SiC [17]. Prior to graphene
growth, the SiC substrate surface, of course, needs to be
properly cleaned by H 2 etching at 1000°C in UHV to remove
native oxide that is often present. In general, the growth
on Si face is slower and self-limiting, resulting in thinner
and better-quality graphene (1–3 monolayers); whereas
graphene on C face is usually much thicker (5–10 mono-
layers) and of lesser q­ uality. The major advantage of the
chemical vapor deposition (CVD) technique is the growth
of quite uniform, wafer scale, and high-quality graphene is
possible, taking advantage of the precise control of process
parameters in a commercial SiC growth chamber. Attempts
have also been made to grow graphene on SiC substrate in
near atmospheric Ar pressure of 900 mbar and at relatively
higher temperature of 1650°C with a goal to obtain larger
area low defect, mono, bi, and tri-layer graphene [18]. One
213
Quality (Mobility) Attributes Commercial Viability
• High structural • Basic research Not suitable for
• Electronic quality • Proof-of-concept commercial production
• High mobility devices
(2.3 × 105 cm2/V/s) [1]
High mobility • Uniform • Expensive substrate
(106 cm2/V/s) [7] • Wafer scale • Transfer on arbitrary
• High quality substrate is difficult
limiting application
Moderate mobility • Large area Suitable for commercial
(6.5 × 104 cm2/V/s) [6] • Good quality production, although
scale up issues remain
of the disadvantages of this method of graphene synthesis
is that it is very difficult to remove or transfer the graphene
to another desired substrate, due to the challenges involved
in controllable etching of SiC. Therefore, processing of gra-
phene devices needs to be done on the SiC substrate itself.
This can be expensive due to the high cost of SiC substrates,
and also it does not readily allow the usage of a back gate
for realizing transistors, or sensors requiring back-gate
modulation.
15.2.1.3  Chemical Vapor Deposition
A very versatile and increasingly popular method of synthe-
sizing graphene film utilizes CVD on transition metal sub-
strates (e.g., nickel, copper, palladium), which acts as catalyst,
by cracking methane (CH4) in mixture with Argon (Ar) and
Hydrogen (H2) at a pressure in the mTorr range and at a tem-
perature of ~1000°C. Growth on these metallic substrates
allows the metal to be etched away easily so that graphene
can be transferred to any desired substrate by a set of simple
processing steps [19]. It has been reported that at low pres-
sure, the CVD growth of graphene on the copper foil is a self-
limiting process, that is, it automatically stops when a single
graphene layer forms [14]. CVD growth technique enables
the production of the large area graphene film, very economi-
cally, which is essential for integrated electronic devices and
sensors fabrication. An added advantage of the CVD growth
is that substitutional doping is feasible by introducing hetero-
atoms (N2, B, etc.) into the carbon lattice. The properties of
CVD grown graphene, however, can deviate to some extent
from that of the pristine SLG (single-layer graphene) (e.g.,
decrease in mobility and shift in the Dirac point) produced
by exfoliation, due to existence of defects and impurities. The
transfer of the as-grown graphene film from the metal sub-
strate to another desired substrate for device fabrication may
introduce additional impurities and defects [20]. However,
the defect in the final transferred graphene can be minimized
with careful attention to the synthesis and transfer process,
214 Graphene Science Handbook

and very low defect density graphene transferred to SiO2/Si
substrates can be routinely obtained at present.
15.2.2 Fabrication of Graphene Sensors
The graphene synthesized by the various techniques men-
tioned above is subsequently used to fabricate sensor devices
(Table 15.3). Epitaxial graphene-based sensors are realized by
patterning the graphene grown on 4H- or 6H-SiC substrate.
The patterning of the sensor area and subsequent metal
contact formation can be done by e-beam lithography, con-
ventional photolithography, or in some cases simply by using
a shadow mask. Unlike epitaxial graphene, sensor fabrication
from CVD grown graphene requires its transfer to a suitable
substrate. There is a large variety of substrate that can be used
for making sensors using transferred graphene, which can be
chosen based on the end use of the sensor. The range of sub-
strate includes SiO2/Si, PVDF, glass, h-BN, sapphire, as well
as biocompatible materials such as SU-8 and polydimeth-
ylsiloxane (PDMS), which offers various advantages such
as possibility of back-gate control, realization of multifunc-
tional, and high-frequency devices, as well as implantable
biosensors.
The various steps for fabrication of FET (field-effect
transistor)-type sensor devices utilizing CVD graphene are
summarized in Figure 15.2. The processing steps to fabricate
sensors from either exfoliated or epitaxial graphene are subsets
of these steps. The fabrication of chem-FET (chemical field-
effect transistor)-type sensors using CVD graphene includes
three major steps: its transfer to a desired substrate, pattern-
ing using lithography, and metal contact formation [21]. In
the first step, graphene grown on Cu foil is spin coated with
two layers of polymethyl methacrylate (PMMA) and baked
at 120°C for a minute. The PMMA-coated sample is then
treated by O2 plasma for 3 min to remove the undesired gra-
phene layer from the back side of Cu foil. After that, copper
is completely etched by dipping the PMMA-coated Cu foil in
concentrated FeCl3 solution for ~6 h. The resulting graphene/
PMMA bilayer in the etchant is then rinsed multiple times in
deionized water and HCl solution. For chem-FET fabrication,

TABLE 15.3
Graphene Sensors Fabrication Techniques, Mechanism of Transduction, and Applications
Graphene Sensor
Configuration Fabrication Transduction Mechanism Special Features/Applications
Two-terminal • Exfoliated [5]: • Conductivity [5] • Chemical sensor [5,23]
devices (resistors) • Transfer → lithography → RIE • Surface work function [23,24] • Pressure sensor [27]
etch → metallization [21] • Surface acoustic wave • ​Magnetic sensor [28,29]
• ​Epitaxial graphene: frequency [25] • Optical sensor (THz and IR) [30]
• Lithography → RIE • Low-frequency noise spectrum
etch → metallization [22] [26]
Two-terminal • Transfer →  lithography → RIE Sensitivity tuning by the back • Sensing tunability in most of the
devices (FETs) etch → contact metallization → gate gate [21] above-mentioned sensors [21]
metallization [21] • Selective detection of wide range of
analytes
• Tunable optical sensor (THz and IR) [31]
NEMS • Exfoliated and CVD graphene: Actuation: Features:
• Graphene suspension over pre- • Electrical excitation [33] • Resonance frequency in MHz range
patterned trench [32] • Optical excitation [34,35] [34,35]
• Release by wet etching after device • ​Microwave reflectometry [36] • Electrostatic frequency tuning up to
fabrication for exfoliated [33] and 400% [33]
CVD graphene [34] Detection: • Extremely high Q of 105 [34]
• Epitaxial graphene: • Frequency mix down (AM/
• Lithography → RIE etch → contact FM) [34] Applications:
metallization → photoelectrochemical • Motion modulated • Ultrasensitive mass sensing [33]
etching of SiC [35] conductance measurement [37] • Probe for electrical and magnetic
• Optical interferometry [34,35] properties of lower dimensional materials
• AFM with frequency [39]
modulation, etc. [38] • High-frequency oscillator, filter,
modulator, mixers, etc. [40]
• Chemical sensing
Heterostructure Substrate patterning (lithography → RIE/ • Transport across the Schottky • Chemical sensor [16,41,42]
wet etch) → graphene transfer → barrier at heterointerface • Optical sensor (THz and IR) with the
lithography → RIE etch → metallization • High sensitivity due to added advantage of high and tunable
[16,41,42] exponential current change sensitivity [43]
• Sensing tunability in
two-terminal devices
Graphene-Based Sensors 215

Graphene PMMA PMMA

coating
Copper foil

O2 plasma etch
SiO2 and Cu etch
Transfer on

n+ Si SiO2 substrate
PMMA Ti/Au
removal Metal
deposition

Graphene channel Define graphene

channel

SiO2

Ti/Au contact Scale bar is 20 μm

FIGURE 15.2  Fabrication process of back-gated chem-FET from CVD grown graphene on copper foil. The major steps involve removal of
back-side graphene from Cu foil in O2 plasma (front-side graphene protected by PMMA coating), removal of Cu in etchant solution, transfer of
graphene on SiO2/Si substrate, metal contact formation, and graphene channel definition. (Reprinted with permission from Singh, A.K. et al.:
Electrically tunable molecular doping of graphene, Applied Physics Letters, 102 (4), pp. 043101–043105. Copyright 2013, American Institute
of Physics.)

the substrate of choice is typically SiO2/Si with the Si substrate
heavily doped to serve as global back gate. The substrate is
usually RCA (Radio Corporation of America) cleaned prior
to graphene transfer as part of the substrate preparation. The
floating graphene/PMMA bilayer (following the removal of Cu
and thorough rinsing) is scooped on the substrate and allowed
to dry for 24 h. The sample is then dipped in acetone for ~1 h
to remove PMMA, which leaves behind the graphene on SiO2.
Typical metal contacts include 20 nm Ti and 80 nm Au con-
tacts evaporated on graphene patterned by optical lithography.
The sensing element of chem-FET, that is, the graphene chan-
nel is finally defined by another round of lithography and O2
plasma etching. Optical micrograph of as-fabricated graphene
chem-FET is shown in Figure 15.2.
15.2.3 Physical Sensors
The unique material properties of graphene make it very
attractive for developing a large variety of physical sen-
sors (Table 15.4). Due to its outstanding electronic proper-
ties, mechanical strength, and single atomic layer thickness
[1,3,39,44], graphene can be considered as the ultimate build-
ing block for NEMS, which are capable of sensing a host of
physical parameters including pressure, mass, charge, electric

TABLE 15.4
Graphene-Based Physical Sensors and Their Applications
Physical Sensors Sensing Mechanism Applications
NEMS resonators • Capacitively coupled mechanical • Ultrasensitive mass sensing [33]
resonance • ​Probe for electrical and magnetic properties of
• Ultrahigh-quality factor lower dimensional materials [39]
• Gate tenability [34] • High-frequency oscillator, filter, modulator,
mixers, etc. [40]
• Chemical sensing
Magnetic field • Detection of magnetic field by High-density magnetic storage application
sensors Hall effect [48,49]
• Gate tunable sensitivity [47]
IR and THz sensor Light absorption from mid-IR to UV • Bolometric sensor [31]
• ​QHE effect-based IR photodetector [50]
• Asymmetric contact IR detector [30]
Pressure sensor Change in electrical/mechanical • Tunable mechanical resonance
properties with applied strain [27] • Chemical reactions and phase transitions [51,52]
216 Graphene Science Handbook

potential, temperature, and magnetic field. Graphene NEMS

can also be used as a versatile device for various RF (radio
frequency) applications. NEMS resonator has been reported
from all three basic types: exfoliated [32], CVD [34], and
graphene. Graphene with its linear energy dispersion rela-
tionship and zero bandgap can absorb also light from mid-
infrared (mid-IR) to ultraviolet wavelength range with almost
flat (2.3% for monolayer thickness) absorption spectra which
makes it very attractive for optical detector. Percentage
increase in light absorption can be possible by employing
multilayer graphene. Graphene-based IR camera has been
reported already [30]. In addition, graphene bolometer [31],
Infrared (IR) detector based upon quantum Hall effect (QHE)
[45], and magnetic field tunable IR detector based on Landau
level (LL) formation [46] have been demonstrated. Some of
the unique physical properties of graphene such as the thick-
ness in atomic scale, very high carrier mobility, and long spin
relaxation time also make it ideally suited for the magnetic
sensor. Graphene magnetic sensor employing Hall geometry
has been reported with performance close to already estab-
lished two-dimensional electron gas (2DEG)-based sensors
[29]. The sensitivity of this sensor can also be varied over a
wide range by applying back-gate bias [47].
Graphene spin capacitor [48] and sensor devices with
nanoconstriction [53] have also been realized. Pressure sen-
sors from exfoliated [54], CVD graphene [55], silicon nitride/
graphene [56], epoxy/graphene [57], and boron nitride/gra-
phene [58] have been demonstrated. Also, graphene-based
charge sensor has been reported where a twin quantum dot
(QD) structure in which the larger QD serves as a single elec-
tron transistor to read out the charge state of the nearby gate-
controlled small QD [59] and, real-time radiation dosimeter
where electrodes are based on graphene [60]. Of the various
applications in physical sensors, we will discuss graphene FIGURE 15.3  Suspended graphene NEMS structures from (a)
NEMS resonators, and graphene-based magnetic field, IR, doubly clamped epitaxial graphene. (Reprinted with permission
THz (terahertz), and pressure sensors in further detail below. from Shivaraman, S. et al., Free-standing epitaxial graphene, Nano
Letters, 9 (9), pp. 3100–3105. Copyright 2009 American Chemical
15.2.3.1  Graphene Resonators Society.) (b) Doubly clamped CVD graphene. (Reprinted with per-
A set of unique properties make graphene attractive for the mission from Zande, A.M.v.d. et al., Large-scale arrays of single-
layer graphene resonators, Nano Letters, 10 (12), pp. 4869–4873.
basic building block NEMS. Among these properties, elastic
Copyright 2010 American Chemical Society.) (c) Fully clamped
stiffness of 340 N/m, which corresponds to a Young’s modu- exfoliated graphene. (Adapted from Bunch, J.S. et al.: Nano Letters,
lus of 1 TPa, the breaking strength of 42 N/m, corresponding 2008, 8 (8), pp. 2458–2462.)
bulk value of 130 GPa [3], and low mass, ρ = 7.4 × 10−19 kg/
μm2 result in very high resonant frequency in MHz range. The of epitaxial graphene grown on SiC, first metal pads were
resonance frequency can be widely tuned by applying strain defined and graphene was patterned into stripes by optical
that is easily possible since in the case of graphene, breaking lithography and subsequently released by photoelectrochemi-
strain is 25% [39]. First fabrication of graphene NEMS was cal etching to remove the underneath SiC (Figure 15.3b) [35].
done by micromechanical exfoliation of graphene on top of a Suspended structure from CVD graphene (Figure 15.3c) was
prefabricated large array of etched trenches [32]. The method fabricated by already mentioned graphene transfer method
requires no processing of graphene, but the yield is very low. from that of copper and utilizing similar methods to that for
To fabricate fully clamped suspended graphene the later holes exfoliated graphene [34].
have been used instead of trenches (Figure 15.3a) [27]. In an Both electrical and optical method have been used for
alternative method, metal pads were patterned by electron actuation and detection of graphene motion which is the
beam lithography on exfoliated graphene, which was followed main challenge in NEMS characterization. In optical trans-
by releasing the graphene channel by wet etching of SiO2 by duction, which is more popular, periodic contraction/expan-
buffered oxide etch. For large-scale production of suspended sion of graphene by a high power laser-induced temperature
graphene, epitaxial or CVD graphene has been used. In case change is detected by shining another probe laser. By setting
Graphene-Based Sensors 217

width of 3 μm is shown in Figure 15.5a [34]. Back-gate bias

fRF fAM or fFM fMod
Lock-in
Current
pre-amplifier
Vbg
FIGURE 15.4  Block diagram of a measurement setup used for
mixing the electrical signal to eliminate background RF signal in a
back-gated suspended graphene device. (Reprinted with permission
from Zande, A.M.v.d. et al., Large-scale arrays of single-layer gra-
phene resonators, Nano Letters, 10 (12), pp. 4869–4873. Copyright
2010 American Chemical Society.)
an interference pattern between the graphene layer and the
substrate, and detecting the reflected signal by a photodetec-
tor where the reflected signal is sensitive to the position of
the graphene [34]. The deflection of graphene membrane can
also be detected by electrical transduction by applying a dc
voltage to the bottom gate which causes static deflection of
the graphene, which an RF force [δF = C*g VgδVg ] is applied
by adding small RF signal to the dc signal applied to the bot-
tom gate to actuate the resonant motion. The deflection of the
graphene can then be measured from the source–drain cur-
rent. However, a substantial background RF signal is present
in the current, due to the large parasitic capacitance of the
gate to the bonding pads, which overwhelms the mechanical
signal [39]. This can be eliminated by mixing two electrical
signals at different frequencies, and locking-in at the desired
frequency as illustrated in Figure 15.4 while rejecting the one
with parasitic capacitance [34].
Distribution of resonance frequency from optical inter-
ferometry measurement of a fundamental mode for doubly
clamped graphene resonator with the length of 2 μm and
dependence of resonance frequency is shown in Figure 15.5b
for graphene resonator at 77 K [37]. Graphene can withstand
ultrahigh strain [3] which has been utilized by electrostatic
means for wide tuning of frequency up to 400% [33]. The
bending rigidity of graphene is extremely small due to its
atomic thickness, and it can be treated as a membrane with
strain tunable resonant frequency [39]. There are contribu-
tions from the built-in strain, the additional strain upon defor-
mation, and the electrostatic attraction to the gate in the gate
voltage tunability. As a result, there is a wide range of strain
that paves the path for application-dependent frequency tun-
ing. Device accompanying low built-in tension is helpful for
applications where wide frequency tuning and high force sen-
sitivity is the requirement while for applications such as mass
sensing requires higher frequencies and quality factor, large
built-in tension devices would be appropriate.
Realization of high-quality factor (Q) is very important
since it quantifies the damping of NEMS. Q is defined as
Q = 2πE/ΔE, where E is time-averaged energy stored in the
resonator, and ΔE is the energy dissipated to the environ-
ment per cycle. In general, with a decrease in device dimen-
sion Q also decreases. At room temperature both exfoliated
and CVD graphene double side clamped resonators exhib-
ited Q in the range of 100 [33,34], which is very good (com-
parable to commercial Si cantilevers used in AFM systems)
considering the atomically thin nature of graphene. In case
of fully clamped circular resonator, Q increases with the
diameter, from 100 to as high as 2500 for diameter increas-
ing from 2 to 24 μm [61] while frequency varies inversely
with the diameter. In graphene resonators, both frequency
and quality factor showed strong temperature dependence.
It has been observed that Q increases with a decrease in
the temperature and has been found to be as high as 105 at
100 mK [34].

(a) 10 (b)
36
dB T = 77 K
–86 –77 Pin = –45 dBm
8
Frequency (MHz)
Amplitude (a.u.)

35
6

4
34

0 33
9 9.5 10 10.5 –10 –5 0 5 10
Frequency (MHz) Vg (V)

FIGURE 15.5  (a) Optical interferometry measurement of a fundamental mode for doubly clamped graphene resonator with the length of
2 μm and width of 3 μm. (Reprinted with permission from Zande, A.M.v.d. et al., Large-scale arrays of single-layer graphene resonators,
Nano Letters, 10 (12), pp. 4869–4873. Copyright 2010 American Chemical Society.) (b) Back-gate bias dependence of resonance frequency.
(Reprinted with permission from Xu, Y. et al.: Radio frequency electrical transduction of graphene mechanical resonators, Applied Physics
Letters, 97 (24), pp. 243111–243113. Copyright 2010, American Institute of Physics.)
218 Graphene Science Handbook

One of the most common applications for graphene (a)

NEMS would be in ultrasensitive mass sensing due
B C3
extremely low mass of the graphene membrane. Minimum
detectable mass, δm change is dependent on the minimum
observable frequency shift δf in the form of δm = K m−1δf ,
where, K m = δf/δm is the mass responsivity and δf can be C1 C2
determined by
+
DC – 2 μm C4 Graphene
− DR 20 2πfo
δf = 10 BW
Q

VH
where DR is the dynamic range in decibel and BW the
measurement bandwidth [62]. By measuring the resonant
frequency as a function of gate voltage before and after (b)
600
deposition of a known amount of mass, the effects of mass

SI (V/AT)
loading on graphene resonators have been studied [33]. The
obtained mass responsivity is 1.3 Hz/zg at zero gate voltage 0.2 550
and form responsivity, quality factor, and dynamic range the
mass sensitivity of 1 zg/√Hz in the large strain limit has been 500
50 100 150 200
extracted. Since the electronic structure of graphene is very
VH (V)
0.0 Ic (μA)
sensitive to a magnetic field, recent investigations showed Ic (μA)
resonant frequency shifts of up to 1 MHz is possible. In addi-
50
tion, with increasing magnetic field the frequency was found
to downshift in partially filled Landau levels (LLs) while the 100
opposite trend was observed in completely full LLs. These –0.2 200
experimental results reveal the potential for NEMS-based
tool for exploring the electronic and magnetic properties of –2 –1 0 1 2
lower dimensional materials. Field (T)

15.2.3.2  Magnetic Field Sensors
A magnetic field sensor very simply is a Hall bar elements that
detects the magnetic field by Hall effect. Some of the unique
physical properties of graphene such as thickness in atomic
scale, very high carrier mobility, and long spin relaxation time
make it ideally suited for the magnetic sensor. In high-density
magnetic storage application employing nanomagnets, it is
desirable to deploy a sensor as close as possible to magnetic
field source (nanomagnets) to capture the magnetic field that
decays exponentially as one moves away from the source [47].
2DEG-based devices have shown promises in such applica-
tions [63]. However, graphene as sensing element will have
the advantage over 2DEG-based sensor since it is atomically
thin and sits on the surface of the sensing device unlike 2DEG
that is several nm away from the surface and is about 4–20 nm
thick.
A simple Hall bar device is shown in Figure 15.6a where
graphene is in the form of the cross where four metal con-
tacts are placed at each end of a cross. A constant current
I or voltage V is applied across the pair of electrodes C1
and C2. The Hall voltage V H is measured across the pair of
electrodes C3 and C4, which develops as a consequence of
the application of magnetic field component perpendicular
to the surface of graphene sensor. The Hall voltage is given
by VH = SIIB or VH = SVVB, where B is the component of
magnetic field perpendicular to graphene sensing element,
FIGURE 15.6  (a) SEM micrograph of a graphene Hall element
with a depiction of measurement scheme. (b) VH versus magnetic
field plots for different Ic values. The inset shows the sensitivity
of Hall element as a function of Ic. (Reprinted by permission from
Macmillan Publishers Ltd. Scientific Reports, Xu, H. et al., Batch-
fabricated high-performance graphene Hall elements, 3, p. 1207,
copyright 2013.)
SI and SV are current and voltage-based sensitivity, respec-
tively, depending upon whether constant current or voltage
was applied across C1 and C2. Hall voltage across C3 and
C4 has been observed to be in proportion to the applied cur-
rent as seen in Figure 15.6b. The sensitivity value exceeding
550 V/AT of these graphene magnetic sensor [28] which is
quite comparable to 700 V/AT demonstrated with 2DEG-
based sensors [29].
Another advantage of graphene-based magnetic sensor is
tunability of sensitivity using a back-gate bias. The sensitivity
varied from −375 to +120 V/AT range when back-gate bias Vg
is applied from −30 to 30 V in an exfoliated graphene-based
device with four parallel electrodes and a nearby shunt element
[47]. The geometry of magnetic sensor also plays an impor-
tant role in determining sensitivity. The sensitivity of two-
terminal measurements of graphene sensor based on circular
van der Pauw geometry was found to exceed 1000 V/AT [49].
These graphene-based van der Pauw elements also exhibit a
Graphene-Based Sensors
very high magnetoresistance of 55,000%, a highly desirable
attribute for sensing head for high-density data storage in
magnetic domains.
Apart from Hall effect sensors, graphene magnetic sen-
sors have also been demonstrated based on spin relaxation
time, and Coulomb blockade operation. Graphene nanoribbon
(GNR)-based spin capacitors were found to be able to detect
magnetic field as low as 10 mOe by assuming spin relaxation
time of 100 ns [48]. A device made from exfoliated graphene
with several nm wide nanoconstriction was demonstrated to
work in Coulomb blockade regime. When decorated with
TbPc2 magnetic molecules (Pc = phthalocyanine), it was found
to detect the magnetization reversal of the molecules. A mag-
neto-conductivity change of 20% marked the spin reversal in
these magnetic molecules [53].
15.2.3.3  Graphene IR and THz Sensor
Graphene, with its linear energy dispersion relationship and
zero bandgap, can absorb light from mid-IR to ultraviolet
wavelength range with almost flat (2.3% for monolayer thick-
ness) absorption spectra, which makes it very attractive for
optical detection applications, especially in the technologi-
cally challenging ranges spanning from near infrared (NIR)
to THz. Graphene IR detectors [30] have been fabricated
through the formation of heterogeneous metal contacts [64]
to have different built-in potentials at the two graphene–
metal contact regions to separate the photo-generated elec-
tron–hole pairs to enable detection. Generated photocurrent
is proportional to the incident optical power. Graphene-based
IR camera has also been demonstrated [30], which works
by incorporating a micro-mirror device to compress the IR
imaging signal to be measured by the graphene detector in a
series of measurements, and decompressed subsequently to
reconstruct the image.
Among its other unique properties, graphene has a small
heat capacity and weak electron–phonon coupling. This makes
graphene ideal for bolometric sensing of IR radiation, where
absorption of the incident radiation induces a temperature
change, which modulates electrical conductivity. Dual-gated
bilayer graphene bolometer with a noise-equivalent power
(NEP) of 33 fW Hz−1/2 at 5 K and intrinsic speed >1 GHz at
10 K has been demonstrated utilizing illumination from a con-
tinuous wave CO2 laser operating at a wavelength of 10.6 μm
[31]. The demonstrated NEP is at least an order of magnitude
smaller compared to commercially available silicon bolometers,
which have typical NEP in the range of 200–2000 fW Hz−1/2.
The intrinsic operational speed of the graphene bolometer is
also 3–5 orders of magnitude higher than commercial silicon
bolometers and superconducting transition-edge sensors at
similar temperatures. Further, improvement in performance is
possible by fabricating devices with smaller dimension and by
virtue of one-dimensional quantized thermal conductance [65],
the sensitivity is expected to exceed that of micromachined
bolometers and at reasonable device temperatures (300 mK for
a 1 μm2 device) would approach the sky background NEP of
~1 × 10−20W Hz−1/2 in the terahertz range.
219
A class of photodetectors operating in the far-IR/THz uti-
lizes the optically induced breakdown of QHE in a 2DEG [50]
typically observed in III–V materials such as GaAs hetero-
structure. One of the limitations of these detectors is that they
require cooling down to near liquid He temperature; basi-
cally, all semiconductor QHE photodetectors operate above
12 K [66]. Compared to these, graphene QHE effect-based
IR photodetector has been reported which can work at 70 K
and can be achievable by liquid nitrogen in vapor evacuation
regime [45]. This IR detector also can be operated in the lower
magnetic field, and a wider range of operating frequency com-
pared to previously demonstrated QHE detectors.
Another IR/THz detection mechanism is based on LL
formation of Dirac fermions of graphene under an externally
applied magnetic field. An incident electromagnetic wave is
resonantly absorbed by graphene when its energy matches
the LL energy. Compared to other semiconductor, LL energy
separation is much larger in graphene and its electron and
hole LLs meets at the Dirac point instead of having band-
gap energy separation, as in the case of other semiconductors.
Due to this graphene-based magnetic field tunable IR/THz
detector over a wide frequency range (0.76–33 THz) has been
demonstrated compared to only (0.76–1.6 THz) for the GaAs
2DEG device [46].
The optical transitions in graphene monolayer and bilayer
can be modified substantially through electrical gating that
is unusual in another semiconductor. In case of bilayer
­graphene absorption spectra, a peak appears at the band
separation energy and becomes stronger with increasing
­
hole concentration as the Fermi shifts down allowing addi-
tional transitions [67]. Although single and bilayer graphene
is one or two atom thick layer, their absorption is strong
enough as well as tunable which would allow the design of
versatile IR detector. Layer-dependent physical responses
of graphene PDMS polymer composites to NIR light have
been reported recently where optical-to-mechanical energy
conversion efficiency decreased in the amount of 30%, per
additional graphene layer [68]. Recently, Ryzhii et al. [69].
proposed multiple-graphene-layer structures with lateral
p–i–n junctions for IR and THz photodetection, which due
to relatively high quantum efficiency and low thermogenera-
tion rate, can substantially surpass the other quantum well,
QD and gapless bulk semiconductor (such as HgCdTe) based
IR and THz detectors.
15.2.3.4  Pressure Sensor
The application of graphene in pressure sensing readily fol-
lows from the demonstration of Bunch et al. [27]. That gra-
phene is impermeable to all standard gases including He,
and can support pressure differences larger than one atmo-
sphere. This impermeability allows uniformly distributed,
well defined large force to be applied across the entire gra-
phene active area resulting in controlled strain which leads
to various different applications such as probing the elastic
properties of graphene itself, tunable mechanical resonance,
and pressure sensing that can be applied to detect the pressure
220
changes associated with chemical reactions, phase transitions,
and photon detection [51,52].
Pressure sensors from exfoliated graphene have been
reported by means of fabricating suspended graphene and
inducing 3% uniaxial tensile strain by in situ nanoindenta-
tion, and the obtained gauge factor of ~1.9 [54]. Lee et  al.
[55] have reported CVD graphene piezoresistive pressure
sensor with a gauge factor of ~6.1 while applying 1% strain.
Graphene piezoresistive pressure sensor has been reported
recently made of square silicon nitride membrane with gra-
phene meander patterns located on the maximum strain area
dynamic range from 0 to 700 mbar and a gauge factor of ~1.6
[56]. Graphene/epoxy hybrid microactuator-based strain sen-
sor was reported as well [57]. In terms of heterostructure, in-
plane pressure sensor consisting of graphene sandwiched by
boron nitride (h-BN) and tunneling pressure sensor consisting
of h-BN sandwiched by graphene was demonstrated with a
current variation of 3 orders of magnitude as pressure changes
from 0 to 5 nM/nm2 [58].
15.2.4 Chemical and Biological Sensors
As discussed earlier, the excellent material properties of gra-
phene make it highly attractive for chemical and biomolecu-
lar sensing applications, since the adsorbed molecules can
strongly affect its physical properties including conductivity
[5] and surface work function (SWF) [23,24]. Demonstration
of its ultrahigh sensitivity, down to a single gas molecule [5],
confirmed its potential application in molecular detection
based on changes in conductance [5,23], SWF [23], frequency
of the surface acoustic waves [25], and low-frequency noise
TABLE 15.5
Graphene-Based Chemical and Biological Sensors
Sensor Type Physical Parameter Measured
Gas and vapor sensors • Conductivity [5]
• ​Surface work function [22,23]
• Surface acoustic wave
frequency [25]
• Low-frequency noise [26]
pH sensors Change in doping with pH
Heavy metal sensors Change in doping with metal
particle attachment [73]
H2O2 sensor Cyclic voltammetry
Glucose sensor Cyclic voltammetry
Nucleic acid sensor Cyclic voltammetry
Sensor for cancer protein Cyclic voltammetry
marker
Dopamine sensor for neural Cyclic voltammetry
diseases
Cholesterol and cellular Cyclic voltammetry
detection
Graphene Science Handbook
[26]. A vast majority of the graphene-based sensors reported
so far are in the form of chemiresistor or chemical field-
effect transistors (chem-FETs) where the surface adsorbed
molecules proportionally change the charge carrier density
in graphene causing its conductivity to vary linearly with
the number of adsorbed molecules. The detection sensitiv-
ity in these sensors, for a specific analyte, is determined by
the mobility of the carriers in graphene (since conductivity is
proportional to the product of mobility and charge density),
and depends on the substrate the graphene film is synthesized
on or transferred to [70]. However, it has been demonstrated
that the sensitivity of these sensors can be tuned by utiliz-
ing a back gate [21]. The various applications of graphene in
chemical and biomolecular sensing are discussed as follows
(Table 15.5).
1. Gas and vapor sensors
Graphene-based sensors have been used to perform
detection of a large number of gaseous and vapor
phase analytes [5,21,23,26,72]. As discussed earlier,
graphene-based gas sensors have demonstrated the
ultimate sensitivity through detection of a single gas
molecule [5]. The various analyte molecules, which
can be broadly classified in terms of their electron
accepting (i.e., NO2) or donating characteristics
(NH3), can be detected by their ability to either
reduce or increase the conductivity of graphene (of
course this also depends on whether the graphene
is p-type or n-type and its Fermi level). However,
unique detection is not possible simply by measuring
the conductivity change, for which multidimensional
Analytes/Applications
NO2, NH3, H2, etc. [5,17,30,71]
Protein, that is, bovine serum albumin [72]
Mercury(II) (Hg2+) [73]
Nitrite (NO2−) [74]
Electrochemical biosensors to investigate
the enzyme-catalyzed reactions in
biological systems [75]
Electrochemical detection of nucleobases,
nucleotides, and DNAs [76]
Sensor to detect prostate-specific antigen
the marker for prostate cancer [77]
Dopamine [78]
Cholesterol [79]
Graphene-Based Sensors
measurements are necessary. A detailed discus-
sion of the sensitivity of graphene to several com-
mon atmospheric gases and vapors are presented in
References 21, 23, 24, and 81.
2. Graphene pH sensors
Epitaxial graphene-based pH sensor is the first gra-
phene sensor reported for detection in solution [72].
Ultrahigh pH sensitivity has been observed in terms
of change in the Dirac (neutral) point from 98 to
59.2 mV/pH. In this sensor, ion adsorption-induced
surface potential change is instrumental in the pH
detection and high sensitivity is due to the excellent
transport properties of graphene compared to that of
hydrogen-terminated diamond or silicon. pH detec-
tion limit as low as 0.025 has been reported employ-
ing exfoliated graphene that is 26 times lower than
that obtained from pH sensors based on the carbon
nanotube (CNT) [82].
3. Graphene heavy metal sensors
Detection of heavy metals such as Hg and Cd is
extremely important due to their well-known det-
rimental effects on human health. The exfoliated
graphene-based heavy metal sensor has been dem-
onstrated with a detection limit of 10 ppm (B5 mM)
for Hg2+ [73]. RGO (reduced graphene oxide) thin
film-based metal ion sensor has also been reported
through microfluidic patterning [83].
4. RGO-based H2O2 sensor
Hydrogen peroxide (H2O2) detection is of great
importance as it is an enzymatic product of many
biological processes. H2O2 sensor fabricated from
the RGO–chitosan composite film entrapped with
hemoglobin (Hb) molecules showed the promise
for this types of sensor which exhibited the detec-
tion limit of 0.51 µM and a wider linear range (6.5–
230 µM) as compared with the conventional H2O2
detection methods [74].
5. Glucose sensor
Diabetics’ diagnosis and management are largely
dependent on glucose detection. Electrochemical
detection of glucose can be realized by using glu-
cose oxidase (GO) as the mediator or recognition
element. Large effective detection surface and high
enzyme loading capacity can be obtained by mixing
RGO and supporting polymers to make a conducting
porous matrix. GO–RGO–chitosan modified elec-
trode has been reported which exhibited linear range
from 0.08 to 12 mM, detection limit of 0.02 mM,
and sensitivity of 37.93 µA/mM cm2 which is bet-
ter than compared to other nanostructured material-
based sensors [75].
6. Nucleic acid sensor
Sensitive and selective electrochemical detection of
nucleobases, nucleotides, and DNAs (single and dou-
ble stranded) is possible using reduced graphene oxide.
The four nitrogenous bases (adenine, thymine, cyto-
sine, and guanine) that are building blocks of DNA
221
can be selectively detected by RGO due to different
oxidation potentials. Such electrochemical DNA sen-
sors may provide a simple alternative approach for
DNA analysis and sequencing. Huang et al. [76]. dem-
onstrated highly sensitive detection of 50 nM guanine
and 25 nM adenine using RGO with a large number
of –COOH group. The high sensitivity toward these
bases comes from unique electrochemical properties
of RGO, the electrostatic attraction between nitrog-
enous bases and –COOH group, and the strong π–π
interaction between the nucleobases and RGO.
7. Sensor for cancer protein marker
Graphene-based electrochemical sensors have been
demonstrated to detect various protein biomarkers.
A graphene oxide-based immunosensor used layers
of electropolymerized thionine film, GO–chitosan
composite, AuNPs, and conjugates of horserad-
ish peroxidase and anti-alpha-fetoprotein (AFP)
antibody to detect cancer marker AFP [84]. The
detection limit of 0.7 ng/mL outperformed the con-
ventional enzyme-linked immunosorbent assays.
This immunosensor was able to identify correctly
negative/positive human serum samples in the same
fashion as a commercial clinical device. A similar
sensor based on sandwich immunoreactions on top
of RGO modified electrode sensor has been reported
to detect prostate-specific antigen the marker for
prostate cancer [77].
8. Dopamine, ascorbic acid (AA), and uric acid (UA)
sensor
Parkinson’s disease is characterized by the absence
of dopamine, an important neurotransmitter. The
detection of dopamine is a challenging task due to
its low physiological concentration (0.01–1 mM) and
the possibility of error from AA and UA which is
present in higher concentration and can interfere
with sensing of dopamine. A chitosan–RGO com-
posite electrode was demonstrated to detect dopa-
mine [78]. Graphene-based AA and UA sensors have
also been developed. An RGO sensor, fabricated by
self-assembly of gold nanoparticles on pyrenebutyr-
ate functionalized RGO sheets was able to detect UA
[71]. AA sensor was demonstrated by Keeley et al.
[85]. by using graphene nano-sheets exfoliated in the
liquid by dimethylformamide.
9. Cholesterol and cellular detection
Detection of cholesterol is extremely important for
medical purposes, and hence there is a huge demand
for the relevant sensors. Functionalized RGO-based
cholesterol sensor has been developed which works
on amperometric property change with a detection
limit of 0.2 mM [79]. In addition, sensitive and selec-
tive electrochemical biosensor for the detection of
cancer cells such as breast cancer cells and human
cervical carcinoma cells at a detection limit of thou-
sand cells per mL has been fabricated from reduced
graphene oxide [86].
222
15.3 MULTIDIMENSIONAL AND
SELECTIVE SENSING
In spite of the excellent sensitivity demonstrated by graphene-
based sensors, it is still not possible to selectively detect ana-
lytes using these sensors without functionalization layers.
However, it has been demonstrated that unique detection of
analytes may be possible using (i) multidimensional sens-
ing based on measurements of multiple physical parameter
changes and (ii) modulation of the Fermi level of graphene
using an electrical bias. The techniques are discussed in as
follows.
15.3.1 Multidimensional Sensing Approach
The multidimensional sensing approach is based on simulta-
neous measurement of SWF and conductance changes of gra-
phene layer due to adsorption of the analyte molecules on it.
It has been demonstrated that simultaneous measurements
of these two parameter changes can lead to the determina-
tion of specific signatures of analytes based on which they
can be uniquely detected [87]. Prior to graphene, unique 2D
signatures of analytes were demonstrated based on simultane-
ous conductance and capacitance signal measurements using
a CNT-network based device [88]. However, for CNT-based
sensor device the responses were found to exhibit a nonlinear
relationship with a voltage that can cause difficulty in unique
signature extraction.
The sensing experiments to determine 2D signatures were
conducted using nanostructured (nanocrystalline) graphite
(NG) surface layers deposited on ceramic substrates prepared
by the mechanical exfoliation of highly oriented pyrolytic
graphite (HOPG) [89]. The change in the SWF due to the
molecular adsorption on the NG surface layer was measured
from the amplitude changes of a resonant microcantilever,
an atomic force microscope (AFM) setup. The measurement
techniques have been discussed in detail elsewhere [89,90,91].
Figure 15.7a and b show the measured SWF change (Δφ)
and normalized conductance changes (ΔG/G0) as a function
(a) 200
Surface work function change (mV)
NO2 Off
150
100
50
NO2 On 8 ppm NO2
0 0
0 200 400 600 800
Time (s)
FIGURE 15.7  Simultaneous SWF and conductance changes measured using NG layers when exposed to (a) 8 and (b) 1.5 ppm NO2.
(c) SWF change plotted against percentage conductance change for 8 ppm NO2 extracted from the third cycle of (a). The inset shows the
same graph corresponding to 1.5-ppm NO2. (Reprinted with permission from Qazi, M., Vogt, T., and Koley, G.: Two-dimensional signatures
for molecular identification, Applied Physics Letters, 92 (10), pp. 103120–103123. Copyright 2008, American Institute of Physics.)
Graphene Science Handbook
of time when the NG was exposed to 8 and 1.5 ppm NO2,
respectively. The SWF is found to change (increase) at a
much faster rate than the conductance, and it quickly reaches
a fairly constant value (saturates) as the surface adsorption
sites become fully occupied. The saturation values of Δφ
upon exposure to 8 and 1.5 ppm NO2 gases can be seen to
be ~150 and ~95 mV, respectively, from Figure 15.7a and b.
The change (increase) in conductance is much slower, and
it continues to increase even after the SWF saturates. The
adsorption of the NO2 molecules increases the free hole den-
sity (by withdrawing electrons) in the NG layers, which are
p-type [5,89,92], causing an increase in the conductance (see
Figure 15.7a and b). The SWF increases as a result of the
sheet charge dipole formation between negatively charged
NO2 molecules on the surface and the compensating posi-
tive charges (holes) in the NG layer. Figure 15.7c shows the
change in the SWF plotted against the fractional change in
conductance corresponding to the third cycle of Figure 15.7a.
We observe a linear relationship between Δφ and ΔG/G0 from
which a gradient of ~75 mV/% change in conductance can
be extracted, which remains fairly constant for the most part
of the adsorption and the desorption process. The gradients
obtained from the first, second, and fourth cycles are 81, 70,
and 67 mV/%, respectively, which can be considered to be
quite consistent. For 1.5 ppm NO2 the 2D signature gradient
of Δφ plotted against ΔG/G0 is ~75 mV/% change in conduc-
tance, which is same as the gradient observed for 8 ppm NO2
(see the inset of Figure 15.7c). This indicates a unique signa-
ture gradient can indeed be obtained for a particular analyte.
Figure 15.8a shows the simultaneous potentiometric and
amperometric responses for a common vapor, acetone, satu-
rated in nitrogen carrier gas for two exposure cycles. The corre-
sponding Δφ versus ΔG/G0 plots for the rise and fall transients
of both cycles are shown in Figure 15.8b. The plots show simi-
lar gradients for both the transients with ­values of ~110 mV/%
conductance change. Plots of Δφ versus ΔG/G0 (desorption
response) for some common gases and vapors (NO2, NH3,
water vapor, acetone, and methanol) are summarized together
in Figure 15.9. The 2D gradients indicate a constant value
5 (b) 120 2.5 (c) 160
Surface work function change (mV)
Surface work function change (mV)
4 100 2 140
Conductance change (%)
Conductance change (%)
80 120
Surface work function change (mV)
3 1.5 95
90
60 100 85
80
2 1
75
40 80 70
0.5
65
1 60
20 60 55
1.5 ppm NO2 0.8 1 1.2 1.4 1.6 1.8 2
Conductance change (%)
0 0 40
1000 0 200 400 600 800 1000 1200 2 2.5 3 3.5 4 4.5 5 5.5
Time (s) Conductance change (%)
Graphene-Based Sensors 223

(a) 80 1 (b) 70
Flow Flow

Surface work function change (mV)

0.8

Surface work function change (mV)

60 on off 60

Conductance change (%)

0.6
40 50
0.4
20
0.2 40

0 0
30
Rise transient 1
–20 –0.2 Decay transient 1
20 Rise transient 2
–0.4 Decay transient 2
–40
–0.6 10
0 50 100 150 200 250 300 350 400 –0.6 –0.5 –0.4 –0.3 –0.2 –0.1 0
Time (s) Conductance change (%)

FIGURE 15.8  (a) Simultaneous SWF and conductance changes measured using NG layer when exposed to saturated acetone vapor
(~0.3%). (b) SWF change plotted against percentage conductance change corresponding to the rise and fall transients of two cycles shown
in (a). (Reprinted with permission from Qazi, M., Vogt, T., and Koley, G.: Two-dimensional signatures for molecular identification, Applied
Physics Letters, 92 (10), pp. 103120–103123. Copyright 2008, American Institute of Physics.)

of +75 mV/% change in conductance for both 8 and 1.5 ppm
NO2, while acetone, ammonia, and methanol have negative
2D gradient values of −110, −45, and −13 mV/%, respectively.
Water vapor has a gradient of +12 mV/% change in conduc-
tance although it belongs to the third quadrant. Considering
the results presented in Figure 15.9, it can be concluded that
100
Acetone
80
Ammonia
Surface work function change (mV)
simultaneous measurement of SWF and conductance changes
can facilitate extraction of very distinct two-dimensional
gradients as signatures (2DGSs) of analyte molecules. Thus,
unknown molecules can be uniquely identified by compari-
son with an existing database containing the 2DGSs of all
relevant molecules. The one-dimensional response, which
traditionally utilizes only conductance change would be inca-
pable of uniquely identifying the molecules since it would be
1.5 ppm NO2 affected by both concentration and nature of the molecules
(+75) whose effects cannot be separated [87]. Although the 2D sig-
(–110)
natures of the various analytes have been included for NG,
similar signatures can also the extracted for other functional-

8 ppm NO2
60 (–45) (+75) ization layers including graphene. In fact, three-dimensional
signatures of analytes have been also been demonstrated
Methanol
40 (–13) using In2O3 ­functionalization layer [22].

20 15.3.2 Tuning Sensitivity and Selectivity

0
–20
Water vapor
(+12)
–40
–3 –2
FIGURE 15.9  2DGS values for NO2 (8 and 1.5 ppm), acetone
(~0.3%), methanol (~0.15%), pure ammonia, and water vapor
(~0.028%). 8 and 1.5 ppm NO2 show very similar gradients of
~75 mV/% change in conductance in the first quadrant. Acetone,
ammonia, and methanol show 2DGSs of −110, −45, and −13 mV/%,
respectively, while water vapor has a 2DGS of ~12 mV/% change
of conductance in the third quadrant. (Reprinted with permission
from Qazi, M., Vogt, T., and Koley, G.: Two-dimensional signatures
for molecular identification, Applied Physics Letters, 92 (10), pp.
103120–103123. Copyright 2008, American Institute of Physics.)
Since most amperometric detections are based on charge
exchange between adsorbed molecules and the functionaliza-
tion layer (i.e., graphene), the relative position of the defect
states induced by the former and the Fermi level of the later
determines the sensitivity of a given functionalization layer
toward a specific analyte. Modulation of the Fermi level by a
–1 0 1 2 3 back-gate bias is, thus, expected to strongly affect the sensitiv-
Conductance change (%) ity of a graphene-based sensor toward various analytes. In this
context, it is important to note that only 2D materials, such
as graphene, can have their Fermi level significantly modu-
lated easily using a realistic back-gate bias. The concept of
tuning the sensitivity of graphene using a back-gate bias was
systematically investigated in graphene FET devices, where
the sensitivity to NO2 and NH3 (common acceptor and donor
molecules) as a function of back-gate bias (varying from −45
to 5 V) was noted [21]. The dependence of sensing responses
on back-gate bias for NO2 and NH3 are shown in Figure 15.10a
and b, respectively.
224 Graphene Science Handbook

(b) 2
(a)
28 Vbg = 5 V
Vbg = 5 V
0 Vbg = 0 V

Percentage conductance change

21
Percentage conductance change

Vbg = –5 V

–2 Vbg = –10 V
14
Vbg = –15 V Vbg = –15 V
–4 Vbg = –20 V
7
Vbg = –25 V
Vbg = –25 V
–6
0 Vbg = –35 V
Vbg = –30 V

–8
0 100 200 300 400 500 0 100 200 300 400 500
Time (s) Time (s)

FIGURE 15.10  Variation of back-gated graphene sensor response for (a) 20 ppm NO2 exposure with the increase in gate bias from negative
to positive values and (b) 550 ppm NH3 exposure with the gate bias change from negative to positive values. The gas flow was turned on after
30 s for both the gases and shut off after 150 s. (Reprinted with permission from Singh, A.K. et al.: Electrically tunable molecular doping
of graphene, Applied Physics Letters, 102 (4), pp. 043101–043105. Copyright 2013, American Institute of Physics.)

From Figure 15.10a, it is observed that graphene’s sensitiv-
ity (percentage conductance change) decreases from 26.1% to
3.6% for 20 ppm NO2 as Vbg changes from 5 to −35V. The
opposite trend is observed for NH3 from Figure 15.10b, where
the conductivity change decreases from 7.6% to 0% as Vbg
changes from −30 to 5 V. Graphene’s sensitivity toward a par-
ticular analyte is inversely proportional to the initial carrier
concentration (before adsorption), p0, and directly proportional
to the change in carrier concentration (due to gas adsorption),
Δp. With the fractional change in conductivity Δσ/σ = Δp/p0,
an increase in p0 would certainly reduce the sensitivity toward
the adsorbed molecules even if Δp remains constant. Since the
graphene film is p-type in nature, a positive gate bias would
reduce the hole concentration. Interestingly, the correspond-
ing movement of the Fermi level, in response to the change in
back-gate bias, was found to affect Δp (charge transfer between
the adsorbed molecules and graphene film) as well, which was
calculated from the experimentally measured σ and Δσ/σ
(caused by gaseous adsorption) at each voltage bias.
For the 30 × 30 μm device used for the experiments, the ini-
tial carrier (hole) density, p [=σt/qμ = GL/(qμW)] at Vbg = 5 V
was calculated as 3.16 × 1012 cm−2, where G is the conductance
of the graphene film. The calculated values of carrier con-
centration at each voltage bias are shown in Table 15.6. The
mobility (μ = 10.15 cm2/V/s) was assumed to remain constant
over the back-gate bias range considered (5–45 V), since the
transconductance gm (the slope of IDS–Vbg curve) was found to
remain fairly constant over that range considered, as seen from
current–voltage transfer characteristics in Reference 17 for a
back-gated CVD graphene FET in air. From Figure 15.10a
for Vbg = 5 V, the fractional change in conductivity due to
NO2 adsorption can be seen to be 0.261. Utilizing the relation
[Δσ/σ = Δp/p] and the value of p for that bias from Table 15.6
(column 3), the change in carrier density, ∆p NO2 is calculated
as 8.25 × 1011 cm−2. The calculated values of ∆p NO2 are sum-
marized in column 4 of Table 15.6, where the charge transfer
doping ∆p NO2 is found to decrease from 8.25 × 1011 cm−2 to
undetectable as Vbg decreases from 5 to −45 V.
Following a similar process p and ∆p NH3 were calcu-
lated for NH3 adsorption for different V bg and are shown
in Table 15.7. In contrast to NO2, and consistent with its
donor-like behavior, the charge transfer doping ∆p NH3 was

TABLE 15.6
Effect of Back-Gate Bias on Initial Carrier Density, Fermi Level Position, and Charge Exchange due to Flow of NO2
Initial Adsorption-Induced Fermi Level Adsorption-Induced
Back-Gate Conductance (µS) Initial Carrier Carrier Density Position, EF Fermi Level
Bias (V) (change in %) Density, po (cm−2) Change (cm−2), Δp (meV) Change, ΔEF (meV)
5 5.13 (26.1) 3.16 × 1012 8.25 × 1011 207.5 106.0
−5 5.32 (22.2) 3.28 × 1012 7.28 × 1011 211.3 99.6
−15 5.88 (17.8) 3.62 × 1012 6.45 × 1011 222.2 93.7
−25 7.09 (10.8) 4.37 × 1012 4.72 × 1011 243.9 80.2
−35 9.04 (3.6) 5.57 × 1012 2.00 × 1011 275.4 52.2
−45 10.87 (0) 6.69 × 1012 Below detection limit 302.0 Below detection limit
Graphene-Based Sensors 225

TABLE 15.7
Effect of Back-Gate Bias on Initial Carrier Density, Fermi Level Position, and Charge Exchange due to Flow of NH3
Initial Adsorption-Induced Fermi Level Adsorption-Induced
Back-Gate Conductance(µS) Initial Carrier Carrier Density Position, EF Fermi Level Change,
Bias (V) (Change in %) Density, po (cm−2) Change (cm−2), Δp (meV) ΔEF (meV)
−30 7.25 (7.6) 4.46 × 1012 3.39 × 1011 246.6 68.0
−25 6.93 (6.76) 4.27 × 1012 2.88 × 1011 241.1 62.7
−20 6.54 (6) 4.02 × 1012 2.41 × 1011 234.2 57.4
−15 5.93 (4.5) 3.65 × 1012 1.64 × 1011 223.0 47.3
−10 5.24 (3) 3.23 × 1011 9.69 × 1010 209.7 36.3
0 4.17 (1.36) 2.57 × 1011 3.49 × 1010 187.0 21.8

found to increase from undetectable to 3.39 × 1011 cm−2 as
V bg decreases from 5 to −30 V. Since NO2 forms acceptor
states (unoccupied molecular orbitals) below the Dirac point
[93], more negative gate bias would lower the Fermi level
and bring it closer to acceptor state energy level, so the mag-
nitude of charge transfer ∆p NO 2 between NO2 molecules and
graphene would reduce. Figure 15.11 shows the band dia-
grams with acceptor and the Fermi energy levels for differ-
ent gate biases. Since the charge transfer is a self-­limiting
process, its rate also depends on the energy difference
between the Fermi level and the acceptor level; hence ∆p NO 2
corresponding to a given time interval will be dependent on
V bg, as observed experimentally (Table 15.6). The reverse is
observed for electron donor NH3, which forms donor states
above the Dirac point, therefore, a change in V bg to more
negative values causes the Fermi level to move downward,
increasing the energy difference and hence the magnitude
and rate of charge transfer doping. It should be noted here
that for p-type graphene, the carrier concentration change
and the Fermi level movement act together to enhance the
detection sensitivity for both donor- and acceptor-type gases.
Thus, the sensitivity for gaseous detection for p-type gra-
phene can generally be expected to be higher than that of
n-type graphene for acceptor-type molecules such as NO2.
Evac
(a) E (b) (c)
k Figure 15.12 illustrates all possible peaks that could be pres-
ϕNO ϕNO ϕNO
2 2
Vbg = 0
Vbg = +ve Vbg = –ve
FIGURE 15.11  Band diagrams showing shift in Fermi level in
back-gated graphene sensor as a result of gate bias and NO2 adsorp-
tion at (a) no bias, (b) positive, and (c) negative gate bias. Fermi
level moves downward upon exposure to NO2 in all three cases.
(Reprinted with permission from Singh, A.K. et al.: Electrically tun-
able molecular doping of graphene, Applied Physics Letters, 102 (4),
pp. 043101–043105. Copyright 2013, American Institute of Physics.)
Overall, the experimental results demonstrate that molecular
doping by adsorbed gas molecules depends on the position of
the Fermi level relative the donor/acceptor states, and it can
be tuned by an appropriate back-gate bias.
15.4 CORRELATION BETWEEN SENSING
AND MATERIAL PROPERTIES
The sensitivity of graphene-based sensors devices are strongly
affected by the presence of defects in graphene, which can be
in the form of grain boundaries, vacancies or point defects,
dopants, wrinkles, change of hybridization from sp2 to sp3,
or simply atomic discontinuity at the edge [94]. Defects in
graphene are generally introduced during their growth or
during subsequent processing for making electronic devices.
In general, the nature and extent of defect depend upon the
technique of making graphene. Some techniques result in gra-
phene with low defect density, such as exfoliation, which can
produce graphene with edge discontinuity as the only defect,
which is unavoidable. Chemical derivation of graphene, such
as reduced graphene oxide, tends to be more defective in gen-
eral, due to incomplete reduction of graphene oxide. The pop-
ular methods of making a large area or wafer size graphene,
such as CVD and epitaxial, can also introduce defects that can
be minimized by optimization of the process parameters. A
recent study suggests that the type of defects can be assessed
by analyzing intensity ratios, peak positions, and shape of
peaks present in the Raman spectrum of defective graphene.
2 ent in a typical defective graphene [94].
In general, defects in a material tend to degrade their phys-
ical properties. This is also true for graphene where degrada-
tion of mobility from 1350 to less than 200 cm2/V/s has been
observed [95], since defects create charge s­ cattering centers.
Defect density can affect chemical sensing and broadband
photodetection of graphene-based sensors. Introduction of
extended defect such as by self-doping [96], and growth on
Ni (111) template [97] to create a line defect that functions as
quasi-one-dimensional metallic wire, can also impart newer
properties to graphene. These designer defects in graphene
can then be used for guiding charge and spin, controlled
chemical reaction, and porous membranes.
226
Fluorinated
D
Anodic bonded
2D
Intensity (a.u.)
G bers are very high for ppm level NO2 detection when com-
D′
D + D′
1200 1500 2600 2800 3000
Raman shift (cm–1)
FIGURE 15.12  Raman spectra of fluorinated and anodic bonded
graphene depicting peaks of interest in 1200–3000 cm−1 range in
a defective graphene. The D and D’ peaks are the defect peaks
resulting from disruption of symmetry in graphene. (Reprinted
with permission from Eckmann, A. et al., Probing the nature of
defects in graphene by Raman Spectroscopy, Nano Letters, 12 (8),
pp. 3925–3930. Copyright 2012 American Chemical Society.)
Theoretical calculations using density functional theory
has been used to predict the sensitivity of pristine, B-doped,
N-doped, and defective graphene [98]. The adsorption ener-
gies of CO, NO, NO2, and NH3 were determined for the
above-mentioned graphene. The adsorption energy was found
to largest for defective graphene and CO, NO, NO2 whereas
in the case of NH3 it was B-doped. These calculations sug-
gest that the defective or doped graphene have higher propen-
sity to adsorb gaseous molecules by virtue of their increase
in adsorption energy or an increase in the adsorption sites,
which may be responsible for two-orders-of-magnitude higher
sensitivity in B-doped graphene [98].
A direct comparison of pristine exfoliated graphene and
defective CVD graphene was made in sensing toluene and
dichlorobenzene to highlight the role of defects in chemi-
cal sensing [99]. Figure 15.13a shows the Raman spectra of
good quality exfoliated graphene with the absence of defect
related D peak and defective CVD graphene showing very
prominent D peak. The response of chemiresistor made
from exfoliated, CVD, and CVD microribbon-based gra-
phene toward dichlorobenzene is depicted in Figure 15.13b.
Clearly, highest response of 11% is shown by microribbon-
based chemiresistor since it has higher density of defects
due micro size ribbon configuration (with defect sides at the
edges), apart from already present defect in CVD graphene
sample. The exfoliated graphene does not seem to have
any noticeable response, whereas defective CVD graphene
shows ~6% response.
The role of defects in sensing is very strongly highlighted
by using chemically derived graphene. Figure 15.13c shows
the Raman spectrum of bare reduced graphene oxide and
Graphene Science Handbook
those functionalized by three different organic functional-
ization layers. All the Raman spectra show D peak inten-
sity same as G peak or even higher. These represent highly
defective graphene. However, these defective graphene-based
chemiresistors turns out to be excellent sensors for 50 ppm
NO2 as seen in Figure 15.13d. The response of bared reduced
graphene oxide is 2 times (200%) and goes as high as 25 times
with the suitable functionalization layer [100]. These num-
pared to good quality graphene-based sensor that does not
surpass even 100% [101,102]. Photodetection is yet another
area where defects have rendered graphene as a highly sensi-
tive broadband photodetector [103]. Regular graphene-based
photodetectors suffer from low photoresponsivity in the range
of 10 mA/W. The low values mainly come from two factors,
low optical power absorption in monolayer graphene and very
low recombination lifetime (in the range of picoseconds).
The lifetime can be enhanced significantly by utilizing the
concept of defect assisted photoconductive gain. The photo-
generated electrons are trapped in defect states that let the
corresponding holes to recirculate many times before recom-
bination thus, providing photoconductive gain. These defect
states are in fact created by dissolving a very thin sacrificial
layer of Ti on top of exfoliated graphene by treating it with
HF, H2O2, and deionized water solution. The Raman spec-
tra of such devices shows generation of very large number
of defects as can be seen in Figure 15.14a where sample A
corresponds to pristine graphene device whereas samples B
and C correspond to 2 and 20 nm thick Ti sacrificial layers
and show very high D peak. The plots in Figure 15.14b shows
the response of highly defective sample C in terms of series
of photocurrent generate by exposure to NIR wavelength of
1.47 µm where optical power varies from a very small range
of 8 to 200 nW. Therefore, defects in graphene (introduced
unintentionally or deliberately) can be very effectively uti-
lized to significantly enhance the sensitivity of chemical sen-
sors and photodetectors.
15.5  FUTURE TRENDS
15.5.1 Graphene Heterostructure Sensors
The unique combination of zero bandgap and adjustable work
function due to the 2D nature of graphene leads to the for-
mation of tunable Schottky contact at the heterostructure
interface of graphene and other semiconductors. Recent
demonstration of graphene/semiconductor heterojunction
Schottky diodes [104–106] encouraged the development of
novel electronic devices such as insulated top gate transistor
called “Barristor,” [107] optoelectronic devices such as solar
cell [105] and photodetectors [108]. Since graphene’s work
function can be modulated by both applied bias and adsorbed
molecules such heterojunctions are attractive from the per-
spective of electronic and photonic devices as well as for sens-
ing applications.
Graphene/n-Si tunable photodetector with photovoltage
responsivity exceeding 107 V/W and NEP reaching ~1 pW/
Graphene-Based Sensors 227

(a) (b) 12
2500 Defected graphene
1,2-dichlorobenzene
Pristine graphene
10
2000
Graphene ribbon
Intensity (a.u.) 8 Graphene
2D

ΔG/G0 (%)
1500 Pristine graphene
G
D 6

1000 4

500 2

0
0
1200 1600 2000 2400 2800 0 30 60 90 120 150 180
Raman shift (cm–1) Time (s)

(d) 30
(c) 50 ppm rGO
25 EDA–G

20 S–G
Intensity (a.u.)

EDA–G

G/G0
15
S–G
10
rGO
5
GO
0
1000 1500 2000 0 1000 2000 3000 4000
Raman shift (cm–1) Time (s)

FIGURE 15.13  (a) Raman spectrum of defect free pristine and defective CVD graphene. The D peak is absent in pristine graphene.
(Salehi-Khojin, A. et al.: Polycrystalline graphene ribbons as chemiresistors, Advanced Materials, 2012, 24 (1), pp. 53–57. Copyright Wiley-
VCH Verlag GmbH & Co. KGaA. Reproduced with permission.) (b) Dichlorobenzene sensing response of pristine, and CVD graphene, and
graphene ribbon suggesting better sensitivity with more defective structure. (Salehi-Khojin, A. et al.: Polycrystalline graphene ribbons as
chemiresistors, Advanced Materials, 2012, 24 (1), pp. 53–57. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permis-
sion.) (c) Raman spectra showing highly defective reduced graphene oxide along with various functionalization layers. (Yuan, W. et al.:
High-performance NO2 sensors based on chemically modified graphene, Advanced Materials, 2013, 25 (5), pp. 766–771. Copyright Wiley-
VCH Verlag GmbH & Co. KGaA. Reproduced with permission.) (d) Sensing response of plain and functionalized reduced graphene oxide
to 50-ppm NO2. (Yuan, W. et al.: High-performance NO2 sensors based on chemically modified graphene, Advanced Materials, 2013, 25
(5), pp. 766–771. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.)

(a) (b) 50
D Off On Off
Graphene 201.31 nW
40 166.65 nW
S D NIR 135.65 nW
2D 118.99 nW
Photocurrent (nA)

G 99.32 nW
Intensity (a.u.)

30 85.66 nW
D′
Sample C D + D′ 65.33 nW
52.66 nW
20 32.66 nW
Sample B 14.99 nW
8.00 nW
10

Sample A
0
1500 2000 2500 3000 3500 100 200 300 400
Raman shift (cm–1) Time (s)

FIGURE 15.14  (a) Raman spectra of pristine and chemically treated graphene in photodetectors. Sample A has pristine graphene whereas
sample B and C have very high concentration of defects in graphene. The inset shows the optical micrograph of the device in sample C
with a scale bar of 20 µm. (b) Photocurrent generated as a response to in the range of 8–200-nW power NIR wavelength in a highly defec-
tive graphene device in sample C. (Reprinted by permission from Macmillan Publishers Ltd. Nature Communications, Zhang, B.Y. et al.,
Broadband high photoresponse from pure monolayer graphene photodetector, 4, pp. 1811, copyright 2013.)
228
Hz1/2 has been reported [108]. In the photocurrent mode, the
response was found to remain linear over six decades of inci-
dent power (P), with tunable responsivity up to 435 mA/W
(corresponding to incident photon conversion efficiency
[IPCE] > 65%) obtained by layer thickening and doping by
drop-casting 1-pyrenecarboxylic acid (PCA). Graphene/p-Si
based metal–semiconductor–metal with graphene acting
as the metal has also been reported with a responsivity of
0.11 A/W and a normalized photocurrent-to-dark current
ratio of 4.55 × 104 mW−1 [109]. IR detector based on graphene/
Si Schottky diode is demonstrated recently utilizing excitation
from 1.55 μm laser [43]. Graphene/p-Si Schottky diode fabri-
cated by micromechanical exfoliation of graphite exhibited a
minimum responsivity in the range of 2.8–9.9 mA/W corre-
sponding to an internal quantum efficiency of 10–30%, which
is on the orders of magnitude larger than regular Schottky
junctions.
Graphene/Si diode sensor (GDS) shown in Figure 15.15a
is an emerging platform for gas, environmental, and bio-
compatible sensors [41]. The responses of the GDS toward
anisole, benzene, chlorobenzene, nitrobenzene, and gaseous
ammonia (electron donor-type and acceptor-type molecules)
are shown in Figure 15.15b, where changes in the Schottky
barrier height (SBH) caused the current across heterojunction
to change, resulting in high sensor response to various adsor-
bents. Since majority carrier transport across the junction
is exponentially dependent on the interface barrier height,
change in graphene work function can affect the diode cur-
rent much more strongly than the normal chem-FET-type
sensors. However, in forward bias, the series resistance of
the diode dominates after turn-on voltage and change in
overall sensor resistance due to adsorbed molecules is domi-
nated by the change in diode series resistance, thus the expo-
nential change in current with change in SBH is generally
not observed. On the other hand, in reverse bias, the cur-
rent can change exponentially with change in SBH, unlike
in forward bias operation, or in chemiresistor-type sensors,
(a)
FIGURE 15.15  (a) Schematic presentation of graphene/Si diode sensor and (b) change of series resistance in GDS exposed to various
aromatic molecules. (Reprinted with permission from Kim, H.-Y. et al., Chemically modulated graphene diodes, Nano Letters, 13 (5),
pp. 2182–2188. Copyright 2013 American Chemical Society.)
Graphene Science Handbook
where a linear response is expected with molecular adsorp-
tion. The reverse bias operation also offers the advantage of
tuning the sensor sensitivity through bias-dependent modu-
lation of the graphene Fermi level and hence the SBH. In
addition, the reverse bias operation results in a drastic reduc-
tion in the operating power requirement of the sensor (with
consequent minimization of heating effects) which is highly
desirable from the sensor design perspective. Improved sens-
ing response of reverse-biased graphene/Si heterojunction
Schottky diodes compared to regular chemiresistor-type
sensors has been reported by Singh et  al. [42]. Compared
to a conventional graphene amperometric sensor fabricated
(fabrication steps are shown schematically in Figure 15.16)
on the same chip, the diode sensor demonstrated 13 times
higher sensitivity for NO2 and 3 times higher for NH3 in
ambient conditions, while consuming ~500 times less power
for the same magnitude of applied voltage bias. The sensing
mechanism based on heterojunction SBH change has been
confirmed using capacitance–voltage measurements as well.
From the C–V measurement, after NO2 exposure the SBH
reduced by 0.23 eV while increased by 0.16 eV. Sensing tun-
ability is achieved by exploiting the semimetallic nature of
graphene by operating the device in reverse bias, and varying
the bias magnitude to vary the work function of graphene,
and hence the barrier height at the graphene/Si heterointer-
face. The sensitivity varied from 268% to 574% for NO2 as
the bias magnitude varied from −1 to −8 V. Optimized sensor
design to detect a particular analyte is also possible by care-
ful selection of graphene/Si heterojunction SBH. For exam-
ple, graphene/p-Si with larger SBH is a better NO2 sensor
while smaller SBH device has better NH3 sensitivity.
Although graphene has an excellent sensitivity to a
large variety of polar molecules (i.e., NO2 and NH3), it is
insensitive to most nonpolar molecules, such as H 2, with
which it does not exchange charge. A surface function-
alization is, therefore, necessary for detecting these non-
polar molecules. Catalytically active noble metal, Pt, and
(b) 6
p-Si
n-Si
Series resistance (kΩ)
2
Nitro Chloro Pristine Benzene Anisole
benzene benzene
Increasing electron Increasing electron
withdrawing ability donating ability
Graphene-Based Sensors 229

Selective removal of SiO2 Ti/Au contact pad on Si by

from SiO2/Si substrate by metal deposition and
lithography and HF etching annealing

CVD graphene growth Patterning graphene on Cu Graphene transfer on

on Cu by lithography patterned SiO2/Si substrate

Graphene/Si functionalization Ti/Au contact pad on

(if any) graphene/SiO2

FIGURE 15.16  Process flow steps for the fabrication of the graphene/Si Schottky diode sensors. (Reprinted with permission from
Perkins, F. et al., Chemical vapor sensing with monolayer MoS2, Nano Letters, 13 (2), pp. 668–673. Copyright 2013 American Chemical
Society.)

Pd functionalized graphene/Si H 2 sensor has also been
demonstrated recently [110]. Extrapolated SBH from the
current–­voltage relationship, before and after few nm metal
decoration, and H 2 exposure showed initial SBH decrease
after functionalization and subsequent increase in the pres-
ence of H 2, respectively. Compared to graphene chemire-
sistor sensor, the chemi-diode sensor offers more than one
order of magnitude higher H 2 sensitivity due to the already
mentioned sensing mechanism for both types of function-
alization. Similarly, the reverse bias operation also enables
low power consumption, tunable sensitivity, and detection
of H 2 down to the sub-ppm range in the air which is close to
the atmospheric background of 0.6 ppm. Between the two
metals, Pd-functionalization always exhibited better sens-
to tetrahydrofuran, (CH2)4O, produced <10% response, while
exposure to dimethylformamide, (CH3)2NC(O)H, produced
no response above the noise level. However, unlike graphene-
based sensors, which shows sensitivity to both donor-type and
acceptor-type molecules, MoS2 sensors did not show sensitiv-
ity to electron acceptor analytes such as o-dichlorobenzene,
1,5-dichloropentane, o-nitrotoluene, and nitromethane at
concentrations as high as 2% P0 (P0 = 1350, 960, 136, and
37,400 ppm, respectively). Figure 15.17 shows the histogram
summarizing the sensitivity and selectivity of both the mono-
layer MoS2 and CNT-network sensors to various analytes.

Cl
ing response irrespective of bias voltage. Remarkably, for
Pd-functionalization, the sensor response showed absolute
exponential change with varying H 2 concentration ranging

Cl
from 2 to 1000 ppm showing its potential for sensing of a TEA THF ACE MeOH NT DCP DCB
wide range of H 2 concentration. 1

15.5.2 Other 2D Material-Based Sensors

Highly encouraging results obtained on graphene-based
Relative ΔG/G0

electronic, optoelectronic devices, and sensors encouraged

researchers to explore other 2D materials, especially BN and
transition metal dichalcogenides (MoS2, WSe2, etc.). Among
them, MoS2 has attracted the most research interest in last few
years. Single and multilayer MoS2-based gas and vapor sen-
sors have been reported recently, where sensitivity toward NO
was demonstrated [111]. Afterward, monolayer MoS2-based
sensor has been reported with sensitivity toward triethylamine
(TEA) (a decomposition product of V-series nerve gas agents)
with a detection threshold of 10 ppb [112]. The sensor showed
linearly varying sensitivity toward TEA concentration in the
range of 1–100 ppm while no response toward dichloroben-
zene, dichloropentane, nitromethane, nitrotoluene, and water
vapor was observed. The sensor is also found to be sensitive to
acetone, with a detection threshold of ~500 ppm. As generally
expected, the response of the MoS2 sensor was lesser for ana-
lytes considered to be weak donors. For example, exposure
0
Positive detection
threshold
MoS2 monolayer
CNT network
–1
FIGURE 15.17  Histogram of MoS2 and CNT-network sen-
sor responses to various analytes. A qualitative summary of the
response of the sensors to the analytes tested. The analytes from
left to right are triethylamine (TEA), tetrahydrofuran (THF), ace-
tone, methanol, nitrotoluene (NT), 1,5-dichloropentane (DCP), and
1,4-­dichlorobenzene (DCB). Ball-and-stick model of the analyte
molecules are show above (From Perkins, F. et al.: Nano Letters,
2013, 13 (2), pp. 668–673.)
230
The monolayer MoS2-based sensor showed good sensitivity,
high selectivity, and its responses were completely opposite to
that of CNT networks. The sensing behavior of monolayer to
few layers MoS2-based sensors toward NO2, NH3, and water
vapor under different conditions have been reported recently
by Late et al. [113]. It was observed that few-layer MoS2 sen-
sor exhibited better sensitivity, recovery, and tunability by
gate bias and green light compared to that of a single layer.
However, further studies need to be carried out on this and
other chalcogenides to fully understand and unravel their
sensing potential.
15.6 SUMMARY
In summary, we have discussed the synthesis, processing,
and various sensing applications of graphene in this chapter.
As discussed in the introduction in Section 15.1, owing to
its extraordinary material properties, graphene is very well
suited for a large variety of sensing applications. This has
been demonstrated through numerous studies that include
the realization of ultimate sensing limit of one analyte mol-
ecule. In Section 15.2, we have discussed the various meth-
ods for synthesizing graphene, of which the most versatile
and technologically significant one is based on CVD. This
has been followed by a description of the fabrication steps for
graphene sensors in a back-gated FET configuration starting
with CVD synthesized graphene. A detailed discussion of the
applications of graphene in physical, chemical, and biologi-
cal sensors has also been included in Section 15.2. In spite
of the excellent sensitivity of graphene-based sensors, they
still suffer from a lack of selectivity in molecular detection.
In Section 15.3, we have described two different approaches
to addressing the selectivity issue. The first one is based on
performing multidimensional measurements based on the
simultaneous acquisition of SWF and conductance sensing
signals to extract unique signatures of the analytes. The sec-
ond is based on the utilization of a back-gate bias to modu-
late the Femi level of graphene, and hence its relative position
with respect to the adsorbent-induced defect state, to control
its propensity for charge exchange with adsorbed molecules.
We have discussed the effects of graphene material qual-
ity on its sensing response in Section 15.4 based on sensing
results reported in the literature, which clearly indicate that
higher defect density in graphene can enhance the sensitivity
of both chemical sensors and photodetectors. In Section 15.5,
we have included discussions on the future trends in this vast
and exciting field of 2D nanoscale materials-based sensors. A
major current research focus in this field is on utilizing hetero-
junctions formed between graphene and other semiconductors
for sensing applications. An emerging trend is to utilize other
2D materials, especially semiconducting ones such as tran-
sition metal dichalcogenides (i.e., MOS2) to perform sensing
either by itself or in heterojunctions with graphene. The later
configuration offers the possibility of incorporating these sen-
sors in flexible biocompatible materials with huge potential
applications in biosensing.
Graphene Science Handbook
ACKNOWLEDGMENTS
Financial supports for this chapter from National Science
Foundation (Grant Nos. ECCS-0846898, ECCS-1029346,
and ECCS-1348166) is thankfully acknowledged. We also
acknowledge Mr. Nicholas DeRoller for his help with gener-
ating an illustration.
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 16 Effect of External Electric
Fields on the Multifunctional
Applications of Graphene
Zhimin Ao, Qing Jiang, Sean Li, Shixue Dou, and Guoxiu Wang

CONTENTS
Abstract...................................................................................................................................................................................... 235
16.1 Introduction...................................................................................................................................................................... 235
16.2 Effect of Electric Fields for Application of Graphene as Hydrogen Storage Materials................................................... 236
16.2.1 Electric Field-Induced Hydrogenation of Graphene for Atomic Hydrogen Storage............................................ 236
16.2.2 Hydrogen Diffusion and Release on/from N-Doped Graphene under an Electric Field...................................... 240
16.3 Electric Field-Induced Reversible Transition of Graphene from Hydrophobic to Hydrophilic....................................... 243
16.4 External Electric Field-Catalyzed N2O Decomposition on Mn-Embedded Graphene.................................................... 246
16.5 Summary.......................................................................................................................................................................... 251
References.................................................................................................................................................................................. 251

ABSTRACT further changes in these materials. These fields can yield

Graphene has shown promising applications as ultrasensitive
gas sensors, transparent electrodes in liquid crystal display
devices, large capacity electrodes in batteries, etc. External
electric fields, which are often met in practical applica-
tions, could induce changes of graphene-based materials in
geometry, binding energies, vibrational spectra, chemical
activities, and electronic properties, thus further widen-
ing their application fields. In this chapter, the dissociative
adsorption of H 2 and H 2O molecules on graphene and N2O
decomposition on Mn-embedded graphene in the presence
of electric fields based on density functional calculations
are reviewed. It is shown that electric fields could act as
catalysts to facilitate these chemical reactions, which can
widen the applications of graphene as an atomic hydrogen
storage material, for reversible tuning of graphene’s wetta-
bility between hydrophobic and hydrophilic, and reducing
the pollution of N2O.
16.1 INTRODUCTION
Graphene has shown promising applications as ultrasensitive
gas sensors, transparent electrodes in liquid crystal display
devices, and large capacity electrodes in batteries.1,2 Various
methods,3–10 have been reported for the synthesis of single-
layer graphene as shown in Table 16.1, where the advantages
and disadvantages are also provided. External electric fields,
which are often met in practical applications, could induce
substantial alternations in geometry,11 binding energies,12
vibrational spectra, chemical activities,13–17 and electronic
properties.4,18–21 Experimentally, angle-resolved photoemis-
sion results showed that an electric field is associated with
the charge transfer from dopants to the carbon atoms in a
K-doped graphene bilayer.20 Newly developed graphene layers
have also exhibited a pronounced response to a perpendicu-
lar electric field due to their promising electronic properties.4
For instance, the band structure of a bilayer graphene can be
controlled by an applied electric field.21 Theoretically, the
superimposition of an external electric field is predominantly
done with the density functional theory (DFT) method.14,22
For example, the generalized gradient approximation (GGA)
functional has computationally studied the electric field-
enhanced hydrogen adsorption phenomenon on nanoscale BN
(boron nitride) sheet, where the calculated adsorption energy
Ead value decreases dramatically from −0.07 to −0.48 eV/
H2 in the presence of a 0.050-au field.23 The field-dependent
bonding of CO and NO at all five hexagonal Pt-group metal
surfaces have been surveyed by DFT calculations, in order to
elucidate the variations in the energetically preferred bind-
ing sites and vibrational frequencies.24–26 In addition, very
recent works revealed that quaterthiophene molecules are
strongly polarizable by electric fields along the long direction
of the molecule, and such a polarization changes the highest-
occupied molecular orbital (HOMO) and lowest-unoccupied
molecular orbital (LUMO) levels and can provide local attrac-
tors for holes and electrons.27

235
236 Graphene Science Handbook

chemical vapor deposition method41 and through electrother-

TABLE 16.1 mal reaction with ammonia.42
Various Synthesis Methods of Single-Layer Graphene, Furthermore, it is well known that an electric field F can
Advantages, and Disadvantages of Each Method effectively modify the properties of low- dimensional sys-
tems.43 In this section, the chemical reaction pathway of H2
Advantages Disadvantages
molecular dissociative adsorption on graphene is investigated
Mechanical exfoliation Low cost Poor quality with the through DFT calculations. The effect of N doping and an elec-
from HOPG [3–5] limited area, difficult, and tric field on the dissociative adsorption is also discussed.
time consuming
As reported previously, the H2 molecule is weakly
Chemical exfoliation from Bulk production A variety of defects present
adsorbed on pristine graphene, which is the reason why many
bulk graphite [6,7]
people paid a lot of attention to modify graphene through dop-
Epitaxial growth on an Good contact Poor uniformity and
insulator surface [8] with the contained a multitude of
ing or by other methods to enhance the interaction between
substrate domains hydrogen and graphene.29,44 The energetic favorable position
Chemical vapor deposition High quality High cost and low efficiency of a H2 molecule adsorbed on graphene is at the hollow site
(CVD) on the surface of of the carbon hexagon as reported by DFT calculations,29,45
metals [9,10] which is shown as initial structure (IS) in Figure 16.1. The
distance of the H2 molecule to the graphene layer dH2-graphene
is 2.612 Å with adsorption energy Eb-H2 = −0.153 eV. The
results are consistent with other simulation results that found
16.2 EFFECT OF ELECTRIC FIELDS FOR dH2-graphene = 2.635 Å and Eb-H2 = −0.159 eV in Reference 29,
and dH2-graphene ≈ 2.8 Å and Eb-H2 = −0.133 eV in Reference 46.
APPLICATION OF GRAPHENE AS
For the case of a H2 molecule dissociative adsorbed on
HYDROGEN STORAGE MATERIALS pristine graphene, the favorable configuration is the two H
16.2.1 Electric Field-Induced Hydrogenation of atoms adsorbed on two face-by-face carbon atoms in the same
hexagon shown as final state (FS) in Figure 16.1, which is con-
Graphene for Atomic Hydrogen Storage
sistent with the reported result.34 The bond length of C–H is
Due to its large surface-to-volume ratio, graphene was believed lC–H = 1.125 Å with binding energy Eb-H = −2.184 eV. In addi-
to be a promising candidate for hydrogen storage after some tion, C atoms bonded with H atoms move up toward the H
modifications.28–32 In most of the previous works, hydrogen was atoms by about 0.322 Å, and the three C–C bond lengths have
stored in the form of molecular hydrogen.28–32 Some works also the same value of 1.493 Å, which are similar to the sp3 bond
considered hydrogen storage in atomic form where H atoms are length of 1.53 Å in diamond that is much longer than 1.420 Å
directly chemically bonded to the carbon atoms.30,33,34 However, of sp2 carbon in pristine graphene. Similar DFT results were
due to the strong chemical sp2 bonding between the C atoms in
graphene, and the π bonding between the pz orbitals of the carbon TS
2 TS
atoms, graphene is repulsive to H2 dissociation and the chemi-
cal adsorption has a reaction barrier between 3.3 and 6.1 eV, 2
depending on the adsorption sites of H atoms.34 Recently, gra-
1
phene was found to transform into an insulator when exposed
Relative energy (eV)

1
to atomic hydrogen. Transmission electron microscopy (TEM) 2
discovered that the obtained system is graphane–hydrogenated IS FS
graphene, which is crystalline and retains the hexagonal lattice
0
structure.35 This experiment confirmed the theoretical predic- FS
tion by Sofo et al.36 that each carbon atom adsorbs one hydrogen
atom, forming an sp3-hybridized carbon frame. IS 1
Doping of graphene is usually used to functionalize gra- –1
phene. For example, Al-doped graphene was theoretically
found to significantly enhance CO adsorption.37 The gas 0.00 0.25 0.50 0.75 1.00
adsorption properties of graphene with other elements, such as Reaction coordinate
N, B, and S, were systemically investigated using DFT calcu-
lations.38 Recently, an ab initio study of hydrogen interaction FIGURE 16.1  Reaction pathway of a H2 molecule that undergoes
with N-doped carbon nanotubes (CNTs) showed that CNTs a dissociative adsorption on a pristine graphene layer. IS, TS, FS,
1 and 2 represent the initial structure, transition structure, final
with nitrogen reduced the energy barrier of hydrogen dissoci-
structure, energy minimum state 1 and 2, respectively. Their atomic
ation from 1.3 to 0.9 eV.39 In addition, N-doped graphene has structures are given by the inserts. The energy of FS is taken to
been prepared by carrying out arc discharge in the presence be zero. (Reprinted with permission from Ao, Z. M., and Peeters,
of H2 and pyridine or H2 and ammonia. Transformation of F.  M. Electric field activated hydrogen dissociative adsorption to
nanodiamond in the presence of pyridine also yields N-doped nitrogen-doped graphene. J. Phys. Chem. C 114:14503. Copyright
graphene.40 N-doped graphene can also be synthesized by the 2010 American Chemical Society.)
Effect of External Electric Fields on the Multifunctional Applications of Graphene 237

(a) (b) (c)

1
2 5
6
Top view 3
4

Side view

FIGURE 16.2  Atomic structure of the N-doped graphene (a), a H2 molecule adsorbed on the N-doped graphene (b), and 2 H atoms dis-
sociative adsorbed on N-doped graphene (c). The dark ball is an N atom. (Reprinted with permission from Ao, Z. M., and Peeters, F. M.
Electric field activated hydrogen dissociative adsorption to nitrogen-doped graphene. J. Phys. Chem. C 114:14503. Copyright 2010 American
Chemical Society.)

also reported, which gave lC–H = 1.13 Å, and demonstrated
that the C atoms that are bonded with H atoms move out of
the graphene plane by 0.35 Å.34
In Reference 34, the dissociative adsorption of a H2 mol-
ecule on graphene was calculated with five other initial and
final configurations. The favorite pathway for the H2 dissocia-
tive adsorption is from the structure of IS in Figure 16.1 to
the structure of FS in Figure 16.1 with an energy barrier of
3.3 eV.34 Following the reaction coordinate shown in Figure
16.1, the reaction barrier for a H2 molecule dissociative adsorp-
tion is 2.734 eV, which is smaller than 3.3 eV found by others.34
Doping graphene by both electrons and holes significantly
changes its electronic structure.47 Recently, nitrogen-doped
graphene was prepared by carrying out the arc discharge of
graphite electrodes in the presence of H2, He, and NH3,40
chemical vapor deposition,41 and through electrothermal
reaction with ammonia.42 Furthermore, using ab initio cal-
culations, N-doped CNTs were reported to reduce the energy
barrier of the hydrogen molecule dissociative adsorption.39
Therefore, the effect of N doping of graphene on the dissocia-
tive adsorption of a H2 molecule is considered. In the experi-
ment, N atoms were doped into graphene by substituting C
atoms. The doping concentration can be controlled by adjust-
are similar to the results above for a H2 molecule physiad-
sorption on pristine graphene. In other words, doping N into
graphene has only little effect on H2 physisorption. The favor-
able atomic structure of two H atoms chemically bonded on
the C atoms is given in Figure 16.2c. Similar results for the
case of pristine graphene are obtained, where the average
binding energy for the C–H bonds Eb-H is −2.028 eV and the
C atoms binding with the H atoms move upward by about
0.35 Å. However, the bond lengths for the two C–H bonds
lC1–H5 and lC4–H6 are different, and they are 1.122 and 1.132 Å,
respectively. Meanwhile, the doped N atom moves downward
by about 0.1 Å.
Figure 16.3 shows a H2 molecule dissociative adsorption
pathway on the N-doped graphene. Following the reaction
coordinate, the reaction energy barrier is 2.522 eV, which is
a little smaller than 2.734 eV for the H2 molecule dissocia-
tive adsorption on pristine graphene. The result is consistent
with the report that N doping into CNTs would reduce the
TS
1
1
TS
Relative energy (eV)

ing the experimental parameters, such as the ratio among H2,

He2, and NH3.40 In this simulation, a 2 × 2 supercell for gra- FS
0
phene is taken, and one of the C atoms is replaced by a N atom, IS FS
which leads to the ratio of N:C = 1:7. After geometry optimi-
zation, the N-doped graphene still keeps the planar state with
a slight deformation with C–N bond length lC–N = 1.41 Å that –1 IS
1
is compared to lC–C = 1.42 Å in pristine graphene, which is
consistent with other simulation results.38 The structure after 0.00 0.25 0.50 0.75 1.00
N doping is shown in Figure 16.2a. Reaction coordinate
The favorable atomic structure of a H2 molecule physiad-
sorbed on the N-doped graphene is shown in Figure 16.2b.
FIGURE 16.3  Reaction pathway of a H2 molecule dissociative
The result shows that the planar structure remains and the adsorbed on a N-doped graphene layer. (Reprinted with permission
adsorbed H2 molecule is located on the hollow site of the from Ao, Z. M., and Peeters, F. M. Electric field activated hydrogen
carbon hexagon. The distance dH2-graphene and adsorption dissociative adsorption to nitrogen-doped graphene. J. Phys. Chem.
energy Eb-H2 are respectively 2.615 Å and −0.159 eV, which C 114:14503. Copyright 2010 American Chemical Society.)
238 Graphene Science Handbook

energy barrier of molecular hydrogen dissociative adsorp- IS TS1 TS2

tion.39 Besides the initial and final structures of the reaction,
the atomic structure of the minimum energy state, State 1, 2
and the transition state are also given in Figure 16.3. For State

Relative energy (eV)

1, the H2 molecule diffuses from the hollow site of the carbon
hexagon to a site near the doped N atom before the transition
state. For the transition state, the H2 molecule is already dis-
sociated into two H atoms but only H5 is adsorbed on C1 and
H6 is a free atom near C4. Subsequently, H6 is also adsorbed
as shown in the final structure.
Since a perpendicular electric field F will lead to a polar-
ization of the charge density, it will have an effect on the dis-
sociative adsorption of hydrogen. To investigate the effect of
the electric field on the hydrogen dissociation desorption on
N-doped graphene, a perpendicular electric field is applied
to the N-doped graphene system. The energies of the ISs,
transition structures (TSs), final structures, reaction bar-
riers, and reaction energies of a H2 molecule dissociative
adsorbed on N-doped graphene under different electric fields
are given in Table 16.1. The positive electric field is found to
reduce the barrier significantly in the N-doped graphene sys-
tem. If the electric field further increases above F = 0.01 au
(1 au = 5.14 × 1011 V/m), no barrier is found, and the reaction
occurs automatically. Note that for F ≥ 0.005 au, the reaction
energy is negative in the N-doped system and it decreases as F
increases. A negative electric field is also applied in this sys-
tem, and the negative electric field leads to an increase of the
energy barrier. It is understandable that reversing the electric
field has an opposite effect on the energy barrier for hydrogen
dissociative adsorption due to the polarization effect of the
electric field. Therefore, Table 16.2 gives the atomic charges
of the two H atoms and the two C atoms that are bound to the
two H atoms, at the transition state in the presence of differ-
ent electric fields in N-doped graphene. As shown in the table,
electrons move toward the H atoms with increasing F, while
the opposite behavior is found for the two C atoms and the N
atom. Thus, a positive electric field leads to a transfer of elec-
trons from the bottom atoms to the top atoms and a negative
electric field has the opposite effect.
It is interesting to note that the reaction barrier is negative,
that is, −0.895 eV, for a H2 molecule dissociative adsorbed on
TS2 FS
IS TS1
1
1
2 2
1
FS
0
0.00 0.25 0.50 0.75 1.00
Reaction coordinate
FIGURE 16.4  Reaction pathway of a H2 molecule dissociative
adsorption on N-doped graphene in the presence of an electric field
F = 0.009 au (1 au = 5.14 × 1011 V/m). In this figure, there are two
transition states TS1 and TS2. (Reprinted with permission from
Ao, Z. M., and Peeters, F. M. Electric field activated hydrogen dis-
sociative adsorption to nitrogen-doped graphene. J. Phys. Chem.
C 114:14503. Copyright 2010 American Chemical Society.)
N-doped graphene under a 0.009-au electric field. Therefore,
this reaction pathway is shown in Figure 16.4. As shown in
this figure, there are two transition states TS1 and TS2, and
two minimum energy states: State 1 and State 2. For State 1
and State 2, the two dissociative H atoms bond on C1 and C4,
which are mostly close to the doped N atom. For TS1 and TS2,
the H2 molecule is dissociated and only one H atom is bonded
with C1, which is mostly close to the doped N atom. The other
H atom is free. However, the positions of the free H atom are
different for the two transition states. The configurations of
the two transition states are similar to those in the N-doped
graphene system without an electric field where there is also
one H atom bonded on C1 and the other one is free.
The reaction barrier of −0.895 eV is the energy difference
between IS and TS2. In this reaction process, there are two
barriers that should be overcome, State 1 to TS1 with a bar-
rier of 0.966 eV, and State 2 to TS2 with a barrier of 0.801 eV.
However, the energy from the exothermic process of IS to State
1 is sufficient to support the endothermic process from State

TABLE 16.2
Energies of Reactants, Productions, Transition State, Dissociation Barriers, and Reaction
Energies for the Reaction of a H2 Molecule with Pristine Graphene or with N-Doped
Graphene and 2 H Atoms Bond on Pristine Graphene or on N-Doped Graphene in the
Presence of Different Electric Fields
Energy of Energy of Transition Dissociation Reaction
F (au) Reactant (Ha) Production (Ha) State (Ha) Barrier (eV) Energy (eV)
Pristine graphene 0 −303.482 −303.452 −303.382 2.734 0.828
N-doped graphene 0 −320.010 −319.966 −319.918 2.522 1.205
0.005 −319.924 −319.941 −319.891 0.878 −0.480
0.009 −319.940 −320.022 −319.973 −0.895 −2.241
−0.005 −319.903 −319.828 −319.791 3.033 2.046
Effect of External Electric Fields on the Multifunctional Applications of Graphene 239

1 to TS2. In other words, the dissociative adsorption reaction
can occur automatically if the energy created from IS to State
1 can be used to provide the energy needed from State 1 to
TS2. Further increasing the electric field beyond 0.001 au, no
transition state is found, and the final structure can be obtained
directly even by the geometry optimization method. Therefore,
the electric field can induce molecular hydrogen dissociative
adsorption in the N-doped graphene system, and the process
changes from an endothermic to an exothermic reaction.
The origin of the differences in the energy barrier of
hydrogen dissociative adsorption on graphene can be under-
stood through the analysis of the partial density of states
(PDOS). Figure 16.5 shows the PDOS of the hydrogen and
carbon atoms in which the H2 molecule dissociates and is
adsorbed on a different electric field. The interaction between
the hydrogen and graphene atoms is mainly determined by the
bonding and antibonding interactions between the σg and σu
states of hydrogen and the p state of the carbon atoms directed
perpendicular to graphene (pz) that bond with the hydrogen
atoms. The C pz-band, which participates strongly in bond-
ing with hydrogen, can be identified between the Fermi level
and is about −2 eV in the PDOS of C atoms in isolated gra-
phene, as they almost disappear in the plots of the PDOS of
the C atoms with an interaction with H atoms in the 2H/gra-
phene system. Therefore, the strength of the interaction and
the trends in the dissociative adsorption energy barriers can
be explained by considering the positions and weights of the
bonding and antibonding states between the C pz and hydro-
gen bands. At the position of the C–H bands, there are obvi-
ous differences in the PDOS of the C atoms with and without
H interaction. At the other positions, their PDOS are almost
identical. Based on the positions of the bands of C and H
atoms, the character of the C–H bands can be easily assigned.
The lowest C–H band around −8 eV is obviously due to the
interaction of the H σg state and C pz state. The second lowest
C–H band around −4 eV is mostly due to the bonding inter-
action of H σu and C pz states because they are above the H
σg state. The highest C–H bands are due to a combination
of the interaction between the C pz and H σu states, and are
above the Fermi level. The position and weight of the highest
C–H bands determine the strength of the interaction and thus
determine the energy barrier heights of the transition states.39
As one can see from Figure 16.5a and b, the third C–H bands
correspond to the high-energy barrier as shown in Table 16.1.
In Figure 16.5d, the weight of the third C–H band is small-
est and in this case has the lowest energy barrier whereas the
weight of the third C–H band is the largest in Figure 16.5a and
it has the highest barrier, which agrees with the result in Table
16.1. When comparing Figure 16.5a and b, N doping induces a
slight weight increase of the two lowest C–H bands and a slight
weight decrease of the highest C–H band. On the other hand,
the presence of an electric field leads to a weight increase of
the two lowest C–H bands and a weight decrease of the high-
est C–H band for the hydrogen dissociative adsorption in the

(a) 40 (b) 40
Graphene N-Graphene
30 F=0 30 F=0
PDOS (States/eV)

PDOS (States/eV)

Isolated C
C
20 H 20

10 10

0 0
–15 –10 –5 0 5 –15 –10 –5 0 5
Energy (eV) Energy (eV)

(c) 40 (d) 40
N-Graphene N-Graphene
30 F = 0.005 30 F = 0.009
PDOS (States/eV)

PDOS (States/eV)

20 20

10 10

0 0
–15 –10 –5 0 5 –15 –10 –5 0 5
Energy (eV) Energy (eV)

FIGURE 16.5  PDOS of the hydrogen and carbon atoms that are bound to hydrogen with and without N doping of graphene in the presence of
different electric fields. (a) H2 dissociation over pristine graphene without an electrical field. (b) H2 dissociation over N-doped graphene without
an electrical field. (c) H2 dissociation over N-doped graphene with F = 0.005 au. (d) H2 dissociation over N-doped graphene with F = 0.009 au.
The black and blue curves are the PDOS of the two H atoms and the two C atoms at the transition states (TSs), the red curves are the PDOS of
the same C atoms in graphene without H, with graphene fixed at the same positions as in the TSs. The vertical lines indicate the Fermi level.
(Reprinted with permission from Ao, Z. M., and Peeters, F. M. Electric field activated hydrogen dissociative adsorption to nitrogen-doped gra-
phene. J. Phys. Chem. C 114:14503. Copyright 2010 American Chemical Society.)
240 Graphene Science Handbook

N-doped graphene system. Therefore, the above confirms that

N doping and a positive electric field have catalytic effects on
hydrogen dissociative adsorption.
O
SX
16.2.2 Hydrogen Diffusion and Release on/from X SX′
N-Doped Graphene under an Electric Field
O′
In order to be an efficient hydrogen storage material, N-doped
graphene, which can be synthesized by different approaches,40–42
is required to capture as much hydrogen as possible. Therefore,
A
it is desirable that the adsorbed H atoms bonded with the C
atoms near the doped N atom can diffuse to the other C atomic
FIGURE 16.6  Supercell of N-doped graphene used in the calcu-
sites, and subsequently, the adsorbed H atoms can be eas-
lations. The gray and dark balls are C and N atoms, respectively.
ily desorbed to form H2 molecules once the electric field is The letters refer to the sites of an adsorbed H atom. (Ao, Z. M. et
removed. In this section, the diffusion of H atoms on N-doped al. 2012. The electric field as a novel switch for uptake/release of
graphene with and without the applied perpendicular elec- hydrogen for storage in nitrogen doped graphene. Phys. Chem.
­
tric field will be investigated by DFT calculations. Hydrogen Chem. Phys. 14:1463. Reproduced by permission of The Royal
desorption and H2 formation will also be studied to understand Society of Chemistry.)
the release procedure of the stored hydrogen.
Based on the reported result,15 it is believed that a H2 mol- hydrogenation of graphene.15 Therefore, the diffusion behav-
ecule can be dissociated and adsorbed on the C atoms near the ior under F is of interest for hydrogen storage applications.
doped N atom in graphene under an applied electric field. As Previously, it was known that hydrogenation occurs around
H atoms are chemically adsorbed on the graphene surface, it F = 0.01 au (1 au = 5.14 × 1011 V/m).15 Table  16.3 lists the
is interesting to know the diffusion behavior of the H atoms results of the diffusion along with four different pathways under
on graphene. This may provide new insights to enhance the F = 0.01 au. It is noted that the diffusion barrier Ebar decreases
hydrogen storage capacity significantly through the diffusion significantly for all the four pathways, and can even be negative
of absorbed H atoms. To simplify the investigation, the dif- for the diffusions of X → O and X → SX′. The energy differ-
fusion of a single H atom on N-doped graphene is first con- ence between the configurations before and after diffusion ER
sidered. For the H atom chemical adsorption, there are five decreases slightly as well. This indicates that hydrogen diffusion
different possible adsorption sites as shown in Figure 16.6. becomes favorable under the applied electric field in an ambient
After structure relaxation, it is found that H adsorption on the environment. Note that further increasing the electric field, it
C atom at the site X, where the C atom coordinates to the is expected that H can diffuse even more easily. However, the
doped N atom, has the lowest energy, that is, this is the most larger electric field costs more energy and results in stringent
favorable configuration for a single H atom adsorption and requirements for the hydrogen storage system. Therefore, only
it is considered as the base structure for studying the diffu- the minimum electric field at 0.01 au of hydrogen dissociative
sion of an individual H atom on N-doped graphene. The C adsorption on N-doped g­ raphene is considered in that work.16
atom bonded with the H atom is displaced from the C plane by Figure 16.7 shows the diffusion pathway of a single H atom
about 0.29 Å. This value is similar to the shift of 0.32 Å that is migration from site X to site O in the presence of an electric
caused by the dissociative adsorption of a hydrogen molecule field of 0.01 au. It is clear that both configurations of initial and
on graphene.15 This is associated with the hybridization of C
atoms from sp2 in graphene to sp3 in graphane.36,48 As shown
in Figure 16.6, there are four possible H atom diffusion path-
TABLE 16.3
ways: X → SX, X → O, X → SX′, and X → O′. Using linear
and quadratic synchronous transit (LST/QST) and nudged Atomic Charge of the Two H Atoms and the Two C
elastic band (NEB) calculation tools, the diffusion barriers of Atoms Bound to the Two H Atoms, at the
the four pathways are listed in Table 16.3, which shows that Transition State under Different Electric Fields in
all the barriers are around 2.5 eV. In addition, the diffusion N-Doped Graphene
increases the energy of the system. Therefore, the adsorption Atom F = −0.005 F = 0 F = 0.005 F = 0.01
of a single H atom on N-doped graphene is considered to be
N-doped H5 0.287 0.126 −0.024 −0.115
much more stable as compared to the case of a single H atom
graphene H6 0.226 −0.031 −0.291 −0.402
adsorbed on pristine graphene, which has a diffusion barrier
C1 −0.293 −0.206 −0.113 −0.071
of ~1 eV.49
C4 −0.264 −0.104 0.008 0.102
It is known that the high stability of H on N-doped gra-
N −0.414 −0.378 −0.368 −0.346
phene is not favorable for hydrogen storage due to the revers-
ible hydrogen uptake and release requirement. As mentioned Note: The different atoms are numbered that are given in Figure 16.2. The
before, applying a perpendicular electric field to graphene in units of the charge and electric field are |e| and au, respectively.
the presence of H2 gas is an alternative approach to facilitate the
Effect of External Electric Fields on the Multifunctional Applications of Graphene 241

IS FS

X to O at 0.01 au FS
0.0
ER = 0.29 eV
–0.2 IS

Energy (eV)
EBar = –0.094 eV
–0.4 TS
ER′ = 0.20 eV
2
–0.6

1 ′ = 0.32 eV
EBar
–0.8
0.0 0.5 1.0
Diffusion coordinate
1 TS 2

FIGURE 16.7  Detailed diffusion pathway of an individual H atom on N-doped graphene, where the structure of the IS, the TS, the FS,
and the two energy minimum states 1 and 2 before and after TS are also given. (Ao, Z. M. et al. 2012. The electric field as a novel switch for
uptake/release of hydrogen for storage in nitrogen doped graphene. Phys. Chem. Chem. Phys. 14:1463. Reproduced by permission of The
Royal Society of Chemistry.)

FSs reconstruct spontaneously in the presence of the electric 0.2–0.8 eV.50 However, if the TM adatoms are coupled to a
field. The reconstructed atomic structures of initial and FSs vacancy, the diffusion barrier would increase and fall into
are shown as State 1 and State 2 respectively in Figure 16.7 the range of 2.1–3.1 eV.50 A similar barrier enhancement was
where the H atom breaks the chemical bond with the N-doped also predicted in the case of H atom diffusion at the graphene/
graphene. For the TS state, the H atom keeps the weak interac- graphane interface.51 Therefore, specific defects, such as dop-
tion with the N-doped graphene. From Figure 16.7 and Table ing, vacancies, and adatoms, will significantly affect the dif-
16.3, the reaction barrier, Ebar = ETS − EIS is negative, where fusive behavior of H on graphene. In this case, the diffusion
ETS and EIS are the energies of the transition state and the of two H atoms on the N-doped graphene will be studied to
initial state, respectively. It implies that there is no energy bar- determine the effect of another H atom on hydrogen diffusion.
rier from IS to State 2. However, there is an energy difference After LST/QST and NEB calculations, it is found that the dif-
(~0.58 eV) between State 2 and the FS. Thus, the minimum fusion barrier is less than 0.31 eV under the electric field of
energy required for the entire reaction from IS to FS is 0.29 eV
as shown by ER in Figure 16.7. As aforementioned, the struc-
tures of States 1 and 2 are the favorite configurations before TABLE 16.4
and after diffusion under the applied electric field. For the ​Diffusion Barriers of Several Pathways (See Figure 16.6)
diffusion from State 1 to State 2, the barrier, Ebar ′  = ETS − E1, for a Single H Atom on N-Doped Graphene without the
is 0.32 eV and the diffusion energy, ER′  = E2 − E1, is 0.20 eV.
Electric Field and in the Presence of an Electric Field of
Thus, a single H atom can diffuse throughout the N-doped
graphene freely with a low-energy barrier. Figure 16.7 also 0.01 au (1 au = 5.14 × 1011 V/m)
reveals why the electric field facilitates the individual H atom Electric
diffusion on the N-doped graphene surface. It shows that the Field (au) Pathway ER (eV) EBar (eV) eR′ (eV) ′ (eV)
eBar
H atom nearly desorbs from the N-doped graphene surface 0 X → SX 0.61 2.21
and has a weak interaction with the graphene layer due to X → O 0.27 2.48
the interaction of the electric field on the positive-charged X → SX′ 0.58 2.48
H atom. Table 16.4 shows the interaction between H and the X → O′ 0.66 2.61
N-doped graphene in the presence and absence of the electric 0.01 X → SX 0.55 0.47
field. It is found that the adsorption energy Eads of H atoms X → O 0.29 −0.094 0.20 0.32
on N-doped graphene reduces significantly in the presence of X → SX′ 0.56 −0.10 −0.012 0.266
the electric field due to the extended bond length between the X → O′ 0.62 0.62
positive-charged H and the C of graphene. Thus, the H atom Note: The energies of ER, EBar, E′R, and E′Bar are defined in Figure 16.7. In the
can diffuse on the surface with a low-energy barrier in the presence of the electric field, the configurations of initial and FSs
presence of the electric field (Table 16.5). reconstruct, and therefore, E′Bar (not Ebar) is the actual diffusion barrier,
Recently, the diffusion barriers of transition-metal (TM) see Figure 16.7 and the related text.
atoms on graphene were reported to be in the range of
242 Graphene Science Handbook

IS FS
TABLE 16.5
Adsorption Energy Eads of H Atoms on
N-Doped Graphene in Different 4
TS
Configurations and in the Presence
3 TS
and Absence of an Electric Field

Energy (eV)
Eads (eV) 2
IS
Configurations F = 0 F = 0.01 au
1
X −3.04 −1.15
FS
SX −2.43 −0.60 0
O −2.77 −0.86 0.0 0.5 1.0
SX′ −2.46 −0.59 Coordinate
O′ −2.38 −0.53
A1 −2.17 −1.94 FIGURE 16.8  Detailed reaction pathway from A3 to B, where the
A2 −1.93 −1.69 structure of IS, TS, and FS are also given. (Ao, Z. M. et al. 2012.
A3 −2.26 −1.89 The electric field as a novel switch for uptake/release of hydrogen for
A4 −2.10 −1.76 ­storage in nitrogen doped graphene. Phys. Chem. Chem. Phys. 14:1463.
A5 −1.55 −1.37 Reproduced by permission of The Royal Society of Chemistry.)
A6 −2.06 −1.70
and combine into a H2 molecule as shown by State 1. This
means that atomic H adsorption on N-doped graphene is
unstable and hydrogen can be released in the form of the H2
0.01 au. Such a small barrier can be easily overcome at room molecule spontaneously. Subsequently, this free H2 molecule
temperature. can diffuse on the N-doped graphene surface with a very low-
Due to the low barrier for H atom diffusion on N-doped energy barrier (inset of Figure 16.9). In other words, the high-
graphene under the applied electric field, it is predicted that est concentration of hydrogen storage in N-doped graphene
N-doped graphene can be fully hydrogenated under an applied is ~0.5 wt% in the absence of an applied electric field. In the
electric field, and all the H atoms are adsorbed at single sides presence of the applied electric field, due to the low dissociated
of graphene, that is, this is the uptake process for the hydrogen adsorption energy barrier for H2 on N-doped graphene and
storage material. After full hydrogenation, the electric field is the low diffusion energy barrier of H atoms on the N-doped
removed and the possibility of releasing the absorbed hydrogen graphene as discussed above, N-doped graphene is expected
is studied. For a hydrogen storage material, it is also required
that the stored hydrogen can be released efficiently. After
FS
the structure relaxation, the preferable configurations before IS
and after desorption are shown as IS and FS in Figure 16.8,
respectively. Note that hydrogen desorption lowers the energy,
thus stabilizing the system. However, there is an energy bar- 1.5 0.015
TS
rier of 2.12 eV that needs to be overcome for desorption. The 1.2 IS
0.010
detailed reaction coordinate is shown in Figure 16.8. Due to 1
the high-energy barrier for hydrogen desorption, a high tem- 0.9 0.005
Energy (eV)

′ = 0.0058
EBar
ER′ = 0.0056
perature is required to release the hydrogen atoms when the 0.6 0.000
FS

hydrogen concentration is below 0.5 wt%.

0.3 –0.005
What would happen if the hydrogen concentration is above 0.4 0.6
TS
0.8 1.0
FS
this value? In this case, the hydrogen desorption process in 0.0
1
the presence of another H atom near the H2 molecule in the
0.0 0.2 0.4 0.6 0.8 1.0
same supercell is considered, which is depicted in Figure 16.9.
Coordinate
All the possible configurations for three H atoms on N-doped 1 TS
graphene are calculated and found that the configuration IS
shown in Figure 16.9 has the lowest energy. If two H atoms
desorb from graphene and form a H2 molecule, the struc-
ture is shown as FS in Figure 16.9. The reaction energy and
FIGURE 16.9  Detailed reaction pathway from A3_H to B_H,
the reaction barrier are −1.24 and −1.23 eV, respectively. In
where the structures of IS, TS, FS, and the energy minimum state
other words, the stored hydrogen can be released automati- before the TS state 1 are also given. (Ao, Z. M. et al. 2012. The elec-
cally when the concentration is above 0.5 wt%. Figure 16.9 tric field as a novel switch for uptake/release of hydrogen for ­storage
shows the detailed pathway. As shown in the figure, the two in nitrogen doped graphene. Phys. Chem. Chem. Phys. 14:1463.
H atoms prefer to desorb from the N-doped graphene surface Reproduced by permission of The Royal Society of Chemistry.)
Effect of External Electric Fields on the Multifunctional Applications of Graphene
to be fully hydrogenated and the hydrogen weight ratio can
reach up to 7.23 wt%, which is in excesses of the target of the
U.S. Department of Energy (DOE), that is, 6 wt%. By remov-
ing the electric field, H atoms can desorb from N-doped gra-
phene and be released efficiently in the form of H2 molecules.
Therefore, the electric field is a novel and efficient switch for
hydrogen storage in N-doped graphene.
From Figures 16.8 and 16.9, it is known that the presence
of the third H atom on N-doped graphene induces a large dif-
ference in the energy barriers for hydrogen release. In other
words, H atoms can be released spontaneously from N-doped
graphene in the presence of the third H atom while a high
temperature is needed to release the two H atoms if the third
H atom is absent. Recently, it was reported that the ease of
adsorbate diffusion on graphene strongly depends on the car-
rier density of graphene.52 Through a Mulliken analysis in
this study, it is known that the H atoms transfer electrons to
the N-doped graphene layer. Therefore, with the presence of
the third H atom, the carrier density in N-doped graphene is
higher, and the diffusion of H atoms on N-doped graphene is
much easier. A similar explanation is made for the phenom-
enon found above that two H atoms diffuse easily on N-doped
graphene than only one H atom, due to the higher electron
concentration from the H atoms. The lower diffusion barrier
means weaker interaction between H- and N-doped graphene,
and the H atoms are much easier to be released. Therefore,
hydrogen atoms in fully hydrogenated N-doped graphene
are predicted to be released easily until the hydrogen weight
ratio of 0.5 wt%, because of the higher carrier density in the
N-doped graphene when the H concentration is higher. In
this way, the hydrogen storage capacity of N-doped graphene
is 6.73 wt%, whereas the electric field is the switch for the
hydrogen uptake/release processes. In addition, the 0.5 wt%
hydrogen left in N-doped graphene can be further removed by
increasing the temperature.
16.3 ELECTRIC FIELD-INDUCED REVERSIBLE
TRANSITION OF GRAPHENE FROM
HYDROPHOBIC TO HYDROPHILIC
The potential applications of graphene significantly depend on
the surface wettability, which is influenced by both the mor-
phology53 and the chemical composition54 of the solid surface.
DFT calculations55 and experimental observations56 indicate
that graphene is strongly hydrophobic. The hydrophobic gra-
phene surface can reduce the possible liquid deposition and
prevent contamination of advanced nanoelectromechanical
systems. Furthermore, controllable manipulation of the wet-
ting properties of materials has various applications, such as
biomaterials and microfluidic devices.57,58
The reversible transition of graphene from hydrophobic to
hydrophilic has not been studied extensively. Recently, Zhang
et  al. achieved a reversible superhydrophobic to superhydro-
philic transition on a graphene film via alternation of ultraviolet
(UV) irradiation and dark storage of the film.59 UV light is con-
sidered to produce hydrophilic OH (hydroxyl) groups, which are
243
kinetically favorable for the physical adsorption of H2O at these
sites. When the graphene film is placed in the dark, the surface
evolves back to its original state, which restores the hydropho-
bicity of the film. However, the UV irradiation method is time
consuming, which needs about 12 h and may hinder some spe-
cial applications. Therefore, an alternative method is demanded
for efficiently controlling the reversible wettability of graphene.
It is well known that the electric field is a powerful method
to modify the chemical potentials of materials. Therefore, an
alternative approach that efficiently changes graphene from
hydrophobic to hydrophilic may be realized through the expo-
sure of graphene to humid circumstances in the presence of
an electric field. In addition, when a reversing electric field is
applied, the dissociated H and OH group may combine into
H2O again. Therefore, the dissociative adsorption and recom-
bination of H2O on graphene with a perpendicular electric
field is investigated through DFT calculations.
For a H2O molecule adsorption on graphene, there are
three different adsorption sites as shown in Figure 16.10a,
the hollow, the bridge, and the top sites. At each site, the
OH bonds may point up, down, or parallel to the graphene
­surface. The orientation with an OH bond pointing to gra-
phene and the other OH bond parallel to graphene is also
considered (named V orientation). Based on calculations,
the favorable adsorption site of the H2O is at the hollow site
with two OH bonds pointing down to the graphene surface, as
shown in Figure 16.10a, which is adopted as the IS in the sub-
sequent transition state search calculations. For the product,
­graphene with chemically adsorbed H and OH on graphene,
there are three positions of OH relative to the position of H
in the six-member ring, which are denoted as Positions 1, 2,
and 3 in Figure 16.10b. The three configurations are named
p1, p2,  and  p3. According to the DFT + D calculations, the
Top view
(a) Top (b)
1 2 3
Bridge
F
Hollow e–
Side view
FIGURE 16.10  Initial (panel a) and final (panel b) structures for
a H2O molecule dissociative adsorption on graphene. The IS is a
molecular H2O physiadsorbed at the hollow site of a carbon hexa-
gon. The final structure is a H atom and an OH group chemically
adsorbed on two face-by-face carbon atoms of a carbon hexagon.
In this figure, the gray, white, and dark balls are carbon, hydrogen,
and oxygen atoms, respectively. The direction of the electric field is
indicated by the arrow. The direction of charge transfer is opposite
to that of the electric field. The numbers in the right panel represent
the possible positions of the OH group. (Reprinted with permission
from Jiang, Q. G. et al. Reversible transition of graphene from hydro-
phobic to hydrophilic in the presence of an electric field. J.  Phys.
Chem. C 116:19321. Copyright 2012 American Chemical Society.)
244 Graphene Science Handbook

relative total energies compared to p1 are 1.054 and −0.019
eV for p2 and p3, respectively. In addition, both the energy
barriers for the dissociative adsorption of H2O on graphene
from the IS to p2 and p3 are calculated, which are 3.880 and
3.455 eV, respectively. Therefore, p3 is preferable for the dis-
sociative adsorption of H2O on graphene and adopted as the
final structure in the subsequent transition search calculations.
Therefore, the pathway from the favorite configuration of
the H2O physisorption on graphene shown in Figure 16.10a to
the configuration of p3 shown in Figure 16.10b is investigated
for the reaction of the H2O molecule dissociative adsorption
on graphene. After LST/QST and NEB calculations, it is
found that the reaction barrier Ebar is 3.455 eV for this pathway
as shown in Figure 16.11a. This Ebar value corresponds to the
literature datum of 3.599 eV.60 From Figure 16.11a, it is also
known that the reaction requires two steps: H2O is first dis-
sociated into H and OH (from IS to TS) with Ebar = 3.455 eV,
and then H and OH move to the exact top sites of C from TS
to the final structure FS with an energy release of 0.921 eV.
As a result, totally 2.534 eV is needed for the H2O dissocia-
tive adsorption on graphene, where the H2O dissociation with
a larger Ebar value is the rate-limiting step.
It is known that a perpendicular F leads to polarization
of the charge density, and affects the dissociative adsorp-
tion of H2O on graphene. To investigate the effect of F, an
electric field is perpendicularly applied on the H2O/graphene
system, and the direction of F is shown in Figure 16.11. The
pathways for this reaction in the presence of the electric field
with different intensity are shown in Figure 16.11, where IS,
TS, FS, Ebar, and reaction energy Er = EFS − EIS for the H2O
dissociative adsorption on graphene under different electric
field intensities are given. In general, Ebar and Er increase with
increasing F as shown in Figure 16.11 when F > 0, whereas
they decrease with decreasing F if F < 0.
In addition, both configurations of the initial and FSs recon-
struct spontaneously in the presence of the electric field, as
shown in Figure 16.11. For example, under F = 0.36 V/Å (Figure
16.11b), the geometry of the reactant is optimized from the IS to
the energy minimum state, State 1, where the positive F pushes
the H2O upward away from graphene and 0.242 e is transferred
from the H2O molecule to graphene. Therefore, the negative-
charged oxygen atom is upward due to the Coulomb repulsion
between the oxygen atom and graphene at State 1. For the prod-
uct under F = 0.36 V/Å, its geometry is optimized from the FS

(a) 4 (b)
F=0 TS 4 F = 0.36 TS
TS FS
TS
3 2
3 FS
IS
Relative energy (eV)

Relative energy (eV)

FS
2
2
FS 2
IS
1
1 1

Er = 3.717, Ebar = 3.711

0 IS Er = 2.534, Ebar = 3.455 0 IS
Er′ = 3.615, E′bar = 3.779
1
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Reaction coordinate Reaction coordinate

(c) F = –0.20 FS (d) F = –0.39 TS

2
TS 0 IS IS
TS FS
Relative energy (eV)
Relative energy (eV)

1 IS FS
1 2
2 –1 1 TS FS

0 IS 2
1
2
Er = 0.990, Ebar = 1.485 Er = –0.990, Ebar = 1.164
1
Er′ = 1.356, E′bar = 1.905 –2 Er′ = 0.020, E′bar = 0.235
–1
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Reaction coordinate Reaction coordinate

FIGURE 16.11  Reaction pathway of a H2O molecule dissociative adsorption on graphene under different electric fields F, (a) F = 0, (b)
F = 0.36, (c) F = −0.20, (d) F = −0.39. IS, TS, FS, and 1 and 2 represent the initial structure, transition structure, final structure, and energy min-
imum states 1 and 2, respectively. Their atomic structures are given by the inserts. The energy of IS is taken to be zero. The unit of F is V/Å,
while that of Ebar, Er, E′bar, and E′r is eV, where Ebar is the energy barrier and Er is the reaction energy, E′bar, and E′r are the energy barrier and
reaction energy for the reaction from State 1 to State 2. (Reprinted with permission from Jiang, Q. G. et al. Reversible transition of graphene
from hydrophobic to hydrophilic in the presence of an electric field. J. Phys. Chem. C 116:19321. Copyright 2012 American Chemical Society.)
Effect of External Electric Fields on the Multifunctional Applications of Graphene 245

to the energy minimum state, State 2. Therefore, in the presence
of the electric field, the H2O dissociative adsorption reaction is
from State 1 to State 2, the energy barrier, Ebar ′  = ETS − E1, is
′
3.779 eV, and the reaction energy, Er′ = E2 − E1, is 3.615 eV. Ebar
and Er′ for the other reaction paths are also indicated in Figure
16.11. While at F = −0.20 V/Å (Figure 16.11c), the geometry of
the reactant is optimized from IS to State 1, where the negative
F pulls the H2O down toward graphene. Due to the charge trans-
fer from graphene to the H2O under F, as an electron accepter,
the OH group points to graphene at State 1 under a negative F.
Therefore, the number of electrons in H2O decreases with
increasing F from −0.39 to 0.36 V/Å, while the bond length of
C–H bond lC–H increases due to the positively charged H atom,
and the bond length of H–O bond lH–O decreases because of the
negatively charged OH.
It is interesting to note that Ebar = −1.164 eV < 0 (the energy
difference between IS and TS, as shown in Figure 16.11d)
for the dissociation of adsorbed H2O on graphene under
F = −0.39 V/Å. Along the reaction coordinate, the reactant is
now reconstructed to State 1, and releases 1.399 eV energy that
can be used to support the subsequent step from State 1 to TS.
Usually, surface reactions at ambient temperature may occur
when Ebar < 0.75 eV61 while the barrier Ebar ′ is 0.235 eV from
State 1 to TS. Thus, the negative F can catalyze the dissociative
adsorption of H2O on graphene and change the reaction process
from endothermic to exothermic. When F < −0.39 V/Å, H2O
automatically dissociates into H and OH by the geometry opti-
mization method. Therefore, the presence of the chemically
adsorbed hydrophilic OH group makes graphene hydrophilic.
Then, the reaction of H + OH → H2O is considered when
F is removed. As the reverse reaction of the dissociative
adsorption, FS and IS shown in Figure 16.11a are now respec-
tively IS and FS with Er = −2.534 eV and Ebar = 0.921 eV. As
Ebar > 0.75 eV, this reaction hardly occurs at ambient tempera-
ture. However, if a positive F of 0.36 V/Å is added, Er = −3.717
eV and Ebar = −0.006 eV, while a small energy barrier of 0.164
eV needs to be overcome from State 2 to TS. In other words,
the H2O recombination reaction takes place easily at room
temperature. Therefore, the desorption of OH and H will
make graphene to become hydrophobic again.
The effect of F on Ebar can be understood by ­considering the
interaction between the bands of H2O and graphene through ana-
lyzing PDOS. In order to understand how H2O ­interacts with the
graphene substrate, HOMO and LUMO of the adsorbed H2O are
also considered. HOMO (1b1) is ­completely located on O, while
LUMO (4a1) is fully located on H (see the inset of Figure 16.12a).

(a) 40 (b) 40
F=0 C F = 0.36 C
H H
30 (α) (β) O 30 O

1b1 4a1 2b2

3a1
DOS

DOS

20 20
1b2

2a1
10 10

0 0
–25 –20 –15 –10 –5 0 5 10 –25 –20 –15 –10 –5 0 5 10
Energy (eV) Energy (eV)

(c) 40 (d) 40
F = –0.20 C F = –0.39 C
H H
O O
30 30
DOS

DOS

20 20

10 10

0 0
–25 –20 –15 –10 –5 0 5 10 –25 –20 –15 –10 –5 0 5 10
Energy (eV) Energy (eV)

FIGURE 16.12  PDOS of the hydrogen, oxygen, and the carbon atoms of IS in the presence of different electric fields F, where the carbon
atom is the nearest one to the hydrogen atom. (a) F = 0, (b) F = 0.36, (c) F = −0.20, (d) F = −0.39 V/Å. The black, light, and dark curves are
the PDOS of the p orbit of the C atoms and the O atoms, and s orbit of H atoms of the reactant, respectively. The vertical lines indicate the
Fermi level. Inset: (α) the HOMO and (β) the LUMO of H2O (the dark and light colors indicate different signs of the orbital wave function).
The molecular orbitals of H2O are also labeled. (Reprinted with permission from Jiang, Q. G. et al. Reversible transition of graphene from
hydrophobic to hydrophilic in the presence of an electric field. J. Phys. Chem. C 116:19321. Copyright 2012 American Chemical Society.)
246
HOMO and LUMO of H2O and their relative positions with
respect to the Dirac point determine the charge transfer between
graphene and H2O.62 As H points to the carbon layer, LUMO
of H2O interacts with the graphene surface and accepts a small
charge of 0.02e from graphene in the absence of the electric
field. Thus, the interaction between the H–s and C–p bands
determines the interaction between H2O and graphene. Since the
interaction between C and H is very weak as shown in Figure
16.10a, a large Ebar is present for H2O dissociative adsorption
on graphene as shown in Figure 16.11a. When F is added, such
as F = 0.36 V/Å, a charge of 0.242 e is transferred from H2O to
C, inducing the increase of the C–H distance. The peaks of the
O–H band shift to the left as shown in Figure 16.12b, indicat-
ing the enhancement of O–H interaction and the difficulty of
H2O dissociation. However, at F = −0.20 and F = −0.39 V/Å,
0.075 e and 0.299 e are transferred from C to H2O, respectively.
The peaks of the O–H band shift to the right with decreasing F
as shown in Figure 16.12c and d, which implies that the O–H
interaction decreases and the H2O dissociation becomes easier.
At F = −0.39 V/Å (Figure 16.12d), the O–H bond is even bro-
ken and the C–H bond is formed. Therefore, the negative F can
enhance the reactivity of the reactant and lower Ebar for the dis-
sociative adsorption of H2O on graphene.
16.4 EXTERNAL ELECTRIC FIELD-
CATALYZED N2O DECOMPOSITION
ON MN-EMBEDDED GRAPHENE
The high greenhouse potential of N2O with a yearly increas-
ing rate of about 0.2% as an important environmental prob-
lem has been attracting considerable attention.63 The emission
of N2O is regarded as the most important ozone-depleting
substance and is thereby expected to remain throughout the
twenty-first century64–67 where the concentration of N2O in
air has increased from about 270 to 322 ppb.64,65 Limiting
future N2O emissions would enhance the recovery of the
ozone layer from its depleted state and would also reduce the
anthropogenic forcing of the climate system, representing a
win–win for both ozones and climates.66,67 Catalytic decom-
position of N2O into N2 and O2 represents a valuable and cost-
effective technology to reduce N2O emissions in agricultural
fertilization, fossil fuel combustion, and other industrial by-
products. Dropping the reaction energy barrier Ebar for N2O
decomposition, platinum group metals (PGMs) have been
made both experimentally68–78 and theoretically,79–88 such as
Pt,68–70,79,80 Rh,71–73,81–84 Pd,74–77,85–88 etc. However, they are
costly and require high reaction temperatures for efficient
operations.70,73,75,77,78,88 Especially, due to the strong adsorption
of PGMs toward O, the desorption of O adatoms from metal
surfaces is cumbersome and is usually considered as a rate-
determining step,70,72,79,84,89–94 that poisons metal surfaces and
limits the low-temperature activity of PGMs for N2O decom-
position. It is therefore desirable to develop low- cost cata-
lysts that can facilitate the easy desorption of O adatoms as O2
from metal surfaces to enhance the activity for N2O decom-
position, such as TMs,95,96 metal alloys,91,97,98 clusters,99,100
TM-exchanged zeolites,101–104 and so on.105,106
Graphene Science Handbook
Graphene has been regarded as one of the most promising
candidates for the next generation of electronic materials.107,108
Recently, graphene as a matrix of heterogeneous catalysts has
been extensively studied due to the huge surface-to-volume
ratio (large catalytic reaction area),109 such as transition-­
metals- embedded graphene (TM/graphene),50,110,111 metal
clusters-embedded graphene,112,113 and even modified graphene
under electric fields.15,114–116 Note that the TM/graphene struc-
tures have been fabricated experimentally with good thermal
stabilities117 where there are stronger bondings between metals
and neighboring carbon atoms.50 Meanwhile, it is well known
that an electric field F can effectively modify the properties of
low-dimensional systems. Based on the above evidences, it is
expected that TM/graphene could exhibit catalytic behaviors
for the decomposition of N2O under electric fields. Herein, a
systematic first-principles study for the adsorption of N2O on
TM/graphene system (from Sc to Zn, Pt, and Au) is ­present.
Gas adsorption is apparently the most essential and the very
first step in the catalytic decomposition reaction. For a cata-
lyst, the ability to efficiently capture the adsorbates plays an
important role, which can promote the associated reaction
rate. In fact, the adsorption energy of N2O on typical cata-
lysts PGMs is relatively small (range 0.12–0.40 eV).79,81–85,87,91
When N2O is present at a low concentration, the efficient N2O
decomposition may hardly occur among the PGMs due to a
weak adsorption and low coverage.84,92 In addition, when the
PGMs surface temperature is raised, the N2O molecules may
thermally desorb from their physisorbed state and lower a
continued catalytic decomposition activity.73,77,78,88,91 However,
the adsorption energy of N2O on the Mn/graphene system Ead
is the most negative among the considered TM/graphene sys-
tems, which is also the most efficient to capture the low con-
centration of N2O among typical catalysts. Note that when Mn
atom is adsorbed on perfect graphene, Ead = 0.33 eV, which
is too small for the purpose. This system has a much better
adsorption ability with Ead = 6.10 eV, which could realize the
processes of N2O adsorption and decomposition. To promote
reactant decomposition and the associated product desorp-
tion, a perpendicular electric field F on the Mn/graphene sys-
tem is used. Under electric fields, the decomposition of N2O
to N2 and O2 and regeneration of the Mn/graphene system can
be finished as a whole catalytic cycle.
The adsorption of N2O on the TM/graphene system is
investigated in two alternative configurations, labeled O-end
and N-end. As shown in Figure 16.13, the first O-end mode
is tilted with the terminal O atom attached to TM/graphene
system, while the second N-end mode is perpendicular on the
system (end-on configuration). Adsorption on the N-end mode
is much more favored than that on the O-end mode where their
Ead values are −1.08 and −0.54 eV. The former is the most neg-
ative among the considered TM/graphene systems. Since Ead
value decides the adsorption ability, the N-end mode on Mn/
graphene is chosen among TM/graphene systems as a starting
point, making the description of the catalytic decomposition
reaction mechanism.
Before the adsorption/decomposition behaviors of N2O
on the Mn/graphene system is considered, the stability of the
Effect of External Electric Fields on the Multifunctional Applications of Graphene 247

–1.2 Mn/graphene system due to possible Mn-clustering problems

1
on the graphene sheet is first studied. Figure 16.14a shows that
–1.0 1 N2O Mn atom is located on top of the single-vacancy H site, estab-
2
lishing three bonds with the nearest C atoms. The bond length
–0.8 between Mn and the neighboring C (lMn–C) is 1.794 Å, and
N-end on Mn/graphene the distance between Mn and the graphene sheet is 1.468 Å,
B A
Ead (eV)

–0.6
–0.4
–0.2
Sc Ti V Cr Mn Fe Co Ni Cu Zn Pt Au
FIGURE 16.13  Adsorption energies, Ead of the N2O molecule
labeled N-end and O-end adsorbed on TM/graphene (dark and light
curves, respectively). The inset shows the most stable configuration
of N2O-labeled N-end on Mn/graphene. The lines are used to guide
the eye. (Reprinted with permission from Song, E. H. et al. External
electric field catalyzed N2O decomposition on Mn-embedded
­graphene. J. Phys. Chem. C 116:20342. Copyright 2012 American
Chemical Society.)
which are a little smaller than that of the literature data
(about 1.81 and 1.60 Å).50 There is a charge transfer (Q) about
0.31e from Mn to graphene sheet while the three neighbor-
ing C atoms of Mn attain 0.07e respectively, according to the
Hirshfeld charge population analysis. The migration barrier
of Mn in graphene from the vacancy site H (Figure 16.14a)
to its neighboring one (Figure 16.14c) is 4.58 eV. During the
migration (Figure 16.14b), one C bond breaks first, and a pen-
tagon then forms. This large size of the migration barrier can
avoid the Mn-clustering problem in the Mn/graphene system.
N2O is adsorbed on Mn through its N-end, and the N2O–
Mn/graphene complex is formed (Figure 16.14d). The charge
transfer of this step essentially occurs from N2O to the Mn/
graphene system with part of the charges immigrating from
N1 to N2 (0.02e) and O1 (0.08e), respectively. N2O and the Mn/

Top
(a) (b) (c) (d)

Side
–0.08 1
0.31 0.25 0.32 1 0.21
2 –0.02
0.16

IS A TS A FS A A
Top
(e) (f ) (g) (h)
1 1
1 1
2 1 21
2
1 1
2
A A A A
Side F = 0.51 V/Å F = 1.275 V/Å F = 1.53 V/Å
–0.10 –0.27 0.17 0.02
0.20 0.05 –0.10 –0.25
–0.01 –0.05 0.05 0.04
0.18 0.26 0.28 0.24

Positive A Positive A A Positive A

FIGURE 16.14  Top and side views of the geometric structures of Mn/graphene and N2O-labeled N-end on the Mn/graphene system.
(a) Atomic configurations of the initial state (IS), (b) TS, and (c) FS for the migration of a Mn-vacancy pair in graphene sheet. (d) The
most stable configuration of N2O-labeled N-end on the Mn/graphene system. (e) The geometric structure of N2O (N-end) adsorbed on
the Mn/graphene system under F = 0.510 V/Å. (f) The geometric structure of N2O (N-end) adsorbed on the Mn/graphene system under
F = 1.275 V/Å. (g) The geometric structure of N2O (N-end) spontaneously decomposed to N2 and O1ad on the Mn/graphene system under
F = 1.530 V/Å. (h) After the electric field is removed, the geometric structures of N2 and O1ad adsorbed on the Mn/graphene system. Arrows
in panel (e) indicate the direction of the electric field. The big green (small gray) ball represents the Mn atom (carbon atoms), and the blue
(red) ball represents the N atom (oxygen atom). (Reprinted with permission from Song, E. H. et al. External electric field catalyzed N2O
decomposition on Mn-embedded graphene. J. Phys. Chem. C 116:20342. Copyright 2012 American Chemical Society.)
248
graphene system act as a charge donor and acceptor whereas
Mn donates 0.16e for the bond formation of N2–Mn. After the
formation of N2O–Mn/graphene, lO1–N1 (1.194 Å) and lN1–N2
(1.149 Å) are slightly shortened and elongated with respect to
gaseous N2O (1.195 and 1.142 Å) respectively, and a strong
Mn–N2 bond is built with a bond length of 1.947 Å. For N2O
adsorbed on Mn/graphene through its O-end, there is about
0.16e from N2O to the Mn/graphene system with the bond for-
mation of O1–Mn (lO1–Mn = 2.115 Å). When the N2O molecule
(O-end) is adsorbed on Mn/graphene, lO1–N1 (1.216 Å) and lN1–N2
(1.140 Å) are slightly elongated and shortened respectively.
The general consensus for the mechanism of N2O cata-
lytic decomposition reaction over pure metal surfaces is the
following: N2O experiences a Langmuir–Hinshelwood reac-
tion mechanism to form N2 and Oad and the surface oxygen
can desorb by direct reaction with another N2O (Eley−Rideal
reaction mechanism) or by recombination of Oad to form O2,
where the decomposition of N2O and desorption of O2 are the
rate-determining steps.70,84,89,95,111 This is also the case of N2O
on Mn/graphene. In Figure 16.14d, a decomposition reaction
step 1 of the transition from N2O–Mn/graphene to the N2 and
O1ad is the rate-determining step of decomposition due to the
large activation barrier while O1ad remains on Mn atom and
N2 desorbs from the Mn/graphene system.
Since a perpendicular electric field F will lead to a polar-
ization of the charge density, it affects the decomposition of
N2O on the Mn/graphene system. In addition, the structure
modification is always attributed to the charge transfer.15,83,104
Since the N − N bond is significantly stronger (474.163 kJ/
mol) than the N − O bond (161.38 kJ/mol),118 F may cata-
lyze N2O decomposition to yield N2 + O, which is energeti-
cally favored. Without F, the N2O (N-end) on Mn/graphene
cannot be decomposed into N2 and Oad. Herein, F = 1.530,
1.275, 0.510, and –0.510 V/Å is applied on the Mn/graphene
system (Figure 16.14d). The results show that lO1–N1 is sensi-
tive to F. Note that when F < 0, it shortens lO1–N1 since the
electric field reversing has an opposite effect on lO1–N1 for N2O
decomposition.49,51–53 When a positive F increases from 0.510
to 1.275 V/Å, lO1–N1 is elongated from 1.237 to 1.751 Å, while
lN1–N2 is slightly changed from 1.131 to 1.158 Å. Although
lO1–N1 has a huge change, the bond still remains. Up to
F = 1.530 V/Å (Figure 16.14g), the O1–N1 bond is fractured,
and the spontaneous decomposition of N2O on Mn/graphene
is present. The critical F value should be located between
1.275 and 1.530 V/Å. Under the electric field, N2O experi-
ences a Langmuir–Hinshelwood reaction mechanism for the
decomposition of N2O into N2 and Oad on the Mn/graphene
system. Meanwhile, the main charge transfer route for this
step is engaged in a transfer from Mn to O1ad atom (0.10e) with
the formation of the Mn–O1 bond (lMn–O1 = 1.575 Å). Due to
the charge transfer to the atomic O1ad, lMn–N2 increases from
1.947 to 2.246 Å. Figure 16.14h shows the last step where F
is removed from the system. Meanwhile, N2 is formed with
Ead(N2) = −0.05 eV, which denotes a weak adsorption and can
be easily desorbed from the Mn/graphene system. During the
N2 desorption, the charge transfer route is nearly the same
as Figure 16.14g, exhibiting that the Mn/graphene system is
Graphene Science Handbook
the main charge donor. In several traditional PGM catalysts,
there are relatively high barriers (Er values are in the range of
0.11 and 0.50 eV70,79,81–83,91) at the transition state of the N2O
decomposition step, which affects the N2O decomposition
reaction rate. However, N2O decomposition in this system can
spontaneously occur under F = 1.530 V/Å where Mn acting as
a bridge can transfer the charges between N2O and the Mn/
graphene system. Thus, this system is kinetically favorable.
Figure 16.15 gives the decomposition process of the sec-
ond N2O molecule adsorbed on the O1ad–Mn/graphene system
where Ead(N2O) = −0.19 eV (Figure 16.15a). The charge trans-
ferred from N2O to Mn and O1ad is little (0.01e). Meanwhile,
the relatively stronger Mn–O1ad bond is elongated from 1.575
to 1.613 Å. Figure 16.15b shows that O2 of N2O approaches
O1ad of the O1ad–Mn/graphene system and reaches TS1 where
Er = 3.21 eV along the minimum energy pathway (MEP).
After calculating the MEP via the N2O + O → N2 + O2 route,
the process is exothermic with a reaction heat value of 0.54 eV.
As analyzed above, the second N2O decomposition with
atomic Oad is conceivable after the first N2O is decomposed
under F. The high-energy barrier decreases with increasing F
(positive) owing to the charge transfer enhancement between
the second N2O and the O1ad–Mn/graphene system. Thus,
as shown in Figure 16.15d with F = 0.765 V/Å, the decom-
position reaction of the second N2O into N2 and O2 atom on
the O1ad–Mn/graphene system spontaneously occurs, and
the adsorbed O2 recombines to form O2. Since Ead = −0.03
eV, here, N2 can be easily desorbed from the Mn/graphene
­system. When a positive F increases from 0.765 to 1.530 V/Å,
the Ead value of O2 on Mn/graphene drops from 1.36 to
0.81 eV. Meanwhile, the main charge transfer route for this
step is engaged in a transfer from O2 (0.13e) to the Mn/gra-
phene system with the elongation of Mn–O2 bond (the average
bond lMn–O2 = 1.852 Å). Up to F = 2.550 V/Å (Figure 16.15f),
O2 has been desorbed from the Mn/graphene system. Due to
the enhancement of the charge transfer from O2 (0.39e) to Mn/
graphene, lMn–O increases from 1.852 to 2.947 Å. Now, the
Mn/graphene system with the whole catalytic cycle is regen-
erated where the recombination of two Oad to O2 is no longer
the rate-limiting step in the N2O decomposition reaction.
To further understand the electronic hybridization behav-
ior of N2O decomposition on Mn/graphene under F, the PDOS
charts are determined and depicted in Figure 16.16. Figure
16.16a shows the projection of PDOS on the Mn-3d and
Mn-4s orbitals and the neighboring C-2p orbital. Because of
the formation of C–Mn bonds and charge transfer from Mn
to C, Mn-4s, Mn-3d, and C-2p orbitals are partially filled.
As a result, the high density of states is localized around the
Fermi level EF while the localized Mn-3d orbital is important
to anchor reactants. The PDOS of N2O–Mn/graphene (Figure
16.16b) shows two peaks at about –5.2 and –0.3 eV below
EF for N2O, C, and Mn atoms, which suggests that N2O-2p
is well integrated with the C-2p and Mn-3d orbitals, forming
the Mn–N2 bond. Additionally, the overlapped peaks in the
vicinity of EF from N2O-2p and Mn-3d orbitals jointly yield
a set of hybridization and subsequently lead to the elonga-
tion of lN1–N2 and shrinkage of lO1–N1. When F = 1.530 V/Å is
Effect of External Electric Fields on the Multifunctional Applications of Graphene 249

Top
(a) (b) (c)
4 4 4
2 2
1 1 1

A A A
Side
–0.094 0.02 4 –0.004 4
0.20 3 0.07 3 0.003 3
2 –0.10
2 –0.15

1 –0.29 1 –0.27 –0.12 1 2 –0.09

0.27 0.28 0.22

ISI TSI FSI

A A A
Top
(d) (e) (f )

2 2 2
1 1 1
24

Side F = 0.765 V/Å F = 1.53 V/Å F = 2.55 V/Å

–0.01 40.05 0.08 0.16 1

2 0.23
–0.03 1 2 3
0.05 1 2
–0.03
0.26 0.27 0.31

ISI Positive Positive Positive

A A A

FIGURE 16.15  Local configurations of the adsorbates on the O1–Mn/graphene system at each state along MEP. In the second decom-
position step, corresponding structures include IS1(a), TS1(b), and FS1(c) along MEP via N2O + O → N2 + O2 route. (d) The corresponding
final structure IS1 on the Mn/graphene system under F = 0.765 V/Å. (e) The geometric structure of O2 adsorbed on the Mn/graphene system
under F = 1.530 V/Å. (f) The geometric structure of O2 desorbed on the Mn/graphene system under F = 2.550 V/Å. (Reprinted with permis-
sion from Song, E. H. et al. External electric field catalyzed N2O decomposition on Mn-embedded graphene. J. Phys. Chem. C 116:20342.
Copyright 2012 American Chemical Society.)

added (Figure 16.16c), there is a strong hybridization between
O1ad-2p and Mn-3d orbitals near EF. Thus, the O1ad-2p orbital
takes part in the fracture of the N1–O1 bond and O1ad–Mn
bond formation (lMn–O1ad = 1.575 Å). Meanwhile, the weak
hybridization between N2-2p and C-2p is observed at –3.7
and –4.8 eV. As F is removed as shown in Figure 16.16d,
the adsorption of N2 is a weak physisorption while the O1ad
atom is chemisorbed on the Mn/graphene system due to the
hybridization situation in the vicinity of EF. As we discussed
above, the partially occupied Mn-3d orbital, being crucial
for the adsorption ability, is localized around EF because of
the interaction between Mn and graphene. When the sec-
ond N2O is adsorbed on O1ad–Mn/graphene (Figure 16.16e),
the weak hybridization among N2O-2p, O1ad-2p, and Mn-3d
is observed at about –2.8 and 4.1 eV, denoting the charge
transfer between  O1ad–Mn/graphene and  N2O. The Mn-4s
orbital has no significant change in the second decomposi-
tion reaction progress and is thus not shown here. Compared
with Figure 16.16e and f, the O1ad-2p and N2O-2p orbitals are
more broadened and involved with the Mn-3d orbital. N2O-2p
strongly hybridizes with O1ad-2p and Mn-3d orbitals near EF,
which benefits the fracture of the O2–N3 bond and N2 forma-
tion. From TS1 to FS1 (Figure 16.16f and g), the O-2p orbital
is gradually elevated and involved within the Mn-3d orbital
near EF to strengthen the O1–O2 bond, as indicated in the O2
formation. The N2O-2p orbital is not involved in the reaction
here since its position is far below EF. It is readily seen from
Figure 16.16h that the PDOS plots in the presence of positive
F are quite similar to those without a field (Figure 16.16g),
although all the orbitals are pushed toward EF. In this case,
mediated by F = 0.765 V/Å, O2-2p strongly hybridizes with
Mn-3d near EF, forming O2 and strengthening the Mn−O2
 250

(a) (b) (c) (d)

Mn-4c N2O-2p N2-2p H2-2p
12 Mn-3d 12 Mn-3d 12 O1-2p 12 O1-2p
C-2p C-2p Mn-3d Mn-3d
C-2p C-2p
10 10 10 10

8 8 8 8

6 6 6 6

4 4 4 4

PDOS (Electron/eV)
PDOS (Electron/eV)
PDOS (Electron/eV)
PDOS (Electron/eV)
2 2 2 2

0 0 0 0
–7 –6 –5 –4 –3 –2 –1 0 1 2 3 4 –7 –6 –5 –4 –3 –2 –1 0 1 2 3 4 –7 –6 –5 –4 –3 –2 –1 0 1 2 3 4 –7 –6 –5 –4 –3 –2 –1 0 1 2 3 4
Energy (eV) Energy (eV) Energy (eV) Energy (eV)

(e) (f ) N2O-2p
(g) (h)
H3O-2p H2-2p H2-2p
12 O1-2p 12 O1-2p 12 O3-2p 12 O3-2p
Mn-3d Mn-3d Mn-3d Mn-3d
C-2p C-2p C-2p
10 10 10 C-2p
10

8 8 8 8

6 6 6 6

4 4 4

PDOS (Electron/eV)
PDOS (Electron/eV)
4

PDOS (Electron/eV)
PDOS (Electron/eV)

2 2 2 2
5
0 0 0 0
–7 –6 –5 –4 –3 –2 –1 0 1 2 3 4 5 –7 –6 –5 –4 –3 –2 –1 0 1 2 3 4 5 –7 –6 –5 –4 –3 –2 –1 0 1 2 3 4 5 –7 –6 –5 –4 –3 –2 –1 0 1 2 3 4
Energy (eV) Energy (eV) Energy (eV) Energy (eV)

(i) (j)
O3-2p O3-2p
16 Mn-4d 16
Mn-4d
C-2p C-2p
14 14
12 12
10 10
8 8
6 6

PDOS (Electron/eV)
PDOS (Electron/eV)
4 4
2 2
0 0
–14 –12 –10 –8 –6 –4 –2 0 2 4 –7 –6 –5 –4 –3 –2 –1 0 1 2 3 4
Energy (eV) Energy (eV)

FIGURE 16.16  PDOS projected onto the Mn/graphene system and N2O-labeled N-end on the Mn/graphene system, respectively. (a) The PDOS projected onto the Mn/graphene system. (b)
The PDOS projected onto N2O (N-end) on the Mn/graphene system. (c) The PDOS projected onto N2O (N-end) decomposed to N2 and O1ad on the Mn/graphene system under F = 1.530 V/Å.
(d) The PDOS projected onto N2 and O1ad on the Mn/graphene system with removal of the electric field. PDOS projected onto the second N2O on the O1ad–Mn/graphene, together with the
3d-projected PDOS of the Mn atom in the (e) IS1, (f) TS1, (g) FS1, and (h) IS1 (F = 0.765 V/Å). (i) The PDOS projected onto O2 adsorbed on the Mn/graphene system under F = 1.530 V/Å.
(j) The PDOS projected onto O2 desorbed on the Mn/graphene system under F = 2.550 V/Å. Black curve, 2p orbital of carbon atom; blue curve, 2p orbital of N2O and N2 on Mn/graphene;
pink curve, 2p orbital of O1 atom and O2 on Mn/graphene; and red curve, 3d orbital of the Mn atom. EF in the figure is set to zero. (Reprinted with permission from Song, E. H. et al. External
electric field catalyzed N2O decomposition on Mn-embedded graphene. J. Phys. Chem. C 116:20342. Copyright 2012 American Chemical Society.)
Graphene Science Handbook
Effect of External Electric Fields on the Multifunctional Applications of Graphene
bond. Although N2-2p is shifted toward EF, weak hybridization
between N2-2p and Mn-3d at about –6.7 and –3.3 eV is found,
denoting the easy desorption of N2. In this case, mediated by
F = 0.765 V/Å, these peaks are continuously hybridized and
shift toward EF where the decomposition reaction activity
of Mn/graphene can be significantly enhanced. As shown in
Figure 16.16i, when a positive F increases to 1.530 V/Å, O2-2p
weakly hybridizes with Mn-3d near EF, forming O2 and weak-
ening the Mn − O2 bond. Especially, as shown in Figure 16.16j
(up to F = 2.550 V/Å), there is little hybridization between the
O2-2p and Mn-3d orbitals near EF, which benefits the fracture
of the Mn–O2 bond and O2 desorption.
16.5 SUMMARY
The effect of an applied electric field on the application of
graphene as a hydrogen storage material, the reversible wet-
tability transition of graphene for possible biosensor applica-
tion, and decomposition of greenhouse gas N2O on Mn-doped
graphene is investigated through DFT calculations. It is found
that applying an electric field can reduce the energy barrier for
the dissociative adsorption of hydrogen molecules on N-doped
graphene, thus facilitating the hydrogenation process. Under
the same electric field, the dissociatively adsorbed H atoms can
diffuse easily on the N-doped graphene. In this case, a fully
hydrogenated N-doped graphene can be obtained with atomic
hydrogen storage capacity of 7.23 wt%. Removing the electric
field, the stored hydrogen can be released spontaneously with
0.5 wt% residual hydrogen. Therefore, N-doped graphene is
a promising atomic hydrogen storage material with a storage
capacity up to 6.73 wt%. The hydrogen storage/release can be
switched by applying/removing the electric field.
To investigate the wettability transition of graphene in
the presence of an electric field, the dissociative adsorption
of H2O on graphene with a perpendicular electric field F is
investigated. It is found that a negative electric field can act
as a catalyst to facilitate H2O dissociative adsorption on gra-
phene, which induces graphene to be hydrophilic. If F > 0, the
opposite effect is found that the desorption of H and OH from
graphene is facilitated, inducing graphene to be hydrophobic
again. The origin of the effect of F on Ebar is discussed through
analyzing the interaction between the s/p orbital band of H/O
and p orbital band of C. As a result, F acts as a switch to
reversibly change graphene from hydrophobic to hydrophilic.
For N2O decomposition on the Mn/graphene system, DFT
calculations with F are carried out, and it is found that the
Ead value of N2O on Mn/graphene is twice as large as that of
PGMs. When a positive F is applied, the N2O spontaneous
decomposition reaction proceeds via a two-step mechanism of
N2O → N2 + O and N2O + O → N2 + O2. The enhanced decom-
position reaction activity is attributed to the charge redistribu-
tion between N2O and Mn/graphene induced by a positive F.
Thus, the Mn/graphene system under F is a good candidate for
N2O decomposition with lower cost and higher activity.
Therefore, applying an electric field is an efficient tool
for the multifunctional applications of graphene, which
could yield substantial alternations of graphene in geometry,
251
binding energies, vibrational spectra, chemical activities, and
electronic properties. All these changes are expected to be
induced by the polarization of the system under the electric
field, which changes the electronic distribution.
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 17 Impact of the Structural Properties
of Graphene on SiC Surfaces on
Their Electronic Applications
An Assessment
Jolanta Borysiuk and Jakub Sołtys

CONTENTS
Abstract...................................................................................................................................................................................... 255
17.1 Introduction...................................................................................................................................................................... 255
17.2 Basic Structural Properties: Multilayered Graphene........................................................................................................ 256
17.3 Synthesis Process and the Defect Creation...................................................................................................................... 257
17.4 Defect Structure................................................................................................................................................................ 262
17.5 Applications...................................................................................................................................................................... 264
17.6 Summary.......................................................................................................................................................................... 265
Acknowledgments...................................................................................................................................................................... 266
References.................................................................................................................................................................................. 266

ABSTRACT
The structural properties of multilayer graphene, their stack-
ing, and angular arrangement determine the electron disper-
sion relation around the K-point that is instrumental in the
application of graphene-based devices in fast electronics. As
revealed by transmission electron microscopy (TEM) stud-
ies, the structure on both sides is drastically different in many
aspects including the attachment to a substrate, layer stacking,
and thickness. The relation between these structural proper-
ties and the dispersion relations, including a possibility of its
modification in functioning electronic devices is discussed
using both tight-binding and density functional theory calcu-
lations. The extended defects, which are currently ubiquitous
in synthesized graphene layers, are highly detrimental for the
mobility of carriers. The influence of local orientational dis-
order on the average electron transport properties is therefore
discussed. The disorder is also related to the grain boundaries,
composed of the chains of extended defects. The low-angle
and high-angle boundaries and their relation to basic defects
are elucidated using a structural analysis. The principal type
of such defects is presented using TEM plan-view observa-
tions. The possible relation between various factors inducing
defect creation, including a built-in strain and coalescence of
the growing nuclei is discussed. Graphene growth on SiC,
the creation of various stackings, and related creation of the
extended defects is discussed.
17.1 ​INTRODUCTION
High-tech applications of graphene, such as high-speed pro-
cessing or molecular sensing depend on a successful solution
of formidable obstacles, both of a physical and technological
nature. Graphene-based devices could exploit the potential of
high-speed processing when massless fermions could convey
or detect electric signals of the basic speed associated with
Dirac-like linear dispersion relations not intensively scattered
by any charged or neutral defects. In addition, these devices
should possess the ability of being switched on/off with a
superior speed. Currently existing graphene-based devices
are not able to fulfill these requirements [1].
The construction of the devices includes requirements of
reliable work for a relatively long period with the perspec-
tives of high-integration circuits that essentially exclude self-
standing graphene flakes. Thus, reliable supports compatible
with the above-mentioned requirement are needed. This chap-
ter entails an exhaustive discussion of the implementation of
graphene on various supports; we therefore limit the scope
of this chapter to graphene synthesized on a silicon carbide
(SiC) substrate. Such a system is particularly attractive as SiC
could be easily doped to n-, p-type, and semi-insulating, and
good-quality, large-size SiC wafers are commercially avail-
able, still at a relatively high cost. Nevertheless, for high-tech
applications, the present-day cost of the SiC substrates can be
dealt with. Natural graphene synthesis techniques based on

255
256
TABLE 17.1
Summary of the Literature: Subjects
No Subject References
1 General [1,4]
2 Transistors [2,3,24,25]
3 Band structure [5–10,17]
4 Synthesis [13,14,18–20]
5 Crystallographic structure [14–17]
6 Defects [11,21–23]
7 Applications [26–28]
the evaporation of silicon at high temperatures opens perspec-
tives for the preparation of desired graphene–SiC systems.
Such a simple road to SiC-based graphene devices turned
out to be painstakingly arduous in practice [2,3]. Graphene,
synthesized on both polar faces of SiC needs to be consid-
erably improved and modified. The current state of the art
for graphene synthesis on SiC substrates with an emphasis on
advanced electric applications is presented. The prospects for
progress in the near future in the advanced application are
discussed (Table 17.1).
17.2 ​BASIC STRUCTURAL PROPERTIES:
MULTILAYERED GRAPHENE
Single-layer self-standing graphene, that is, an sp2-bonded
carbon layer, crucial for the investigation of its basic physi-
cal properties, could not be directly used for the devices. The
most important aspect is the linear dispersion relation (Dirac
dispersion) of single-layer graphene, in the vicinity of the
K-point [4]. Such dispersion could be found in many solids
but the Fermi level is at the K-point energy, and the excitation
of electrons (and holes) is therefore possible, promising the
application of fast particles (υ ~ c/300, c is the speed of light)
in electronics [5]. As the band gap is closed, the excitation of
the electrons and holes is easy.
It is worth mentioning that several sp2-bonded carbon
(graphene) layers may be differently stacked, creating various
types of the carbon material, known as graphite. All these
allotropic systems are characterized by an open bandgap and
parabolic dispersion relation. Thus, massive electron trans-
port is typical for these systems. The basic difference between
graphite and graphene is the open/closed bandgap and the
parabolic/linear dispersion. The promising perspectives of
graphene in electronics cannot be fulfilled by graphite.
The two different theoretical approaches provided a con-
sistent explanation: in the carbon sp2-bonded system, the
π-bonded pz orbitals create the band which, due to the six-
fold symmetry of a single graphene plane, is characterized
by the linear dispersion relation [5]. The multilayer graphite,
such as Bernal (AB) or rhombohedral (ABC) stacking has
this symmetry broken due to an overlap of the wave func-
tions of the neighboring layers; hence, the massive transport
is observed. It was also shown that the AA-stacked sp2 carbon
layers preserve the sixfold symmetry and the Dirac dispersion
Graphene Science Handbook
is retained equally for self-standing and synthesized graphene
on the Si-terminated face of SiC [6].
The role of symmetry in single- and multilayered graphene
was systematically investigated using density functional
theory (DFT) calculations. It was shown that the sixfold
symmetry is necessary to assure a closed gap and linear dis-
persion. The symmetry breaking of a different nature, such as
adsorption of hydrogen atoms or the presence of a differently
stacked neighboring layer, is sufficient for opening of the gap
and the emergence of mass [6]. The symmetry argument was
finally confirmed by the DFT analysis of various cases of
hydrogen adsorption at single graphene layers. The perspec-
tives of applications were opened for graphene synthesized
on SiC polar surfaces, as it was shown that all three types
are synthesized on the C-terminated 4H-SiC surface, includ-
ing AA stacking. Note that the interlayer distance is close to
3.4 Å, close enough to a significant overlap of the orbitals of
the neighboring layers (Figure 17.1). It is also well known,
however, that the dominant stacking is AB, which is charac-
terized by parabolic dispersion. Surprising data were there-
fore obtained during investigations of graphene synthesized
on the C-face of SiC proving that linear dispersion dominates
electronic transport, as shown by measurements in high mag-
netic fields [7,8]. The phenomenon was attributed to several
different types of systems: the existence of tightly bound
bilayers [9], surrounded by other more distant carbon layers
or by a twist of the neighboring layers [10,11]. Another pos-
sible explanation was that the separation of the carbon sheet
is increased so that a covalent overlap is negligible and the
dispersion is typical of a single layer.
All these scenarios were investigated by DFT calculations.
It was shown that the reduction of the overlap so that it could
explain the massless dispersion, is far above 5 Å (Figure 17.2)
[12]. Such an explanation is clearly incompatible with the
existing high-resolution transmission electron microscopy
(HRTEM). Similarly, the twin AB-stacked bilayer has a
parabolic dispersion, in accordance to the symmetry role;
such explanation is therefore not valid [12]. The alternative
scenario was a large-angle rotation of the neighboring layers
which, as shown by DFT data, could really explain the mag-
netic field measurements. A rotation may be analyzed only
on the small scale; nevertheless, the obtained dispersion is
linear, closely resembling the postulated graphene dispersion.
Naturally, the proposed scenario is still disputed as the defini-
tive proof of existence of such a rotated structure still needs
verification.
A A A
A B B
A A C
A B A
FIGURE 17.1  HRTEM-filtered images showing the presence of
AAAA, ABAB, and ABCA stacking in graphene layers, grown on
the C-terminated face of 4H-SiC. The positions of the carbon atom
columns are marked by the circles.
Impact of the Structural Properties of Graphene on SiC Surfaces on Their Electronic Applications 257

AAAA ABAB ABCA

1.5 1.5 1.5
1 1 1
E (eV) 0.5 0.5 0.5
3.2 Å

0 0 0
–0.5 –0.5 –0.5
–1 –1 –1
–1.5 –1.5 –1.5
1.5 1.5 1.5
1 1 1
0.5 0.5 0.5
E (eV)
3.4 Å

0 0 0
–0.5 –0.5 –0.5
–1 –1 –1
–1.5 –1.5 –1.5
1.5 1.5 1.5
1 1 1
0.5 0.5 0.5
E (eV)
3.8 Å

0 0 0
–0.5 –0.5 –0.5
–1 –1 –1
–1.5 –1.5 –1.5
1.5 1.5 1.5
1 1 1
0.5 0.5 0.5
E (eV)
4.8 Å

0 0 0
–0.5 –0.5 –0.5
–1 –1 –1
–1.5 –1.5 –1.5
M K Γ M K Γ M K Γ

FIGURE 17.2  Dispersion relations obtained from DFT simulations of self-standing four-layer graphene systems at various spacing for the
following interlayer distances: 3.2, 3.4, 3.8, and 4.8 Å in AAAA, ABAB, and ABCA stacking. (Reproduced with permission from Soltys,
J. et al. 2012. Experimental and theoretical investigation of graphene layers on SiC (000-1) in different stacking arrangements. J. Vac. Sci.
Technol. B 30: 03D117-1-6. Copyright 2014, American Vacuum Society.)

17.3 ​SYNTHESIS PROCESS AND
THE DEFECT CREATION
The graphene synthesis process is technically relatively sim-
ple as it may be conducted by annealing of an SiC crystal,
evaporation of silicon, and creation of a C-rich layer on the
surface [13,14]. Despite such simplicity, the results of anneal-
ing are markedly different on both polar faces of SiC. On the
Si-terminated surface, the graphene layer grows slowly, with
the resulting multilayer graphene comprising three to four
carbon layers at most. The synthesis is then terminated and
the application of a longer process or higher temperature does
not increase the number of carbon sheets. Such graphene is
strongly attached to the underlying SiC crystal that affects
its electric properties, as shown by the ab initio calculations,
presented in Figure 17.3. The characteristic feature is the
presence of a buffer layer connecting the graphene with the
underlying substrate by covalent bonds [15]. The connection
that introduced an additional 6 × 6 periodicity affecting elec-
tric charge distribution is shown in Figure 17.4. It is therefore
expected that the graphene layers on the Si-side are strained
by the lattice mismatch with the SiC substrate [15].
The first C-rich layer, usually denoted as the buffer layer
is markedly different from all the above ones, and its nature
is still disputed. The lattice mismatch between graphene and
the SiC substrate induces high strain, leading to wrinkles
(bending layers) and other structures [16]. The characteristic
features of graphene topography on the Si-face are steps and
macrosteps as shown in Figure 17.5 [16].
The C-face graphene grows markedly faster, consecutively
increasing the number of carbon sheets so that the structures
with more than 4–5 layers are readily obtained [14,17]. Alas,
258 Graphene Science Handbook

FIGURE 17.4  Total charge density of the graphene layer above the
C buffer layer for the Si-terminated surface. (a) Total charge den-
sity in the 6R3-SiC unit cell, (b) cross section of the total charge
density along the line defined in (a). (Reprinted with permission
from Varchon, F. et  al. 2008. Ripples in epitaxial graphene on
the Si-terminated SiC(0001) surface. Phys. Rev. B 77: 235412-1-8.
Copyright 2014 by the American Physical Society.)

(a)

FIGURE 17.3  Graphene layer above the C buffer layer for the
Si-terminated surface. (a) Large-scale image (11 × 11 nm2) of the
total charge density of 0.04 nm above the uppermost atom. It exhib-
its the characteristic 6 × 6-SiC periodicity (full-line diamond). The
6R3-SiC (6 3 × 6 3 R30) common cell corresponds to the dashed
line diamond. (b) Fourier transform of a large-scale image of the 3 nm
total charge density. The solid arrow points to a 1 × 1-G spot, the
dashed arrow points to a 6 × 6-SiC spot. (Reprinted with permis- (b)
sion from Varchon, F. et al. 2008. Ripples in epitaxial graphene on
the Si-terminated SiC(0001) surface. Phys. Rev. B 77: 235412-1-8.
Copyright 2014 by the American Physical Society.)

the crystallographic structure of such graphene is markedly

worse and the carbon sheets are weakly attached to the sub-
strate. The structure is evidently less strained but the crystal-
lographic quality is far more inferior. It seems that the built-in
strain is not the determining factor of graphene quality.
The kinetic scenario of the graphene synthesis needs con-
sideration of the molecular processes involved. As expected,
the silicon atoms evaporate, leaving excess C atoms at the
surface. Thus, the interaction of the Si and C adatoms with
the polar SiC surfaces is important. The energy landscape
of Si and C adatoms at the Si- and C-terminated face of SiC
was investigated by large-scale DFT calculations. The energy
landscape of these adatoms at the Si-terminated surface is
presented in Figure 17.6. The lattice is stable and to diffuse,
the adatoms have to overcome the energy barriers, equal to 0.4
and 1.11 eV for Si and C, respectively, which is quite possible
(c) (d)
1 nm 1 nm
FIGURE 17.5  (a) Atomically resolved scanning tunneling micro-
scope (STM) image of a graphene-covered SiC step imaged at
UT = −0.159 mV and IT = 5 pA. The z scale is 0–0.52 nm. (b)
Three-dimensional (3D) visualization of the image shown in (a).
(c) Close-up of the upper terrace. (d) Close-up of the lower terrace.
(Reprinted with permission from Lauffer, P. et al. 2008. Atomic and
electronic structure of few-layer graphene on SiC(0001) studied with
scanning tunneling microscopy and spectroscopy. Phys. Rev. B 77:
1554226-1-10. Copyright 2014 by the American Physical Society.)
Impact of the Structural Properties of Graphene on SiC Surfaces on Their Electronic Applications 259

(a) SiC (0001)

C atom
Si atom

(b) Si atoms (d) 0.5

1.79 Å
0.4

Energy (eV)

0.27 eV
0.3

0.40 eV
0.2
Scale: Δ n(r) Top C
–565.28
–564.92
0.1
–564.56 Hollow
–564.20 0
–563.84 Diffusion path
–563.48

(c) C atoms (e) 1.4

1.2 1.79 Å
1
Energy (eV)

1.13 eV

1.03 eV
0.8
0.6
Scale: Δ n(r)
–567.25 0.4
–566.46
–565.68
0.2
Hollow Top C
–564.89 0
–564.10 Diffusion path
–563.31

FIGURE 17.6  Atomic structure of SiC Si-terminated surface and the energy surface of the adsorbed Si and C atoms derived from DFT
results: (a) the atomic structure of an SiC surface, (b) the energy surface of the silicon atom, and (c) the energy surface of the carbon atom,
at the (0001)SiC surface. On the right-hand side (d, e), the energy profiles along the black line correspond to the distances shown in the
diagrams.

at a relatively high temperature of graphene synthesis, usually
close to 1800 K.
A drastically different picture was obtained at the
C-terminated face. The Si adatom behaves typically, diffus-
ing over the SiC lattice, having to surmount the energy bar-
rier of about 1 eV [18]. The presence of C-excess adatoms
brings a dramatic change; the surface undergoes a local trans-
formation to an sp2-bonded structure liberating a single Si
atom. The embryo of a new graphene layer is created in the
process with no energy barrier (Figure 17.7) [18]. The latter
result sheds some light on the graphene synthesis mode on the
C-terminated face. The excess of the carbon leads to force-
ful nucleation of the new graphene layer, occurring at random
positions. The graphene leaves then coalesce to a continu-
ous sheet. Naturally, the layer is not strongly attached to the
substrate, as the experimental distance between the carbon
sheet and the C-face is close to 4 Å. Such small islands are
therefore rotated by a relatively large angle that leads to the
creation of defects and dislocations. The layer is of a poor
crystallographic quality. In addition, the liberated Si atoms
diffuse underneath the carbon sheets to arrive at the undu-
lations and finally escape from the underneath of graphene.
This is possible despite the small size of the graphene hexa-
gons that blocks the penetration of the silicon atoms across
single C-layer graphene sheets.
It is worth mentioning that the graphene synthesis on the
C-face may proceed indefinitely as the outdiffusion of the sili-
con adatoms is possible, due to the existence of the channel
and the wrinkles or discontinuities facilitating a fast escape of
the excess silicon. New carbon sheets are created underneath
the existing multilayer graphene. The relatively weak bonding
of graphene to the substrate and also the graphene layer above
allows a fairly easy rotation of the small emerging graphene
pieces, facilitating the coalescence of differently oriented
nuclei and the creation of a high density of defects [17].
The structure of the graphene layer is marked by a dense
network of wrinkles, readily observed in the optical and
atomic force microscopy scans as presented in Figure 17.8
260 Graphene Science Handbook

–
(a) SiC (0001 )

C atom
Si atom

(b) (d) 1.4

Si atoms
1.2
1.79 Å
1

Energy (eV)

0.41 eV
0.8

0.96 eV
0.6 Top Si
Scale: Δ n(r)
–560.68
0.4
–560.19 0.2
–559.70
–559.21 Hollow
0
–558.72 Diffusion path
–558.24

(c) C atoms (e) 1.2

1
Energy (eV)
0.8 3.09 Å
0.6

0.95 eV

0.95 eV
Scale: Δ n(r) 0.4
–561.97
–561.04 0.2
–560.11
–559.18
–558.26
0
–557.33 Diffusion path

FIGURE 17.7  Atomic structure of SiC C-terminated surface and the energy surface of the adsorbed Si and C atoms derived from DFT
results: (a) the atomic structure of an SiC surface, (b) the energy surface of the silicon atom, and (c) the energy surface of the carbon atom,
at the (000 1 ) SiC surface. On the right-hand side (d, e), the energy profiles along the black line correspond to the distances shown in the
diagrams. (Reprinted with permission from Borysiuk, J. et al. 2012. Role of structure of C-terminated 4H-SiC (000 1 ) surface in growth of
graphene layers: Transmission electron microscopy and density functional theory studies. Phys. Rev. B 85: 045426-1-7. Copyright 2014 by
the American Physical Society.)

(a) (b)
1.0
3.0 nm

1.5 nm 0.75

0.0 nm
0.5

0.25

10 μm

0
0 0.25 0.5 0.75 1.0 μm

FIGURE 17.8  Morphology of the SiC (000 1 ) surface with graphene observed by an optical microscope with Nomarski contrast (a) and
atomic force microscopy (AFM) image of a magnified part of the surface (b). (Reprinted with permission from Borysiuk, J. et al. 2012. Role
of structure of C-terminated 4H-SiC (000 1 ) surface in growth of graphene layers: Transmission electron microscopy and density functional
theory studies. Phys. Rev. B 85: 045426-1-7. Copyright 2014 by the American Physical Society.)
Impact of the Structural Properties of Graphene on SiC Surfaces on Their Electronic Applications
FIGURE 17.9  TEM images of discontinuities and bendings of the
graphene multilayers created near a macrostep (a) and at the small
steps (b). Graphene with bending layers is marked by dashed lines.
(Reprinted with permission from Borysiuk, J. et  al. 2012. Role of
structure of C-terminated 4H-SiC (000 1 )  surface in growth of gra-
phene layers: Transmission electron microscopy and density func-
tional theory studies. Phys. Rev. B 85: 045426-1-7. Copyright 2014
by the American Physical Society.)
[18]. Different types of structures are observed at the multi-
step islands obtained in the polishing and etching of the SiC
surface. The atomic structure of wrinkles (discontinuities) is
presented in Figure 17.9. A model encompassing the multi-
layer creation and impenetrability of graphene sheets to car-
bon atoms was described [18].
In contrast to the proposed scheme, the growth scenario on
the opposite Si-terminated face is not well established. The
described several schemes were created using results of vari-
ous types of microscopic observations. The first scenario was
proposed by Hannon, and accounts for the fact that carbon
atoms are densely packed in the graphene lattice so that more
than three layers of SiC are needed to be in the registry with a
single graphene layer [19]. Thus, the layer of graphene grows
at the step in the direction of the upper terrace (Figure 17.10).
Depending on the step height of the new graphene, the new
graphene layer implodes to the depth in an irregular manner
as presented in Figure 17.11. The coalescence of these grow-
ing parts could lead to the creation of defects and dislocations.
The silicon atoms outflow at the edge of the new graphene
layer. The model could explain the creation of a single layer
and the coalescence defects. No explanation of multilayer gra-
phene was proposed.
Another graphene synthesis scenario, proposed by
Norimatsu, was based on transmission electron microscopy
(TEM) observation, considering a multistep at which the new
layers start to develop [20]. According to their model, pre-
sented in Figure 17.12, the graphene layer grows at the slope,
terminating at the edge of the island. The layer was terminated
in a bending type of the defect. No consideration of a deep
reconstruction related to registry, as in the Hannon model,
was proposed. The model explains the creation of multilayer
261
(a)
500 nm
(b) (c)
(d)
3 step
0.0 0.5 1.0 1.5 2.0
Distance (μm)
FIGURE 17.10  ​(a) 5.3-eV bright-field low-energy electron micros-
copy (LEEM) image at 1140°C of large buffer layer domains
(bright). (b) AFM image from the same surface illustrating the flow
of 3 steps around the buffer layer (arrows). (c) AFM phase image
from the right of (b) showing a contrast between the buffer layer
(dark) and 3 (bright). (d) Line scan from the dotted line indi-
cated in (b). Tall steps (left) are 1.0 nm and short steps (right) are
0.2 nm. The schematic starting profile is shown in gray. (Reprinted
with permission from Hannon, J. B. and Tromp, R. M. 2008. Pit
formation during graphene synthesis on SiC(0001): In situ electron
microscopy. Phys. Rev. B 77: 241404-1-4(R). Copyright 2014 by the
American Physical Society.)
graphene of a finite extent without the mechanism of defect
creation during the growth.
It is evident that Norimatsu’s model does not provide a satis-
factory picture of the graphene synthesis on the Si-terminated
face. Since the model could not explain the impenetrability
of graphene and the existence of a multilayer structure, we
propose the model in which several carbon layers grow simul-
taneously that could take into account the creation of sev-
eral carbon sheets and their impenetrability by silicon atoms
262 Graphene Science Handbook

FIGURE 17.11  Model of 6 3 growth on SiC (0001) − 3 . (a) The buffer layer (gray) nucleates at the lower sides of 3 steps. (b) 3 steps
retract uphill as the buffer layer grows. (c) Eventually, a state is reached in which all 3 steps have been consumed, and with the buffer layer
covering roughly half of the surface. (d) Canyons or pits form when the domains of the buffer layer on each terrace are not continuous and
3 steps (thick black lines) advance to the next terrace. (Reprinted with permission from Hannon, J. B. and Tromp, R. M. 2008. Pit forma-
tion during graphene synthesis on SiC(0001): In situ electron microscopy. Phys. Rev. B 77: 241404-1-4(R). Copyright 2014 by the American
Physical Society.)

(a) Si (e) transformation of the stacking. The role of the strain in these
processes remains unclear, both of the uniform one and that
SiC related to the presence of defects and the related misorienta-
SiC tion of the lattice.
Si
(b) (f )
Graphene
17.4 ​DEFECT STRUCTURE
IV
SiC
Future technological advances could provide a possible
SiC recipe for the creation of the AA stacking that is needed
(c) to exploit the Dirac-type dispersion in electronic devices.
Growth (g)
I Such an exploitation will be possible if a large size, stable
AA-stacked graphene is routinely fabricated. In addi-
SiC SiC tion, the structure has to have a relatively small density of
defects with no or few dislocations. The point-defects struc-
(d) (h)
II ture results from the thermodynamic and chemical condi-
III
tions during growth. Their density may be controlled by the
SiC SiC chemical factors and also by temperature. Naturally, in the
case of an SiC/C system, the presence of the silicon dopant
(i)
is an inherent feature of the synthesis method and cannot be
Graphene removed. Still, some other chemical factors could be modi-
fied to some extent.
SiC Another problem is related to omnipresence of extended
defects in the synthesized graphene. As it was argued above,
the synthesis mode entangles the incorporation of a high den-
FIGURE 17.12  ​(a) through (h) Schematic diagrams of the forma-
sity of dislocations or dislocation arrays in the coalescence
tion process of graphene layers on SiC. Circles with broken lines
correspond to the regions in Figure 17.1. (i) Morphology of graphene processes. The process is indirectly related to the lattice mis-
layers formed on SiC. (Reprinted from Physica E, 42, Norimatsu, match, as the independent nuclei are moved and rotated by
W. and Kusunoki, M., Formation process of graphene on SiC (0001), the strain that leads to misorientation by a small and large
691–694, Copyright 2014, with permission from Elsevier.) angle.
Exploiting the analogy between graphene and other sys-
simultaneously. Such a new model could also explain the cre- tems, Yazyev proposed some examples of the creation of
ation of coalescence-related defects. dislocations, dislocation pairs (dislocation dipoles), and dislo-
All these above models could not explain why several cation arrays and related them to the misorientation angle via
stacking are possible to obtain. The most important AA the Frank equation [21]. It allowed them to obtain a relation
stacking is usually observed close to the step edges that have between the misorientation angle of the neighboring domains
not been explained so far. Moreover, it is not clear whether and the distance between dislocations in the array, creating
the presence of the remnant silicon atoms could induce a small-angle grain boundary. The examples of the single
Impact of the Structural Properties of Graphene on SiC Surfaces on Their Electronic Applications 263

(a) (b) (c)

a2
a1
T

T
T

b(1,0) b(1,1) b(1,0) + (0,1)

(1,0) Dislocation (1,1) Dislocation (1,0) + (0,1) Dislocation

(d) (e) (f )
T x
T
5 y
7
T
T
T ~3Å
θ1 θ2
θ1 θ2
5
T y x 7
T

T
x y
LAGB I LAGB II

FIGURE 17.13  ​(a through c) Atomic structures of (1,0) and (1,1) dislocations, and a (1,0) + (0,1) dislocation pair, respectively. The dashed
lines delimit the introduced semi-infinite strips of graphene originating at the dislocation core. Non-six-membered rings are shaded. (d) and
(e) Atomic structures of θ = 21.8° (LAGB I) and θ = 32.2° (LAGB II) symmetric large-angle grain boundaries, respectively. The dashed
lines show the boundary lines and the solid lines definite angles θ1 and θ2. (f) Buckling of the graphene layer due the presence of a (1,0)
dislocation. (Reprinted with permission from Yazyev, O. V. and Louie, S. G. 2010. Topological defects in graphene: Dislocations and grain
boundaries. Phys. Rev. B 81: 195420-1-7. Copyright 2014 by the American Physical Society.)

and pair of dislocations considered by Yazyev are presented

in Figure 17.13. These diagrams indicate a possibility of the
accommodation of the finite angle misorientation by the dis-
location array. The above dislocations could cover the range
between 0° and 21.8°. For larger angles, the (1, 1) dislocations
are compatible, thus allowing the coverage of the entire range
between 0° and 60°. A different, multiple structure could 1
–
accommodate the same misorientation; the large-angle mis- d11 00
orientation is therefore possible, at the cost of the increased
dislocation density.
Such a phenomenon was experimentally observed by
– 2
TEM measurements, where the high-angle grain boundary d11 00
was identified [22]. The presence of such boundaries is char- – 1 2
11 00
acteristic for graphene on the C-terminated SiC surface. The ~30°
typical size of multilayered graphene ranges from several
nanometers to several micrometers. Relatively dislocation- 2 nm
free grains are divided by high-angle boundaries, such as
the one presented in Figure 17.14. The defects will scatter
FIGURE 17.14  ​High-angle boundary between two areas, rotated
carriers, both electrons and holes, limiting a mean-free path by about 30°. The balls denote the overlapping C atoms in the
and the speed of the signal transfer in the devices. The ab AB-type stacking. The pairs of dotted lines described as (1) and
initio calculations could be used to obtain the transfer rate (2) are positions of the {1 100} planes. In the corner, the fast Fourier
across the boundary [23]. The results of such calculations are transform (FFT) image with spots arising from the {1 100} planes
presented in Figure 17.15. As expected, the presence of the and grain boundary is located.
264 Graphene Science Handbook

(a) (b) 1.0 (c) 1.0

1.0

0.5 0.5 0.5

E (eV)
E (eV)
(2,1) (2,1) 0 0

–0.5 –0.5

–1.0 –1.0
0 π 2π π 0 0.5 1.0 1.5
(2,1)|(2,1)-class Ib
3d 3d d T
k||

(d) (e) 1.0 (f ) 1.0

1.0

0.5 0.5 0.5

0
E (eV)

E (eV)
(5,0) (3,3) 0 1.04 eV 0

–0.5 –0.5

–1.0 –1.0
(5,0)|(3,3)-class II 0 π 2π π 0 0.5 1.0 1.5
3d 3d d T
k||

FIGURE 17.15  ​Electronic transport through grain boundaries in graphene from first principles. (a) Atomic structure of the (2,1)|(2,1)
(θ = 21.8°) class Ib grain boundary. (b) Transmission probability through the (2,1)|(2,1) grain boundary as a function of transverse momen-
tum k‖ and energy E. (c) Zero-bias total transmission per unit length through the (2,1)|(2,1) grain boundary as a function of energy (solid
line) compared to the one of ideal graphene (dashed line). (d) Atomic structure of the (5,0)|(3,3) (θ = 30.0°) class II grain boundary. (e, f)
Corresponding k‖-resolved and total charge carrier transmissions through the (5,0)|(3,3) (θ = 30.0°) class II grain boundary. (Reprinted with
permission from Macmillan Publishers Ltd: Nature Materials, Yazyev, O. V. and Louie, S. G. 2010. Electronic transport in polycrystalline
graphene. Nat. Mater. 9: 806–809, Copyright 2014.)

grain boundaries seriously affects the transport properties of
graphene.
It is also interesting, however, whether the heavy presence
of the point or extended defects affects the dispersion rela-
tions. The vacancy defect induces the presence of local states
and the magnetic moment within the lattice. More impor-
tantly, the extended defects change the dispersion relations as
shown in Figure 17.16.
These examples prove that defects, either point or
extended ones, exert a profound influence on the transport
of graphene, thus impeding the development of graphene-
based electronic devices. Their presence may signifi-
cantly deteriorate their performance. Yet, the removal of
the defects could potentially improve these devices open-
ing the route to high-speed applications. It is also worth
noting that the design of such a device, exploiting linear
dispersion is still in its infancy. The proposed solutions are
presented below.
17.5 APPLICATIONS
Fast signal processing is considered as the primary goal
of the investigation of graphene properties and the devel-
opment of graphene technology [3,24,25]. Its device
application needs several basic problems to be solved. In
comparison to the standard semiconductor devices, such as
field-effect transistors (FETs), graphene is significantly dif-
ferent that prevents a simple adjustment of the designs used
so far.
The standard FET devices work in the open-bandgap
regime, and the open/closed gate could be realized by the
mere shift of the Fermi level from the band into the gap.
Impact of the Structural Properties of Graphene on SiC Surfaces on Their Electronic Applications 265

(a) 1 (b) 1

0.5 0.5

E–EF (eV)

E–EF (eV)
0 0

–0.5 –0.5

–1 –1
Γ k|| X Γ k|| X

FIGURE 17.16  ​Calculated band structures for the models of (a) LAGB I and (b) LAGB II large-angle grain boundaries along k|| at k┴ = 0.
Correspondence between the van Hove singularities and the band extrema in the band-structure plots is highlighted with arrows. (Reprinted
with permission from Yazyev, O. V. and Louie, S. G. 2010. Topological defects in graphene: Dislocations and grain boundaries. Phys. Rev.
B 81: 195420-1-7. Copyright 2014 by the American Physical Society.)

–1

–2
E (eV)

–3

–4 E (eV)

–5
Γ K Γ k k
ky E=0 E>0

FIGURE 17.17  ​Application of the parallel electric field in graphene-based transistor: left dispersion relation of a single-graphene sheet
without the field vanishing (solid line) and 0.3 V/Å (dashed line); right—generic design of a Dirac logical device, based on the parallel
electric field effect; sides: the electrodes that apply the electric field to a carbon plane, and the carbon conduction channel is located in the
middle; and below—the two dispersion relations obtained for a non- and vanishing electric field. (Reprinted from J. Cryst. Growth, 401,
Krukowski, S. et al., Influence of a parallel electric field on the dispersion relation of graphene—A new route to Dirac logics, 869–873,
Copyright 2014, with permission from Elsevier.)

In the case of a Dirac-type device, the gap is closed; a shift
of the Fermi level could not shut the device. Thus, other solu-
tions have to be invented. Essentially, the only possible route
is a change of the dispersion relation and the opening of the
gap. This is difficult as the change should be reversible and
fast. That excludes the application of chemical and structural
factors leaving the electric and magnetic fields as possible
solutions.
A necessary condition of a successful Dirac device is that
in the case of the gate open, the dispersion relation should be
linear. The system should have the sixfold symmetry, typical
for single-layer graphene or AA-stacked structure. The tran-
sition to open the gap structure should be fast; so, the suit-
able candidate is the electric field. It was shown that the field
directed perpendicularly could open the gap. The construc-
tion of the electrode such as the fields is applied but there is
no direct contact with the graphene sheet. This solution is one
possible option.
Another choice is the application of the field parallel to the
graphene plane [26]. In this case, the field breaks the sixfold
symmetry of the system, opening the gap [27,28]. The change
of the electric state of the device should be possible in much
lower fields.
The proposed scheme allows opening of the gap in the
field, thus closing the gate (Figure 17.17) [26]. Without the
field, the linear dispersion controls the transport, and the gate
is open. The essential aspect of that design is that the electric
channel is open all the time but in the case without the field,
the signal travels faster. The construction of the electric field-
based graphene transistor is possible but probably technically
difficult.
17.6 ​SUMMARY
The relation between the structural and the electric proper-
ties of single- and multiple-layer graphene was presented. It
266
was shown that linear dispersion, being an essential part of
graphene is linked with the sixfold symmetry of the graphene
lattice. To exploit the advantages of graphene, such a mate-
rial has to be synthesized that includes single-layer, AA, or
AA′-stacked multilayer graphene. The current state of the art
does not allow to control the stacking of graphene toward the
synthesis of the desired material.
It was shown that graphene synthesized on both polar
SiC surfaces is characterized by a high density of defects,
including dislocations. The graphene on the Si-terminated
surface is strongly attached to the substrate by a buffer layer
and is therefore highly strained. On the other, C-terminated
surface, graphene is weakly attached. This high defect
density is related to the growth mode of a graphene layer
starting independently in many locations: on the Si-side at
the steps, while on the C-terminated surface, on the whole
terrace surface. The coalescence of these nuclei leads to
the creation of a large number of defects and defect arrays
connecting misoriented grains. Such a heavy presence of
defect affects the graphene properties deteriorating its elec-
tric properties.
The possible implementation of a Dirac dispersion transis-
tor, switched electrically by the manipulation of the gap and
the dispersion relation was proposed. It was shown that the
parallel electric field may be used for the gap opening and
opening/closing the device gate. Basically, fast-switching
logic is possible but the route to that requires a large number
of obstacles to be overcome.
In summary, the successful implementation of graphene
in electronics requires a dramatic progress in the synthesis
methods, device design, and implementation.
ACKNOWLEDGMENTS
J.B. would like to thank Dr. W. Strupinski from the Institute of
Electronic Materials Technology (Warsaw) for providing the
graphene/SiC sample. TEM investigations were performed
using the JEOL JEM 3010 microscope at the Faculty of
Materials Science and Engineering of the Warsaw University
of Technology.
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 18 Resistive Nonvolatile Memories Based
on Graphene-Related Materials
State of the Art
P. Bondavalli, D. Ihnatov, D. Pribat, and P. Legagneux

CONTENTS
Abstract...................................................................................................................................................................................... 269
18.1 Introduction...................................................................................................................................................................... 269
18.1.1 What Is a Memristor and a RRAM?.................................................................................................................... 270
18.2 Graphene-Based Nonvolatile Resistive Memories........................................................................................................... 270
18.2.1 Graphene and Graphitic Layers............................................................................................................................ 270
18.2.2 GO and R-GO Layers........................................................................................................................................... 272
18.3 Consideration on the Switching Mechanism.................................................................................................................... 274
18.4 Conclusions and Potential Applications........................................................................................................................... 275
References.................................................................................................................................................................................. 277

ABSTRACT number of directions such as novel graphene-based transistors

This contribution deals with the main scientific results on
graphene-related materials for resistive nonvolatile memo-
ries. Nonvolatile memories are identified as the key device for
the future of computational system considering the reduced
energy consumption compared with volatile memories.
However, a specific new technology has not been identified
until now considering the issues related to scalability and cost.
Graphene-related materials offer an interesting and extremely
promising alternative to existing technologies. In this con-
tribution, we show the main works dealing with graphene
layers, graphene oxide, and reduced graphene oxide. These
works are quite recent but show impressing results especially
in terms of writing time and endurance/cyclability compared
with common flash memories. The other main advantage of
these materials is the potential of developing a highly scal-
able complementary metal–oxide–semiconductor compatible
technology. Moreover, the carbonaceous materials are easily
available compared with rare earths and also compatible with
flexible applications and can open a new field of innovation.
18.1 INTRODUCTION
In electronics, it is hoped that graphene is rapidly becom-
ing a potential candidate for replacing and improving silicon
semiconductors for future high-performance devices. Since
silicon semiconductors remain the basis of most commercial
electronics (especially computing), it has become a great chal-
lenge for the next-generation materials. The potential appli-
cations of graphene are attracting a lot of research funding,
which in turn attracts researchers to probe opportunities in a
or spintronics. Another approach currently under develop-
ment by some teams is to employ graphene and other related
nanomaterials to achieve nonvolatile memories exploiting
their “memresistive” behavior. Indeed, for example, computer
high-density storage memory, transistors work by storing an
electrical charge. Thanks to “memresistive” materials, we can
store electrical resistance. That is, when a current is passed
through these materials, their level of resistance to electric-
ity (in ohms) changes in a nonvolatile and in an energetically
“friendly” way. Resistive memory exploits the electric field
responsive resistive switching of materials as an information
write/erase principle for nonvolatile data storage. The read-
ing of resistance states is nondestructive, and the memory
devices can be operated without transistors in every cell [1,2],
thus making a crossbar structure feasible. A large variety of
solid-state materials have been found to show these resis-
tive switching characteristics [3], including solid electrolytes
such as GeSe and Ag2S [2], perovskites such as SrZrO3 [4],
Pr0.7Ca0.3MnO3 [5–7], and BiFeO3 [8–10], binary transition
metal oxides such as NiO [11–13], TiO2 [14–16], ZrO2 [17,18],
and ZnO [19,20], organic materials [21], amorphous silicon
(a-Si) [22,23], and amorphous carbon (a-C) [24,25]. The main
advantages of graphene-related materials are not only that
they are likely to show extremely promising performances,
but also that these materials provide more flexibility (physi-
cally) and potentially can lower the final cost of the devices,
if scalable fabrication methods will be developed in parallel.
Moreover, we need only a two-terminal device, which dra-
matically reduces the circuitry and allows the implementation
of 3D architectures. Finally, this type of circuit commonly
used for computer memory could be potentially easily printed

269
270 Graphene Science Handbook

or deposited (e.g., by spray gun) on plastic sheets and used
wherever flexibility is needed, such as in wearable electronics.
18.1.1 What Is a Memristor and a RRAM?
Historically, electrical circuits were crafted with three basic
building blocks: the capacitor, the resistor, and the induc-
tor. But in 1971, Professor Leon Chua from the University of
California at Berkeley predicted the existence of a fourth—
the memristor, short name for memory resistor. Similar to an
ordinary resistor, a memristor would create and maintain a
safe flow of electrical current across a device, but unlike a
resistor, it would “remember” charges even when the power
is turned off. This would allow it to store information in a
nonvolatile way. More recently in 2011, Leon Chua has stated
that the memristor definition could be generalized to cover all
forms of two-terminal nonvolatile memory devices based on
resistance switching effects [26]. In this context, this contri-
bution will deal with the main results concerning graphene
and related nanomaterials (graphene oxide [GO], and reduced
graphene oxide [R-GO]) for the fabrication of nonvola-
tile resistive memories (memresistive-like memories). The
interest for these nanomaterials for this application is quite
recent and it has also been outlined in the 2011 International
Technology Roadmap for Semiconductors (ITRS) [27] chap-
ter on emerging research devices (ERD). In this chapter, it
is stated that memory devices where ultrathin graphite lay-
ers are interesting materials for macromolecular memories,
thanks to the potential fabrication costs that are considered as
the primary driver for this type of memory, whereas extreme
scaling is deemphasized. However, ITRS outlines that the
memory operation mechanisms, as for more generally resis-
tive random access memories (RRAMs), are still unclear and
that the research in this field is strictly necessary to improve
the comprehension of the phenomenon and the efficiency of
the devices.
Some very important works have been issued demon-
strating the fabrication of carbon nanotube (CNT)-based
nonvolatile memories. Indeed in the case of CNTs, the physi-
cal phenomena exploited were or the contact between two
CNTs as a mechanical switch, as pointed out by Rueckes
et  al. [28], the local change of sp2 structure by local pulse
[29], the charge trapping in CNTs [Tour09] or photoactiva-
tion [30–32]. These are apparently not the same mechanisms
that act in case of graphene and its related nanomaterials as
GO and R-GO.
18.2 GRAPHENE-BASED NONVOLATILE
RESISTIVE MEMORIES
18.2.1 Graphene and Graphitic Layers
Indeed, the first paper pointing out the potential for the utili-
zation of graphene for nonvolatile memories exploiting two-
terminal structures was issued in 2008 by Stadley et  al. at
Caltech [33]. Stadley and coworkers reported the development
of a nonvolatile memory element based on graphene break
junctions. These junctions were simply obtained achieving
two-terminal devices, transferring graphene sheets on SiO2/Si
substrate, and depositing metal electrodes on them using the
e-beam lithography process. Indeed, after applying a specific
voltage under ultravacuum condition (10−7 ​Torr) to avoid gra-
phene interaction with ambient gases, the graphene between
the two electrodes tended to break (see Figure 18.1).
However, after repeating the voltage cycles many more
times, it has been demonstrated that the resistance value
changed as a function of voltage (see Figure 18.2); scientists

Memory devices

Volatile memory Nonvolatile memory

BL
WL

Polarization Resistance
SRAM DRAM Charge trap SL
change change

FLASH SONOS FRAM PRAM MRAM RRAM

BL
WL
Phase
change VIVO
Oxide
PL
Charge-based Current-based Phase- Magneto- Interface
programming programming dependent resistance or bulk
and reading and reading resistance changes resistance
changes changes

Moving Moving Moving

Moving electrons
atoms spins atoms

FIGURE 18.1  Different kinds of memories and their operating principles.

Resistive Nonvolatile Memories Based on Graphene-Related Materials 271

200 nm

Original After breakdown

FIGURE 18.2  SEM image of the device before (left panel) and after breakdown (right panel). The arrows indicate the edges of the
nanoscale gap (Reprinted with permission from Standley B. et al. Graphene-based atomic-scale switches, Nano Lett., 8, 10, 3345–3349.
Copyright 2008 American Chemical Society.)

were able to move from a high resistance state (OFF state) to a industrial implementation of this technology. Researchers
lower one as a function of voltage (ON state). This effect was also tried to evaluate the voltage necessary to break the lay-
nonvolatile and the devices demonstrated thousands of writ- ers. After calculating Joule heating, the so-called breakdown
ing cycles (105) and long retention times (more than 24 h to, voltage was calculated by
perhaps, indefinitely at room temperature). 1/ 2
The observed switching behavior of graphene was impres-  (CργTbreak ) 
Vbreakα   l = Al
sive considering the robustness and reproducibility of this  τ 
phenomenon. One evoked explanation for the switching mech-
anism was the dielectric breakdown and conduction through where C, ρ, γ are, respectively, the specific heat, the density of
the substrate. However, the researchers affirmed that such a CVD-grown carbon, and resistivity. Tbreak is the temperature
process was not expected to be cycleable, as the conductance of breakdown; A is independent of the devices, and l is the
usually continued to increase upon further electrical stress, and length of the device. The main conclusion is that the voltage
the ON state conductance was far too large to be accounted necessary to break the layer and so to electroform the device
for, by the current flow through stressed oxide. Another poten- is directly proportional to the length. This is very interesting,
tial explanation was that the conductance occurred along a
small graphene ribbon that bridges the contacts. The absence 8
On Read Off Read On Read Off Read
of a gate voltage effect excluded switching mechanisms aris-
V (V)

ing from the storage of charge in traps in the oxide layer or 4

from the formation of a small metallic island that may func-
tion as a quantum dot. To better understand the underlying 0
physical mechanism, researchers at Caltech investigated the ≈500
1.0 cycles
time-resolved behavior of the switching from the OFF to ON
I (mA)

states, as shown in Figure 18.3. The conductance I/V showed

well-defined steps, with magnitude ~GQ. Here, GQ is 2e2/h, the 0.5
conductance quantum, where e is the electron charge, and h 100 μS 5.6 μS 113 μS 3.3 μS
the Planck constant. Since GQ is the conductance of a spin- 0.0
degenerate one-dimensional conductor, for example, a linear 0.0 0.4 0.8 397.6 398.0 398.4
chain of gold atoms [34], observation of the conductance steps Time (s)
suggests that the device conductance states are likely multiples
of highly transmitting quantum channels. Therefore, they pro- FIGURE 18.3  Repeatable programming over hundreds of cycles.
posed a model for device operation based on the formation and Upper left panel: Voltage applied to the junction versus time. A ramp
breaking of carbon atomic chains that bridge the junctions (see with a peak value of ~4 V corresponds to an ON pulse, whereas a
Figure 18.4). This mode and the results seem to put in evidence ramp with a peak value of ~6 V corresponds to an OFF pulse. A
the potential for multiresistive states. small sawtooth-shaped readout pulse is applied after each write to
The same physical explanation can be evoked from determine the junction conductance. Lower left panel: Current flow
through the junction, with the low-bias conductance labeled above
the results obtained in 2009 by Sinitski et  al. [24] at Rice.
each readout pulse. Right panels: Similar data taken after approxi-
However, in this case, the layer was not composed of gra- mately 500 intervening cycles, demonstrating the reproducibility of
phene but some staked layers of graphene, reaching 10 nm of the switching behavior. (Reprinted with permission from Standley
thickness grown by the CVD (chemical vapor deposition) pro- B. et al. Graphene-based atomic-scale switches, Nano Lett., 8, 10,
cess. This is extremely interesting, considering the potential 3345–3349. Copyright 2008 American Chemical Society.)
272
(b)
On
(a)
I/V (2e2/h) 2 v
40 V/s l
1 Off
0 v
2 3 4 l
V (V)
FIGURE 18.4  (a) Change in I/V as a function of V pointing out
the quantic behavior linked to the formation of atomic chains. (b)
Proposed physical mechanism at the base of the nonvolatile resis-
tive behavior (formation of atomic carbon chains). (Reprinted with
permission from Standley B. et al. Graphene-based atomic-scale
switches, Nano Lett., 8, 10, 3345–3349. Copyright 2008 American
Chemical Society.)
considering that by reducing the dimensions, we will be able
to reduce the energy consumption to write the information.
Using a different approach, in 2008 the same team from the
University of Rice [35] had grown graphitic layers on a free-
standing silicon oxide nanowire (see Figure 18.4a). Indeed,
they used the nanowire in order to preserve the mechanical
integrity of the device after applying a specific voltage that
broke the graphitic layers (as in the case of planar junctions).
In the case of utilization of CNTs, breaking the graphitic lay-
ers also meant to break the nanoobject definitively, without
any possible reversibility of the phenomenon.
The team from Rice fabricated two-terminal devices
consisting of discontinuous 5–10 ​nm thin films of graphitic
sheets grown by chemical vapor deposition on nanowires pos-
sessing stable, rewritable, nonvolatile, and nondestructive read
memories with on/off ratios of up to 107 (see Figure 18.5a) and
switching times of up to 1 µs (tested limit), which is competi-
tive with the performances of flash-type memories. One of the
most important results was the extremely good stability of the
performances after several days and also after x-radiation (see
Figure 18.5b).
Finally, concerning graphene, as mentioned in the very
recent work of Wu et  al. [36], who analyzed the electrical
properties of graphene sheet suspended on a patterned ITO
(indium tin oxide) electrode pair. They measured very promis-
ing on/off of six orders and retention time of <104 s in ambient
conditions. Data storage in this case can be realized by apply-
ing voltage bias and rewritten after a simple heat treatment. In
(a)
(b)
G
SiO2
250 nm
As-fabricated After opening
FIGURE 18.5  (a) Silicon oxide nanowire with graphitic layers grown on its surface. (b) Physical principle at the base of the fabrica-
tion of nonvolatile graphitic memories exploited by Rice University. (Adapted from Li Y., Sinitskii A., Tour J. M. 2008. Nat. Mater.,
7, 966.)
Graphene Science Handbook
this case, the scientists evoked the local oxidation of graphene
sheet at the graphene/electrode interface, although more stud-
ies have to be performed to confirm this hypothesis.
18.2.2 GO and R-GO Layers
Other teams focused their work on the fabrication of GO lay-
ers in order to achieve nonvolatile resistive memories. GO is a
wide bandgap material (6 ​eV) with potential for modulation,
thanks to the oxidation/reduction process providing tunabil-
ity of the electronics, mechanical, and optical properties. GO
[37] is commonly obtained by oxidation of graphite using the
modified Hummer’s method where the long oxidation time is
combined with a highly effective methods for the purification
of reaction products shown in Figure 18.6.
Owing to its high solubility in water, GO flakes can be put
in stable solutions quite easily and deposited on a large surface
using simple methods as spray coating or drop casting. In this
case of the utilization of GO, we deal with a configuration,
which is no more “planar” but more similar to crossbar mem-
ories (vertical junctions composed of piling up of the different
layers and sandwiching the active one as metal–insulator–
metal (MIM)-type structures. In this context, we mention the
work of He et al. [38] where reliable and reproducible resistive
switching behaviors were observed in GO thin films prepared
by the vacuum filtration method. The Cu/GO/Pt structure
showed an on/off ratio of about 20, a retention time of more
than 104 s, and switching threshold voltages of less than 1 V.
The switching effect suggested was the desorption/absorption
of oxygen-related groups on the GO sheets as well as the dif-
fusion of the top electrodes. Even though these experimental
results were not satisfying, it indicates that GO was poten-
tially useful for future nonvolatile memory applications. One
of the most important works on this material was issued in
2010 by Jeong et al. [39] at KAIST (Korea Advanced Institute
of Science and Technology, South Korea). They demonstrated
the nonvolatile effect on the resistance of a 70 nm layer thick
GO IN, a junction composed of Al/GO/Al (see Figure 18.7).
One of the major results of this chapter is that it has
explored the performances of these kinds of layers on flexible
substrates. The researchers from KAIST demonstrated that
using GO layers they were able to achieve flexible nonvola-
tile resistive memories with impressive performances under
traction and compression (they kept three orders between on
[LRS] and off [HRS] levels).
After writing After erasing
Resistive Nonvolatile Memories Based on Graphene-Related Materials 273

Read Write Erase

(a) 10–4
On

10–6

Current (A)
10–8

10–10 0–10 V (first sweep)

Off 0–10 V (second sweep)
0–10–0 V (third sweep)
10–12

10–14
0 2 4 6 8 10
Voltage (V)

(b) 10–4 Write: 6 V, 1 ms

X-ray irradiation
Erase: 8 V, 1 ms Air exposure, 24 h
10–5
Current at 1 V (A)

10–6
10–7
Day 2 Day 4 Day 6 Day 8 Day 10 Day 12 Day 14
10–8 Day 1 Day 3 Day 5 Day 7 Day 9 Day 11 Day 13 Day 15

10–9
10–10
10–11
10–12
0 20 40 60 80 100 120 140 160
Reads

FIGURE 18.6  (a) The logarithmic I–V behavior of a G–SiO2 nanocable; the “write” or “erase” regions can be achieved through a voltage
pulse in the noted regions. After writing or erasing, the high- or low-conductivity state of the system is recorded in the “read.” (b) Data reten-
tion by two other G–SiO2 nanocable devices. (Adapted from Li Y., Sinitskii A., Tour J. M. 2008. Nat. Mater., 7, 966.)

Concerning the physics explanation of the phenomenon, This drastically reduced the device lifetime (only 100
Hong et  al. [41,42] tried to deeply understand the mecha- cycles) because of the formation of a definitive conductive
nism of switching of this kind of devices. Hong et al. under- path between the two electrodes. These results have been
lined that these structures had performances dependent pointed out by x-ray photoelectron spectroscopy (XPS)
on the origin of the top contacts. For example, in the case measurements that pointed out the permanent presence of
of Au-based top electrodes, there was no oxygen migra- Al near the bottom electrode as the main reason for failure.
tion as in the case of Al. The effect of bottom contacts Evaluating the effect of the migration of oxygen versus the
was also quite important. Indeed, if the roughness is too formation of Al-based filaments, Hong et al. stated that the
high, the GO layer had such cracks and rough surface that formation of conducting filaments was a local phenomenon
the top electrode material could easily penetrate and then and that the oxygen migration was the dominant mecha-
build filaments which hindered the switching operations. nism. Indeed, they discovered that the current leakage

OH
OH
O O OH
OH OH
OH
OH
OH OH O
OH O
O OH O
O O O
OH OH OH
OH OH
OH OH
O OH OH
O O O
O OH O
O OH
OH
OH OH OH
O
O

FIGURE 18.7  Typical structure of GO. (Adapted from He H. et al., 1998. Chem. Phys. Lett., 287, 53.)
274
between the bottom and lower electrodes was dependent on
the dimension of the cell. In fact, when the cells were larger,
the effect of the oxygen migration or reduction on conduc-
tion was enhanced, proportionally to the surface. To avoid
the failure mechanism linked to the formation of permanent
conductive filaments through the material cracks, one sug-
gestion is to exploit deposition techniques which allow a
more uniform distribution of the deposited material. One
technique is the deposition by spray coating (heating) the
substrate to avoid the so-called “coffee-ring effect” [43,44],
which is responsible for the nonuniformity of the deposi-
tion. This deposition helps to preventing the formation of
cracks linked to the roughness in the GO layers.
Finally, concerning GO layers, Panin et  al. [45] used a
different approach. Indeed, they fabricated planar devices
depositing flakes of GO using the spray coating technique on
patterned substrates. The GO flakes had dimensions of sev-
eral tens of nanometers. The distance of the prepatterned elec-
trodes were around 20 µm. Panin and coworkers observed,
after applying a forming voltage of 5 V, a sharp unipolar resis-
tive switching. The on/off ratio was around 103 as in the other
studies (see Figure 18.8). These measurements were carried
out at room temperature. The local changes of resistance in
the layer near the Al/GO interface under bias voltage as a
result of sp3 to sp2 structure reconstructions are assumed to be
responsible for the observed resistive switching. The mecha-
nism of the resistive switching in the structure is supposed to
be related to the electrodiffusion of oxygen and the formation
of sp2 and graphene clusters in the sp3- insulating GO layer
formed near the electrode by a preforming process.
Another important study was carried out by Vasu et al. at
the University of Bangalore (India) in 2011 [45]. They reported
(a)
Al electrode Graphene oxide
Flexible plastic substrate
(b)
FIGURE 18.8  Physical phenomenon at the base of the forma-
tion of nonvolatile resistive memories through GO layers. (a) A
schematic illustration of a GO based flexible crossbar memory
device. (b) Real crossbar memory devices. (Reprinted with permis-
sion from Jeong H. Y. et al. Graphene oxide thin films for flexible
nonvolatile memory. Nano Lett., 10, 4381–4386. Copyright 2010
American Chemical Society; http://spectrum.ieee.org/semicon-
ductors/nanotechnology/flexible-graphene-memristors, American
Chemical Society.)
Graphene Science Handbook
a very simple unipolar resistive switching device using ultra-
thin (~20 nm) films of R-GO with on/off ratios reaching five
orders of magnitude. The thin films were formed at room
temperature simply by drop-casting R-GO from suspension
on indium tin oxide glass electrode, followed by aluminum
or gold deposition (no difference was pointed out after the
measurements). A very interesting result was also the switch-
ing time of 10 µs. In this case, the formation of nanofilaments
of carbon atoms was evoked as the main physical working
principle. Finally, we evoke the approach of Sinitski and Tour
[24], where in parallel to planar graphene junctions, as men-
tion previously, they fabricated a sort of vertical graphitic
devices with a high on/off ratio (see Figure 18.9). These were
obtained by depositing carbon inside silica and contacting
the bottom and top side (see Figure 18.10). This approach is
very interesting considering the very limited dimension of
the device.
The main results present in the literature obtained using
the targeted materials are summarized in Table 18.1.
18.3 CONSIDERATION ON THE
SWITCHING MECHANISM
We will discuss about the switching mechanism in the gra-
phitic layer, GO and R-GO. There are two things which
play an important role in the switching mechanism. First
is an insulating layer. In this case, we are using a graphitic
layer, GO and R-GO. The insulation layer ensures the transi-
tion mobile species. For oxygen-containing compounds, the
oxygen anions are the mobile species [3]. It means that GO
and R-GO have this manner of transition. Hence, an oxygen
motion tends to change a valence of the GO/R-GO as a result
of changes in resistance. Moreover, different defects take part
in resistance switching because they are able to change the
electronic transport preferably (willingly) than the electronic
structure of insulating materials.
The second is electrode materials. The electrodes have a
direct relation to the switching mechanism. If we use electro-
chemically active metals in the capacity of one electrode and
for the opposite electrode, one will use an electrochemically
inert metallic material; generally, we will receive to create
the filament of an electrochemical active metal. In this case,
we can utilize electrolyte materials between two electrodes.
Using oxide materials increase the switching voltage from
below 0.3 V to above the operating voltage of complementary
metal oxide semiconductor (CMOS) devices [3].
Now we can imagine what is the switching mecha-
nism in the case of graphite, GO, and R-GO. If we use an
electrochemically active metal as the top electrode for Pt/
(GO or R-GO)/top electrode memory device, the switch-
ing mechanism will occur by forming the filaments on the
top electrode metal. The difference between GO and R-GO
consists in the switching parameters such as: switching volt-
age, switching time, resistive contrast on/off, etc. (see Table
18.1). This result was described by Zhuge et al. [46] although
they used Cu, Ag, and Ti. GO is a very good oxidizer; there-
fore, GO has a mobile oxygen ion O+2 which also plays an
Resistive Nonvolatile Memories Based on Graphene-Related Materials 275

(a) 1. E-beam lithography 4. Carbon deposition 6. E-beam lithography

2. Cr deposition 5. Cr etching 7. Pt deposition
3. RIE

Cr C Pt

SiO2 SiO2 SiO2

p++-Si p++-Si p++-Si

SiO2 Pt
Cr

C
100 nm 100 nm 100 nm

(b) (c) Write (7 V, 1 μs)

Erase (15 V, 1 μs)
10–4 10–3
On
10–6 Pt 10–5
I (A)

C I (A)
10–8 SiO2 10–7
~ ~

10–10 10–9
Off p++-Si
Cracks
10–12 10–11
0 5 10 15 20 0 50 100 150 200
V (V) Operations

FIGURE 18.9  Fabrication and electrical properties of the vertical graphitic devices. (a) Top: process flow for obtaining carbon films
within oxide holes that ultimately have an Si bottom contact and a Pt top contact (see text for details), bottom: corresponding SEM images
at  each step. (b) I/V behavior whereas the inset shows the presumed crack within the filled or partially carbon-filled (as shown) hole
that is generated upon voltage sweeping. (c) Cyclic memory operations of the vertical device writing at 7 V and erasing at 15 V for 1 s
each. (Reprinted with permission from Sinitskii A., Tour J. M. Lithographic graphitic memories, ACS Nano, 3 (9), 2760. Copyright 2009
American Chemical Society.)

important role in the switching process. The conductivity

1E-9
process occurs by the participation of electrons on the Π−Π*
orbital, which is also responsible of optical absorption. The
1E-10 sheet of graphene with sp2 hybridization has zero bandgap
but after joining epoxide, hydroxyl, and carboxyl groups,
hybridization change to sp3, which has a bandgap of some
Current (A)

1E-11 size. It means that the GO layer has two types of hybridiza-
tion and bandgap depending on the type of joining groups
and their concentration. Under an applied electric field, this
1E-12 concentration is able to change the size of the bandgap. In the
case of GO, the sp2/sp3 relation will change under an applied
electric field because the oxygen ions are very mobile. In
1E-13
the case of Pt/(GO or R-GO)/Pt memory device, the switch-
ing mechanism will be passed by the changing sp2/sp3 rela-
–1.0 –0.5 0.0 0.5 1.0 tion. After applied positive voltage bias on the top electrode,
Voltage (V) the oxygen inside the GO layer is removed which lead to
increasing sp2/sp3 relation (on state/low resistance and state/
FIGURE 18.10  Resistive switching of the Al/GO/Al structure pre- high conductance state). When we applied the negative volt-
formed at 5 V. (Adapted from Vasu K. S., Sampath S., Sood, A. K. age bias, oxygen diffuses back to the GO layer which leads
2011. Solid State Commun., 151(16), 1084–1087.) to decreasing sp2/sp3 relation (off state).
276 Graphene Science Handbook

TABLE 18.1
Main Results on Nonvolatile Memories Built with Graphene, GO, and R-GO
Material and On/Off Switching Energy Consumption
Source Configuration Max Time Cyclability Retention Time Character to Write (J)
[Li08] Graphitic layers on 107 1 ​µs At less 1000 with no 1 day at less (15 days of Unipolar ~4 × 10−15
nanowire (planar) variation consecutive switching)
[Stadley08] Graphene (planar) 102 100 ms 105 without visible To be performed on more Unipolar Not clear
changes in signals than 24 hours
[Sinitski09] Graphene (planar) 107 1 µs At less 22000 with Not specified, even if the Unipolar ~8 × 10−17
(tested limit) no variation device is defined very stable
Carbon (vertical) 106 1 ​µs At less than 200 Not specified, even if the Unipolar ~7 × 10−17
(tested limit) device is defined very stable
[He09] GO (vertical) 20 No data At less than 100 104 s Bipolar No switching time
[Jeong10] GO (vertical) 103 No data At less than 100 105 s Bipolar No switching time
[Hong11] GO (vertical) 103 No data 100 and failure Not specified, even if the Bipolar No switching time
device is defined very stable
[Panin11] GO (planar) 103 No data No data No data Bipolar and No switching time
unipolar
[Vasu11] RGO (vertical) 105 10 µs Few hundreds Not specified, even if the Unipolar ~10−13
device is defined very stable

Note: We have not found any results concerning nanodiamonds.

18.4 CONCLUSIONS AND POTENTIAL
APPLICATIONS
In conclusion, although a better understanding of the mecha-
nisms ruling the resistive nonvolatile memory of graphene-
related materials, as well as for the other materials would
be extremely helpful in order to optimize the device per-
formances, the highly interesting memory properties of the
planar and vertical junctions based on graphitic materials are
evident and promising. The stability (also in temperature),
resilience, nonvolatility, and on/off ratio that in certain cases
can attain 107 or a switching time of 1 µs (competitive with
flash-type memories), potential switching voltages of 3–4 V,
combined with predictable fabrication-controlled I–V behav-
ior, simple two-terminal geometry (no need for a gate and so
dramatically reducing circuitry), and access to mass fabrica-
tion for the two approaches make them extremely attractive
structures for nonvolatile memories.
Indeed, thanks to thin-film technologies, electronic func-
tionality can be foreseen in very large quantity and at very low
cost on substrates such as plastic and paper. As outlined by
Heremans et al. [47], items, where today’s integration of sili-
con chips is not economical, such as toys, cards, labels, badges,
value paper, and medical disposable could be imagined to be
equipped with electronics and memories. Additional function-
ality is also an attractive feature of carbon-based memories.
For example, by using these kinds of materials, we open up
the route for memories on flexible substrates, a key building
block to enable the success of flexible electronics. Carbon-
based resistive memories should also offer the capability for
multilevel storage and “memristive-like” behavior, as seen in
other resistive memory materials. Multilevel storage allows
for the storage of more than one bit per cell, thereby increas-
ing data storage densities, whereas memristive-like behavior
can be exploited to provide a remarkable range of signal pro-
cessing/computing-type operations, including implementing
logic, providing synaptic and neuron-like “mimics,” [48] and
performing, in a very efficient way, analogue signal process-
ing functions (such as multiply–accumulate operations).
Another huge potential market is the RFID (radio fre-
quency identification device) applications. Within the scope
of low-cost RFID, a key component is the memory circuit
responsible for the unique identity of each individual tag.
An innovative alternative pathway to reduce RFID costs is
to eliminate the silicon substrate completely, and produce
RFID on the same flexible plastic substrate as the antenna.
If the antenna and chip are built on the same low-cost sub-
strate, attachment costs are removed. Cheap substrates also
allow large antennas to be employed, enabling lower frequen-
cies and increasing RFID penetration through metals and
liquids. The most ambitious approach for producing low-cost
item-level RFID is fully printed thin-film electronics (organic
and potentially graphitic-based materials). As opposed to sili-
con processing, the process for making all-printed circuits is
fully additive. That is, lithographic patterning steps and film
etching costs are directly removed from production costs.
Moreover, if all layers of the circuit are printed, vacuum depo-
sition processes can also be eliminated, further reducing the
costs. This is an advantage of materials such as GO or R-GO
that can be processed in ambient conditions (the deposition of
GO and R-GO using the spray-gun machine is performed at
ambient conditions). These materials could really impact the
Resistive Nonvolatile Memories Based on Graphene-Related Materials
market, not only proposing low-cost alternatives to existing
technologies but also opening the horizon toward new kinds
of concepts for devices and applications and thereby changing
our everyday life. Indeed, other promising new applications
range from smart food packaging to wearable health moni-
tors. All these applications require programmable nonvola-
tile memory, and the more complex the application, the more
memory it needs. However, flexible memory development had
not kept pace with other areas of flexible electronics, limiting
up-to-now market opportunities.
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 19 Applications of Graphene-Based
Materials in Electronic Devices
Gaurav Gupta, Minggang Zeng, Argo Nurbawono,
Wen Huang, and Gengchiau Liang

CONTENTS
Abstract...................................................................................................................................................................................... 279
19.1 Introduction...................................................................................................................................................................... 279
19.2 Graphene and GNRs......................................................................................................................................................... 280
19.3 Graphene Devices............................................................................................................................................................. 281
19.3.1 Electro-Optic Devices.......................................................................................................................................... 281
19.3.2 Radio-Frequency Transistors................................................................................................................................ 283
19.3.3 Thermal Transport Device.................................................................................................................................... 284
19.4 GNR Devices.................................................................................................................................................................... 284
19.4.1 Metal–Oxide–Semiconductor Field-Effect Transistor......................................................................................... 284
19.4.2 Tunneling Transistors........................................................................................................................................... 285
19.4.3 Resonant Tunneling Devices................................................................................................................................ 287
19.4.4 Interconnects......................................................................................................................................................... 288
19.5 Spintronic Devices............................................................................................................................................................ 288
19.5.1 Magnetoresistance Device.................................................................................................................................... 289
19.5.2 Spin Diode............................................................................................................................................................ 289
19.5.3 Spin-Logic Device................................................................................................................................................ 290
19.5.4 Spin Transistor...................................................................................................................................................... 290
19.5.5 Spin Caloritronic Device...................................................................................................................................... 292
19.6 Recent Commercial Developments.................................................................................................................................. 293
19.7 Conclusion........................................................................................................................................................................ 293
References.................................................................................................................................................................................. 293

ABSTRACT
Graphene is a forerunner in research on two-dimensional
materials and their applications. The large mean-free path,
excellent thermal conductance, high mobility, and gapless
Dirac bands in graphene mark the unique opportunities and
challenges for its adaption for electronic devices. This chap-
ter reviews the theoretical and experimental progress to date
in deploying graphene and its variants in pure electronic and
spin-hybrid devices. For digital applications, the switching
transistors based on field-effect, electro-optics, and tunneling
have been considered. The radio-frequency operation of gra-
phene field-effect transistors (FETs) has been appraised for
analog applications. The thermal management and suitabil-
ity for interconnect in integrated circuits has also been dis-
cussed. The magnetoresistive devices and the spin analog of
traditional electronic devices such as diodes, bipolar junction
transistors, FETs, and digital logic have been discussed in this
chapter for spintronic applications. The electrical and spin-
transport driven by thermal nonequilibrium in the absence
of an electronic bias across the channel is another important
emerging field that has been reviewed in this chapter.
19.1 INTRODUCTION
Although the bandstructure of graphene, a perfect two-
dimensional (2D) sheet with carbon atoms arranged in a
honeycomb crystal lattice, had been predicted in 1947 [1], it
has been very difficult to obtain such a thin one-atomic-layer
material and it was generally expected that monolayer gra-
phene was unstable in nature [2]. In 1991, a one-dimensional
(1D) carbon material called carbon nanotube (CNT) was dis-
covered [3]. CNT evinces metallic or semiconducting elec-
tronic bandstructure depending on the chirality of the tube,
and shares a lot of fundamental properties and applications
with graphene. The chirality of CNTs can be understood and
predicted from different orientations of a rolled graphene
sheet [4]. In 2004, finally, a thermodynamically stable single
layer of graphene was successfully synthesized by the physi-
cal exfoliation method [5] and an ambipolar transport was
demonstrated to verify the Dirac bandstructure. Subsequent
experiments on graphene nanoribbons (GNRs) also veri-
fied the chirality-dependent metallic and semiconducting
characteristics analogous to CNT. Graphene, since then, has
attracted the attention of researchers and has become the star

279
280
material in the fields of physics, chemistry, bioscience, and
engineering over the last decade.
The carbon atoms in graphene form in-plane sp2-hybrid-
ized σ-bonds and out-of-plane π-bonds at each site. The for-
mer provides graphene a robust lattice resulting in high stress
tolerance, and the latter offers graphene a unique electronic
bandstructure with a linear dispersion at the Dirac points at
the edge of first Brillouin zone (K points in the reciprocal
lattice of graphene). Benefiting from the Dirac dispersion
relation, a lot of interesting properties of graphene have been
proposed and demonstrated. The Dirac fermions are massless
and have the ability to travel at very high speed (~106 m s−1
[2]). The experimentally reported values of mobility have
exceeded 200,000 cm2 V−1 s−1 [6,7] and 35,000 cm2 V−1 s−1 [8]
for suspended and chemical vapor deposited (CVD) grown
(on born-nitride substrate) graphene, respectively. For hexag-
onal-boron-nitride (hBN) heterostructure with graphene [9],
electron mobility upto 100,000 cm2 V−1 s−1 at room tempera-
ture (T ), and 500,000 cm2 V−1 s−1 at low T have been reported
recently. Furthermore, other important features such as quan-
tum electrodynamics effects, the anomalous integer quantum
Hall effect [10,11], Klein paradox [12], electro-optical effects
[13], and extremely high thermal conductivity [14] have been
reported theoretically and experimentally. Therefore, this
chapter will focus on graphene’s possible applications in elec-
tronic devices such as RF transistors chip-interconnects and
others based on electro-optical effects. Furthermore, due to
the possibility to fabricate GNRs from top-down or bottom-
up approaches to create a band gap for the graphene-based
material by quantum confinement effect [15–17] and some
unique behaviors with spin polarizations under the external
magnetic [18,19] and electric field [20], we summarize some
research studies on metal–oxide–semiconductor field-effect
transistors (MOSFETs) [17,21,22], tunneling field-effect tran-
sistors (FETs) [23–25], resonant-tunneling diodes (RTDs)
[26], and spintronic devices based on GNRs [27–29]. For the
fundamentals of graphene and GNRs, readers are encouraged
to peruse further discussions in this book series, Volume 2,
Chapter 26. Finally, Section 19.6 summarizes some recent
developments from the commercial perspective.
19.2  GRAPHENE AND GNRs
From the application perspective, fabrication issues are the
most important aspects of graphene devices since experi-
mental measurements to date show strong sample-dependent
performances. The highest quality of graphene that has been
manufactured so far relies on the mechanical exfoliation of
graphite [5]. This technique serves best for laboratory and
experimental purposes which demand the highest quality
and reasonably large (micron size) graphene flakes. High-
quality transport measurements with the highest mobility are
mostly exhibited by mechanically exfoliated graphene, being
suspended or deposited on a suitable substrate like boron
nitride [30]. There are also other methods to produce reason-
ably high-quality graphene by unzipping single-walled car-
bon nanotubes (SWCNTs) [31,32]. This method can achieve
Graphene Science Handbook
suspensions with well-defined distributions of graphene plate-
lets and allow control over chemical functionalization with
good quality of the edges. Chemical exfoliations of graphite
with organic solvents have also been used and can produce
high-quality samples at even cheaper price than unzipping
SWCNTs [33]. Much larger graphene films of square meter
size have also been fabricated using a so-called roll-to-roll
technique by Bae et al. [34] in collaboration with Samsung.
The films have been transferred onto 200 mm Si wafers suit-
able for direct industrial production. Despite more defects
found on these large films and some inclusions of thicker
layers, they can already be used in transparent conductive
coating applications such as touch screen devices. A review
on various fabrication methods and their figure of merits has
also recently been discussed by Novoselov et al. [35] (also see
Table 19.1).
As mentioned in the introduction, the most recent cited
[9] mobility of graphene is over 200,000 cm2 V−1 s−1, which
is close to the theoretical predictions. This ultrahigh mobil-
ity of Dirac particles was measured on large-area graphene
samples fabricated with mechanical exfoliations, and they do
not have a band gap. A band gap is, however, indispensable
for practical devices in order to have an off-state. In practice,
moreover, instead of a large-area graphene flake, often a high-
quality graphene nanoribbon (GNR) is more desirable because
they can be used as transistors or p–n junction devices. The
required band gap also can be introduced easily on GNRs
simply by transverse confinements. The tight-binding model
of graphene predicts both armchair graphene nanoribbons
(AGNRs) and zigzag graphene nanoribbons (ZGNRs) to have
a band gap that is approximately inversely proportional to the
width of the nanoribbon. As we explained in Chapter 26 of
Volume 2 in this book series, AGNRs are theoretically semi-
conducting and their band gap vary with the width in three
distinct families. On the other hand, ZGNRs are theoreti-
cally always metallic with ferromagnetic edge states point-
ing in opposite spins. However, these preliminary theoretical
TABLE 19.1
Summary of GNR Fabrication Techniques
GNR Fabrication
Techniques Main Characteristics
Mechanical exfoliation High mobility, small crystalline flakes (several
of graphite microns), suitable for lab purposes
Chemical exfoliation Lower mobility due to introduction of chemical
of graphite complex and smaller crystalline flakes (few
microns), suitable for labs. Overall sample size
can be much larger than mechanical exfoliation
techniques
Thermal epitaxial Much lower mobility due to more defects and
growths from SiC smaller crystal sizes. It may be suitable for
applications where SiC semiconductor
substrates are required
Roll to roll technique Low mobility and higher defects concentrations.
with chemical vapor Suitable for large-scale industrial fabrications of
deposition transparent conducting surfaces
Applications of Graphene-Based Materials in Electronic Devices
models exclude disorders which may change the properties
significantly. The opening of a band gap in nanoribbons has
been verified experimentally for widths down to about 1 nm
[36,37], and they show band gaps more than 0.2 eV for widths
<20 nm. Typical GNRs have edges with defects and their
widths vary along their lengths. These disorders often smear
out any difference in the band gap of AGNRs and ZGNRs
[38]. Larger band gaps in GNRs are more desirable for practi-
cal devices; however, this at the same time makes the valence
and conduction bands become more parabolic around the
Dirac point, and increases the effective mass of the charge
carriers. This in turn decreases the mobility of the charge car-
rier in graphene [19].
The wisdom from conventional semiconductor theory dic-
tates that the mobility decreases as the band gap increases,
and a similar fate applies to GNRs [39,40]. This implies that
the mobility of electrons in GNRs with a band gap compa-
rable to silicon devices (1.1 eV) is expected to be lower than
bulk silicon and not necessarily higher than silicon chan-
nels in conventional MOSFETs. The actual mobilities mea-
sured in the different experiments show <200 cm2 V−1 s−1 for
nanoribbon widths between 1 and 10 nm [37,41] and around
1500 cm2 V−1 s−1 for nanoribbons with 14 nm width [42], and
these mainly arise from edge disorders and defects. Therefore,
in order for graphene to be more superior to the silicon coun-
terparts, better fabrication technologies are required to sup-
press disorder and defects during the fabrication process. The
tendency for smaller band gap in GNRs also reduces the cur-
rent on–off ratios required for the efficient operation of FETs.
Despite encouraging progress in graphene transistors [43],
most graphene transistors still show some subtle problems
such as high off-state currents and peculiar current-saturation
behaviors at high frequency. It is tempting to make narrower
GNRs to improve the off-state current but this makes edge
disorders become dominant and deteriorate the mobility even
further.
High-speed transistors require shorter gates and fast car-
riers in the device channels, but making shorter channels in
typical MOSFET will make them suffer from short channel
effects arising from proximity electrostatics such as drain-
induced energy barrier lowering, and deteriorating satura-
tion currents [44]. To compensate for these, a thinner channel
will reduce the short channel effects dramatically, and since
reducing the conventional MOSFET to one-atom thick will
never be possible, graphene is therefore promising in this
respect as suggested by Schwierz [43]. This should be taken
as a more important incentive for using graphene instead of
silicon in future devices, rather than relying on graphene
mobility trade-off.
Theoretical models for charge transport in graphene often
rely on the low energy, low carrier density regime around
the Dirac point as explained previously in Chapter 21 of
Volume 2, and it is imperative to mention a few facts from
the literature on this important subject [45]. At low carrier
density (109 to 1012 cm−2), the transport in graphene is domi-
nated by disorder, and particularly long-range disorders on
larger flakes by charge impurities that break up the carriers
281
into electron–hole puddles. This often makes the observed
minimum conductivity at the charge neutrality point become
larger than the theoretical prediction and strongly sam-
ple dependent. The puddles arise from incomplete charge
screening, and monolayer graphene is therefore a weakly
interacting system and the interaction gets stronger at higher
carrier density. Intrinsic ripples and substrate roughness also
contribute to the puddles. The puddles disappear when an
energy gap is introduced such as in nanoribbons. The first
direct observation of the puddles distribution in exfoliated
graphene close to the Dirac point was performed by Martin
et  al. [46] who used a scanning single-electron transistor
(SET). After analyzing the width in density of the incom-
pressible bands in the quantum Hall regime, Martin et  al.
extracted the amplitude of the density fluctuations which is
found to be 2.3 × 1011 cm−2. This is also consistent with typi-
cal mobility at high density. At high density, the graphene
conductivity is qualitatively similar to 2D semiconductors in
that it follows the power law in terms of density, σ ∝ n α and
α = 1 in the case of graphene (refer Chapter 26 of Volume 2
for details).
19.3  GRAPHENE DEVICES
19.3.1 Electro-Optic Devices
The lack of band gap in graphene has restricted its pros-
pects for replacing [43] silicon in MOSFETs despite the high
mobility of electrons in the former [2]. Without a band gap,
a MOSFET cannot be switched off which results in a poor
current switching ratio (on current to off current, i.e., Ion /Ioff).
Although, GNR FETs with sub-10 nm width [37,41] have
exhibited a switching ratio >106, the mobility has been seri-
ously compromised. The reliable fabrication of such narrow
GNRs is also a challenge. The other schemes to induce the
band gap such as strained GNR [47] and bilayer graphene
[48] have also indicated limited suitability for graphene FETs
(GFETs). Therefore, unconventional phenomenon such as
negative refraction [49] and pseudospins [50] have been sug-
gested to achieve the required switching.
As an optical analog of the Veselago lens, a p–n junction
in graphene exhibits negative refraction that focuses [13] the
obliquely incident electron waves. The normally incident
wave perfectly transmits (reflects) through the junction for
monolayer (bilayer) graphene [12], a phenomenon known as
Klein tunneling. Graphene thus enables devices with a unique
control over electron waves, such as electromagnetic waves
harnessed in photonic systems. The electrons, however, have
smaller de Broglie wavelength than photons, a property that
allows for higher resolution in an electron microscope, and
since device size is limited by the operating wavelength,
graphene electro-optic devices can be much smaller than their
optoelectronic counterparts. The mean-free path (mfp) longer
than the targeted channel lengths of future computing devices
and high mobility of electrons complemented with the elec-
tro-optic effect offers an optimized solution for high-speed
low-power electronic components. The electro-optic effect
282
TABLE 19.2
Summary of Graphene Electro-Optic Devices
Device Uniqueness
Electronic fiber Gate-controlled guided propagation
of electron wave
Transistors Large switching ratio, point source,
physical barrier in channel
Tilted p–n Tilted gate, large switching ratio
junction switch
in graphene has hitherto engendered following three types of
device investigations (see Table 19.2 for summary):
1.
Electronic fiber: A combination of back-gate, under
the entire graphene channel, and a centrally overlaid
top-gate along the direction of transport (length) can
be used to spatially modulate the doping along the
width in a graphene channel. The positive (negative)
and negative (positive) gate voltage on back-gate
and top-gate, respectively, forms an n–p–n (p–n–p)
junction (see Figure 1 of Reference 51). For such a
device, it has been shown [51,52] that electron waves
undergo angle selective transmission [53] and total
internal reflection at the p–n junction, to be guided
through the central region of graphene channel-like
lasers propagate through an optical fiber. The gate
voltages control the Fermi wavevector of the propa-
gating electrons and hence the refractive index (η)
(ratio of Fermi wavevector on two sides of the junc-
tion) which in turn determines the critical angle
(θC = arcsin(η)). For a large critical angle, substan-
tial leakage to adjacent regions may occur and lower
the guiding efficiency of the fiber. For an efficient
guiding of electron wave through the central region,
besides an optimal control of gate voltages, per-
pendicular magnetic fields can also be applied to
increase the incidence angle [54] and thus reduce the
transmission across the n–p interface.
(a) Upper barrier angle Lower barrier angle
(UBA) (LBA)
Source
(VS)
Gate voltage (VG1) Insulating barrier Gate voltage (VG2)
For symmetrical barrier: UBA = LBA = θB
FIGURE 19.1  Electro-optics-based graphene switching device as proposed in (a) Reference 49 and (b) Reference 58. (a) Point source
injects electrons over all angular modes (circular wave front) into the channel. At the electronic junction formed between two gates, only
the electron waves with incidence angle between barrier angle and critical angle are allowed to transgress the junction and are subsequently
collected at the extended drain. (b) Planar wave front of electron waves injected from source suffer refraction at the tilted junction due to
electrostatically controlled refractive index via VG1 and VG2.
Graphene Science Handbook
2.
Transistors with high Ion /Ioff : A dual-gate graphene
transistor with a point source and extended drain
has been advanced in References 49 and 55, as
References illustrated in Figure 19.1a. With electro-optics
[51–54]
as an operating principle, the design suggests an
Ion /Ioff ratio of five orders and subthreshold slope
[49,55,56] (SS) of less than (K BT/q) loge 10. A physical insu-
lating barrier has been advocated in the design to
[56–58] suppress the Klein tunneling and adjacent high-
transmission transverse modes that would have
otherwise resulted in considerable leakage cur-
rent. The gate voltages modulate the angular band-
width over which the electrons can propagate from
graphene segment under VG1 to VG2, by inducing
a virtual energy band gap expressed by Equation
19.1. The performance of this design is, however,
comparable [56] to a graphene quantum reflective
switch [57] which may be easier to fabricate.
2 sin θ B
EG = q(VG1 − VG 2 ) (19.1)
cos2 θ B
3.
Tilted p–n junction switches: Low-power logic
devices have been proposed [57,58] to exploit the
electro-optic effect in graphene. A tilted top-gate
(see Figure 19.1b) over the back-gated graphene
serves a dual purpose. Besides regulating the car-
rier doping in the graphene segment under it, the
inclination angle δ at the junction administers a
virtual energy band gap [56] like barrier angle θB
in Equation 19.1. The two gate voltages coordi-
nate the refractive index (η) at the tilted junction
and hence the critical angle (θC). The planar wave
front of electron waves from the source observes
an incidence angle of θi = π/2 − δ at the junction,
and can suffer total internal reflection if θi exceeds
θC. Switching an appropriate VG1 can therefore
transmit or reflect the electron waves to switch the
transistor.
(b) Gate voltage (VG1)
Source Drain
Drain (VS) Gate inclination (VD)
(VD) (δ)
Gate voltage (VG2)
Applications of Graphene-Based Materials in Electronic Devices 283

19.3.2 Radio-Frequency Transistors exfoliated [67], 300 GHz (350 GHz) on 40 nm long for CVD
(epitaxial) [63], and 50 GHz extrinsic f T on 170 nm long for
Only the large signal operation of a transistor entails a CVD [68] grown graphene, it is important to understand the
switch-off state. For a small signal operation, a transistor is factors that limit the performance. Specifically, f T = gm /2πCox,
biased at the quiescent point, over which a small alternat-
fmax = fT / (2 gDS ( RGate + Ri + RS ) + 2πfT CGD RGate ) [60], and
ing component (ac) is superimposed. The high mobility and
Av = gm /(gDS + 1/Rload), where gm is the transconductance, Cox
saturation velocity [59] of graphene are congruous for such
the gate dielectric capacitance, gDS the differential source/
a small signal operation required for radio frequency (RF)
drain conductance, RS the source resistance, Ri the channel-
and microwave (μW) applications [43]. The recent advances
sided charging resistance of the gate/source capacitance, CGD
in the fabrication of small channel length (Lg) RF GFETs have
the gate-to-drain capacitance, RGate the gate resistance, and
indeed demonstrated intrinsic cut-off frequency (f T) (>1 THz)
Rload the load impedance during measurement. Particularly
[60,61] approaching that of mature III–V semiconductors.
note that gm is proportional to mobility and inversely propor-
Simulations [62] have furthermore shown that down scaling
tional (roughly independent) to length in diffusive (ballistic)
below the state-of-the-art 40 nm Lg GFET [63] to sub-10 nm
regime, Cox is directly proportional to length, which gives f T
regime [64] can drive f T to few tens of THz. Moreover, in con-
a direct linear dependence on mobility and inverse second-
trast to other semiconductors, the RF performance in GFETs
order (first-order) dependence on length, indicating that high-
has a larger thermal window for operation as they do not suf-
mobility small channel length GFETs should have high f T.
fer from carrier freeze-out [65] at cryogenic temperatures.
The mobility of graphene can significantly degrade due to
Therefore, tapping the immense potential of graphene RF
the underlying substrate [69] and the top dielectric because of
technology and its challenges is currently a subject of inten-
their phonon modes and substrate-induced doping [60]. The
sive research.
acoustic phonons in graphene itself have relatively negligible
The most commonly used figure-of-merit for an RF tran-
effect on gm [70]. Therefore, RF performance has improved on
sistor is high cut-off frequency f T, at which short-circuit cur-
migrating from silicon dioxide (SiO2) [66] to diamond-like-
rent gain is unity, and high maximum-oscillation frequency
carbon (DLC) [63] substrate and boron-nitride (BN) dielectric
fmax at which unilateral power gain (U) for an impedance
[71]. Furthermore, the lack of band gap in graphene coupled
matched system is one, both of which are extracted by de-
with the substrate effect makes it difficult to achieve current
embedding S-parameters. Short-circuit output and good
saturation [43] and thus results in an unstable quiescent point
impedance matching, however, do not represent a real system,
and gm. Recent research has, however, demonstrated current
for which open-circuit voltage gain (Av) becomes a more prac-
saturation with a reasonable RF performance of GFET on a
tical criterion for comparing performance [63]. Experiments,
polyimide substrate [72]. A second level of f T degradation
mainly at IBM Thomas J. Watson Research Center (Yorktown
results from top-gate deposition-induced misalignment. It abets
Heights) [60] and Duan’s Group (Los Angeles) [61], have con-
parasitic-like large access resistance and overlap capacitance.
siderably improved these parameters for graphene RF tran-
Much improvement has now been achieved by using self-
sistors. To understand the unmet challenges and appreciate
aligned gate structures with nanowire gates or metal-T gates
the advancement (see Table 19.3) from the first demonstra-
[73,74] by shadow masking and the conventional complemen-
tion of 26 GHz intrinsic f T on mechanically exfoliated 150 nm
tary metal oxide semiconductor (CMOS) technique [75]. Next,
long graphene channel [66] to 1 THz on sub-60 nm long for
the metallic contacts that form source and drain terminal are
bottlenecks in achieving high fmax and Av. Charge carriers have
to tunnel through the electrostatic barrier created at the metal–
TABLE 19.3 graphene interface, due to the difference in work function (φ),
Deterrents for Graphene RF Transistors and the p–n junction created between the graphene segments
Attained fT or under contacts and channel [60]. Use of palladium electrodes
Problem Solution fmax (GHz) that have lower φ mismatch and placing the back-gate under
Bottom substrate and top Transition from SiO2 fT: 300 (I) [63]; the entire device to first control the metal-induced doping in
dielectric substrate to DLC 44 (I) [71] (but the graphene under contacts and second to reduce the output
substrate and BN highest fmax/fT) conductance (gDS) has recently [76] improved both fmax and Av.
dielectric Experimental studies have not been limited to isolated gra-
Absence of current Polyimide substrate to fmax: 10 [72] phene RF transistors. Although yet only operating in 10 MHz
saturation implying achieve current to 10 GHz frequency range, integrated circuits with unique
unstable quiescent point saturation functionalities such as transceiver [77], ambipolar mixers
Gate misalignment- Self-aligned gates fT: 100–300 (I) [78,79], triple mode amplifiers [80], frequency multiplication
induced parasitic [73]; 23 (E) [74]
beyond the transit frequency range [81,82], and audio ampli-
Work-function difference Palladium contacts fmax: 30 [76]
fier [83] have been successfully demonstrated. The detailed
at contacts’ metal– with full back-gating
graphene interface
review of applications is, however, beyond the scope of the
current work. Operational frequency has mainly been limited
Note: I: intrinsic; E: extrinsic. due to nonoptimized parasitic and degradation due to integra-
tion of passive elements [60].
284
19.3.3 Thermal Transport Device
There is an increasing interest in the thermal properties of
graphene ignited by experiments revealing the superior ther-
mal conductivity of graphene. It has been demonstrated that
the thermal conductivity of the suspended single-layer gra-
phene is in the range of about 3000–5000 W m−1 K−1 [14,84],
which suggests its potential use as a future thermal manage-
ment material. Experiments have also shown the exception-
ally high thermal conductivities for few-layer graphene and
graphene flakes depending on the width and temperature
[85–87]. Despite the high thermal conductivity, investiga-
tions on transport properties of graphene high-field devices
have shown that the mobility and current situations are very
sensitive to the scattering of electrons by surface phonons of
the SiO2 substrate [88,89]. In addition, low thermal boundary
resistance at the interface of graphene and substrate necessi-
tates efficient heat dissipation for thermal interface material
applications. Hence, vertically stacked graphene in a three-
dimensional (3D) architecture is good to overcome the weak
van der Waals interactions in out-of-plane thermal coupling
owing to very high anisotropy of thermal properties of gra-
phene. Theoretical and experimental works have demonstrated
3D nanostructures such as nanoporous pillared graphene with
combined forms of CNTs and graphene sheets [90], graphene
foams with direct synthesis of 3D foam-like graphene macro-
structures [91], and 3D vertically aligned functionalized mul-
tilayer graphene architecture [92], which are beneficial for an
enhanced hydrogen storage, flexible conductors, and energy
management applications. Moreover, thermoelectric transport
measurements of graphene have shown thermoelectric power
of ~80 µV K−1 at room temperature and ~50 µV K−1 at low tem-
perature in high-mobility graphene samples [93,94]. However,
besides high electronic conductivity and moderate thermo-
electric power, the thermal conductivity must be suppressed to
achieve an efficient thermoelectric energy conversion device.
19.4  GNR DEVICES
19.4.1 Metal–Oxide–Semiconductor
Field-Effect Transistor
Semiconductor transistors, especially MOSFETs, have
become the most successful electronic devices in the world.
There are billions of transistors in our routine devices used for
computing, communication, display, and data storage applica-
tions. To enhance their performance, the endeavor for higher
speed and larger transistor density, in the past few decades,
has successfully driven the miniaturization of silicon planar
MOSFETs. Continuing this scaling trend, however, silicon-
based MOSFETs will face its fundamental physical limita-
tion. Therefore, novel channel materials with high carrier
mobility are required to meet future generation technol-
ogy requirements as predicted by International Technology
Roadmap for Semiconductors (ITRS) [95]. As introduced
previously, graphene with extremely high mobility [9] is
expected to be the best candidate to close this technology gap.
Graphene Science Handbook
Unfortunately, the lack of a band gap in graphene restrains its
applicability to conventional MOSFETs, which rely on band
gap to switch-off the transistors to provide a large ratio of on
to off state currents. Therefore, the AGNR has been of great
interest as a potential candidate to overcome this problem
because of its intrinsic semiconducting property with a tun-
able energy band gap that depends on the ribbon width and
atomic configurations at its edges. Particularly, the AGNR is
theoretically expected to exhibit promising electronic proper-
ties and extremely high electron/hole mobility [39], similar to
the properties observed in CNTs. Furthermore, recent stud-
ies based on the semiclassical transport model coupled with
bandstructure of nanoribbons using a single pz -orbital tight-
binding method have shown that the upper-limit performance
of ballistic GNR-FETs is similar to CNT-FETs and should be
able to outperform silicon MOSFETs in terms of drive current
capabilities by over 100% [17].
In addition, more panoptic atomistic simulations based
on quantum transport theory, in terms of the nonequilibrium
Green’s function (NEGF) approach, self-consistently coupled
to a 3D Poisson’s solver for the treatment of electrostatics has
been implemented to investigate the current–voltage charac-
teristics of GNR MOSFETs and GNR Schottky barrier (SB)
FETs [21,22,96]. This approach can capture the tunneling
behavior and a realistic real-space potential profile which are
overlooked in the classical model. However, these play an
important role in the short channel effects of nano-scale FETs,
such as leakage current, caused by the direct tunneling from
the source to the drain, and drain-induced-barrier lowering
(DIBL). Based on simulation results [96], it has been found that
GNR MOSFETs with 1.5 nm width might have the potential to
outperform a double-gate 10-nm-scale Si MOSFETs in terms
of SS, DIBL, and on-current. However, tunneling processes
should bar the larger width GNRs from such applications
because tunneling will degrade the performance of the GNR
MOSFET-type device. It also indicates that graphene with an
infinite width is not suitable for digital MOSFET applications.
However, the high tunneling rate in GNR through the direct
band gap may find other potential applications such as GNR
MOSFETs operating in band-to-band tunneling (BTBT) mode
or tunneling FETs, which will be introduced in Section 19.4.2.
Another important aspect of the GNR FET device is that
for the SB contacts, the metal should be deposited in the source
and drain region, which might be challenging and expensive
from the fabrication and experimental point of view. On the
other hand, graphene/doped graphene can be treated as a metal
with high mobility. As a result, it is of great interest to make
use of the graphene sheet itself as the devices’ contacts to have
a full graphene device, and understand the dependence of the
device behavior of the GNR FETs on the contact types and
shapes of the graphene sheet [97]. As shown in Figure 19.2,
the effect of the following five different types of contacts has
been investigated: (a) the semi-infinite normal metal with con-
stant surface density of states in the energy region of interest
(L and W → ∞), (b) the semi-infinite graphene sheet contacts
(L and W → ∞), (c) the finite-size rectangular graphene type
of contacts, (d) the finite-size wedge-shaped contacts, and (e)
Applications of Graphene-Based Materials in Electronic Devices 285

(a) (d)
SiO2 tins
S D L
SiO2 tins
W
2D contact SB FET
(b)
∞ (e)
Source Drain L

∞ W

(c) (f )
W
∞

∞ L

FIGURE 19.2  (a) Schematic of the simulated dual-gate graphene nanoribbon SBFETs. The oxide thickness (tins) is 1 nm and the channel
length is 12.5 nm. (b–f) Top view of (a) for different contact shapes. (b) The source and drain parts are composed by a semi-infinite metal (L and
W→∞). (c) The source and drain parts are composed by a semi-infinite graphene (L and W→∞). (d) The source and drain parts are composed
by a finite rectangular shape graphene electrode. (e) The source and drain parts are wedge shaped graphene sheets with zigzag edges. These
contacts gradually decrease their width from infinite (far from the channel) to the size of the channel (at the contact points). (f) The GNR con-
tact with zigzag edges and same width as the channel. (Adapted from G.C. Liang et al., Nano Letters, vol. 8, no. 7, pp. 1819–1824, Jul, 2008.)

the 1D zigzag GNRs contacts. Note that the nanoribbons are
designated as zigzag or armchair by the shape of their edge; it
is in a sense opposite to the designation of CNTs. As shown in
Figure 19.3, it is observed that the intrinsic (undoped) semi-
infinite graphene contacts have poor performance, but the
doped (chemically or electrostatically) graphene can exhibit a
better performance in terms of Ion to Ioff ratio. Furthermore,
the finite-size wedge-shaped graphene contacts and the finite-
size rectangular-shaped graphene contacts show better Ion to
Ioff ratios compared to the two former cases. The best of these
different graphene contacts might be zigzag GNRs which not
only show promising Ion to Ioff ratios but also high Ion because
of their strong metallic nature. It has also been found that they
could be the candidates for interconnects [98] between the
metallic or graphene electrodes and the channel.
All of the results introduced so far have been based on
coherent transport. However, in realistic devices, scattering
mechanisms play an important role in the carrier transport
and normally reduce device performance. For example, the
experimental results suggested that at low VDS, Ion preserves
only about 15% of ballistic efficiency whereas at high VDS,
the ballistic efficiency of Ion can reach up to 40% [41]. This
interesting phenomenon can be attributed to mainly two scat-
tering mechanisms, phonon vibrations and edge roughness
(ER) (disorders). The former includes acoustic and optical
phonons that commonly exist at room temperature in most
materials. It has been understood that the acoustic phonon can
reduce current for long channels, though its effect is negligi-
ble in short-channel devices. For the optical phonon, its mfp is
around 10 nm, which although of the order of the device chan-
nel under study, has less significance on impact on the device
performance [99]. It is mainly the high optical phonon energy
around 160 meV that results in less probability of backscat-
tering in the device channel. Another important effect is ER
in GNRs, which has been identified as the most challeng-
ing work from the fabrication’s point of view due to the dif-
ficulty in making perfect edges, even though some groups
have claimed to fabricate smooth-edged GNRs. As has been
discussed in Chapter 26 of Volume 2, the electronic struc-
ture of a GNR is very sensitive to its width. Even for a very
small change, it can cause significant variation in the band
gap and its effective mass, which subsequently affects the car-
rier transport properties. Several studies have shown similar
results that the ER can degrade the device dramatically [100].
For example, an average leakage current for 2.2 nm wide
GNR SBFET increases by 2.7 times when the ER increases
from 5% to 10%, whereas for 1.4 nm width it increases by a
factor of 11.2. In addition, a small ER of 5% is tolerable for
all GNR SBFETs, with the average Ion /Ioff lowered from 4012
to 3075 for 1.4 nm width. However, a further increase in ER
to 20% degrades the performance significantly, dropping Ion /
Ioff to 273. Therefore, it becomes an important challenge to
maintain the reliability of GNR FETs in real applications, and
therefore requires more efforts to overcome this issue to real-
ize a more practical device in the future [101].
19.4.2 Tunneling Transistors
Although novel channel materials, such as III–V materials,
GNR, etc., might enhance device performance and keep the
device successfully scaling down in the near future, it increases
the power consumption in each chip. It has been predicted that
286
10–6
10–8
IDS (A)
10–10
10–12
0 0.2 0.4 0.6
VG (V)
10–6
10–8
IDS (A)
10–10
0 0.2 0.4 0.6
VG (V)
FIGURE 19.3  (a) Transfer characteristics of the armchair GNR
SBFET with widths of 1.4 nm (solid), 1.6 nm (dashed), 3 nm (dot-
dashed), and 4 nm (triangle) under VDS = 0.5 V. The contact in all
cases is a semi-infinite normal metal. The bandgaps for these dif-
ferent width armchair GNRs are around 0.66, 0.95, 0.5, and 0.26 eV
respectively. The 1.6 nm wide armchair GNR FET shows the best
Ion/Ioff ratio compared with the other three types because it has the
largest bandgap. (b) Transfer characteristics of the 1.6 nm wide GNR
SBFET with different types of graphene type of contacts: the semi-
infinite normal metal (dashed line), the semi-infinite graphene sheet
[solid line, intrinsic (undoped) and dot-dashed line, doped], finite size
rectangular shape graphene sheet (L = 3 nm, W = 5 nm as in Figure
19.2d; square markers), wedge shape graphene sheet (L = 3 nm, W =
5 nm as in Figure 19.2e, triangle markers), and zigzag GNR contacts
(L = 3 nm, W = 1.6 nm as in Figure 19.2f, diamond markers). The ON
(Imax) to OFF (Imin) ratio are 1.5×105, 4×103, 1×104, 3×104, 5×103, and
3×104 for the contact cases: normal metal, intrinsic graphene sheet,
doped graphene sheet, rectangle shape graphene sheet, the wedge
shape graphene sheet, and the 1D armchair GNR, respectively. VDS =
0.5 V is applied in the simulations. (Adapted from G.C. Liang et al.,
Nano Letters, vol. 8, no. 7, pp. 1819–1824, Jul, 2008.)
the power density in a high-end microprocessor can soon reach
the level of a nuclear reactor and even the level of the sun’s
surface in decades, a situation which is obviously untenable.
The reason is that the power density, due to dissipated heat in
chips, has been increasing exponentially with the increase in
the number of transistors per chip. Unfortunately, this prob-
lem may not be overcome with conventional CMOS technol-
ogy because power dissipation constitutes a fundamental limit
of the conventional operation principle of MOSFETs due to
its reliance on thermionic electron transport, that is, 60 mV/
decade of the SS at room temperature. This thermionic mecha-
nism limits the ability to down scale the operating bias, result-
ing in high power consumption in MOSFETs [102]. As a result,
novel device structures based on different device physics and
Graphene Science Handbook
MOS FET TFET
off-state off-state
N I N P I N
on-state on-state
Length Length
FIGURE 19.4  Schematics of operation principle of MOSFETs and
TFETs.
carrier transport mechanisms have been suggested to reduce
the bias and power consumption of electronic devices. Among
the different devices proposed, tunneling field-effect transistors
(TFETs) have attracted a lot of attention from the device engi-
neering community because of their simple operation principle
and a device structure which is similar to MOSFETs, the latter
reason being of greater interest for the semiconductor industry.
Unlike MOSFETs, the TFET is a three terminal p–i–n
device. As shown in Figure 19.4, the off-state current of
TFETs is regulated by the electron tunneling through the
source to the drain. Due to the long tunneling path, the current
is suppressed and should be very low. As a positive gate bias is
applied, the channel potential moves down until the conduc-
tion band edge of the channel and the top of the valence band
edge of the source align, when the current abruptly increases
due to the short tunneling path and a strong electrical field
between the tunneling junctions. It is identified as the on-state
current. Since this device is not relying on the thermionic
electrons to transport through the barrier, the operation bias
can be small, few hundred mV in principle, resulting in a sig-
nificant reduction in the power consumption of each device.
Although Si-based TFETs have been studied previously,
their on-state current is too small because of their heavy
effective mass and indirect band gap, which renders them
unsuitable for practical applications. A few other improved
structures have also been proposed, such as Ge TFETs, III–V
TFETs, and broken gap TFETs, to provide a higher on-state
current due to their smaller effective mass, direct band gap,
and a sharper electrical field between the channel and drain.
In addition to these materials, AGNR has also been consid-
ered a potential candidate for TFETs because of the smaller
effective mass of the carrier and the tunablity of the band gap
by controlling the GNR’s width. As a result, a heterojunction
can be fabricated using the same materials to avoid lattice
mismatch from different semiconductor materials.
The previous theoretical studies [25] have shown that GNR
TFETs can reach an on to off current ratio of more than 1010
with a gate voltage sweep of just 300 mV and the SS can be
<10 mV/decade. Furthermore, it is found that, in general,
AGNR tunneling FETs from the 3p + 1 family outperform
the other two groups (3p and 3p + 2), in terms of larger Ion
to Ioff ratio because of the smaller effective mass of electrons
in 3p + 1 AGNR. To optimize a TFET, the doping concentra-
tion at the source plays an important role. As it increases, Ion
Applications of Graphene-Based Materials in Electronic Devices
increases due to the higher electrical field and short channel
length; however, the subthreshold swing degrades because the
thermionic electrons increase resulting in the degradation of
the off-state current. Furthermore, compared to ITRS require-
ments, the intrinsic delay and power-delay product of the
GNR tunneling FETs shows very promising scaling behaviors
to meet future requirements [25].
Another promising property of GNRs is their tunable band
gap and a feasible geometry change from CNT to form a par-
tially unzipped CNT–GNR interface [103], interface strain-
engineering [104], and heterojunction [105], resulting from
different widths. Based on these fabrication technologies, there
have been several theoretical proposals of enhancing tunneling
current in TFETs. For example, it has been shown that using the
heterostructure to add a small Eg material in the channel near
the source and a large Eg material in the middle improves Ion
and reduces Ioff resulting in a larger Ion /Ioff [105]. Such a device
structure is also promising for device scaling. As the chan-
nel length scales down to 10 nm, the theoretical simulation
predicts Ion to reach 1.5 mA μm−1 and Ion /Ioff to four orders of
magnitude. However, the bigger challenge for devices is from
the fabrication perspective to devise perfect GNRs. The struc-
tural defects, vacancies, or ER always play an important role
in device performance. Especially for TFET, recent work [106]
on ER has reported that ER can create a defect state inside the
band gap in the channel to assist the tunneling, resulting in the
degradation of the Ion to Ioff ratio. However, recent fabrication
technology has also encouragingly reported promising prog-
ress in the high-precision dimensional control for graphene-
based materials with sub-10 nm GNR via chemical means and
of epitaxially grown smooth-edged graphene. Hopefully, this
problem can be overcome in the near future [41].
19.4.3 Resonant Tunneling Devices
Another interesting device operated in tunneling mode is a res-
onant tunneling diode (RTD), which is expected to have good
potential for low-power and high-speed applications [107].
Unlike a FET device, the RTD is a two-terminal device, and
its operation principle is based on the quantum states gener-
ated between two wells to provide resonant tunneling, and a
semiconductor source to prevent the electron transport as these
resonant states drop into the band gap region of the source. As
the bias is applied, electrons start tunneling through the two
barriers with the small tunneling probabilities, and then as the
quantum states formed by the two wells drops into the electron
sea of the source, the current increases abruptly because of
the high transmission rate contributed by the resonant states,
the so-called peak current (state). However, as the state keeps
dropping under the conduction band edge of the contacts, the
current drops since no electron in the band gap region of the
source can feed into the state according to coherent transport.
Therefore, the current only relies on the low tunneling prob-
ability and in principle, remains low, the so-called valley cur-
rent (state). As a result, a negative resistance or conductance
can be generated between the peak and valley states, which
provides two distinguishable states for circuit design.
287
∞ 5.1 nm 7.0 nm 5.1 nm ∞
(a)
1.4 nm 3.6 nm 2.8 nm
(b)
(c)
(d)
Energy (eV)
0.35 E
Ef
0.25
–2 0 2 4 6 8 10 12 14 16 18
X (nm)
FIGURE 19.5  Schematics of the simulated AGNR RTDs with dif-
ferent shapes, namely (a) H, (b) W, and (c) S shapes. Energy band
diagram for these differently shaped AGNR RTDs at equilibrium
is shown in (d), illustrating the DBQW structure for RTD operation.
(Adapted from H. Teong et al., Journal of Applied Physics, vol. 105,
no. 8, pp. 084317, Apr 15, 2009.)
Conventionally, RTDs consist of heterojunctions of dif-
ferent semiconductor materials such as the InGaAs/AlAs
double-barrier structure [108]. Unfortunately, phonon scatter-
ing, dislocations and mismatched lattice degrade the peak-to-
valley ratio (PVR), and hinder progress and development. On
the other hand, as suggested previously, the different widths
of GNRs are capable of effectuating different Eg that offers
the required double-barrier structures for RTDs from a single
material. Interestingly, as shown in Figure 19.5 [26], devices
of different shapes (H, S, and W shape) can also be made to
satisfy the same electronic requirement. A recent study based
on the nearest-neighbor-orbital tight-binding coupled with
quantum transport simulations show that all of these three
different-shaped RTDs exhibit negative differential resis-
tance (NDR) characteristics and similarly the peak state posi-
tion indicates that the robust mechanism of RTD operation
is mainly dependent on its double-barrier structure and to a
lesser extent on the geometrical shapes. However, the geomet-
rical shapes still play an important role on the magnitude of
the peak and the valley current. For example, it is found that
W-shaped AGNR RTD provides the largest Ipeak but H-shaped
AGNR RTD offered a higher PVR. The observations can be
attributed to interface scattering for different shapes. The W-
and S-shaped cases have the direct paths to allow an electron
to pass through, whereas electrons in the H shape face more
interface variation resulting in the suppression of the trans-
mission rate. Fortunately, it also assists to block the current in
the valley states, and therefore, increases the PVR.
However, akin to the MOSFETs and TFETs, ER signifi-
cantly impacts the performance of GNR RTDs. As reported
by a theoretical study [109], the ER will perturb the electronic
structures resulting in a nonuniform barrier higher than the
well and broadening of the resonant states. Furthermore, defect
288
states inside the wells are created. Both effects allow the tail of
the wave function of the electrons in the contact to penetrate
deeper into the quantum well region and increase the valley
current considerably, resulting in the degradation of the PVR.
19.4.4 Interconnects
The transistors have to be integrated into functional blocks
that further communicate with other such sections on an inte-
grated circuit. The data, clock, power, and ground signal are
routed among these through a wiring system or interconnects
of varying dimension, bandwidth, and current-carrying capa-
bility depending on the design. For smaller technology nodes
(beyond 16 nm), ITRS [110] expects carbon-based materials
such as CNT and GNR to be a replacement of traditional cop-
per interconnects because of latter’s high resistivity for small
wire widths, due to grain boundary scattering, and electromi-
gration effects. The fabrication ease of GNR gives it an edge
over CNT for deployment in devices. The strong sp2-hybridized
σ-bonds in GNR enable conduction of large current densities
(>109 A cm−2 [111]) without material breakdown. Additionally,
low in-plane dielectric constant (κ) [112], large thermal con-
ductivity [14], that pacifies electromigration, and large mfp
(~1 μm [113]), hence high momentum relaxation time, positions
GNR as a good interconnect material for high-frequency chips.
However, monolayer GNR interconnect [114] has low mode
density which makes it highly resistive, while interlayer cou-
pling in multilayer GNR (MLGNR) degrades electron mobility.
The intercalated zigzag-edged MLGNR (side contacts) of high
specularity (p ~ 1), that is, inducing approximately no momen-
tum change along the length of ribbon due to edge scattering,
of sufficient interlayer separation is thus considered an immi-
nent solution for power interconnects [115] and interconnects
that carry low [116] and high [117] frequency signals. Note that
subsequent discussion on GNR for interconnects refers to only
doped zigzag MLGNR unless specified otherwise.
A physics-based model of a GNR interconnect [118] is
illustrated in Figure 19.6. Using this model it has been shown
Rcontact RQ/2 dx RQ/2 Rcontact
RSC dx LM dx LK dx
CQ dx
CE dx
FIGURE 19.6  Transmission line equivalent circuit of GNR inter-
connects wire [116]. dx is small segment of wire, Rcontact the metal–
graphene interface resistance, RQ the quantum contact resistance, RSC
the scattering resistance due to defects, phonons, and ER (specularity),
L M the magnetic inductance, LK the kinetic inductance, CQ the quan-
tum capacitance, and CE is electrostatic capacitance. RQ = (h/2q2)/
NchNlayer, CQ = NchNlayer 4q2/hvf, LK = (h/4q2vf)/NchNlayer, Nch is number
of modes, Nlayer number of GNR layers, vf Fermi velocity, h Planck’s
constant, and q is charge. As can be seen from equations, CQ and LK
start to dominate for low mode density and regulate high-frequency
small-signal propagation characteristics of the wire [143].
Graphene Science Handbook
[116] that stage-2 AsF5 doping in MLGNR of moderate
specularity (p = 0.8) has much better (comparable) perfor-
mance than Cu local (global) interconnects at 11 nm node,
though SWCNT betters MLGNR for global interconnects
(see Table 1 of Reference 116 for comparison among Cu,
SWCNT, multiwalled (MW) CNT, and GNR for 11 nm tech-
nology node). The transient analysis [119] of step response
and Nyquist stability of the MLGNR interconnect using
the same model with finite contact resistance, furthermore,
shows that although the propagation delays are smaller than
SWCNT, it has marginally stronger overshoots and lesser
stability which worsen as its width and length decrease.
Therefore, if the overshoots are within the design con-
straints, MLGNR should enable faster signal propagation as
a local interconnect. Next, the wire width can be of the order
of 1 μm for global interconnects which is much larger than
the skin depth at high frequencies (>1 GHz) [117]. The ensu-
ing anomalous skin effect (ASE) redistributes the current–
density in GNR and has to be modeled by self-consistently
solving the Boltzmann equation with nonlocal electric field
in the wire [120]. Comprehensive simulations estimate [120]
the resistance of MLGNR, even of low specularity, to be
lower than the resistance of the SWCNT bundle (Cu) up to
200 GHz (entire μW range).
There are two key differences between the experiments
[111,121,122] and side-contact MLGNR model discussed
above. Substrate-induced doping shifts the Fermi energy
from the neutral point, but the effect decreases exponentially
[110] toward top layers. The disparate conductance of each
GNR layer results in divergence from the uniformly conduct-
ing independent layer model. Second, contacts are connected
on top of the MLGNR in experiments [111]; therefore, unlike
the assumption that conductance increases with number of
GNR layers, conductance has recently been shown [123] to
saturate with layers because the contacts effectively couple
only with few top layers. The signal delay and energy-delay
product (EDP) is minimized for an optimal number of lay-
ers, which is a function of interconnect length, interlayer cou-
pling, and specularity. Top-contacted MLGNR interconnect
with very smooth edges may still perform better than Cu for
short lengths, though with doping optimizations [124] the per-
formance can be improved even for longer interconnects. It
should also be noted that MLGNR may transition to graphite
[125] around eight layers of thickness rending it useless for
interconnects. This puts an upper boundary on choice of opti-
mized number of layers calculated from the analytical model.
For more comprehensive review on performance evaluation
of GNR interconnects against copper/low-κ interconnects, the
reader is referred to Reference 126.
19.5  SPINTRONIC DEVICES
Graphene manifests a rich set of characteristics conducive
for spintronic devices. Long spin-diffusion length, high ther-
mal conductivity, and band gap tunability has been maneu-
vered for new device possibilities as discussed below (also
see Table 19.4).
Applications of Graphene-Based Materials in Electronic Devices 289

TABLE 19.4
Summary of Graphene-Spintronic Devices
Spintronics
Devices Features Challenges
Magnetoresistance 1. Tunability of band gap and conductance in GNRs by magnetic fields [128,129] Wide GNRs are required to have a reasonable
device 2. The MR ratio of GNRs is stable against edge roughness band gap modulation with practical
magnetic fields at room temperature
Spin diode The transmission selection rule in even-N ZGNRs allows highly spin-polarized Magnetized ZGNRs with smooth edges are
currents to be generated and tuned by source–drain voltages and/or magnetic necessary
configurations [18,131]
Spin-logic device A complete set of logic gates (AND, OR, NAND, and NOR) can be designed based
on the above spin diode [28]
Spin caloritronic The current flowing through magnetized ZGNRs can be driven by a temperature
device difference between the source and drain [29]
Spin transistor Datta-type spin transistor by introducing spin–orbital coupling into graphene sheet Weak spin–orbital coupling and metallic
through the proximity effect using a ferromagnetic insulator or through the states near the Fermi level due to the
hybridization effect with heavy 5d-elements [134,135] proximity or hybridization effect
BJT- or FET-type spin transistors exploited the edge states of ZGNRs [27,131] ZGNRs with smooth edges are necessary

19.5.1 Magnetoresistance Device
(a) B field
Theoretical studies have predicted n = 0 Landau level in the Channel
presence of a very high magnetic field [2], a property unique Source Drain
to graphene-based materials. Although it is difficult to observe y
this phenomenon for practical magnitudes of magnetic field, a P N
x I
recent experimental study has successfully reported a decrease Oxide
(b) B=0 gate (c) B > 0
in the band gap of GNR with the increase in magnetic field
[127] as expected from theoretical studies of this phenome-
non. According to this interesting characteristic, the electron μs μs
conductance can be modulated by the magnetic field resulting μD μD
in magnetoresistive effects in GNR devices [128,129]. A very Nonequilibrium Nonequilibrium
large magnetoresistance (MR) has been demonstrated experi- LOW-state HIGH-state
mentally [127]. The benefit of this device is that unlike con-
ventional spin-valves which need ferromagnetic lead, this MR FIGURE 19.7  (a) A schematic of a back-gate p–i–n heterostructure
is the intrinsic material behavior and just requires a full gra- AGNR device, consisted of the p-type source, intrinsic channel, and
phene (GNR) sheet, which should be easier for industrial fab- n-type drain. The external magnetic field is applied to modulate the
rication. Furthermore, unlike MOSFETs, TFETs, and RTDs bandgap of AGNRs in order to obtain MR. (b) and (c) Schematics of
band profile under B = 0 T and B > 0, identified as LOW-state and
in which ER degrades the performance significantly, for GNR
HIGH-state, respectively. The inset in (b) shows the multiple source-
MR-devices, the impact of ER is relatively less because the drain channel strips used in the simulation. (Adapted from G. Liang
Lorentz force bounds the electron to the edge that results in a et al., Applied Physics Letters, vol. 99, no. 8, pp. 083107, 2011.)
high transmission rate. However, a theoretical study [19,128]
has also found that to have a band gap modulation for smaller other devices in the circuit. As shown in Figure 19.7, it has
magnetic fields, a large width GNR with a small band gap is been found that the MR of this p–i–n heterostructure AGNR
necessary. A small band gap also indicates that thermionic device can reach three orders under 5 T of field, in contrast to
electrons can take over the transport properties and suppresses around 10% MR using normal metal contacts.
MR at a higher temperature due to the spread of the Fermi
distribution function. Therefore, to circumvent this problem,
a p–i–n heterostructure AGNR device has been theoretically
proposed [130]. In this structure, a narrow GNR and a wide
19.5.2 Spin Diode
GNR are implemented in the contact and channel region, In addition to half-metallic and spin filter effects, ZGNRs
respectively. Like tunneling FETs, the function of the former have been predicted to show MR effect, which is essential for
is to block the thermionic electrons in the source due to its graphene-based magnetic storage applications. Kim et al. [18]
band gap and operate the larger width GNR in the channel predict that very large MR can be obtained in a ZGNRs-based
under a small magnetic field. Moreover, because of the dif- spin valve. They first find that a moderate magnetic field >2.2
ferent size of channel and contacts, multiple GNR strips can T is enough to transit a wide ZGNR with 8.73 nm width for
be implemented as contacts to enhance the current to drive its ground state to a magnetized state; and a weaker magnetic
290 Graphene Science Handbook

(a) I MR = 0 magnetization of the terminals. The logic output is encoded

ML = 1 to be 1 (0) if the output current includes (excludes) the spin-
VR
up current. Figure 19.10 shows the schematic of a NOT gate.
VL
If the magnetization of the left electrode is set to −1 (logic

G
N
ectrons input 0), the spin-up channel is conducting, corresponding to

R
ction of el
Flow dire

le
a logic output 1. On the other hand, the spin-down channel is

d a
G

conducting (logic output 0) when the magnetization of the left

N
R
le

I electrode is set to 1 (logic input 1). The NOT logic operation

ad

is thus realized. Similarly, other logic gates, such as AND,

(b)
tr ons
ion of elec
Flow direct
y
x z
FIGURE 19.8  Schematic of a ZGNR-based bipolar spin diode.
ML ,R represent the magnetization of the electrodes, whose values
can be ±1 and 0 which correspond to magnetization along ±y direc-
tion and nonmagnetic lead, respectively. (a, b) For [ML ,MR] = [1,0],
a positive (negative) bias can only drive spin-down (up) electrons
through the device. The circuit diagram of this bias-controlled bipo-
lar spin diode is shown in the inset. (Adapted from M.G. Zeng et al.,
Physical Review B, vol. 83, no. 11, pp. 115427, Mar 14, 2011.)
[ML, MR]
[1, 1] [1, –1] [1, 0] [1, 0]
Bias
+ has also been observed when Au is intercalated at the gra-
– FETs can be designed by exploring the unique edge states in
FIGURE 19.9  Spin current flowing through ZGNR channel can
be selected by source–drain voltages and magnetic configurations.
(Adapted from M.G. Zeng et al., Physical Review B, vol. 83, no. 11,
pp. 115427, Mar 14, 2011.)
field can be used for a ZGNR of larger width. They calculate
the MR ratio as MR = (R AP − RP)/RP, where R AP and RP are
the resistances in the magnetic parallel and antiparallel con-
figurations, respectively. The calculated MR ratio can be as
high as 106 for an 8-ZGNR at room temperature. The large
MR is contributed to the transmission selection rule due to
the matching/mismatching wave function symmetry in spin
sub bands. A further design exploited the transmission selec-
tion rule in a spin diode shown in Figure 19.8, in which highly
spin-polarized currents can be generated and tuned by the
source–drain voltages and/or magnetic configurations [131],
which is summarized in Figure 19.9.
19.5.3 Spin-Logic Device
ZGNRs-based spin diodes make it possible to build spin-
logic devices [28]. The logic inputs are encoded by the
OR, NAND, and NOR gates, can also be realized based on
the above design concepts. These logic gates allow further
designs of complex spin logic operations and pave the way
for the full implementation of spintronic computing devices.
19.5.4 Spin Transistor
Long spin diffusion length and large spin relaxation time in
graphene have attracted great attention for utilizing graphene
as a channel for the Datta-type spin FET [132,133]. However,
two crucial issues need to be resolved. Due to the fact that gra-
phene is nonmagnetic, an efficient spin injection and detection
at the source and drain requires ferromagnetic metals and a
high-quality tunnel barrier. Moreover, the negligible spin–orbit
coupling (SOC) in graphene is a strong limitation for designing
Datta-type spin FETs. Using a ferromagnetic insulator (FMI)
as the gate dielectric may overcome this limitation. The elec-
[0, 0]
tric-field-controlled proximity effect originating from exchange
interactions between graphene and FMI can induce a large spin
splitting at graphene [134]. This externally induced large SOC
phene–Ni interface because of the hybridization of Dirac elec-
trons in graphene with Au 5d states [135]. New types of spin
ZGNRs. Compared to Datta-type spin FETs, the chief advan-
tage of these designs is to eliminate the requirement of SOC
and ferromagnetic metals for spin injection and detection.
1.
Bipolar junction transistor (BJT) type: Using
ZGNR-based spin diodes as building blocks, three-
terminal spin transistors can be designed [131]. Two
designs of the transistor, one for spin-up current and
another for spin-down current, are shown in Figure
19.11a and b, respectively. The side view and equiv-
alent circuit diagrams of the device are shown in
Figure 19.11c through e, respectively. Each transistor
consists of three terminals, an emitter, a collector,
and a base. The emitter is grounded and the collec-
tor voltage (VC) is fixed to a positive value, while the
voltage of the base (VB) can be varied which controls
the flow and polarization of the current. The polarity
of the spin transistor is determined by the magnetic
configuration between the emitter and the collector.
As shown in Figure 19.11f, the current gain (IC /IB)
increases dramatically when VB /VC = 1/2, indicat-
ing a high amplification for spin-polarized currents
with a suitable bias condition. Transistors operat-
ing as voltage amplifiers can be designed similarly.
Applications of Graphene-Based Materials in Electronic Devices 291

Mi = 1 ≡ ‘1’ Spin-up current

Input (i = 1 or 2)
Mi = 1 ≡ ‘0’ Spin-down current
A Y
Include spin up current ≡ ‘1’ Mref Reference of 0 1
Output magnetization
Exclude spin up current ≡ ‘0’ 1 0

Y Y NOT
Mref = 0 Mref = 0
A Y

M1 = –1 M1 = 1
A=0 A=1
Y=A

FIGURE 19.10  Schematic illustrations of the spin NOT gates. The input and output terminals are labeled as A and Y, respectively. A mag-
netization-fixed terminal (Mref) is used as a reference. The logic input and output 1 (0) are, respectively, encoded by the magnetization 1 (−1)
of the input terminals and the output current for 1 (0) including (excluding) the spin-up current. (Adapted from M.G. Zeng et al., Applied
Physics Letters, vol. 98, no. 9, pp. 092110, Feb 28, 2011.)

(a) (b) (c) → – + →

(ME, MB, MC) = (1, 0, –1) (ME, MB, MC) = (–1, 0, 1) H H →
H M
E B C
E C E C ZGNR (1, –1)
IE IB IC
IE IC IE IC → → →
V1 V2 H Substrate H H M
(–1, 1)
– IB – + IB 15
+
B B (f )
10
Spin-up current Spin-down current IC
IB
(d) (e) E 5
E
Spin-up B Spin-down
B 0
transistor transistor 0.0 0.2 0.4 0.6 0.8 1.0
C C VB/VC

(g) E C G (h) Diffusion

VBE
→ current (ID) V
IE ID 0 Iin H C
E B G
0 Iin V1 V2 FM FM
→ ZGNR
H IE ID
VBE
B V Substrate

FIGURE 19.11  Schematic illustrations of ZGNR-based BJT-type transistors. (a)–(c) Top and side view of a spin current amplifier. Their
circuit symbols are shown in (d, e). (f) Current gain (|IC /IB |) as a function of (VB /VC). (g, h) Top and side views of a Johnson-type spin voltage
amplifier. (Adapted from M.G. Zeng et al., Physical Review B, vol. 83, no. 11, pp. 115427, Mar 14, 2011.)

In Figure 19.11g and h, a Johnson-type voltage ampli- which source–drain conductance is controlled by
fier has been designed. Here, a ferromagnetic cobalt a transverse gate electric field [27]. The proposed
electrode is used as the collector to detect the spin- device consists of a transport channel which is modu-
polarized current. The spin-polarized current flows lated by two pairs of electrodes. The voltages on the
from the emitter to the base under a bias voltage and left pair of electrodes are fixed; and the source–drain
then diffuses from the base to the collector, gener- conductance is controlled by a transverse electric field
ating a voltage difference which can be measured. generated by the right pair of electrodes. Transmission
With proper choices of the parameters, it is possible of spin-up or spin-down electrons can be effectively
for the transistor to act as a voltage amplifier. controlled by the value and direction of the transverse
2.
FET type: Besides the above bipolar-like transistors, electric field. The on/off ratio can reach 103 when the
Guo et al. [27] propose a ZGNR-based spin FET in transverse field is varied from −0.1 to +0.1 V/A.
292 Graphene Science Handbook

19.5.5 Spin Caloritronic Device
Even without an external bias voltage, spin-polarized currents
can be generated in ZGNRs with a thermal bias. Figure 19.12a
shows the schematic illustration of a ZGNR-based spin calo-
ritronic device [29]. The current flowing through the magne-
tized ZGNR (M-ZGNR) is driven by a temperature difference
(TSD), the difference between the source temperature (TS)
and the drain temperature (TD), that is, TS − TD. As shown
in Figure 19.12b, opposite flowing spin-up and spin-down
currents can be generated in M-ZGNRs with a temperature
difference. This interesting spin Seebeck effect is attrib-
uted to the asymmetric transmission spectra of spin-up and
spin-down electrons in M-ZGNR. Furthermore, a back-gate
voltage can be applied to control the spin currents shown in
Figure 19.12c. Spin currents (ISD) increase and reach satura-
tion as VG is fixed and TSD increases, indicating a thermal
spin transistor. Moreover, for a fixed TSD and TS, spin cur-
rents with complete polarization can be achieved by tuning
a back-gate voltage. In addition, as shown in Figure 19.12d,
a very large thermal MR effect is found when the magnetic
state of ZGNRs is transformed from the ferromagnetic state
to its ground state. The sensitivity of thermally induced spin
currents to the magnetism of ZGNRs provides a unique way
to distinguish the electronic states of ZGNRs. The flex-
ible control over thermally induced spin-polarized current
in M-ZGNR, by thermal (i.e., temperature), electrical (gate
voltage), and magnetic means, provides a rich set of thermal
spin components (spin filter, spin diode, spin FET, and MR
device). Theses spin components help to dissipate heat in a
working nanoelectronic device and open the door to carbon-
based spin caloritronics applications. Besides the magnetized
ZGNRs, the effect of thermally induced spin currents has also
been investigated in ZGNRs-based heterostructures and spin
valves [136,137]. The reason for the ZGNRs system to be a
good candidate for creating thermally induced spin currents
is the fact that its low-energy electronic states are sensitive to
the environment, such as different edge terminations, external
magnetic, or electric fields, which breaks the electron–hole
symmetry and gives rise to thermal-induced spin currents.
Moreover, it is found that the local magnetic moment around
a magnetic atom in a ZGNRs-based spin valve is strongly
related to the thermal bias [136,137]. This thermally controlled
magnetic distribution provides an effective way for storing
information in a spin valve. As shown in Figure  19.13, the
ZGNR-based spin valve is in the antiparallel configuration and
with a Ni atom absorbed on one edge of the ZGNR. For TSD = 0,
the absorbed Ni atom in the ZGNR carries a magnetic moment
around −0.01 µB. This value is much smaller than that of an
isolated Ni atom, which can be as large as 5.6 µB. The quench-
ing of the Ni magnetic moment in the ZGNR indicates the
strong coupling, or charge transfer, between the Ni atom and
its surroundings. Interestingly, as shown in Figure 19.13b, the
thermally induced current can considerably restore the mag-
netic moment of the Ni atom, which can be enhanced greatly
to 1 µB by applying a thermal bias of TSD = 40 K. Therefore,
despite the strong coupling between the Ni atom and its sur-
roundings, the injected spin currents can partially align the Ni
magnetic moment to its original value.

(a) (b) 5
T S–T SD
TS
0
Current (nA)

TD TSD = 20 K, spin-up
TSD = 40 K, spin-up
R
TS M-ZGN –5 TSD = 60 K, spin-up
TSD = 20 K, spin-down
Back gate –10 TSD = 40 K, spin-down
TSD = 60 K, spin-down

100 150 200 250 300 350 400

TS (K)
(c) (d)
600 Spin-up GS-ZGNR
Spin-down 40 M-ZGNR
300
Current (nA)

Current (nA)

30 MR
5.0 × 104
0
MR (%)

20

–300 10
0.0
100 200
–600 0
–0.4 –0.2 0.0 0.2 0.4 0 50 100 150 200 250
VG (V) TSD (K)

FIGURE 19.12  (a) Schematic of thermally induced spin currents in a M-ZGNR. A temperature bias can induce opposite-flowing spin-
up and spin-down currents in the M-ZGNR (spin Seebeck effects). (b) Spin-dependent currents as a function of TS for different TSD. (c)
Gate-dependent spin polarized currents (TSD = 60 K, TS = 400 K). (d) Spin currents as a function of TSD for M-ZGNR and GS-ZGNR
(VG = −0.02 V, TS = 400 K). The inset shows MR can be as high as 5 × 104% by translating ZGNRs from ferromagnetic to ground state.
(Adapted from M.G. Zeng, Y.P. Feng, G.C. Liang, Nano Letters, vol. 11, no. 3, pp. 1369–1373, Mar, 2011.)
Applications of Graphene-Based Materials in Electronic Devices
(a) TSD = 0 K
0.2600
0.1933
0.1265
0.05975
S Scattering region D –0.0070
–0.07375
Ni
–0.1405
–0.2073
–0.2740
(b) TSD = 40 K
1.030
0.8656
0.7012
0.5369
S D 0.3725
0.2081
0.04375
Ni –0.1206
–0.2850
FIGURE 19.13  Thermal-controlled magnetic moment of a mag-
netic impurity in a ZGNR-based spin valve. (a, b) Spatial magnetic
moment in the scattering region for TSD = 0 and 40 K, respectively.
The magnetic moments of the Ni atom in (a) and (b) are −0.01 µB and
1 µB, respectively. (Adapted from M.G. Zeng, W. Huang, G.C. Liang,
Nanoscale, vol. 5, no. 1, pp. 200–208, 2013.)
19.6  RECENT COMMERCIAL DEVELOPMENTS
Graphene devices have yet to be commercially deployed in
electronic systems. The implementation of GNRs for elec-
tronic device applications still has a long way to go due to
performance degradation caused by the ER and precise con-
trol of nanoribbon size and direction. To realize GNR devices,
more efforts from both the academic world and industry are
required. On the other hand, the recent progress [138] in fab-
ricating large wafer-scale [34] graphene sheets has, however,
brought down the cost from $100,000,000/cm2 in 2008 [139]
to <$100/cm2 [140] ($50/cm2 at Graphenea for an online order
in April 2014), which has expedited the possibility of mass
production of lightweight flexible graphene electronics. This
has attracted industry to make forays into graphene research
and the more recent efforts toward commercial aspects
have chiefly been led by Nokia, IBM, and Samsung. Nokia
is specifically targeting optoelectronic properties (sensors
for charge-coupled devices) of graphene for future digital
cameras and has shared a $1.35 billion grant in 2013. IBM
has been spearheading the designs of RF circuits on gra-
phene wafers [77] (also see Section 19.3.2 on RF transistors).
Samsung, however, is propelling the field of graphene touch
screens [141] by exploiting transparency of graphene sheets in
congruence with their recent achievement of attaining current
switching ratio (Ion /Ioff) of 105 [142] required for controlling
screen transistors. Previous to this demonstration, switching
ratio has been limited to ~100 [43] in traditional field-effect
architectures because of the gapless Dirac energy bands in
graphene. Therefore, graphene devices may soon find their
way into technological products to unleash a whole new set of
possibilities and consumer experiences.
293
19.7 CONCLUSION
In summary, we have reviewed the potential applications of
graphene and GNRs in various electronic devices. Although
graphene may not be suitable to be used for the digital tran-
sistor due to its low Ion /Ioff, it can be the candidate for the RF
transistor because of its high foot frequency (f T). It has been
theoretically predicated that the graphene RF transistor can
potentially reach few tens of THz as the channel is scaled down
to sub-10 nm regime. Furthermore, using the unique proper-
ties of graphene, such as electro-optic effect, graphene is also
proposed to be functionalized as an electronic fiber to guide
electrons propagating in the designed path, and p–n junction
switches operating like an optical switch. The most interesting
part is that even though graphene lacks band gap, it still can
be activated with high Ion /Ioff through its electro-optic behavior
instead of the conventional operation principle. Finally, gra-
phene is also promising in the field of thermoelectric and heat
dissipation materials because of its high thermal conductivity.
Furthermore, due to the band gap opening of GNRs
from the confinement effect, we have first introduced the
possible applications in conventional semiconductors such
as MOSFETs and novel functional devices, such as TFETs
and RTDs. It is found that benefiting from their light car-
rier effect mass and feasibility of structure variations, GNRs
show promising device performance to establish themselves
as strong candidates to replace semiconductor materials
for these device applications. However, ER scattering plays
an important role in degrading performance. Therefore, to
overcome this challenge, a more precise fabrication technol-
ogy to make smooth edge GNRs is necessary in the future.
Furthermore, because of their high mobility and large mfp,
stacked multilayer GNRs can be potentially implemented as
interconnects in integrated circuits based on all-graphene
electronics. Beyond these charge-based devices, GNRs also
stimulate another field of device community, namely, spin-
tronic devices, because of their unique spin properties. It has
been shown that the bandstructure, magnetization, and spin
polarization of GNR can be modulated by the external electric
and magnetic fields. Therefore, we have given short descrip-
tions of several interesting proposals for MR devices based
on n = 0 Landau level, spin diodes and spin-logic devices that
operate by controlling magnetization direction, spin transis-
tors by controlling spin polarization, and spin caloritronic
devices by applying different temperature on GNR terminals.
These devices can be functionalized either as charge-based
devices or spin information-based devices. It would be very
important and worthwhile to keep an eye on future graphene-
based quantum information and computing technology.
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20 Graphene- and Graphene-Oxide-Based
Gas Sensors
Vladimir Aroutiounian

CONTENTS
Abstract...................................................................................................................................................................................... 299
20.1 Introduction.................................................................................................................................................................... 299
20.2 Synthesis of Graphene and GO...................................................................................................................................... 300
20.3 Some Electronic Properties of Pristine (Intrinsic) Graphene........................................................................................ 301
20.4 Gas Sensors Made of Graphene..................................................................................................................................... 301
20.5 Bandgap Opening in Graphene...................................................................................................................................... 302
20.6 Detection of Gases by Graphene Resistive Sensors....................................................................................................... 303
20.7 Field-Effect Transistor Gas Sensors............................................................................................................................... 304
20.8 Acoustic Wave and Functionalized Graphene Gas/Vapor Sensors............................................................................... 305
20.9 Analysis of Experimental Results Obtained for Different Graphene Sensors.............................................................. 306
20.10 Conclusion...................................................................................................................................................................... 307
References.................................................................................................................................................................................. 307

ABSTRACT distances without scattering at room temperature” (Geim

Exceptional physical properties of graphene and possibili-
ties of its electronic applications have evoked a great deal
of research interest for the last few years. From a theoreti-
cal point of view, electrons in graphene behave like mass-
less Dirac fermion and equivalent to a massless neutrino in
two dimensions. Therefore, mobility of electrons in graphene
is the highest among all solids. Graphene exhibits ballistic
charge transport properties. Graphene is actually a semi-
metal. However, the lack of an energy gap in its electronic
spectra, for example, prevents the use of graphene in making
transistors, logic circuit devices, and sensors. Several meth-
ods have been developed to break the lattice symmetry in gra-
phene and open an energy gap. The opening of the bandgap
in graphene is a unique phenomenon. Several versions of gap
opening are discussed in the chapter after a short introduc-
tion on the synthesis procedures of graphene and graphene
oxide. The best surface-to-volume ratio is in graphene-like
two-dimensional (2D) materials, every atom of which may be
considered as a surface atom; therefore, the use of graphene
has opened up the opportunity for the detection of gases and
vapors with excellent sensitivity, fast response time, and high
stability. Different types of sensors are considered. Besides
resistive sensors, field-effect transistor, and acoustic wave
and functionalized gas/vapor sensors have been reported.
20.1 INTRODUCTION
Graphene is a zero-bandgap 2D semimetal. “Charge carriers
in graphene exhibit giant intrinsic mobility, have the small-
est effective mass (it is zero) and can travel micrometer-long
2009). The unique structural characteristics and exceptional
physical properties of graphene (Table 20.1) have attracted
enormous research interest in the last years (Mikhailov
2011a,b).
Previous volumes of this book and the December 2012
issue of MRS Bulletin (vol. 37, 2012) are focused on fun-
damental functionalities of graphene (Lu et  al. 2012). Note
that graphene has shown ultrahigh intrinsic carrier mobility
far larger than for any other material (Morozov et al. 2008,
Mikhailov 2011a,b, Lu et al. 2012) and has potential applica-
tions in high-speed transistor electronics and integrated cir-
cuits. The research group at IBM has demonstrated silicon
carbide (SiC)-based graphene field-effect transistors (FETs)
with a cutoff frequency of more than 300 GHz (Avouris
and Xia 2012), which is very important for nanoelectronics.
Otsuji et  al. (2012) note that graphene devices will operate
in the terahertz frequency range. A very long spin diffu-
sion length is typical for graphene. It opens, along with high
electron ­velocity related to their linear dispersion relation,
­possibilities  to use graphene for spintronics (Seneor et  al.
2012).
A half-integer quantum Hall effect for both electron and
hole carriers in graphene has been observed at higher than
helium temperatures (Novoselov et al. 2005, Xiao et al. 2011,
Schopfer and Poirier 2012). In addition, graphene is highly
transparent for visible light (Avouris and Xia 2012). Graphene
can sustain current densities 6 orders of magnitude higher than
copper and shows record thermal conductivity and stiffness
(Geim 2009). Its thermal conductivity is measured at a value
of ~5000 W mK−1 for a single-layer sheet at room temperature
(RT) (Balandin et al. 2008). It is promising for thermoelectric
299
300
TABLE 20.1
Physical Properties of Graphene
Structural Dimension 2D (Thickness: 0.34 nm)
Young’s modulus 1 TPa
Tensile strength 130 GPa
Bandgap 0 eV (zero-gap semimetal)
Electrical conductivity ~106 S cm−1
Intrinsic carrier mobility Up to 200,000–250,000 cm2 V−1 s−1 at low
temperature and ~10,000–20,000 cm2 V−1 s−1
at room temperature
Thermal conductivity 3000–5000 W m−1 K−1
Solubility ~2800°C under Ar
4.7 ± 1.9 μg mL−1 in NMP
4.1 ± 1.4 μg mL−1 in DMF
Density 2.2 g cm−3
Source: Lee, S. H. et al., Advanced Functional Materials 21, 1338–1354.
applications (Lu et  al. 2012, Pop et  al. 2012). The  excellent
breaking strength of graphene is equal to 42 N m−1. Its high
Young’s modulus shows that it is one of the strongest mate-
rials ever measured. High-efficiency energy conversion and
energy-storage devices based on graphene materials have
been achieved (Cao et al. 2012). The optical properties of gra-
phene are also of great interest. Broadband absorption coef-
ficients from UV to near IR region, and sub-picoseconds to
microsecond responses are typical for graphene (Du et  al.
2012). Biosensing and bioimaging applications in enzyme bio-
sensors, immunosensors, DNA biosensors, and cell imaging
have been reported (Singh et al. 2011). Although many papers
on gas/vapor sensors made of graphene and graphene oxide
(GO) have been published, there is only one review in this
field (Basu and Bhattacharyya 2012). This chapter focuses on
the physical properties and applications of graphene and GO
gas/vapor sensors.
20.2  SYNTHESIS OF GRAPHENE AND GO
The preparation, production, placement, and handling
of graphene and GO have been recently reviewed by
Bonaccorso (2012). A detailed discussion of these questions
is beyond the scope of this chapter. We will very shortly
stop on some questions, which are important for gas sensor
applications.
Single-layer graphene was first obtained by Novoselov
et al. (2005) using the simple method of dry exfoliation (the
process of splitting of layered materials into atomically thin
sheets in air, vacuum, or inert environment). The splitting can
be realized via mechanical and other forces and adhesive tape.
Micromechanical cleavage allows realizing high-quality lay-
ers, with size limited by the single crystal grains in graphite
(up to millimeters). RT mobility of up to 20,000 cm2 V−1 s−1
was measured in graphene layers. Of course, such a method
is not practical for large-scale devices, but it allows obtain-
ing basic results and devices as well as understanding of new
physical results (Shmavonyan et al. 2013a,b).
Graphene Science Handbook
IV V
I Δ
II III
FIGURE 20.1  The existence of an energy gap between the con-
duction and valence bands makes it possible for graphene to act as
a semiconductor. In pristine graphene, the conical conduction and
valence bands meet at a point—the bandgap is absent. Electrical
fields introduce asymmetry into the bilayered structure (bottom),
yielding tuned bandgap (Δ). Allowed optical transitions between
different subbands of a graphene bilayer are also shown. (Adapted
from Craciun, M. F. et al., Nano Today 6, 42–60.)
 Anodic bonding (Figure 20.1b) allows sticking a few lay-
ers of graphite, including single-layer graphene, to a glass
(see, e.g., Shukla et al. 2009). A laser beam can in principle
remove material from a solid surface and prepare graphene
flakes (Miyamoto et al. 2010). The process is called photo-
exfoliation. Graphite can also be exfoliated in a liquid using
ultrasound to extract graphene layers. The technique can
be used for the exfoliation of graphite oxide and graphite
intercalated compounds, which have different properties
compared with pristine graphite. There are several ways to
obtain GO and reduced graphene oxide (rGO) (Bonaccorso
2012).
Sensors made of SiC are very promising (Buniatian and
Aroutiounian 2007). It is possible to grow graphene on SiC
though there are large lattice mismatches between graphene
and SiC. SiC is annealed in vacuum or argon atmosphere
above 1000°C. Silicon near the surface of the SiC lattice
desorbs, and free carbon atoms rearrange itself in a hexagonal
lattice structure (graphene). An electronic structure modifi-
cation by hydrogen intercalation in graphene on the carbon
face of SiC is considered by Hiebel et al. (2011). RT mobil-
ity (μ) of ~5800 cm2 V−1 s−1 on the Si-face has been reported
(Bonaccorso 2012). Growth of epitaxial graphene on SiC
allows organizing large-scale production of different elec-
tronic devices (microwave devices, light-emitting devices,
and radiation-hard devices) (Buniatian and Aroutiounian
2007, Nyakiti et  al. 2012, Ruan et  al. 2012, Iezhokin et  al.
2013). The cost of SiC wafers is much higher compared with
that of Si wafers of the same size. One approach to reduce
substrate costs is to grow thin SiC layers on sapphire, cost of
which today is much lower. Layers produced in this way have
structural and electronic properties comparable to those on
bulk SiC.
Graphene- and Graphene-Oxide-Based Gas Sensors
Carbon can be deposited on a Ni, Co, Ru, Ir, Pt, and Pd
surface by a number of techniques. The carbon source can be
a solid, liquid, or gas (Barlett and McCarty 2012, Bonaccorso
2012).
Chemical exfoliation from graphite powders through the
formation of graphite oxides by oxidation of graphite in solu-
tion is another well-studied fabrication technique. This pro-
cess has low cost, high throughput, chemical versatility, and
scalability to large quantities (Jaber-Ansari and Hersam 2012).
Graphene is a single-element material; therefore, it is eas-
ier to deposit it than a multicomponent system. Versions of
chemical vapor deposition (CVD) of graphene on metals and
dielectrics are described by Bonaccorso (2012). It is unlikely
that very expensive molecular beam or atomic layer epitax-
ial technology is useful for the growth of graphene layers of
high-enough quality. Apart from the above-mentioned meth-
ods for the synthesis of graphene, there are few other synthe-
sis methods. It is also noteworthy that the growth of graphene
on diamond-like carbon film as a substrate is very promising
due to its lower surface trap density.
GO sheets have been recently proposed for the manufac-
ture of graphene. Such single-layer GO sheets can be pro-
duced by sonication of hydrophilic graphite oxide in water.
20.3 SOME ELECTRONIC PROPERTIES OF
PRISTINE (INTRINSIC) GRAPHENE
Electronic properties of graphene are unique and very differ-
ent from many other known materials (Novoselov et al. 2004,
2005, Castro Neto et al. 2009, Geim 2009, Mikhailov 2011a,b,
Lu et  al. 2012). As shown earlier, electron waves propagat-
ing through the honeycomb lattice of graphene completely
lose their effective mass, which results in quasiparticles that
are described by the Dirac-like equation rather than by the
Schrödinger equation. The Dirac electrons behave in unusual
ways in tunneling, confinement, and the integer quantum Hall
effect. The valence band and conduction band of graphene
look like conical valleys and touch the high-symmetry points
of the Brillouin zone. The energy varies linearly with the mag-
nitude of momentum. Linear dispersion relation leads to zero
effective mass near the Dirac point (Geim 2009, Mikhailov
2011a,b, Lu et al. 2012).
Electron waves in graphene propagate within a layer that is
only one atom thick, which makes graphene very sensitive to
different imperfections and exposure. To manufacture a sensor,
we have to change the resistance of the material in order that it
can be changed under the influence of some outer force (electric
or magnetic field, concentration of gas, illumination, etc.) It was
shown that the Dirac electrons can be controlled by application
of external electric and magnetic fields or by altering the sam-
ple geometry and/or topology. Usually, the Fermi level can be
altered by changing the concentration of vacancy defects or by
doping. Graphene can become either n- or p-doped. A substrate
like SiO2 has a larger influence on the mobility than scattering
by graphene’s own phonons at room temperature. It leads to a
mobility of ~40,000 cm2 V−1 s−1 at RT.
301
Usually, pristine graphene is poorly sensitive to gas. It
was established that graphene can be decorated with metal
by first adding metal salt precursors to a solution of the GO
and then converting them to metallic nanoparticles. Graphene
can adsorb and desorb various atoms and molecules (e.g.,
H2, NO2, NH3, or OH). Weakly attached adsorbents often
act as donors or acceptors and lead to changes in carrier
concentration. Other adsorbents give rise to localized (“mid-
gap”) states, which results in poorly conductive derivatives
(Novoselov et al. 2004, 2005, Geim 2009, Mikhailov 2011a,b,
Lu et al. 2012).
Such changes in the conductivity of graphene are lead-
ing to the possibilities to manufacture different sensors. We
will discuss below the properties of only gas/vapor sensors.
Most of them are operating in the resistive mode, and a
change in resistance under gas/vapor influence can be mea-
sured easily.
20.4  GAS SENSORS MADE OF GRAPHENE
It is shown in Ao et al. (2008) that the aluminum incorporated
into graphene causes a distortion of the energy density dis-
tribution around Al atoms. C atoms surrounding this dopant
attract electrons due to their high electron affinity, whereas a
decrease in electron density on the Al dopant is observed. The
charge redistribution makes Al an active site for CO adsorption
and ultrasensitive carbon monooxide detection. This charge
redistribution effect is confirmed by theory. The results show
that the Al-doped graphene has strong chemisorption of CO
molecule by forming an Al–CO bond, whereas CO undergoes
weak physisorption onto intrinsic graphene. Furthermore, the
enhancement of CO sensitivity in the Al-doped graphene is
determined by a large electrical conductivity change after
adsorption, where CO absorption leads to an increase in the
electrical conductivity via introducing large amounts of shal-
low acceptor states. N substitutionally doped graphene syn-
thesized by the CVD method is sensitive to the presence of
CH4 and NH3 (Wei et al. 2009).
Nitrogen plasma treatment of graphene can remarkably
change its work function (Akada et al. 2014).
Graphene can be decorated with metallic nanoparticles by
first adding metal salt precursors to a solution of the GO, and
then converting them to metallic nanoparticles by reduction
(Si and Samulski 2008, Xu et  al. 2008, Gotoh et  al. 2009).
Other methods include electrochemical deposition of metal-
lic nanoparticles on thin layers of graphene (Sundaram et al.
2008). Composites of graphene with gold (Xu et  al. 2008),
ruthenium (Gotoh et  al. 2009), platinum (Si and Samulski
2008, Xu et al. 2008, Gotoh et al. 2009, Shafiei et al. 2010),
and palladium (Xu et al. 2008, Gotoh et al. 2009) nanopar-
ticles were synthesized by this method.
The catalytic properties of palladium are well known
(Paremuzyan and Aroutiounian 2012). This material is often
used in chemical hydrogen gas sensors (Aroutiounian et  al.
2012) due to a hydrogen-induced decrease in the work func-
tion of Pd or Pd–Pt alloy and modification in the distribution
of defect states due to gas adsorption. Palladium-decorated
302
graphene can serve as a sensor material for hydrogen at lev-
els from 0.5% to 1% in synthetic air. The incorporation of
Pd nanoparticles increases graphene sensitivity by more
than an order of magnitude compared with pristine graphene
(Lange et al. 2011). Application of palladium in the form of
nanoparticles allows fabricating chemical sensors using a
very small amount of this low-cost material. Performance of
graphene resistive H2 sensors made of nanosheets deposited
on SiC substrate has recently been investigated by Chu et al.
(2011). Graphene-like nanosheets with Pd/Au electrode were
investigated as graphene NO2 sensors by Ko et  al. (2010).
Their sensitivity down to parts-per-billion (ppb) levels, fast
response, recovery, and appreciable selectivity toward NO2 in
the presence of commonly interfering gases such as CO2, H2O
(saturated vapor), NH3 (550 ppm), and O2 were observed by
Nomani et  al. (2010). Multilayer graphene–Pd sensors with
Au electrode were also investigated by Lange et al. (2011) for
H2 detection at levels from 0.5 to 1% in synthetic air (see also
Johnson et al. 2010, Wu et al. 2010, Chung 2012a,b, Lee et al.
2012, Das and Prusta 2013). For 2% H2 at 40°C, response
time of less than 2 s and a recovery time of 18 s are observed
by Kumar (2013). Deng et  al. (2012) reported NO2 gas sen-
sors fabricated reduced graphene-conjugated Cu2O nanowire
mesocrystals. Esfandiar et  al. (2013) reported that DNA-
decorated graphene nanomesh can detect several chemical
vapors.
20.5  BANDGAP OPENING IN GRAPHENE
Graphene exhibits ballistic charge transport properties.
However, the lack of an energy gap in its electronic spectra,
for example, prevents the use of graphene in making transis-
tors, logic circuit devices, and sensors. It was discovered that
the graphene band structure is sensitive to lattice symmetry.
As a result, several methods have been developed to break
this symmetry and open an energy gap. The opening of the
bandgap in graphene is a unique phenomenon.
3.5
3.0
2.5
Band gap (eV)
2.0
1.5
1.0
0.5
0.0
–15 –10
Strain (%)
FIGURE 20.2  The bandgap of the fully hydrogenated (H-type) and doped with B (B-type) bilayer graphene. (Adapted from Boukhvalov,
D. W., Katsnelson, M. I. and Lichtenstein, A. I. 2008. Physics Review B 77, 035427.)
Graphene Science Handbook
Several efforts have been made to open the bandgap of gra-
phene (see Figure 20.1). One possibility to open the bandgap in
graphene is to use bilayer graphene (Ohta et al. 2006, Castro
et al. 2007, 2010, Zhang et al. 2009, Johnson et al. 2010). The
bandgap around 0.25 eV is opened when the electric field is
applied up to 2 V/nm (Zhang et  al. 2009). However, a large
external voltage of several tens to hundreds of volts makes this
approach not practical (Guo et al. 2008, Nanda and Satpathy
2009, Choi et al. 2010). The bandgap of bilayer graphene can
be opened larger (up to 3.3 eV) by a combination of strain
(along the z axis) and electrical field (Figure 20.2) (Gui et al.
2008, Yang et al. 2011, Zhang et al. 2011a,b).
Graphene made on a Cu foil can also have the bandgap
under strain. Few-layer graphene sensor developed by Jung
et  al. (2009) can detect B2 and J2. Here, a bandgap of 0.2–
0.3 eV was observed. The bandgap in graphene can also be
opened under infrared laser beam or at a high level of humid-
ity (0.26–0.73 eV) (Yavari et al. 2010). Bandgap engineering
of bilayer graphene can be realized by chemical conjugating
double sides of bilayer graphene, one side with an electron-
donating group and the other side with an electron-withdraw-
ing group. The compensated charges not only created a large
bandgap of 0.3 eV by invoking an internally strong local
dipole field in bilayer graphene but also removed degeneracy
by shifting the Fermi level within the bandgap.
The bandgap of graphene can be opened by the use of
a quantum confinement effect of carriers by narrowing the
width of graphene to a nanometer scale. Such graphene is
called nanoribbon (NR). NRs can be fabricated from solution
phase, by e-beam lithography of large-area graphene or by
local heat treatment using atomic force microscopy (Barone
et  al. 2006, Bonaccorso et  al. 2012, Han et al. 2007). A
bandgap of ~30 meV and corresponding FETs were reported
when NRs were prepared (Chen et  al. 2007, Li et  al. 2008,
Jiao et al. 2010, Wei et al. 2010, Bonaccorso et al. 2012). Sub-
10 nm NRs with a bandgap of up to 400 meV were reported
by Ponomarenko et al. (2008). NRs were used as channels in
B-type
H-type
–5 0 5
Graphene- and Graphene-Oxide-Based Gas Sensors 303

FETs. A direct to indirect bandgap transition is possible in NR

by the application of an external bias along the width of NR TABLE 20.2
(Majumdar 2010). It is very promising for applications of gra- Bandgap Opening in Different Structures of Graphene
phene in nanophotonics and at terahertz applications. Direct Layers and Influences
observation of a widely tunable bandgap in bilayer graphene
Structure of Graphene Layers Bandgap
was reported by Zhang et al. (2009). and Influence (eV) Reference(s)
BN–graphene–BN antidot systems (Zhang et  al. 2011a,b,
Bilayer graphene and electric field 0.25 Zhang et al. (2009)
Ouhe et  al. 2012) are also very interesting versions for gra-
Bilayer graphene, combination of Up to 3.3 Yang et al. (2011),
phene applications. The construction of periodic structures strain and electric field Zhang et al. (2011a,b),
such as antidot lattices (Eroms and Weiss 2009, Pedersen 2008, Gui et al. (2011)
Vanevic et al. 2008, Balog et al. 2010) and the corresponding Few-layer graphene and gas 0.2–0.3 Jung et al. (2009)
confinement potential for the carriers in pristine graphene led environment (B2 and J2)
to the bandgap opening. Unfortunately, the size in NRs and Graphene and infrared laser beam 0.26–0.73 Yavari et al. (2010)
dots is difficult to control due to high sensitivity to their width, or high humidity
edge geometry, and chemical functionalization (Berger 2006, Graphene Moiré superlattice and 0.73 Balog et al. (2010)
Son et al. 2006, Giovannetti et al. 2007, Lu et al. 2009, Balog hydrogen environment
et al. 2010). It is also worth noting that the manufacture of NRs Half-hydrogenated graphene 0.43 Zhou et al. (2009)
is still far from being realized in the industry level. Tunable bandgap and water Up to 0.206 Yavari et al. (2010)
In nanomesh graphene structure (Guo et al. 2008), lateral molecules
quantum confinement and localization effects due to edge dis-
order, such as variable edge roughness, were proposed as the
mechanism responsible for the bandgap opening. chemical methods, is carried out currently. Patterned adsorp-
Epitaxial growth of graphene on the carbon face of SiC tion of atomic hydrogen onto the Moiré superlattice positions
under vacuum leads to a gap of ≈0.26 eV, which originates of graphene (Balog et  al. 2010) led to a bandgap opening
from the breaking of sublattice symmetry due to the gra- of ≈0.73 eV, while half-hydrogenated graphene (Zhou et  al.
phene–substrate interaction. As a result of the creation of the 2009) led to a bandgap of ≈0.43 eV. A single hydrogen atom
gap, sensors on epitaxially grown graphene for ultrasensitive in a 32-carbon-atom slab generated a gap of about 1.25 eV. A
NO2 detection with extremely high sensitivity were reported widely tunable bandgap in bilayer graphene was observed by
by Pearce et al. (2011). Zhang et al. (2009). Yavari et al. (2010) demonstrated that a
The hydrogenation of the graphene surface can create a tunable bandgap up to ≈0.206 eV can be engineered in gra-
stable material with a large energy band (Boukhvalov 2008, phene by the controlled adsorption of water molecules to the
Sofo et al. 2007, Savchenko et al. 2009). It is crystalline and surface of graphene. It opens a possibility to prepare sensitive
retains the hexagonal lattice, but its period becomes mark- humidity sensors.
edly shorter than that of graphene. Here, alternating carbon The earlier reported data on bandgap opening in differ-
atoms are pulled out of the plane in opposite directions by ent graphene structures under different influences are sum-
the attached hydrogen atoms. Their concentration controls the marized in Table 20.2.
size of the gap in hydrogenated graphene (Elias et al. 2009). We discussed earlier (Aroutiounian et al. 2012) that open-
Zhou et  al. (2009) showed that the energy gap can be ing of a tunable bandgap is necessary for the manufacture of
produced without cutting graphene into a ribbon. They also efficient resistive graphene chemical sensors, as pristine gra-
showed that the chemical modification of graphene is revers- phene is not a good material for gas sensing. There are other
ible; the properties of graphene can be largely restored by possibilities to make them.
annealing the hydrogenated samples at high temperatures.
The hydrogen gas, which exposed a graphene sample, is 20.6 DETECTION OF GASES BY
dissociated into hydrogen ions during hydrogen plasma
GRAPHENE RESISTIVE SENSORS
discharge (Elias et  al. 2009). The electrical conductance
becomes strongly temperature dependent, which is connected The tuning of graphene’s sensing properties can be real-
with electron “hopping,” because the presence of the gap after ized by the charge transfer between a gas and graphene. It is
the hydrogenation forces electrons to “hop” from one site to known that NO2, NH3, CO2, CO, H2O, and O2 are active gases.
another. Therefore, conduction mechanism is much more effi- Adsorption of NO2 induced higher doping compared with NO
cient at high temperatures. From the diffraction image of the (Leenaerts 2008). Gautam and Jayatissa (2011, 2012) reported
new crystal lattice, a noticeable decrease in the separation on NH3 and oxygen detection at the substrate preheating tem-
between the carbon atoms caused by hydrogen atoms is seen. perature in the 150°–200° range. The single-layer graphene
The Raman spectroscopy, which is sensitive to the vibrations changed the type of conductivity from electronic to hole on
of atoms in the crystal lattice (phonons), also shows the evolu- exposure to increased concentration of NO2.
tion of the lattice during hydrogenation. The reversible hydro- Outstanding results were obtained by Schedin et  al.
genation of graphene is important for device applications. A (2007). Figure 20.3 shows the response of zero-field
search for optimal ways of graphene hydrogenation, including resistivity of graphene to NO2, NH3, H 2O, and CO in its
304 Graphene Science Handbook

response was detected. Fast adsorption/desorption is asso-

4 ciated with pristine sites, whereas slow adsorption/desorp-
NH3 b tion is attributed to the defective sites (Ko et al. 2011). It is
interesting that the exposure of graphene to ozone dramati-
2 cally improved NO2 sensing behavior of graphene (Chung
2012a,b). Graphene chemiresistor sensor for trimethylamine
gas was realized by Rapola et al. (2014).
Δρ/ρ (%)

CO
0
H2O 20.7  FIELD-EFFECT TRANSISTOR GAS SENSORS
–2 Characteristics of FETs are changing upon exposure to differ-
ent gases. It is shown that such FET sensors are very sensitive
I II III IV and have fast response time, low noise, and cost. Rumyantsev
–4 NO2 et  al. (2012) discussed the properties of selective gas/vapor
FET sensors made of graphene. It is very important that the
0 500 1000 noise spectral density of graphene FETs changed remarkably
t (s)
under different gases (Figure 20.4).
Vapors of different chemicals (methanol, ethanol, tetra-
hydrofuran, chloroform, acetonitrile, toluene, and methylene
FIGURE 20.3  Sensitivity of graphene to chemical doping.
Changes in the resistivity ρ are caused by graphene’s exposure to chloride) lead to different forms of the low-frequency noise
various gases. The positive (negative) sign of changes is chosen spectra of graphene. The same phenomena were detected
here to indicate electron (hole) doping. Region I—the device is in earlier for porous silicon gas sensors (Aroutiounian et  al.
vacuum prior to its exposure; II—exposure to a 5 L volume of a 2008, 2009). A remarkable change in the characteristic fre-
diluted chemical; III—evacuation of the experimental setup; and quency of the Lorentzian noise was observed, which is dif-
IV—annealing at 150°C. The response time was limited by the gas- ferent for different chemicals. Rumyantsev et al. (2012) have
handling system and a several-second delay in lock-in-based mea- shown that their FET sensors are selective to different gases
surements. The annealing caused an initial spike-like response in ρ, without any surface functionalization or fabrication. The
which lasted for a few minutes and was generally irreproducible. For
low-frequency noise can be used as the sensing parameter to
clarity, this transient region between III and IV is omitted, as indi-
cated in Figure 20.5. (Adapted from Schedin, F. et al., 2007. Nature enhance selectivity and help in discriminating between dif-
Materials 6, 652–655.) ferent gases. It was also shown for porous silicon gas sensors
by Aroutiounian et  al. (2008, 2009). However, some vapors

concentration of 1 ppm. As mentioned above, gas molecules

Noise in graphene devices
adsorbed by the graphene’s surface change the electrical
Tetrahydrofuran
conductivity of graphene resistive sensors. They are acting Methanol Acetonitrile
as donors or acceptors. As the whole surface of graphene 10–7
is a 2D material, a few extra electrons can cause notable
Chloroform
relative changes in carrier concentration. The adsorbed gas
SI/I 2 × f

molecules change the local carrier concentration in gra-

phene one by one electron, which leads to stepwise changes
in resistance. Therefore, it is possible to increase the sen-
sitivity to its ultimate limit and detect individual dop-
ants. The Hall measurements revealed that NO2, H 2O, and Open air
iodine acted as acceptors whereas NH3, CO, and ethanol
were donors. There is the linear response of change of the fc1 fc2 1/f
local carrier concentration to the concentration of the gas. 10–8
100 101 102 103 104 105
It makes the use of graphene-based sensors simple. Schedin
et al. (2007) did not observe notable changes in the mobility Frequency f (Hz)
despite additional scatterers and make the conclusion that
graphene-based gas sensors allow the ultimate sensitivity FIGURE 20.4  Noise spectral density multiplied by frequency f
to the adsorption of gas molecules, that is, they have large versus frequency f for the device in open air and under the influ-
ence of different vapors. Different vapors induce noise with dif-
dynamic range of gas detection. In addition to NO2 and
ferent characteristic frequencies fc. The frequencies, fc, are shown
NH3, dinitrotoluene can be detected by graphene sensors explicitly for two different gases. The difference in the frequency
(Fowler et al. 2009). Yoon et al. (2011) reported a rather fast fc is sufficient for reliable identification of different gases with the
(10 s) linear response of the sensor to CO2 at RT and in the same graphene transistor. For comparison, the pure 1/f noise depen-
concentration range of 10–100 ppm at low power consump- dence is also indicated. (Adapted from Rumyantsev, S. et al., 2012.
tion. A two-step adsorption/desorption mechanism for such Nano Letters 12, 2294–2298.)
Graphene- and Graphene-Oxide-Based Gas Sensors 305

change the electrical resistance of graphene without change (a) 40

in the form of their noise spectra. Therefore, it is necessary to CCG
Gas off ZnO NRs/CCG
estimate the response (sensitivity) and selectivity to different
20 Gas on
gases very accurately and carefully.
Recently, GO has received great attention because it

Sensitivity (%)
readily exfoliates as single sheets in water and, from these
0
solutions, it is straightforward to produce films. Its chemi-
cal reduction increases the conductivity by several orders of
magnitude by the removal of oxygen and recovery of aro- –20
matic double-bonded carbons. The rGO is both conductive
and has chemically active defect sites making it a promis-
ing candidate for the sensors allowing detection of chemical –40
agents in the ppb range with significant reduction of noise
level. Wang et al. (2014) reported recently about the realiza- 0 2500 5000 7500 10,000
tion of GO hydrogen sensors working without the heating
of their work body. Hafiz et  al. (2014) reported about CO2 (b) Gas on CCG
Gas off ZnO NRs/CCG
GO sensors. Lu (2009) investigated rGO-based FET sen-
sors for NO2 and NH3 detection at a low concentration level. 0
These gases were diluted in air at RT. FET with intrinsic

GO sheets have no response to these gases. Electron trans-
fer from GO to adsorbed strong oxidizer NO2 leads to an
enriched hole concentration and enhanced electrical con-
duction in the rGO sheet annealed at 300°C (Leenaerts
et al. 2008, Lu 2009). Faster response time and much longer
recovery time are typical for such sensors after annealing
at 300°C in comparison with sensors annealed at 200°C.
Response (sensitivity) to NH3 is smaller. The sensor was fab-
ricated by dispersing the aqueous GO suspension onto Au
electrodes. Source–drain separation was about 1 μm. Such
electrodes were fabricated using the e-beam lithography on
a silicon wafer. Low-concentration NO2 diluted in dry air
starting from 1 ppm was detected in rGO gas sensors at RT
(Lu 2009).
Two important parameters characterize the response (sen-
sitivity)—the conductance response to molecular adsorbents
and low-frequency noise, where 1/f noise generally dominates
(Robinson et  al. 2008). Authors have shown the 10–100-
fold reduction of 1/f noise in rGO sensors over single-walled
nanotube (SWNT)-based sensors. The noise level in rGO
devices strongly decreases with an increase in film thick-
ness. Figure  3b in Robinson et  al. (2008) demonstrates the
important role of noise reduction in the responses to 0.5 ppb.
2,4-Dinitrotoluene (DNT) is a stimulant for the explosive
TNT. The lower noise levels in the rGO device lead to a nota-
ble increase in the ­signal-to-noise ratio.
It is important to note that the conductance-based rGO
sensors are sensitive to explosive gases and their stimulants
as well as to the three main classes of chemical warfare
agents and nerve agents. Dependence of change in conductiv-
ity of rGO sensor on the concentration of hydrogen cyanide
(HCN) in nitrogen is linear in double-logarithmic scale from
a minimal detectable level of 70 ppb of HCH:N2 (Figure 20.4
in Robinson et  al. 2008). Note that the detection of HCN
by carbon nanotube (CNT) sensors is impossible even at a
much higher concentration of HCN. In addition, rGO sensor
is able to detect other stimulants such as organophosphates
(i.e., dimethyl methylphosphonate [DMMP]), aromatics, and
Sensitivity (%)
–10
–20
–30
0 5000 10,000 15,000
Time (s)
FIGURE 20.5  (a) The response curve of the chemically reduced
graphene sensor to the DMMP vapor under concentrations of
5–80 ppm and (b) response of the sensors versus the concentrations
of DMMP. (Adapted from Hu, N. et al., 2012. Sensors and Actuators
B 163, 107–114.)
alkane derivatives (i.e., DNT and CEES, respectively). For
example, the response curve of rGO to DMMP is demon-
strated in Figure 20.5 (Hu et al. 2012). Note that the depen-
dence of the response on the concentration of DMMP is linear,
which is very convenient during analysis of measurements in
practice.
Chemical or biological selectivity of sensors are discussed
by Zhu et al. (2010), Singh et al. (2011), and Hu et al. (2012).
Cuong et al. (2010) used MEMS technology for the manufac-
ture of back-gated graphene FET sensors.
20.8 ACOUSTIC WAVE AND FUNCTIONALIZED
GRAPHENE GAS/VAPOR SENSORS
Gas/vapor sensing is possible using surface acoustic wave
(SAW) devices. Here, the frequency of operation of the
sensors changes with exposure to gas molecules. The shift
in frequency is proportional to the mass of adsorbed gas/
vapor molecules. SAW chemical sensors for sensing of H2
and CO at RT and 40°C, respectively, made of graphene-like
nanosheets deposited on lithium tantalate, were reported by
306 Graphene Science Handbook

(a) 16 80 ppm
ethanol, CO, NH3, H2O2, and NO with appreciable selectivity
toward electron donor gases such as CO and NH3 was carried
60 ppm out using such composite structures. They have much better
12 response to gases over ZnO nanorod or GO-based gas sen-
40 ppm
sors alone. Singh (2011) proposed that probably two differ-
ΔR/R0 (%)

20 ppm
8 ent depletion layers were coexisting, one on the ZnO surface
10 ppm
5 ppm
and the other at the interface of GO and ZnO, which improve
4
the sensitivity of the integrated system. It is possible to use
such sensors at RT. Such a composite sensor has higher gas
response, probably, due to the larger specific surface area of
0 ZnO nanoparticles on GO islands compared with the use of
ZnO alone as a gas sensor. The ZnO–GO composite sen-
0 2000 4000 6000 8000 10,000 sor is more selective to reducing gases and shows a poor
Time (s) response to oxidizing gases. Cuong et al. (2010) reported the
(b) 16
ZnO nanorod–graphene structures. Such sensors were able to
Linear fit detect 2 ppm of H2S in oxygen at RT and nitrogen at 279°C
14 (Figure 20.6). High-efficiency H2S sensors made of Fe2O3/
graphene nanosheets are reported by Jiang et al. (2014). Sun
12 and Lin (2012) reported a simulation model, where it was
y = 0.1217x + 4.9715
assumed that the sensing mechanism is based on the varia-
ΔR/R0 (%)

R2 = 0.995
10
8 for an understanding of the complicated physicochemical
6 ferometric NH3 gas graphene sensor has been reported by
4
0 20 40 60
DMMP concentration (ppm)
FIGURE 20.6  The sensitivity of ZnO NRs—a chemically con-
verted graphene thin film sensor to H2S gas in (a) oxygen at RT
and (b) nitrogen at 270°C. (Adapted from Cuong, T. V. et al., 2010.
Materials Letters 64, 2479–2482.)
Arsat et al. (2009). A bandgap of 0.1 eV was opened in such
a graphene–LiTaO3 sensor. Other type of mass sensitive sen-
sors is bulk acoustic wave (BAW) sensors (graphene-based
quartz crystal microbalance (QCM) gas/vapor sensors).
Here, the mass is linearly dependent on frequency quite
similar to that of SAW sensors. A down to nanogram change
in the electrode mass can be detected in acoustic wave sen-
sors very efficiently (Yao et al. 2011). High sensitivity and
stability are typical for the mass-sensitive BAW and SAW
devices. SAW made of a single graphene layer was used
for the detection of the noble gases He, Ne, Ar, Kr, and Xe
(Arash et al. 2011).
Functionalization (decoration) of graphene became prom-
ising for gas detection metal oxides such as TiO2, ZnO, etc.,
leading to dramatically improving the selectivity aspects.
This was demonstrated, for example, by us for CNT sensors
(Aroutiounian 2014, Aroutiounian et al. 2012). For example,
we observed synergetic effect in the TiO2–CNT system—the
response to e-butane which was absent for TiO2 and CNT
separately. Such graphene-metal oxide functionalized gas
sensors made of ZnO–nanorod–GO were investigated by
Palanisamy et al. (2012), Yi et al. (2011), Singh et al. (2012),
Sun and Lin (2012), and Cuong et  al. (2010). Detection of
tion of conduction of the nanoscale wire placed between two
graphene leads. Other theoretical models should be proposed
processes in such systems. All-optical Mach–Zender inter-
Yao et al. (2014).
80
20.9 ANALYSIS OF EXPERIMENTAL
RESULTS OBTAINED FOR DIFFERENT
GRAPHENE SENSORS
The development of sensors with high response, short
response, and recovery times, as well as high selectivity is
still necessary. We are today on the stage of collecting infor-
mation about parameters of graphene/GO gas/vapor sensors.
Anyway, the best results for the response t1 and recovery t2
times are today for resistive and functionalized sensors.
Earlier graphene sensors functionalized with catalytically
active Pd or alloys containing Pd provide faster response
and recovery times at hydrogen sensing by graphene–metal
composite layers. Resistive hydrogen sensors working at RT
have t1 ~ 10–30 s, but t2 ~ few min in the detection range
40–8000 ppm (Johnson et al. 2010) and 40 and 50–60 s in the
0.5%–1% range (Lange et al. 2011). Correspondingly, t1 and t2
are equal to 70–100 and 200–300 s during NO2 detection in
the 100–1000 ppm range (Ko et al. 2010). In the case of CO2
detection, t1 and t2 were 8 and 10 s in the range 10–100 ppm
(Yoon et al. 2011). The FET detection of ethanol vapors with
t1 = 5–10 s and t2 = 30–40 s was reported by Chen et  al.
(2012). The situation with functionalized graphene–metal
oxide sensors at RT is rather good. t1 = 5–6 s and t2 = 2–5 s
were reported in the case of CO2 and NH3 detection (Singh
et al. 2012). t1 and t2 are equal to several min—10–25 min for
other above-reported graphene sensors detecting NO, H2, O2,
CO, CO2, NH3 gases, and ethanol vapor. No details of param-
eters (including the selectivity and stability) of sensors to
Graphene- and Graphene-Oxide-Based Gas Sensors
chemical warfare agents and other important toxic gases such
as H2S and O3 are available. We think that the development of
graphene gas/vapor sensors is in the beginning. We hope that
valuable parameters for practical applications of such sensors
will be reported in the near future.
20.10 CONCLUSION
A brief information about different synthesis procedures for
graphene and GO is given in this chapter. We have reviewed
the recent developments in the field of gas/vapor sensors made
of graphene and GO. Sensing of different gases and vapors
(in particular, NO2, NO, NH3, CO, etc.) is of great practical
interest for industrial, domestic, environmental, medical, and
scientific applications. The manufacture of gas/vapor sensors
demands a detailed knowledge of its sensitivity, selectiv-
ity, stability, interface, mechanical and electrical properties,
transduction efficiency, etc. But in many cases, the lack of an
energy gap in the electronic spectra of pristine graphene, for
example, prevents its use in making transistors, logic circuit
devices, and sensors. Several methods have been developed to
break the lattice symmetry in graphene and open an energy
gap. Note that the opening of the bandgap in graphene is a
unique phenomenon.
Several versions of gap opening are discussed in the chap-
ter. The best surface-to-volume ratio is in graphene-like 2D
materials. Every atom of graphene, being a surface atom, is
capable of interacting with the target gas or vapor species,
which eventually results in the ultrasensitive sensor response
with the detection capability of even a single molecule of gas/
vapor. In particular, graphene should be doped with P, B,
N, and H2, as nonmodified graphene is no an ideal material
for gas/vapor sensing. Moreover, B-doped graphene is a two
orders of magnitude higher sensitive sensor of NO, NO2, or
NH3 than N-doped graphene. The response and selectivity of
graphene sensors could be remarkably improved by the intro-
duction of controlled defects and impurities into graphene.
Therefore, the use of graphene has opened up an opportunity
for the detection of gases and vapors with excellent sensitiv-
ity, fast response time, and high stability. It is very important
that gas/vapor sensors made of graphene and GO have mainly
room-temperature operational temperature, and can work
without preheating of work body of the sensor.
Different types of graphene/GO gas/vapor sensors are con-
sidered in this chapter. Besides resistive sensors, FET, noise,
acoustic wave, functionalized sensors, as well as graphene-
based quartz crystal microbalance sensors are reported.
We have discussed the possibilities, specific properties, and
parameters of detection of the following gases and vapors: H2,
O2, NO2, NO, CO2, CO, NH3, H2S, J2, H2O2, SO2, chloride,
arsenic, humidity, ethanol, methanol, nonanal, tetrahydrofu-
ran, chloroform, acetonitrile, octanoid acid, hydroquinone,
dinitrotoluene, trimethylamine, dopamine, HCN, DMMP,
DNT, TMA, CEES, noble gases, other chemical warfare
agents, and important gas/vapors.
As the graphene films have lower resistance (typically a
few hundreds of ohms) compared with the metal oxide–based
307
gas sensors, graphene/GO sensors can be integrated with ICs
easier. Graphene and its oxides promise the development of
more efficient gas sensors in the near future.
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Section IV
New Applications
 21 Approaches and Applications
Graphene-Based Materials for Fuel Cells

Junrui Li and Haolin Tang

CONTENTS
Abstract.......................................................................................................................................................................................313
21.1 Introduction.......................................................................................................................................................................313
21.2 Composite Graphene Oxide/Polymer as Proton Exchange Electrolyte.............................................................................314
21.2.1 GO as Additives in Polymer Composite Membranes: Improved Mechanical Strength,
Proton Conductivity, and Depressed Methanol Permeability...............................................................................314
21.2.2 Functionalized GO for Novel PEMs: Surface Decoration of the Versatile GO....................................................317
21.3 Graphene as Support for Metal Catalyst in Fuel Cells......................................................................................................319
21.3.1 Bare Graphene as Support for Noble Precious Metal with Enhanced Electrocatalytic Activity......................... 321
21.3.1.1 Synthesis of Graphene-Supported Noble Metal and Noble-Metal Alloys............................................ 321
21.3.1.2 Interaction between Noble-Metal Particles and Bare Graphene Support: Principles for
Immobilization and Enhanced Electrocatalytic Activity...................................................................... 321
21.3.2 Modified/Functionalized Graphene as Support for Noble Metals: Improved Durability.................................... 323
21.4 Graphene-Based Non-Noble-Metal Me─N─C (Me ═ Fe, Co) Complex Catalyst for Fuel Cells.................................... 323
21.5 Graphene-Based Metal-Free ORR Electrocatalyst.......................................................................................................... 325
21.5.1 Principle for Graphene-Based Metal-Free ORR Electrocatalyst......................................................................... 325
21.5.2 Advances in Graphene-Based Metal-Free ORR Electrocatalyst.......................................................................... 326
21.6 Other Applications in Fuel Cell and an Outlook on the Commercialization
of Graphene-Based Materials for Fuel Cells.................................................................................................................... 327
21.7 Summary.......................................................................................................................................................................... 328
References.................................................................................................................................................................................. 328

ABSTRACT hydrogen storage systems, etc. By means of the nanoscaled

Graphene, the two-dimensional sp2-hybridized carbon, has
emerged as a versatile material. Characterized by a long-range
π-conjugation and a comb-like network, graphene possesses
extraordinary mechanical and electronic properties, which
makes it a very promising candidate for critical materials in
fuel cell systems. Graphene has already been intensively stud-
ied as an ideal support for catalysts used in fuel cells. Owing
to its large surface area, fast electronic transfer process, supe-
rior mechanical, and chemical stability, graphene-based sup-
port can significantly prompt oxygen reduction kinetics and
enhance the durability of a well-dispersed catalyst layer under
fuel cell operation conditions. The benefits offered by gra-
phene and its derivatives also make them important compo-
nents for the nonprecious metal catalyst, Me─N─C (Me ═ Fe,
Ni, Co, etc.), and the metal-free oxygen reduction reaction cat-
alyst, which have been currently considered as the potential
material to solve the efficiency and cost problems in fuel cell
commercialization. The utilization of graphene-based mate-
rial in fuel cells is not only limited as the catalyst support or
as a metal-free catalyst, but it has also been developed as (i)
an additive in the polymer/graphene oxide composite proton
exchange membrane, (ii) bipolar plate materials, and (iii) as
manipulation of physical geometry and chemical functional-
ity, a selectively facilitated transport behavior of graphene/
polymer composite can be achieved. Hence, graphene has
been recognized as a cost-effective and performance-superior
alternative with the potentially large-scaled production for the
traditional key components in fuel cells.
21.1 INTRODUCTION
With the depletion of traditional fossil fuels and increasingly
severe environmental pollution, fuel cells have been receiving
intensive attention as one of the most attractive clean power
sources, in which the inherent chemical energy of fuels such
as hydrogen, methanol, ethanol, and natural gas are directly
converted into electricity via the interfacial electrocatalytic
reaction at the triple-phase boundaries (TPBs), the inter-
nal ionic transport through the electrolyte (or membrane),
and by the external electric conducting process. Among the
diverse types of fuel cells, proton exchange membrane fuel
cell (PEMFC), including direct methanol fuel cell (DMFC),
direct ethanol fuel cell (DEFC), etc. have received consider-
able attention for commercialization from portable electronic
devices to vehicle transportation and to a stationary power

313
314
source owing to their high-energy density and low operating
temperature. However, there are still some critical obstacles
inhibiting the broad application of fuel cells, such as the low
performance of the key component materials and high cost of
the noble metal platinum (Pt)-based catalysts.1
Among the recently emerging materials for application
in fuel cells, graphene, a two-dimensional (2-D) sheet with
a thickness of only a carbon atom diameter, and its deriva-
tives, such as graphene oxide and functionalized graphene,
have been commonly studied as key materials for fuel cells,
including (i) additives in proton exchange membrane (PEM)
for PEMFCs,2,3 (ii) support for the noble-metal catalyst and
nonprecious metal catalyst for methanol oxidation reaction
(MOR), ethanol oxidation reaction (EOR), oxygen reduction
reaction (ORR), hydrogen oxidation reaction (HOR), as well
as oxygen evolution reaction (OER) and hydrogen evolution
reaction (HER) for fuel cells and water-splitting devices,4–6
(iii) a metal-free electrochemical catalyst for fuel cells,7,8
(iv) the main component for the electron-conducting bipolar
plates, and (v) hydrogen storage material via either physisorp-
tion or chemisorption.9 The graphene-based materials for fuel
cells have achieved extraordinary benefits derived from the
inherent properties of graphene, such as high surface area,
exceptional electric conductivity, good mechanical strength
as well as chemical tolerance, a broad electrochemical win-
dow, unique graphitized basal plane structure, and potential
low manufacturing cost.10,11
However, similar to the other newly developed materials
for fuel cells, the processability and availability of graphene
have been restricting its broad application and development.
The theoretical mass-specific surface area of up to 2630–
2965 m2 g−1 of graphene makes it a perfect support for the
fuel cell catalyst and provides an ideal interface for electro-
catalytic reaction,12 whereas the big challenge in the synthesis
and preparation process is that the strong integrating energy
of π-stacked layers in graphite, namely the high cohesive van
der Waals (VDW) energy (5.9 kJ mol−1 carbon), should be
surmounted.10 A myriad of research for graphene-supported
metal fuel cell catalyst focus on inserting additional electro-
catalytic active metals between the basal planes or intercala-
tion. Deposition of inorganic materials, especially the noble
precious metal, onto the graphene nanosheets has greatly stim-
ulated research interests since the high electric conductivity
(103 ~ 104 S m−1) of long-range π-conjugation in graphene can
significantly facilitate the electrocatalytic reaction and thus
decrease the amount of the precious metal used. In addition,
graphene has a chemical perspective similar to carbon nano-
tubes (CNTs), in which it can be functionalized with polymers,
nanoparticles (NPs), or atomic dopants, making graphene and
its derivatives versatile materials for application in fuel cells.
This chapter will review and discuss the diversified graphene-
based materials recently emerged for application in fuel
cells. Moreover, the approaches and routines via which the
graphene/polymer composite, NPs-decorated graphene, func-
tionalized or heteroatom-doped graphene, and so forth have
been prepared will be summarized. Simultaneously, the rela-
tionship between the graphene structures and the enhanced
Graphene Science Handbook
performance of graphene-based materials will be included as
a reference for research and development (R&D) of graphene.
Finally, a summary and outlook on graphene-based materials
in fuel cells will be briefly presented in Table 21.1.
21.2 COMPOSITE GRAPHENE OXIDE/POLYMER
AS PROTON EXCHANGE ELECTROLYTE
The PEM, which conducts the protons generated at the elec-
trochemical interfaces of the membrane and the catalyst layer
via either a Faradaic or a non-Faradaic process, is at the heart
of PEMFCs. As the benchmark PEM material in a fuel cell,
Nafion, a perfluorosulfonated ionomer (PFSI) with a bicon-
tinuous structure, has received significant attention due to its
high proton conductivity together with good chemical and
mechanical stabilities.130,131 However, some drawbacks, such
as high methanol permeability, high cost, sharp decline of
proton conductivity at temperatures above 100°C, and con-
siderable swelling or shrinkage due to water adsorption or
desorption, limit its broad commercialization and application
in fuel cells.132
Recently, graphene has emerged as one of the most fas-
cinating alternatives for membrane materials due to its ther-
mal stability, extremely high Young’s modulus (~1.0 TPa),
and due to its large breaking strength of 42 N m−1 despite its
astonishingly small thickness. However, the pristine graphene
is highly electron conductive that can lead to a short circuit
in the proton-conductive membrane and has a tendency to
agglomerate in the polymer/graphene composite membrane.
Therefore, graphene oxide (GO), which is an electronic insu-
lator and formerly called graphite oxide or graphic acid, has
been recognized as an ideal membrane filler for polymer elec-
trolytes to drastically reinforce the mechanical strength of
PEMs, decrease the membrane thickness, and consequently
reduce the ohmic loss in the membrane.133,134 Moreover, car-
boxylic acid or hydroxyl groups on the GO surface partially
exist in the format of ─COO− and H+ or ─O− and H+ in acid
environment, providing abundant protons and chemically
active sites for further functionalization on the surface.135 The
synthesis approaches, properties, performance, and applica-
tions of advanced GO-based composite PEMs are listed in
Table 21.2.
21.2.1 GO as Additives in Polymer Composite
Membranes: Improved Mechanical
Strength, Proton Conductivity, and
Depressed Methanol Permeability
GO is generated from the oxidation of graphite and can be
easily dispersed in polar solvents such as water, before the
casting process of the composite membrane. As for the fab-
rication process of the composite membrane, solution mixing
is the most straightforward routine. However, GO is hardly
soluble in nonpolar solvents; thus, a sonication treatment was
usually employed for GO dispersion. Jung and coworkers111
have employed the sonication treatment followed by directly
Graphene-Based Materials for Fuel Cells 315

TABLE 21.1
Overview of Graphene/Graphene Derivative-Based Materials for Fuel Cell Application
Type of Graphene Application in
in Materials Fuel Cells Synthesis Methods Comments Reference
Heteroatom-doped Metal-free (i) CVD of carbon and heteroatom sources, (i) The introduction of heteroatoms break the 7,13–44
graphene, such as electrocatalyst (ii) heat treatment of graphene materials electron neutral of graphene and facilitate
N-doped, S-doped, (for ORR in with heteroatom sources (either solid or adsorption of oxygen molecules, (ii) easy
B-doped, P-doped, most cases) gas), (iii) direct carbonization of organic control of a number of the catalytically active
or several heteroatom-containing precursors, and (iv) sites, (iii) comparable activity and stability to
elements of ball milling Pt/C for ORR and a higher richness of
codoped graphene elements, and (iv) most of them suffer from
low activity in acid medium
Graphene/ Support for (i) Atomic layer deposition (mostly used for (i) Enhanced electrocatalytic activity 5,13,45–91
functionalized electrocatalysts preparing metal NPs supported on pure compared to commercial metal catalysts, (ii)
graphene graphene or GO), (ii) one-pot solvothermal reduced charge-transfer resistance in some
reduction of GO and metal precursors (in functionalized graphene supports, and (iii)
some cases, microwave assisted), (iii) potential degradation problem due to
sputtering, (iv) polymer functionalization of aggregation of metal NPs on the smooth
graphene, followed by metal precursor surface of graphene
reduction, (vi) surfactant-stabilized metal
colloids supported on graphene, and (vii)
electrodeposition
Graphene Nanoadditives Mixed with polymers (i) Significant increase in thermal, mechanical, 92–94
in conducting and electrical properties with only a low
bipolar plates content, and (ii) good dispersion in polymers
due to the special 2-D topography
Multilayers of Hydrogen — (i) Chemical functionalization can improve the 9,95,96
graphene storage hydrogen storage, (ii) the physisorption can
only be achieved effectively at low
temperature and high pressure, (iii) a very
high gravimetric density via chemisorption,
and (iv) most studies are theoretical
Graphene/ Component in Thermal treatment of carbon, N, and metal (i) Enhanced activity and higher stability 97,–110
functionalized Me─N─C precursors compared to Me─N─C (disordered carbon)
graphene nonnoble catalysts, (ii) the electrocatalytic activity
electrocatalysts depends on the type of N elements and
(Me ═ Fe, Co, metals in the catalysts, and (iii) some suffer
Ni, Cu, etc.) from low activity in acid medium
GO/functionalized Nanoadditives Mixed with polymer solutions and filtration (i) Easy functionalization of GO to introduce 2,3,111–129
GO in PEM or to prepare a pure functionalized GO PEM hydrophilic groups (─SO3H, ─COOH, and
free-standing ─OH), (ii) enhanced mechanical strength,
PEM materials increased proton conductivity, and decreased
methanol permeability compared to parent
polymers, (iii) increased water-retention
ability and self-humidification effects, and
(iv) the pure SGO PEM suffers from a higher
hydrogen crossover than polymer membranes

Note: Oxygen reduction reaction (ORR), nanoparticles (NPs), graphene oxide (GO), proton exchange membrane (PEM), sulfonated graphene oxide (SGO).

mixing the GO dispersion and Nafion solution to cast homo-
geneous GO/Nafion composite membranes, with a GO con-
tent ranging from 0.1 wt.% to 2 wt.%. Meanwhile, despite
the simple operation of sonication treatment, the sonication
effect may lead to breaking of the graphene structures. Tang
and coworkers112 introduced a facile preparation of rolled-up
graphene oxide nanosheets (GOSs) by “evaporating” GOSs
from their aqueous dispersion to an aluminum foil surface,
where the GOSs self-assembled into hole-like structures that
can be easily controlled via simply adjusting the H2O con-
tent in the original GOSs dispersion (see Figure 21.1). Then a
GO/Nafion composite membrane was successfully prepared
by impregnating concentrated Nafion solutions into the hole-
like matrix of rolled-up GOSs. GOs can interact with both
the nonpolar backbone and the polar ionic clusters in Nafion
due to its amphiphilic characteristics of GOs attributed to its
316 Graphene Science Handbook

TABLE 21.2
Synthesis and Performance of Different Graphene-Based Composite Membranes
Type of Composite Methanol
Membrane Synthesis Method Proton Conductivity Permeability Mechanical Strength Reference
PEO/GO Mixed solution casting 0.086 S cm−1 (25°C, 100% — Tensile strength of 133
RH), 0.134 S cm−1 (60°C, 52.22 MPa and
100% RH) Young’s modulus
3.21 GPa
SGO/Nafion Mixed solution casting 10 wt.% f-GO/Nafion was Both composite — 2,111–113,​
GO/Nafion 0.047 S cm−1 at 120°C and membranes have 115,119,122
30% RH, whereas the proton lower than pure
conductivity decreases with Nafion membranes
the increase of the amount of
GO in the nonfunctionalized
GO/Nafion membrane
SPI/GOs A solution comprising Superior than Nafion 117 at SPI/GO_0.9 wt.% SPI/GO_0.9 wt.% 3
different ratios of GO 90°C and 60% RH, but 4.31 × 10−7 cm2 s−1 ~90 MPa
(or PSS-G) and inferior than Nafion 117 at
DMSO (1 mL) casting 60°C and 60% RH
SGO/PBI/PA Mixed solution casting, 0.052 S cm−1 at 175°C and — — 114
followed by anhydrous condition
immersing the
membrane in PA
SPI/graphene/IL Mixed solution casting with 0.5 wt.% — Young’s modulus and 136
grapheneloading, was tensile strength reach
7.5 × 10−3 S cm−1 at 160°C 2.04 GPa and
and anhydrous condition 57.9 MPa, respectively
SPEEK/SDBS- Mixed solution casting SPEEK/SDBS-GO (8 wt.%) 0.95 × 106 cm2 s−1 — 117
adsorbed GO 162.6 mS cm−1 at 65°C and (SPEEK/SDBS-GO
100% RH [8 wt.%])
comparable to
Nafion 112
Free-standing SGO Filtration of SGO In-plane proton conductivity — — 121
colloids (0.04 S cm−1) is higher than
through-plane proton
conductivity (0.012 S cm−1)
at 40
SGO/SPEEK Mixed solution casting 5 wt.% of SGO in the SGO/ 3.8194 × 10−7 cm2 — 116,124
SPEEK, 0.0983 S cm−1 at s−1 (5 wt.% of
65°C (RH was not controlled) SGO)
GO nanosheets — In-plane proton conductivity as — — 118
high as 1.5 × 10−2 S cm−1 at
87°C and 100% RH

Note: Sulfonated poly(ether ether ketone) (SPEEK), sodium dodecylbenzene sulfonate (SDBS), sulfonated graphene oxide (SGO), graphene oxide (GO),
sulfonated polyimide (SPI), ionic liquid (IL), polybenzimidazole (PBI), phosphoric acid (PA), poly(ethylene oxide) (PEO).

hydrophobic π-conjugation and the hydrophilic functional
groups at the surface. The mutual interaction between GOSs
and Nafion matrix caused the rearrangement of the micro-
structures of Nafion moiety in the composite membranes,111,112
resulting in an enhanced proton conductivity of the composite
membrane compared with pristine Nafion, especially under
low humidity conditions.113
Furthermore, the abundant carboxylic acid groups on GO
surface endow it with proton-conductive capability; there-
fore, GO can be employed as the proton-conductive filler
into diverse polymers for developing novel PEMs to replace
Nafion membranes. Additionally, the interconnected ionic
channels in Nafion polymer electrolyte, through which the
protons are transported, also act as a methanol-permeating
pathway in DMFCs and gas diffusion channels for hydrogen
PEMFCs.137 The laminated GOs incorporated in polymers
can not only promote the proton conductivity significantly,
but can also result in a positive effect on reducing the metha-
nol permeability of the composite membranes by means of
the barrier and molecular sieve effect of the 2-D-structured
GO.138 Cao et  al.133 cast a novel GO/poly(ethylene oxide)
(PEO) composite membrane as an excellent alternative for
Graphene-Based Materials for Fuel Cells 317

400 nm 45°C –48 h –50 v/v% H O(THF)

2 Height (2D) (b) Phase (c) (d) Height (3D)
(a)

Rolling up
Rolling up 50 nm 50 nm

C Al: 0.35 wt.%

Cu
O Al Cu 500 nm 500 nm
500 nm 0 1 8 9 10
Energy (keV)
C O Al: 4 B4 wt.%
(e) Height (2D) (f ) Phase (g) (h) Height (3D)
Al Cu
Cu
0 1 8 9 10
Energy (keV)
50 nm

Further rolling
500 nm 500 nm
200 nm 45°C –48 h –80 v/v% H2O (THF)

1) 2) 3) 4) 5) Perspective
4) 3)
5) 2)

1)

(i)

H2O content increasing

Al3+
CNS
GOS Rolled-up GOS

FIGURE 21.1  (a through h) TEM, EDS, and AFM images of the rolled-up GOSs prepared at 50/80 v/v% (volume ratio) H2O under 45°C
for 48 h (H2O/THF); (i) schematic quantity (of Al3+ ions)-dependent rolling process of the “evaporated” GOSs on the aluminum foil surface.
(Reprinted with permission from K. Feng, B. Tang, P. Wu, “Evaporating” graphene oxide sheets (GOSs) for rolled up GOSs and its applications
in proton exchange membrane fuel cell. ACS Applied Materials and Interfaces, 5, 1481–1488. Copyright 2013 American Chemical Society.)

the commercially used Nafion membrane, which possesses a
superior proton conductivity at low temperatures from 20°C
to 60°C than the conventional PEMs. In this polymer/GO
composite membrane, both PEO and GO are hydrophilic,
and humidity is necessary since water absorbed in the for-
mer acts as a proton-transporting medium, while the latter
provides available protons released from the ─COOH groups
on the GO sheet. Hwang and coworkers3 replaced Nafion
with a sulfonated polyimide (SPI)/GO composite mem-
brane and studied its proton conductivity, water retention
ability, and water diffusion behavior. GOs incorporated in
the composite membranes were found not to accommodate
additional water because the water diffusion coefficients of
SPI/GO composite membranes were lower than that of the
pristine SPI membrane. Despite the incorporation of GO that
resulted in inferior ion exchange capacity (IEC) of SPI/GO
composite membranes compared with that of the pristine SPI
membrane, the bound water content, namely, the water reten-
tion ability was yet enhanced. Proton conductivities of this
type of SPI/GO membranes increased with the GO content
(not more than 0.5 wt.%) in the composite and were several
times higher than that of Nafion 117 membrane at 90°C.
However, the increase of proton conductivity with the GO
content was never monotonous, as shown in Figure 21.2. It
seems there exists a balance between the positive effect and a
blocking function of the incorporated GO in composite mem-
branes. When the content of GO surpassed a critical value
(~0.5 wt.%) in the composite membrane, the blocking effect
of GO will become much more dominant than its positive
effect on water retention and proton transport, thus resulting
in a decreased proton conductivity in general. The blocking
effect of GO was further demonstrated by the monotonous
reduction of methanol permeability in the SPI/GO composite
membranes with increasing the content of GO.
21.2.2 Functionalized GO for Novel PEMs:
Surface Decoration of the Versatile GO
Owing to the presence of carboxylic acid, hydroxyl groups, and
epoxy oxygen on the surface, GO has become a versatile plat-
form for further functionalization like sulfonation and poly-
mer decoration to develop diversified PEMs with enhanced
performance. When in contact with water, the sulfonic acid
moiety can form a hydrophilic domain with a size of about
40 Å, which can result in enhanced water retention ability and
the consequent higher proton conductivity; thus sulfonated
graphene oxide (SGO) has been extensively studied, especially
for application in DMFCs.2,114–116 Choi et  al.2 compared the
SGO/Nafion composite membrane with the GO/Nafion com-
posite membrane, SGO/Nafion. The strong mutual interaction
318 Graphene Science Handbook

(a) 0.12

Proton conductivity (S/cm)

90°C at RH 0.10
60°C 60%
0.08

0.06

0.04

0.02

Nafion 0
117 0.9
0.7 0.5 0.3
SPI/PSS GO conten 0.1 0
_G 0.5 t (wt.%)

(b)

%
≤0.5

>0.
5%

Water MeOH SPI Graphene oxide

FIGURE 21.2  (a) Influence of 60% relative humidity on the proton conductivity of composite membranes at 60°C and 90°C. (b) Scheme
showing the GO loading in the prepared membrane. (Adapted from C. Y. Tseng et al., Advanced Energy Materials, 2011, 1, 1220–1224.)

between the SGO and Nafion resulted in folding of the SGO
sheets, reflected by the smaller size of SGO in the transmission
electron microscope (TEM) image (Figure 21.3a) compared
with that of original GO sheets.139 The microstructures and
reorganization of these two composite membranes and Nafion
have also been compared by using small-angle x-ray scattering
(SAXS) and wide-angle x-ray scattering (WAXS), as shown in
Figure 21.3c and d. The reduced intensity of scattering peaks of
SGO/Nafion and GO/Nafion composite membranes compared
with that of pristine Nafion membrane can be attributed to the
compatibility of amphiphilic GO and SGO on the hydrophilic
and hydrophobic domains of Nafion, given that the intensity is
proportional to the difference in the electronic density between
the backbones and ionic clusters in Nafion. Among these three
membranes, SGO/Nafion composite membrane exhibited the
largest IEC value and subsequently superior proton conduc-
tivity than both GO/Nafion and pristine Nafion membranes at
the same condition, though the water uptake of SGO/Nafion
is slightly smaller than Nafion. High-temperature-operated
polymer electrolyte membranes have been successfully pre-
pared by intercalating an ionic liquid such as polybenzimid-
azole (PBI) or inorganic acid into the layers of SGO.114 PBI/
SGO composite membrane, with a low phosphoric acid (PA)
loading, exhibited an extraordinarily high proton conductiv-
ity of 0.052 S cm−1 compared with 0.023 S cm−1 of a pure PBI/
PA membrane at 175°C and 0% humidity, where the commer-
cially used Nafion membranes significantly lose their proton
conductivity.114
The introduction of protic functional groups, such as sul-
fonic and carboxyl groups in GO can also be achieved via the
organo-decorated or organo-absorbed method except the con-
centrated sulfonic acid treatment.117 Huang and coworkers136
reported a novel composite membrane based on the protic
ionic liquid polymer-modified graphene sheets, in which the
three-dimensional (3D) network formed by graphene sheets
through the polymer matrix provides interconnected transfer
Graphene-Based Materials for Fuel Cells
(a)
200 nm
(c)
Nafion 112
SGON
Relative intensity
GON
1 2 3 4
Scattering vector (nm–1)
FIGURE 21.3  (a) Cross-sectional TEM image of SGON membrane. (b) Cross-sectional SEM and photo (inset) images of SGON mem-
brane and (c) SAXS and (d) WAXD curves of Nafion 112, SGON, and GON membranes. (Reprinted with permission from B. G. Choi
et al., Innovative polymer nanocomposite electrolytes: Nanoscale manipulation of ion channels by functionalized graphenes. ACS Nano, 5,
5167–5174. Copyright 2011 American Chemical Society)
channels to facilitate proton transport and enhance the adhe-
sion of the polymer–graphene fillers to reinforce the mechan-
ical strength of the membrane. Nicotera and coworkers
prepared a series of organo-modified graphene sheets as addi-
tives in Nafion membranes, with 3-amino-1-propanesulfonic
acid (SULF), 5-aminovaleric acid (VAL), and 2-amino-3-hy-
droxypropanoic (SER) as organomodifiers. It is noticeable
that GO-based PEMs have an evident difference in the in-
plane proton conductivity and the through-plane proton con-
ductivity. GO nanosheets can possess a significantly higher
proton conductivity than GO in the bulk phase, indicating a
size-dependent effect and the anisotropy of the proton con-
ductivity in this proton-conducting material.118
21.3 GRAPHENE AS SUPPORT FOR
METAL CATALYST IN FUEL CELLS
In fuel cells, the conversion of chemical internal energy into
electrical energy is initiated by the electrochemical reaction
occurred in the catalyst layer. The performance of a fuel cell
is primarily dominant by the catalytic efficiency. The noble-
metal Pt has been treated as the benchmark for the electro-
chemical catalyst used in fuel cells. However, the practical
utilization of Pt-based fuel cells has been severely hampered
due to the high cost, poor utilization efficiency of metal load-
ing per unit area, and sensitivity to the carbon monoxide (CO)
319
(b)
2 μm
(d)
Nafion 112
SGON
Relative intensity
GON
10 15 20 25 30
Scattering angle (2 θ)
poisoning of Pt. The size, dispersion, as well as the distribution
and stabilization of metal catalyst particles are mainly depen-
dent on the catalyst support. The characteristics of the catalyst
support should meet the following requirements to be used
in fuel cells: (i) high specific surface area to create sufficient
immobilizing and effective TPB sites, where the electrocata-
lytic reaction of fuel or oxygen on the surface of the catalyst
happens; (ii) chemically and electrochemically stable at the
strong acid or alkaline and high-potential ambient in a running
fuel cell; (iii) strong interaction with the metal catalyst parti-
cles to ensure fine dispersion and prohibit the agglomeration of
metal particles during the cycle condition; and (iv) satisfactory
electric conductivity for a fast charge-transfer process.
Carbon black (Vulcan XC-72) is the most commonly used
catalyst support for fuel cells, but its property is not sufficiently
satisfactory. To overcome the drawbacks of the state-of-the-art
noble Pt catalyst, various novel supports have been extensively
studied, among which graphene arose as the most promising
and intriguing. The benefits offered by graphene can not only
improve the catalyst efficiency to reduce the amount of noble
metals used via its unique electric property and high surface
area, but can also enhance the catalyst durability due to its sta-
ble graphitized basal plane structure. Table 21.3 summarizes
bare graphene and functionalized/doped graphene as an effi-
cient support for noble-metal electrocatalysts with enhanced
performance and/or durability applied in fuel cells.

TABLE 21.3
Synthesis, Properties, and Applications of Diverse Graphene- and Functionalized Graphene-Supported Noble-Metal Catalyst
Type of Electrocatalyst
Pd2PtFe/3DGF (three-
dimensional graphene
framework)
FeCN/NG (N-doped
graphene-supported
carbon-containing iron
nitride)
PtRu/FGSs (functionalized
graphene sheets)
Pt/graphene (ALD)
Pt–Au–graphene
Pd NPs on graphene
TDMAC-RGO
(tridodecylmethylammonium
chloride-functionalized
reduced graphene oxide)
Pd-deposited N-HOPG (highly
oriented pyrolytic graphite)
Pt/graphene-wrapped MWNT
hybrids
TP-BNGN (3D Pt-on-Pd
bimetallic nanodendrites
supported on GNs)
Graphene multilayer-
supported gold NPs
PdAg–GNs
320
Metal NP Size and Metal Maximum Current/Power
Synthesis Method Applications Loading ECSA Density Reference
Solvothermal Formic acid PtFe nanowires, 2 ~ 5 nm in −2
0.04 mg cm (Pd), — 66
oxidation diameter 0.036 mg cm−2
(Pt)
Chemical impregnation of iron and ORR Catalyst loadings of 200 mg cm−2 — Steady-state catalytic current 140
N-containing precursors in the presence of density at 0.05 V, GO:
ammonia under thermal treatment 20.18, NG: 20.60, and
FeCN/NG: 23.53 mA cm−2
With the assistance of supercritical carbon MOR PtRu NPs with an average size of 205.7 mA per — 141
dioxide (SC CO2), ultrafine PtRu NPs 2.87 nm; the PtRu/FGS mg Pt
uniformly distributed on the surfaces of composites loaded with 20 wt.%
functionalized graphene sheets (FGSs) by Pt and 10 wt.% Ru
the reduction of a mixture of H2PtCl6 and
RuCl3 precursors
Atomic layer deposition (ALD) technique MOR Loading of Pt on graphene can be — 22.9 mA cm−2 53
precisely controlled, ranging
from 1.52 wt.% to 2.67 wt.% and
10.5 wt.%
Electrodeposition of Pt–Au nanostructures ORR and MOR The size and shape of the prepared 82.2 m2 g−1 — 142
on the surface of graphene sheets NPs can be easily controlled by
Solution phase reduction of palladium Formic acid 4.5-nm Pd NPs — — 143
acetylacetonate with morpholine borane in electrooxidation
a mixture of oleylamine and 1-octadecene
A simple physicochemical process ORR — — — 144
Ion implantation on the nucleation and ORR — — — 145
stabilization of metal NPs
CVD ORR 6.9, 4.2, 4.4, and 3.4 nm 20% Pt — Pt/GC-240 and Pt/GC-500- 146
based fuel cells are 661 and
653 mW cm−2 respectively
Wet-chemical approach ORR The Pt-on-Pt bimetallic 81.6 m2 g−1 — 5
nanodendrites had an average
size of 15 nm
Electrostatic interaction of two oppositely Methanol — — — 50
charged suspensions of the GO nanosheet oxidation
with Au NPs
A facile two-step approach ORR PdAg nanorings, 27.3 ± 6.3 and — 1.9 mA cm−2 at the 147
27.5 ± 6.2 nm, respectively PdAg–GNs/GC electrode
Graphene Science Handbook
Graphene-Based Materials for Fuel Cells
21.3.1 Bare Graphene as Support for Noble
Precious Metal with Enhanced
Electrocatalytic Activity
21.3.1.1 Synthesis of Graphene-Supported Noble
Metal and Noble-Metal Alloys
One-pot simultaneous reduction of GO and the metal pre-
cursors (i.e., chloroplatinic acid) in the presence of reduc-
ing reagents, including ethylene glycol,45,148 NaBH4,149,150
hydrazine,151 ammonia,5 sodium citrate,152 ethanol,153 and so
on, or by the microwave-assisted reduction154–156 was one of
the most frequently used methods to prepare graphene-sup-
ported metal nanocomposites. To differentiate graphene syn-
thesized by reducing GO from graphene obtained via other
routines, researchers usually name the former as reduced
graphene oxide (RGO). In the simultaneous reduction pro-
cess, metal NPs were proposed to not only precipitate in the
catalytic reduction of GO, but also act as a spacer in the
layer structures of graphene nanosheets (GNS) to prevent
the aggregation and restacking of RGO.157 To prepare the
graphene-supported metal electrode for further character-
ization, lyophilization method was usually used to prevent
the restack of the composite nanosheets during liquid water
departure in the conventional drying process.149 Conductive
spacers such as carbon blacks have also been added to the
interlayers of graphene to further increase the specific sur-
face area of the nanocomposite, resulting in a higher electro-
chemical surface area.158
Liu et al.46 introduced a sequential reduction of GO and Pt
through electrochemical reduction and electrodeposition on
a conductive indium tin oxide (ITO) glass electrode, during
which no reducing reagents were involved and the synthesis
process is environmentally friendly. However, the electro-
deposited Pt NP size seems difficult to be controlled in this
method.159 Shang et al. deposited high-density Pt nanoclusters
with various thicknesses (2 ~ 85 nm) by using the magnetron-
sputtering approach. The mass-specific real surface substan-
tially decreased from 89.9 to 12.6 m2 g−1 with the Pt layer
thickness ranging from 2 to 85 nm.
For the Pt catalyst used in the DMFC, a CO-poisoning
problem during the MOR exists at the anode side of DMFC,
namely, the catalytic activity of Pt rapidly declined due to
CO as the impurities in the hydrogen gas fed in the anode. In
this case, Pt─Ru alloys have been widely used in the anode
catalyst layer of PEMFC, in which CO molecules were sup-
posed to be preferentially captured or oxidized by Ru. Au NPs
supported on some metal oxides were also found to have a
superior catalytic activity for CO oxidation.160 The bimetallic
alloy NPs received increasing attention due to their enhanced
electrocatalytic properties relative to individual metal NPs by
exposing the Pt layer in the alloys and thus increasing its sur-
face area and using efficiency.161
Bong et  al.47 prepared uniformly dispersed Pt─Ru
alloy NPs with an average size of 2 nm supported on GNS
despite the large metal loading of 80 wt.% by a surfactant-
stabilized colloidal method. Quaternary ammonium salt
321
(tetraoctylammonium hydrotriethylborate) was used as the
surfactant to ensure the fine dispersion of metal NPs dur-
ing the thermal reduction process from their metallic salts
(PtCl2 and RuCl3), and the surfactant can be simultane-
ously removed by the thermal treatment. Ternary Pt/Pd Cu
nanoboxes supported on 3D graphene framework have been
reported by Hu et al.162 by a dual solvothermal process. The
electrocatalytic activity of this novel multicomponent metal
catalyst on EOR is significantly higher than those of both
pure Pt and Pd Cu electrodes with a fourfold improvement
over the commercial Pt/C catalysts (E-TEK 20% Pt/C) as
normalized to the total mass of active metals and extraor-
dinarily superior durability relative to Pt/C (see Figure
21.4f and g). The improved electrocatalytic performance
and the enhanced use efficiency of Pt have been ascribed
to the introduction of nonnoble metals in the alloys and the
well-controlled nanobox geometry, as shown in Figure 21.4a
through e.
21.3.1.2 Interaction between Noble-Metal
Particles and Bare Graphene Support:
Principles for Immobilization and
Enhanced Electrocatalytic Activity
Okazaki-Maeda et al.163–165 applied the first-principles calcu-
lations to study the growth process of Pt particles on graphene
sheets. An individual Pt atom can be stably adsorbed on the
bridge site between two adjacent carbon atoms on the gra-
phene sheet with an adsorption energy of about 2 eV. For the
case of a single Pt-atom and Pt2–dimer adsorptions, the bridge
sites are in stable anchoring positions. The calculated adsorp-
tion energy for a Pt atom on a vacant site is 8.00 eV/adatom,
which is much stronger than the formation energy of a Pt─Pt
bond (about 2 eV/bond) for small clusters, thus demonstrating
the possibility of immobilization on the defect-free graphene
surface.163 However, when the number of Pt atoms in the clus-
ter increases, the interaction between the Pt cluster and the
graphene surface per Pt atom becomes weaker, implying that
the nano-sized Pt particles are favored to be immobilized on
the graphene surface.
Huang et al.166 compared the two synthesis pathways (see
Figure 21.5a) of graphene-supported Pt NPs: the facile syn-
thesis process of directly reducing Pt(NO3)2 on graphene
nanoplates (GNPs), and the commonly employed simultane-
ous reduction of a metallic precursor and GO. In the former
soft chemical procedure, Pt(NO3)2 solution was added to the
N-methyl-2-pyrrolidone (NMP)-exfoliated graphene, fol-
lowed by the solvothermal treatment at 120°C for 12 h. The
resultant nanocomposite was denoted as GNP/Pt, while the
RGO-supported Pt from the traditional oxidation–reduction
method was denoted as RGO/Pt. Pt NPs supported on the
RGO were observed to aggregate easily and possess a larger
average size (~3.7 nm) than that of GNP/Pt (~2.3 nm), prob-
ably due to the uneven distribution of the oxygen functional
groups (hydroxyl, carboxyl, and epoxide) on the GO surface,
as shown in Figure 21.5b through e. These oxygen functional
322 Graphene Science Handbook

(a) (f )
Pt/PdCu
180

20th
180 1000th
160

j/mA cm–2

j/mA cm–2
120

60
140
0
–0.8 –0.4 0.0
200 nm 120
E/V

0 200 400 600 800 1000

(b) (c) Cycle numbers

(g) 50
Pt
40

j/mA cm–2
10 nm 30 20th
Cu 40
1000th

j/mA cm–2
(d) (e) 20 20

10 0
–0.8 –0.4 0.0
E/V
0
0 200 400 600 800 1000
Pd Pt Cycle numbers

FIGURE 21.4  (a) TEM images of Pt/PdCu nanocubes on graphene sheets, (b) high-angle annular dark-field scanning transmission elec-
tron microscopy (HAADF-STEM) image of a hollow Pt/PdCu nanocube, (c through e) HAADF-STEM-EDS mapping images of Cu, Pd,
and Pt elements, respectively; and (f and g) forward peak current density (j) as a function of potential scanning cycles of Pt/PdCu and Pt
on three-dimensional graphene frameworks (3DGFs) between −0.8 and 0.2 V in 1 M CH3CH2OH + 1 M KOH electrolyte, respectively. The
insets in (f) and (g) are the corresponding 20th and 1000th CV curves of Pt/PdCu and Pt on 3DGF. The scan rate: 50 mV s−1. (Adapted from
C. G. Hu et al., Advanced Materials, 2012, 24, 5493–5498.)

(a) HOOC O
O
O Structural defects in graphene
n
id atio OH
COOH K2PtCl4
Ox HOOC O
ti on O Reduction
olia HO O Pt nanoparticles
Exf OH
Graphene oxide sheets Reduced graphene oxide–Pt composite

Exf
ol
Natural flake graphite in N iation Pt(NO3)2
MP

Ethylene glycol

Graphene nanoplates Graphene nanoplates–Pt composite

(b) (c) (d) d=0.22 nm (e)

pt(111)
20 30
Percentage (%)

Percentage (%)

15 5 nm
20
10
10
5

100 nm 0
100 nm 0
1 2 3 4 5 6 7 8
1 2 3 4 5 6 7 8
Particle size (nm) Particle size (nm)

FIGURE 21.5  (a) Illustrations of the synthesis of RGO–Pt composite and GNP–Pt composite by the traditional oxidation–reduction
method and our soft chemical method, respectively. TEM images and histograms of Pt particle size distribution of RGO/Pt (b and c) and
GNP/Pt (c and d). The inset of (d) is an HETEM image of GNP/Pt. (e) size distribution of GNP/Pt. (Adapted from H. J. Huang et al., Journal
of Power Sources, 2012, 204, 46–52.)
Graphene-Based Materials for Fuel Cells
groups can stabilize the dispersion of the GO sheets in water
and act as anchoring sites for Pt NPs. However, oxidizing
graphite to obtain GO will introduce structural defects on
the graphene basal planes owing to the transformation of
carbon atoms from the intrinsic sp2-hybridized geometry
to a distorted sp3-hybridized geometry. On the basis of the
theoretical study, surface defects and voids on the graphene
planes have a much stronger interaction with the Pt or Au
clusters than that between the perfect graphene surface and
noble metals.167
Kim and Jhi168 have shown that the binding of Pt NPs to
graphene and the molecular adsorption on Pt can be con-
trolled by introducing defects on the graphene surface. The
defects introduced in graphene can remarkably enhance the
Pt-binding strength (Eb) and lower the Pt d-band center (εdc),
which is closely correlated with the binding energy differ-
ence between CO and H2. Hence, by optimizing Eb and εdc
via adjusting the defects in graphene, graphene-supported Pt
NPs can be designed to be more durable and less CO sensitive.
21.3.2 Modified/Functionalized Graphene
as Support for Noble Metals:
Improved Durability
Recently, the modified- or functionalized-graphene nanosheets
(f-GNS) have been intensively investigated as metal supports.
The straightforward deposition of metal NPs on the highly
hydrophobic and smooth graphene surface is extremely difficult.
In contrast to the bare graphene as catalyst support, the f-GNS
generally has a larger interlayered space and higher specific
surface area due to better exfoliation. The functional groups
and other organic modifiers not only function as anchoring sites
for the metallic precursor and consequently prevent the aggre-
gation of metal NPs, but also inhibit the restacking of GNS via
the electrostatic repulsion and/or VDW forces. The f-GNS can
be obtained by thermal treatment to introduce heteroatoms (i.e.,
nitrogen [N] and sulfur),48 or by self-assembling organic modi-
fiers via adsorption169 or π–π stacking170 with the π-conjugated
graphene surface, for example, poly(diallyldimethylammonium
chloride) (PDDA)-functionalized graphene,171,172 ionic liquid-
functionalized graphene,173,174 and poly(pyrogallol)-functional-
ized graphene.175
Compared with the one-pot simultaneous reduction
method to prepare bare graphene-supported metal NPs, a
sequential reduction route is used to prepare f-GNS-supported
metal NPs.171,172 Geng et al.48 showed that the N-doped gra-
phene-supported Pt exhibited higher durability than the com-
mercially used Pt/carbon black (Vulcan XC-72) (see Figure
21.6a and b). The enhanced durability has been ascribed to the
enhanced interaction of Pt NPs with the delocalized π-bond,
and the existence of a lone electron pair of N atom to stabilize
Pt NPs. Moreover, as illustrated in Figure 21.6c, the pyridine-
like N may create ultramicropores on the N-doped graphene
surface, which can probably function as geometry-binding
sites to prevent Pt from aggregating during the electrochemi-
cal reaction. Further studies are necessary to fully understand
323
the enhanced durability of the heteroatom-doped graphene-
supported electrocatalysts.
Guo et  al.49 reported on deoxyribonucleic acid (DNA)-
functionalized graphene-supported Pd NPs with an ultrasmall
average size of 5 nm and uniform distribution for direct for-
mic acid fuel cells (DFAFCs). The DNA-functionalized
graphene-supported Pd NPs possessed an electrochemically
active surface area of up to 147.1 m2 g−1, more than 2 times
higher than the bare graphene-supported Pd. The Pd─DNA
at graphene toward formic acid oxidation exhibits a low
oxidation peak potential, high current density, low charge-
transfer resistance, and long-term operation capability. The
functionalized DNA on the graphene surface via π–π stack-
ing not only well dispersed graphene against aggregation, but
also rick the negatively charged PO4−3 groups to induce Pd2+
deposition and direct the NPs growing process. Li et  al.176
deposited high-density Pt NPs on chemically reduced gra-
phene sheets (CRGSs) by employing 1-pyrenemethylamine
(Py-CH2NH2) as the interlinker to form a self-assembled
layer on the surface of GNS via π–π stacking. A similar route
based on the electrostatic interaction has been reported by
Choi et al.,50 in which positively charged 4-dimethylamino-
pyridine (DMAP)-coated Au NPs were self-assembled on
the negatively charged GOS to form a layer-by-layer (LbL)
3D electrocatalytic thin films. The LbL methods have been
recognized as a powerful and tunable method to well control
the amount of Au NPs on a graphene sheet and adjust the
catalytic efficiency by changing the numbers of bilayers and
thermal treatment temperature.177
21.4 GRAPHENE-BASED NON-NOBLE-
METAL ME─N─C (ME ═ FE, CO)
COMPLEX CATALYST FOR FUEL CELLS
Recently, intense efforts have been made on the non-noble-
metal catalysts (NNMCs) to replace Pt for ORR, among
which the Fe (or Co) coordinated to heterocyclic N are the
most promising NNMCs. The NNMCs with the Fe─N2+2
(with four pyridinic N, which are different from Fe─N4 struc-
ture in the macrocycles having pyrrolic N5) possess higher
ORR performance.178 Carbon black has been typically used to
react with the Fe and N precursor, like Fe macrocycles such as
Fe–phthalocyanine and Fe–porphyrin with an Fe─N4 moiety
(Fe[III] coordinated with 4-pyrrolic N) to obtain Me─N─C
catalyst. Another way to introduce N moiety is to react the
metallic salts with N-containing gas (i.e., NH3) to form Me─N
moieties directly. However, due to the insufficient stability of
carbon black during the pyrolysis treatment, the carbon gasifi-
cation can lead to severe carbon loss and subsequently shorten
the lifespan of these catalysts. Hence, the novel Me─N─C
catalyst based on the thermally stable graphene has ignited a
strong interest.13,97
The graphene-based Me─N─C catalyst is generally pre-
pared via a three-step procedure: (i) the reduction of GOs;
(ii) modification of graphene by N-coordinated metallic
salts; and (iii) one-pot pyrolysis treatment of N-coordinated
324 Graphene Science Handbook

(a) 0.00015 (b)

100
0.00010 PtNG
90 Pt/C (home-made)
0.00005 Pt/C (E-TEK)

Normalized ESA (%)

80
0.00000
Current/A

Initial 70
–0.00005 500
1000 60
–0.00010 1500
2000 50
2500
–0.00015 3000 40
3500
–0.00020 4000 30

0.0 0.2 0.4 0.6 0.8 1.0 1.2 0 1000 2000 3000 4000
E/V versus SHE Cycles of potential sweep

(c) N N N
N N
N N
Cl N N
N N N
N
Cl
N N N
+ K N N N
N N
Cl Cl N N

Cl N N N
N
N
N N
N
N
N N

FIGURE 21.6  (a) CV curves of Pt/N-doped graphene for the different cycles. Scan rate: 50 mV s−1. (b) Normalized electrochemical surface
area (ESA) of Pt/NG, Pt/C (homemade), and commercial Pt/C. Pt loading in each carbon: 30 wt.%. (c) Schematic description of NG forma-
tion process. (Adapted from D. S. Geng et al., Electrochemistry Communications, 2012, 22, 65–68.)

metallic salts with the RGO. N-coordinated reagents such
as graphitic carbon nitride (g-C3N4),13,140,179 1,10-phenanth-
roline,140 phthalocyanine (and its derivatives),98,99 porphyrin
(and its derivatives),100 aniline,101,102 and melamine180 have
been used to coordinate metallic ions and subsequently
anchor them on the graphene surface usually through π–π
stacking. Different from the functionalized graphene as a
support for the metal catalyst, the transitional metal (Fe, Co)
conjugates are chemically bonded on the graphene surface in
this type of Me─N─C catalyst; thus, the stability of metal
particles is highly improved and the charge-transfer process
between metal conjugates and graphene can be facilitated.
The metal–Nx moieties were theoretically and experimen-
tally demonstrated to be responsible for the ORR activity in
the Me─N─C complex,181,182 while graphene functions as the
mechanically solid catalyst framework that also prompts the
charge-transfer process and significantly increases the spe-
cific surface area.13
Parvez et  al.13 reported an efficient Fe-incorporated
N-doped graphene (Fe-N-C) ORR electrocatalyst with an
almost four-electron-transfer process and superior stability
in both alkaline (~94%) and acidic (~85%) solutions, which
outperformed the Pt and N-doped graphene-based metal-free
catalysts. However, a majority of the stable graphene-based
Fe-N-C has been demonstrated to only possess a superb ORR
activity under alkaline conditions. Peng et  al.103 prepared a
novel graphene-structured Fe-N-C with a high surface area
(702 m2 g−1) and high ORR performance in an acidic medium
via pyrolysis of an iron-containing precursor with melamine
and aniline. It is noteworthy that the graphene-structured
Fe-N-C exhibits a comparable ORR activity and stability
to that of the commercial Pt/C catalyst in the rotating disk
electrode (RDE) test, while the single-cell performance and
stability of this novel Fe-N-C catalyst is far lower than those
of Pt/C. The existence of transitional metals, especially iron
and cobalt, was found to promote the formation of ORR elec-
trocatalytically active sites in the Me─N─C materials during
pyrolysis.99,101,183,184 It also seems that the type of the transi-
tional metals also plays a very important role in determining
the electrocatalytic mechanism of Me─N─C in either acid or
alkaline medium.104,185
For this type of non-noble-metal ORR catalysts, the inter-
face between the graphene moiety and the Me─N moiety,
as well as the chemical state of N elements in the compos-
ite are the key issues dominating the electrocatalytic activity.
Thus, creating specific active Me─N sites and facilitating the
Graphene-Based Materials for Fuel Cells
charge-transfer process between the Me─N moiety and the
graphene moiety can be effective ways for improving the elec-
trocatalytic activity.
21.5 GRAPHENE-BASED METAL-FREE
ORR ELECTROCATALYST
The scarcity of precious metals such as Pt and their high cost
have been the major obstacle to mass market introduction of
fuel cells for large-scaled commercial applications. Carbon-
supported nonprecious metals such as iron, cobalt, and their
N impurities have been reported to reduce the total cost.
However, these nonprecious metal alternatives usually suffer
from lower activity compared with the Pt benchmark and/or
gradual degradation in performance during cyclic use.184,186 In
addition, metal-based electrocatalysts are sensitive to deac-
tivation in the presence of CO and methanol. N-containing
CNTs have been demonstrated as effective metal-free ORR
electrocatalysts in alkaline electrolytes, while their ORR
activities were found to be poor in acids.187 As an analog
of CNT, GNS exhibited a much larger specific surface area
(>2600 m2 g−1) than that of CNT in the case of a single wall
(>1200 m2 g−1), providing significantly more available active
electrocatalytic sites and larger TPB. Hence, graphene-based
metal free, such as heteroatom-doped graphene, polyelec-
trolyte-functionalized graphene, and graphene-based carbon
nitride, have attracted tremendous attention as metal-free
ORR electrocatalysts for fuel cells.
21.5.1 Principle for Graphene-Based Metal-
Free ORR Electrocatalyst
Among many factors affecting the chemical–electrical con-
version process in fuel cells, ORR is the kinetically slug-
gish step that dominates the overall performance of fuel
cells.1 The ORR can proceed via two routes in fuel cells:
(i) the direct four-electron pathway, in which O2 is directly
reduced to water without the involvement of hydrogen per-
oxide, O2 + 4H+ + 4e− → 2H2O and (ii) a less efficient
two-electron pathway that generates hydrogen peroxide,
O2 + 2H+ + 2e− → H2O2. The efficient four-electron path-
way is preferable to facilitate the fuel cell performance. The
number of electron transfers (n) per O2 molecule involved
in the ORR process can be calculated from the slope of the
Koutecky–Levich equations as follows:188,189
1 1 1 1 1 with that of Cl. It is reasonable that the larger atom sizes of Br
= + = + (21.1)
J J L J K Bω1/ 2 nFkCo and I suggest less compactly bound valence electrons for facili-
−1/ 6
B = 0.62nFCo ( Do )2 /3 v (21.2)
where j is the measured current density, jk and jl are kinetic- and
diffusion-limiting current densities, ω is the angular velocity
of the disk (ω = 2πN, N is the linear rotaion speed), n is the
overall number of electrons transferred in oxygen reduction,
325
Co is the bulk concentration of O2, Do is the diffusion coef-
ficient of O2, v is the kinematic viscosity of the electrolyte,
k is the electron-transfer rate constant, and F is the Faraday
constant (96,485 C mol−1). Deep insights into the mechanism
of ORR in graphene-based metal-free catalysts can be highly
beneficial for developing novel ORR electrocatalysts with an
activity equal or superior to the state-of-the-art Pt.
Modulations and calculations have been reported on inves-
tigating the geometry and electronic structure of heteroatom-
doped graphene and understanding the ORR mechanism of
this typical metal-free electrocatalyst.14,190–195 The following
ORR mechanisms were proposed as the most probable path-
ways for metal-free N-doped graphene surfaces (Equations
21.3 through 21.8)196 and glassy carbon (Equations 21.3, 21.4,
and 21.6):197
Gr (aq) + O2 (g)  Gr : Oad
2 (aq ) (21.3)
+ −
  Gr : O2 (aq) + H (aq) + e  Gr : OOH (aq)
ad ad
(21.4)
− −
  Gr : OOH (aq) + e  Gr : O (aq) + OH (aq)
ad ad
(21.5)
− −
  Gr : OOH (aq) + e  Gr (aq) + OOH (aq)
ad
(21.6)
+ −
  Gr : O (aq) + H (aq) + e  Gr : OH (aq)
ad ad
(21.7)
+ −
  Gr : OH + H (aq) + e (aq)  Gr (aq) + H 2O (l)
ad
(21.8)
The enhancement in the ORR activity with heteroatoms
doping has been attributed to the difference in the electronega-
tivity (χ) of the dopant and the resident carbon (2.55), namely
the doping-induced charge-transfer mechanism. The higher
electronegativity of atom dopants, such as N (3.04), S (2.58), Cl
(3.16), Br (2.96), and I (2.66), can polarize the adjacent carbon
atoms in graphene frameworks to efficiently facilitate oxygen
adsorption and charge transfer. Additionally, the dopant atom
sizes also impose a significant effect on the valence electron
availability and consequently impact the charge-transfer pro-
cess. Jeon et al.198 have observed the ORR activities of edge-
halogenated graphene nanoplatelets (GnPs) in the following
order: ClGnP << BrGnP < IGnP. They ascribed the seemingly
reverse order of ORR activities to the sequence of halogen
atoms’ electronegativity to larger sizes of Br and I compared
tating the charge polarization in BrGnP and IGnP electrodes.
The larger sizes of Br and I can also result in partially formed
−Br+ and −I+ ionic bonds beneficial for the charge-transfer pro-
cess. X-ray photoelectron spectra (XPS) and density functional
theory (DFT) calculations can be employed to estimate the
bond formations between dopant heteroatoms and sp2 carbons,
as well as to evaluate the binding or adsorption energy on the
heteroatoms doped in graphene frameworks.
326 Graphene Science Handbook

21.5.2 Advances in Graphene-Based Metal-
Free ORR Electrocatalyst
Nitrogen-doped graphene nanosheets (NGNSs) or N-doped
graphene as a typical metal-free ORR electrocatalyst have
been numerously reported recently.7,15–18 To create catalytic
centers, N is doped within the crystalline graphitic lattice in
many different forms, including pyridinic N in a six-mem-
brane ring, pyridinic N oxide, pyrrolic N in the five-member
ring, and N atoms doped into the graphene basal plane (qua-
ternary N), as presented in Figure 21.7a. The most accepted
ORR-active N dopant sites are pyridinic N and quaternary N,
possibly due to the lone pair of electrons with one electron
donating to the big π-bond conjugation in pyridinic N15,200
and the π-conjugation structure in quaternary N.190,201 Thus,
synthesis optimization toward pyridinic N and quaternary N
is highly preferred. The surface compositions of these four
types of doped N can be evaluated by the XPS, as shown in
Figure 21.7b.
Lee et  al.15 prepared the N-doped graphene possessing
quaternary N (together with pyrrolic N) and pyridinic N with
contents of 41.1% and 42.7%, respectively. This N-doped gra-
phene from GO exhibited a significantly high ORR activity
contributed by the high electric conductivity, high surface
area, and a large amount of pyridinic N sites. The active cen-
ter structure of N-doped graphene-based metal-free catalyst
has been thoroughly investigated by Lai et al.19. In their study,
N-doped graphene was synthesized by annealing GO under
ammonia or by annealing of an N-containing polymer/RGO
composite (polyaniline/RGO or polypyrrole/RGO). The for-
mer approach preferentially formed graphitic N and pyridinic
N centers, while the latter one tended to generate pyridinic and
pyrrolic N moieties, as shown in Figure 21.8.19 The electrocat-
alytic activity was found to depend on the graphitic N content
that determines the limiting current density, while increased
pyridinic N content can improve the onset potential for ORR.
Three typical approaches have been commonly employed
to produce N-doped graphene: (i) a three-step procedure
involving the preparation of GO from natural graphite, exfo-
liation of GO by sonication, and reduction of exfoliated GO
with N-containing reducers, such as hydrazine;15,202,203 (ii) a
direct thermal and/or pyrolysis treatment of graphene or GO
in the presence of N-containing gases (e.g., ammonia) or with
N-containing compounds (e.g., melamine and cyanamide) or
by exposing to N plasma in the inert gas ambient;16–20,200–206
and (iii) metal-catalyzed chemical vapor deposition (CVD) of
methane in the presence of ammonia, in which transitional

(a)

+N +N N

–O Pyridinic
H N nitrogen
Pyridinic H
nitrogen oxide Quaternary Pyrrolic nitrogen 398.6 eV
nitrogen
402–405 eV 400.5 eV
401.3 eV
6.E+04
(b)
Counts per second (counts/s)

N
C≡N, R–C–O, 5.E+04
N
N N
N H
H
4.E+04

N Quaternary N Pyridinic
Other oxidized
N nitrogen 3.E+04
O

2.E+04
406 405 404 403 402 401 400 399 398 397 396 395
Binding energy (eV)

FIGURE 21.7  (a) Schematic representing some of the different forms of N incorporation in graphene;199,213 and (b) detailed N peak with
the deconvolution displaying the different N species present. From right to left: (1) pyridinic, (2) nitrile and Me─N, or various C ═ N groups,
(3) pyrrolic, (4) graphitic/quaternary groups, and (5) pyridinic oxide or other forms of oxidized N. (Adapted from D. M. Binny, J. L. Meunier
and D. Berk, IEEE, 2012, 1–6, DOI: 10.1109/NANO.2012.6322208.)
Graphene-Based Materials for Fuel Cells 327

Pyridinic N Pyridinic N
An n ia N
N N ilin mo
e Am
N N N N
0°C
55 N
N
PANi/RGO N-RGO 550°C

le Am
Pyrolic N rro mo Pyridinic/
Py

Ammonia
nia graphitic N

1000°C
N 85
N 0°C N
N
N N
N
N N N
Ppy/RGO N-RGO 850°C

Pyridinic/
N graphitic N
N N
N N
N-RGO 850°C

FIGURE 21.8  Schematic diagram for the preparation of N-doped graphene with different N states. N-doped RRGOGO at 550°C, 850°C,
and 1000°C is prepared by annealing of GO powder at temperatures of 550°C, 850°C, and 1000°C under an NH3 ⋅ N precursor. Polyaniline/
RGO (PANi/RGO) and polypyrrole/RGO (Ppy/RGO) are prepared by annealing of PANi/GO and Ppy/GO composites at 850°C.

metals are employed as CVD catalysts.7,21 The direct thermal
annealing of GO or graphene with the low-cost N source was
recognized as a facile and cost-effective approach for large-
scaled synthesis of N-doped graphene, as discussed in the sec-
ond approach above.18,20,201 This thermal-annealing approach
can be achieved at low temperatures, which is catalyst free
and thus avoiding the metal impurities in the synthesized
metal-free N-doped graphene. Heteroatom-doped graphene,
including B-doped,207 S-doped,20 Se-doped,208 halogen-
doped,198,209 and two heteroatoms codoped22,210 graphene have
also been studied. The heteroatom dopants generally play a
similar role of polarizing the adjacent carbon atoms, among
which boron is highly electron deficient and has a strong
electron-withdrawing function. The doping content is tun-
able through adjusting the amount of heteroatom sources.23
Li et al.105 presented that few-walled CNTs, followed by outer
wall exfoliation via oxidation and high-temperature reaction
with ammonia to form a CNT–graphene complex, can act as
a metal-free ORR electrocatalyst in both acid and alkaline
solutions.
Polyelectrolyte-functionalized/adsorbed graphene as a
metal-free ORR electrocatalyst has also been reported by
Wang et  al.51 by using PDDA. Polyelectrolyte can be used
as an electron acceptor to impart the electrocatalytic activity
for ORR. The subsequent adsorption of PDDA on graphene
after the GO reduction positively charged its surface and
solubilized the graphene sheets, resulting in a considerably
improved dispersion of the functionalized graphene via elec-
trostatic repulsion among individual graphene sheets. Raman
and XPS study indicated an intermolecular charge-transfer
process from graphene to PDDA. Further studies still need
to be conducted to fully understand the ORR mechanism
induced by the intermolecular charge transfer of this type of
polyelectrolyte-functionalized graphene.
21.6 OTHER APPLICATIONS IN FUEL
CELL AND AN OUTLOOK ON THE
COMMERCIALIZATION OF GRAPHENE-
BASED MATERIALS FOR FUEL CELLS
Besides the common applications of graphene-based mate-
rials in fuel cells, graphene can also be used as reinforcing
additives in composite conducting plates (CPs)92,93 for PEMFC
bipolar plates due to its excellent electric conductivity and
extraordinary mechanical strength. Hsiao et al.92 showed that
with adding only 0.2 phr (parts per hundred rubber) of gra-
phene as a reinforcement in vinyl ester remarkably enhanced
the thermal, mechanical, and electrical properties of the com-
posite CP, by increasing the thermal conductivity from 18.4 to
27.2 W m−1 K−1, the in-plane electric conductivity from 155.7
to 286.4 S cm−1, and flexural strength from 28.0 to 49.2 MPa.
The composite CPs based on graphene and organics/polymers
are suitable alternatives for bipolar plates in PEMFCs.
One of the major challenges facing the use of PEMFCs is
the CO poisoning of the anode catalyst. The CO impurity in
the hydrogen feed gas is formed during the fuel-refining pro-
cess that is currently the main approach to generate hydrogen.
Metal/graphene or metal/GO composites were proved through
the DFT analysis by Durbin and Malardier-Jugroot 211,212 to be
328
an effective filter membrane support for the removal of CO
from the hydrogen feed gas in fuel cells, which can be placed
outside the fuel cells to remove the CO impurity before feed-
ing hydrogen gas into the anode. All the studied model metal/
graphene systems bind to CO stronger than H2, and CO binds
very strongly to nickel, Pt, and particularly iridium/gold sys-
tems. However, due to the high cost of precious metals and
their considerable binding to H2, the nickel/GO composite is
the most promising candidate for the external CO-capturing
membrane for hydrogen fuel cells.
In addition, the 2-D π-conjugated, interlayered molecular
structures and the tremendous surface area of GNS make it
the state-of-the-art alternative for hydrogen storage materi-
als.9,95,96 Hydrogen can be absorbed on the surface of gra-
phene either by physisorption (e.g., interacting with graphene
via VDW forces) or by chemisorption (e.g., forming chemi-
cal bonds with the π-conjugated carbon atoms). Physisorption
within the layered or nanostructured graphene can potentially
lead to reasonable storage (gravimetric density and volumet-
ric density). Functionalizing graphene or GO with metals
can also improve the chemisorption of hydrogen and tune
the H-binding energy on the graphene basal plane. However,
more work is still needed since the current studies on gra-
phene-based hydrogen storage materials are scarce and are
mostly theoretical studies by calculation and modeling.
Recently, graphene-based anode and/or cathode for bio-
fuel cells and microbial fuel cells (MFCs) have also garnered
strong interest. Biofuel cells and MFCs are capable of degrad-
ing organic waste and meanwhile generating electricity by
making use of the enzyme catalyst and the metabolic process
of bacteria, respectively. Owing to their structural and mate-
rial difference with the commonly used fuel cells, the detailed
advances are not included in this chapter and have been dis-
cussed in other reviews.213
The commercialization of graphene-based materials for
fuel cell application has received intensive attention due to
its superior electrical and mechanical properties, as well as
due to the abundant resources in nature. Except the exfoliated
graphene produced from the nature-rich graphite, recently,
most graphene materials were obtained by the CVD method.
The complex and expensive synthesizing processes involved
in both the chemical synthesis and mechanical synthesis
methods of pure graphene make it difficult for a large-scale
use of graphene in the industry. Companies such as Bluestone
Global Tech (USA), Vorbeck Materials (USA), Graphenea
(Spain), Graphene Supermarket (USA), Graphensic (Sweden),
and 2-D Tech (UK) have been devoting to developing novel
technologies to manufacture monolayer graphene materials
at large scale or a large graphene area. However, the process
of preparing small graphene particles to produce graphene in
large scale can cause significant deterioration in the electric
and mechanical properties of graphene materials. Despite
this, many graphene-based materials applied in fuel cells are
modified or functionalized graphene or GO materials, which
can be directly obtained from a simple functionalization treat-
ment of graphite or GO dispersions. Besides, the properties of
graphene-based materials produced in bulk or in nanoscale
Graphene Science Handbook
can be significantly different. Recently, an edge-halogenated
graphene, which showed a comparable electrocatalytic activ-
ity toward ORR in an alkaline medium and much higher dura-
bility as well as higher methanol selectivity to Pt, has been
successfully produced via a cost-effective method (ball-mill-
ing graphite in the halogen gas atmosphere).198 Opportunities
may lie in the direct synthesis path via functionalizing graph-
ite or transforming other graphite structures such as chemicals
under catalysis to obtain functionalized graphene/GO materi-
als, which bypass the production and dispersion of multilayer
or monolayer pure graphene.
21.7 SUMMARY
As discussed and reviewed above, graphene and its derivatives
have been demonstrated to be versatile candidates for different
key components in fuel cell applications. GO or functional-
ized GO as compatible and beneficial additives in the polymer
electrolyte can significantly increase the mechanical strength
and improve the methanol resistance of composite PEMs for
DMFCs. However, there is a significant difference between
the in-plane and through-plane proton conductivity of GO and
f-GO materials due to the special 2-D structure of graphene.
Graphene and f-GNS have also been widely investigated as an
ideal support for metal NP catalysts because of their strong
electrochemical corrosion resistance, high specific surface
area, superb electric property, and strong adhesion with metal
NPs. Owing to the enhanced use efficiency of the noble-metal
catalyst supported on graphene, the amount of noble-metal
use can be significantly reduced. Additionally, graphene-
based Me─N─C non-noble-metal and graphene-based metal-
free ORR catalysts have received intense research interest due
to their cost-saving benefits and performance and/or stability
comparable to the commercially used Pt/C.
Further work is still required to develop suitable and facile
synthesis methods for either pristine or modified/functional-
ized graphene/GO applied for fuel cells. Systematic studies on
understanding the chemical and physical mechanism govern-
ing the performance of graphene-based electrocatalysts and
the graphene/polymer composite PEMs can be beneficial for
facilitating the R&D of graphene-based materials in fuel cells.
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22 Chemistry and Applications of
Supramolecular Graphene Derivatives
Hugo Bares, Jean-Baptiste Verlhac, and Dario M. Bassani

CONTENTS
Abstract...................................................................................................................................................................................... 337
22.1 Introduction...................................................................................................................................................................... 337
22.2 Covalent and Noncovalent Grafting of Graphene with Molecules for Supramolecular Recognition.............................. 337
22.2.1 Graphene Derivatives Grafted with Cyclodextrins or Calixarenes...................................................................... 338
22.2.2 Graphene Hybrids with Porphyrin Derivatives.................................................................................................... 340
22.2.3 Graphene Hybrids with Nucleic Acids................................................................................................................. 341
22.3 Supramolecular Gel-Based Materials Incorporating Graphene....................................................................................... 341
22.4 Self-Organization of Functionalized Graphene Derivatives............................................................................................ 345
22.5 Supramolecular Graphene Derivatives for Device Applications...................................................................................... 346
22.6 Summary.......................................................................................................................................................................... 347
References.................................................................................................................................................................................. 348

ABSTRACT propensity of graphene’s extended aromatic structure toward

The use of supramolecular interactions to tailor the proper-
ties of graphene and its derivatives represents a very attractive
solution to improving its mechanical and chemical properties
without scarifying its attractive electronic properties. This
chapter covers the use of small molecules to modify the prop-
erties of graphene via supramolecular interactions, as well as
the covalent grafting of molecular recognition groups onto
the graphene plane. Applications of these supramolecular
constructs in the fabrication of functional gels and electronic
devices for sensing (DNA, small molecules) through supramo-
lecular association with cyclodextrins, calixarenes, porphyrins
and other polyaromatic receptor molecules is also covered.
22.1 INTRODUCTION
Among known carbon allotropes, the unique electronic and
physical properties of graphene are a consequence of its pla-
nar architecture that defines—and confines—its chemistry.1–3
Unmodified, pristine graphene is unstable in solution and will
rapidly aggregate due to the large van der Waals forces gener-
ated through the stacking of their extended aromatic surface.
Chemical modification via oxidation to graphene oxide (GO,
see Table 22.1) or covalent grafting can be used to diminish
the intermolecular interactions between the individual flakes
and thus provide a means to improve the dispersibility of gra-
phene in view of solution-processing applications.4,5 Although
viable, this approach entails a disruption of the π-conjugated
skeleton in graphene, which directly affects its electronic
properties.6–8 Therefore, improved solubility and dispersibil-
ity come at the price of altered or reduced electronic proper-
ties. In an alternative approach, it is possible to make use of the
π-stacking to construct supramolecular assemblies that can
stabilize and independently tune the physical, chemical, and
electronic properties of the material. Such a supramolecular
approach thus offers a promising route toward more com-
plex graphene-based architectures.9 This chapter covers the
use of small molecules to modify the properties of graphene
via supramolecular interactions, as well as the covalent graft-
ing of molecular recognition groups onto the graphene plane
with a view to instilling molecular recognition properties onto
the graphenoid structure. The fabrication of graphene-based
molecular devices and organogels are covered separately due
to their significance. Although a diversity of compounds have
been grafted onto graphene or GO, only a few of them possess
the characteristics that make them suitable for supramolecu-
lar self-assembly applications. This chapter is also dedicated
to the supramolecular chemistry of graphene derivatives and
focuses on those substituents that give rise to a supramolecu-
lar association, such as cyclodextrins, calixarenes, porphy-
rins, and other polyaromatic receptor molecules.
22.2 COVALENT AND NONCOVALENT
GRAFTING OF GRAPHENE WITH
MOLECULES FOR SUPRAMOLECULAR
RECOGNITION
Owing to its planar structure, the chemical reactivity of gra-
phene is less pronounced than that of curved allotropic forms of
carbon such as fullerenes or carbon nanotubes. Moreover, any
derivatization of the sp2 carbon atoms within the basal plane
of the graphene sheet will lead to the formation of a defect
in the honeycomb structure associated with the increased
337
338 Graphene Science Handbook

TABLE 22.1
Noncovalent Functionalization of GO Using Different Modifying Agents,a Their Concentration in Various Solvents,
and Electrical Conductivity
Modifying Agent Solvent Concentration (mg/mL) Electrical Conductivity (S/m) References
SPANI Water >1 30 [10]
PBA Water 0.1 200 [11]
Amine-terminated 1,3-Dimethyl-2-imidazolidinone, butyrolactone, 0.4 1500 [12]
polymer 1-propanol, ethanol, ethylene glycol, and DMF
PPE-SO3− Water 0.25 30 kΩ (resistance) [13]
SDBS Water 1 80 Ω (resistance) [14,15]
Porphyrin Water 0.02 5 kΩ [16]
PIL Water 1.5 3600 [17]
Nafion Water/1-propanol 0.5 1176 [18]
PEDOT:PSS Water 0.4 2.3 kΩ/sq (resistance) [19]
Thionine Water – 10.1 [20]
Arachidic acid NMP 0.13 10–25 kΩ/sq (resistance) [21]
Phenyloctane NMP 0.1 10–25 kΩ/sq (resistance) [21]

a PBA: pyrenebutyric acid; PEDOT:PSS: poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate); PIL: ionic liquid polymers (hydrophilic ionic liquid
polymer which consists of an imidazolium polycation and a bromide anion); PPE-SO3−: poly(2,5-bis[3-sulfonatopropoxy]-1,4-ethynylphenylene-alt-
1,4-ethynylphenylene); PSS: poly(sodium 4-styrenesulfonate); SDBS: sodium dodecyl benzene sulfonate; SPANI : sulfonated polyaniline.

strain due to the presence of an sp3 center. For these reasons,
functionalization of the carbon atoms located at the edges of
the plane is easier to perform, and chemical reactions on the
basal plane are limited to very reactive reagents.22 On the other
hand, the π system associated with the honeycomb graphene
lattice is responsible for the strong association of various
planar aromatic species via either strong π–π interactions or
charge transfer interactions.23 This ability to give rise to strong
π interactions with numerous planar aromatic compounds has
led to the development of an active area in the supramolecular
chemistry of graphene. But, in order to harness the conduct-
ing properties of graphene for applications in the design of
electronic devices or sensors, the grafting of substrates that
are able to provide selective supramolecular recognition is
of interest. Samori and coworkers21 showed that long-chain
hydrocarbons and aromatics can self-organize onto graphene
sheets and assist their solubilization, and the analogous organi-
zation of oligothiophenes has also been documented.24,25
Chemical approaches for grafting substrates to graphene
or even GO are scarce and, in the case of modifications to the
basal plane, mainly involve reactions such as coupling with
aryl diazonium salts,22,26–30 the Friedel–Craft acylation reac-
tion,31 the 1,3-dipolar cycloaddition (the so-called “Prato reac-
tion”),32 [2 + 1] cycloaddition reactions with carbenes (such as
in the Bingel reaction)33 or nitrenes,34,35 [2 + 2] cycloaddition
reactions with arynes, and also [4 + 2] Diels–Alder cycload-
ditions; in the latter case, graphene acts either as a diene or a
dienophile due to its zero energy gap electronic structure.36,37
In contrast, GO possesses abundant functional groups on the
plane edges, including carboxylic acid groups, and it is there-
fore possible to link a large variety of substrates by classical
peptide-coupling reactions. Typical electrical conductivity (or
resistance) of electrodes prepared using noncovalent modifi-
cation of graphite are summarized in Table 22.2.
22.2.1 Graphene Derivatives Grafted with
Cyclodextrins or Calixarenes
Cyclodextrins are oligosaccharides made from a cyclic assem-
bly of glucose units (the number being between six and eight
units). Their shape is represented as a truncated cone or a
torus and due to the pendant hydroxyl groups associated with
the glucose subunits, they possess an outer hydrophilic shell
whereas the inner part of the cone is hydrophobic.44 The com-
bination of these two properties gives rise to the formation of
a cavity with a hydrophobic environment that can form stable
host–guest inclusion complexes and that has found numer-
ous applications in sensing and molecular recognition.45
Owing to graphene’s large surface area and conductivity, its
grafting with cyclodextrins is an attractive route toward the
design of new active components for chemosensors in elec-
tronic devices. Wang and coworkers46 have prepared hybrid
graphene nanosheets from hydrazine reduction of GO in the
presence of a mixture of α-, β-, or γ-cyclodextrins. In the com-
posite material obtained, it is assumed that the reduced GO
dispersion is stabilized by the strong hydrogen-bonding inter-
actions with the cyclodextrin moieties rather than by the cova-
lent bond between the two partners (Figure 22.1). This strong
interaction favors the formation of very stable graphene dis-
persions in aqueous media. The evidence for a strong H-bond
interaction is demonstrated by the presence of the expected
red-shifted O–H stretching vibrations in the IR (infrared)
spectra. These interactions can arise from either side of the
conical surface of the cyclodextrins, and the strong bonding
Chemistry and Applications of Supramolecular Graphene Derivatives 339

TABLE 22.2
Noncovalent Functionalized Graphene and Graphene Composites Directly from Graphite Using Different
Modifying Agents,a Their Concentration in Various Solvents, and Electrical Conductivity
Concentration Electrical
Substrate Modifying Agent Solvent (mg/mL) Conductivity (S/m) References
Graphene SDBS Water 0.05 35–1500 [38,39]
Graphene Sodium cholate Water 0.3 7000–17,500 [38,39]
Graphene Benzoyl peroxide Water 2.1 212 Ω (resistance) [40]
Graphene–epoxy composite Py-SASS Water – 1.95 × 10−6 [41]
Graphene–epoxy composite PVP Water – 3.06 × 10−6 [41]
Graphene–PVA composite C10 – 1.84 × 10−4 [42]
Graphene–PVP composite PVP Water, ethanol, methanol, – 2.6 × 10−5 [43]
DMF, NMP, DMSO, and VP

a C10: (2,3,6,7,10,11-hexakis[10-carboxydecyloxy] triphenylene); DMF: N,N-dimethylformamide; DMSO: dimethyl sulfoxide; NMP: 1-Methyl-2-
pyrrolidinone; PVA: poly(vinyl alcohol); PVP: polyvinylpyrrolidone; Py-SASS: 1-pyrenesulfonic acid sodium salt; VP: N-vinylpyrrolidone monomer.

CD + Ammonia Guest molecule

Hydrazine + Heating

Hydrazine
Ammonia
+ Heating
Graphene oxide OH
High
electrochemical
response
COOH
Graphene

CD Guest molecule

Guest molecule

Low electrochemical response

FIGURE 22.1  Illustration of the procedure for preparing cyclodextrin–graphene hybrid nanosheets and their application in electrochemi-
cal sensing of guest molecules. (Reprinted with permission from Guo, Y. et al. Cyclodextrin functionalized graphene nanosheets with
high supramolecular recognition capability: Synthesis and host–guest inclusion for enhanced electrochemical performance. ACS Nano 4:
4001–10. Copyright 2010 American Chemical Society.)

allows the grafting of almost one cyclodextrin unit per 152
carbon atoms. It is proposed that this high coverage of the
graphene surface area prevents the coalescence of graphene
sheet suspension. Once deposited on glassy carbon electrodes,
cyclic voltammetry was used to detect small molecules such
as neurotransmitters or drugs through their inclusion within
the cyclodextrin units. These dispersions can therefore be
used to prepare chemical sensors as the electrochemical sig-
nal (current intensity) is proportional to the analyte concen-
tration (within a 0.1–10-µM range). A lower detection limit
for dopamine and acetaminophene was determined to be ca.
20–40 nM. With a similar analytical platform (cyclodex-
trin–graphene hybrid material deposited on a glassy carbon
electrode), the same authors were able to enhance the analyti-
cal response of the electrode by 10- to 80-fold to a particular
substrate, carbendazim (a benzimidazole fungicide), thanks to
the specific supramolecular interactions between the hetero-
cycle and the cyclodextrin grafted onto the graphene layer.47
Various adducts of graphene with cyclodextrin derivatives
have been reported using variations in the tethers connecting
340 Graphene Science Handbook

OH

OH O
OH OH
OH
O
O O Hydrazine hydrate
HO
O O
O Ammonia
OH
HO O
OH

O OH O
C C
O X O
HO
O O
O O
X
OH HO HO e
OH

HO OH
HO O O OH X NO2
HO O OH
O NH2
OH HO O
O O Cl
OH HO
HO O
OH HO O OH OH
HO OH OH
O CH3
O O O
HO O OH
OH OH

FIGURE 22.2  Schematic of the synthesis procedure of HP-β-CD-RGO composites and the interaction between the guest (o-nitrophenol)
and the host (cyclodextrin moiety linked up to RGO). (Xu, C. et al. 2011. Microwave-assisted covalent modification of graphene nanosheets
with hydroxypropyl-β-cyclodextrin and its electrochemical detection of phenolic organic pollutants. J. Mater. Chem. 21: 10463–71.
Reproduced by permission of The Royal Society of Chemistry.)

the oligosaccharide to the graphene plane. For instance, ionic
interactions instead of hydrogen bonding were employed by
Ogoshi et al. in order to functionalize GO with per-6-amino-
β-cyclodextrin. The conjugates were then assembled into
supramolecular structures using host–guest interactions with
an adamantyl dimer that can bind two cyclodextrins simul-
taneously.48 Covalent linkage via the formation of an ester
bond was achieved using microwave radiation to activate
hydroxypropyl β-cyclodextrin and promote its coupling to
the carboxylic acid groups on the plane edge.49 The material
thus obtained showed promising response toward the electro-
chemical detection of phenol pollutants via supramolecular
recognition (Figure 22.2). A sensitive electrochemical sensor
was developed to detect flavonoid drugs using cyclodextrin-
functionalized graphene electrodes.50 The use of cyclodextrin
platforms for electrocatalytic transformations improved the
catalytic oxidation of methanol, which is of interest for the
construction of methanol fuel cells.51
Calixarenes, which can be considered polyaromatic analogs
of cyclodextrins, can be linked onto graphene sheets using a
similar methodology as for cyclodextrins. Using an approach
based on the hydrazine reduction of GO possessing covalently
bound calixarines, Zhou et al.52 developed an electrochemical
sensor for small molecules  including ­dopamine, uric acid, or
tryptophan. The authors reported a larger linear response range,
but slightly lower detection limit compared to the cyclodextrin
hybrids. The d­ etection of diethyl stilbestrol has been performed
using the same p­ rocedure except that an ascorbic acid was used
as a ­reducing agent instead of hydrazine.53 The detection limit
and the linear range response using glassy carbon electrodes
were almost identical to the previously reported studies.
22.2.2 Graphene Hybrids with Porphyrin Derivatives
Owing to their propensity toward π–π interactions and their
chelating properties, porphyrins have been frequently associ-
ated with graphene derivatives in order to modify their prop-
erties by supramolecular interactions. Moreover, the electronic
absorption of porphyrins in the visible range of the spectrum
makes them good candidates for the design of optoelectronic or
photovoltaic devices. It has been shown that the interaction of
negatively charged GO with tetracationic 5,10,15,20-tetrakis(1-
methyl-4-pyridino)porphyrin induces a large bathochro-
mic shift due to flattening of the porphyrin. This interaction
is responsible for the rapid incorporation of Cd2+ ions in the
porphyrin-chelating site, thereby allowing the detection of
Chemistry and Applications of Supramolecular Graphene Derivatives
cadmium salts.54 Porphyrins have been noncovalently attached
to reduced GO in order to give a stable hybrid material through
the π–π interactions between the graphene plane and the por-
phyrin ring preventing further aggregation of graphene. When
the porphyrin is negatively charged such as meso-tetra(4-car-
boxyphenyl) porphine (TCPP), specific interactions with dopa-
mine (which is positively charged) have been used to enhance
the electrochemical response of a graphene-doped glassy
carbon electrode.55 Electrochemical detection of explosive
materials (2,4-dinitrotoluene, 2,4,6-trinitrotoluene, 1,3-dinitro-
benzene, and 1,3,5-trinitrobenzene) was achieved at the level of
ultratrace concentration (ppb) with the aid of a porphyrin–gra-
phene sensor.56 In this work, GO was treated with tetra(4-pyri-
dyl)porphin and, after the hydrothermal reduction and removal
of excess porphyrin, the dispersion of the porphyrin–graphene
adsorb was isolated and deposited on a glassy carbon electrode.
The electrochemical detection of nitroaromatics benefits from
an enhancement of the electrochemical signal, thanks to the
specific interactions between the electron-poor nitroaromat-
ics and the porphyrin ring. Furthermore, Jung and coworkers16
reported that the conductivity of a graphene film obtained by
reduction of GO in the presence of tetra-sulfonatophenyl por-
phyrin was greatly enhanced with respect to that of reduced
GO. The lowering of the graphene sheet resistance is explained
by both π–π interactions and electrostatic interactions with the
negatively charged sulfonate groups. An interesting effect is
observed when a PEG (polyethylene glycol)-functionalized gra-
phene derivative is associated with chlorin e6 (Ce6) in photo-
dynamic therapy assays.57 The photosensitizers (Ce6) associate
via weak interactions to the water-soluble modified graphene
derivative and show a considerable enhancement of their cyto-
toxic activity due to the generation of singlet oxygen. Moreover,
the authors reported that the photothermal effect of graphene
could also be harnessed in order to deliver the Ce6 molecules
by local heating with the aid of near-IR laser, thus enhancing
the photodynamic therapy efficiency against cancer cells.
A multicomponent supramolecular assembly involving a
GO unit acting as a support, an adamantly porphyrin linker,
and a folic acid-modified cyclodextrin used as a target unit
was reported by Liu et  al.58 The supramolecular assembly
organizes thanks to the host–guest interactions with the ada-
mant moiety and can recognize folic acid receptors in tumor
cells with high specificity owing to the very high association
constant between folic acid and folate receptors. Moreover,
this supramolecular construct has been used in order to
deliver doxorubicin (DOX), a well-known antitumor agent,
into tumor cells as their acidic environment is able to induce
DOX release from the graphene support by lowering its inter-
action in the acidic medium. Because the microenvironments
of tumor tissues are more acidic than normal cells, this pH-
controlled release process can be used in drug-delivery appli-
cations involving graphene.59–61
Besides using supramolecular interactions, the covalent
linkage of porphyrins onto graphene or graphene derivatives
is a direct route toward stable hybrid materials that can exploit
the self-assembly properties of porphyrins (e.g., via axial
coordination of a metalloporphyrin). Covalent attachment
341
of porphyrins onto graphene or GO has been studied mainly
for the modification of photochemical or optical properties of
both the graphene plane and the porphyrin. Functionalization
of the graphene plane with porphyrins via the Prato reaction
using graphene flakes and a formyl-functionalized porphy-
rin in the presence of sarcosine was reported by Feringa and
coworkers.62 The hybrid material thus obtained contained
about 20% tetraphenyl porphyrin (TPP), and the authors
observed a quenching of porphyrin fluorescence due to
energy/electron transfer between excited TPP and graphene.
An enhancement of the nonlinear optical behavior of a por-
phyrin–graphene adduct compared to graphene or to the por-
phyrin component alone was observed in several cases.63–65
This nonlinear effect is attributed to π–π interactions between
the porphyrin chromophore and the graphene plane.
22.2.3 Graphene Hybrids with Nucleic Acids
Nucleotides and oligonucleotides, in particular single-
stranded deoxyribonucleic acid (ss-DNA), spontaneously
adsorb onto the surface of graphene through electrostatic and
π-stacking interactions.66,67 Thus, the use of graphene and GO
as a generic platform for the fluorescent-based detection of
biopolymers is an actively pursued research area that generally
relies on the nonspecific adsorption of a fluorescently labeled
polynucleotide on the graphene surface.68–73 Fluorescence
quenching by graphene efficiently extinguishes the probe
strand’s emission, which is restored upon binding to the target
since this induces desorption of the probe from the graphene
surface. Some examples of such “turn-on” fluorescent sensors
are given in Section 22.5. There are also a few examples of
covalent or a specific noncovalent functionalization of gra-
phene with nucleic acids. Pumera and coworkers73 described
the covalent modification of GO with an ss-DNA via amide
coupling. The hybrid material thus obtained could be used for
detection of DNA hybridization using impedimetric methods
(Figure 22.3). A supramolecular variant to graphene function-
alization with DNA has also been reported by Luo et al.74 It
relies on the adsorption of 1-aminopyrene onto the graphene
plane, followed by grafting of an amino-terminated oligonu-
cleotide via a glutaraldehyde cross-linking tether.
22.3 SUPRAMOLECULAR GEL-BASED
MATERIALS INCORPORATING GRAPHENE
Interest in the preparation of graphene-containing organogels
stems from the potential electronic properties of the materials
which, compared to conventional organogels, should possess
both a high surface area and low electrical resistance.75 That
this is indeed the case was demonstrated in 2010 by Shi and
coworkers using a hydrothermal process to reduce GO and, in
one step, form a hydrogel.76 The resulting material possessed
ohmic behavior with a conductivity that reached 5 mS/cm for
samples with the lowest residual oxygen content. Therefore, an
efficient reduction of GO is necessary to obtain good charge
transport in the gel material. Conducting aerogels were subse-
quently prepared by Worsley et al. starting from gels prepared
342 Graphene Science Handbook

(a) O O O
O S O–
O
OH O
O

+EDC/sulfo-NHS

+NH2-ssDNAprobes

C A T

(b) O O O O O O
O P O O P O O P O
O– O– OH
NH O–
O

+ssDNA target

O– O O–
OH O P O O P O O P O
O O O O O O
G T A

C A T
O O O O O O
(c) O P O
O P O O P O OH
NH O O– O–

FIGURE 22.3  Covalent functionalization of graphene by ssDNA. (a) Sulfo-NHS esters formed on carboxylated graphene react with
amino-modified ssDNA probes to form an amide bond; this results in (b) covalently functionalized graphene by ssDNA. (c) Hybrid forma-
tion after incubation with a complementary DNA sequence. A: adenine, G: guanine, C: cytosine, and T: thymine. (Bonanni, A., Ambrosi,
A. and Pumera, M.: Nucleic acid functionalized graphene for biosensing. Chem. Eur. J. 2012. 18. 1668–73. Copyright Wiley-VCH Verlag
GmbH & Co. KGaA. Reproduced with permission.)

from GO suspensions by covalent cross-linking of a resor-
cinol and formaldehyde mixture in the presence of a base.77,78
Polymerization at 85°C leads to the formation of a gel in which
the GO flakes (1 wt.%) are dispersed in the material. The cor-
responding xerogel was obtained by drying using supercriti-
cal CO2 and subsequently pyrolized at 1050°C to carbonize
the polymerized gel and simultaneously thermally reduce the
GO. The resulting aerogels contained graphene densities of ca.
10 mg/cm3 and possessed a large surface area (580 m2/g with a
pore volume = 3.0 cm3/g) and excellent electrical conductivity
(87 S/m measured over 3–6-mm distances).
These initial promising results demonstrated the poten-
tial of gel materials incorporating graphene for applications
in, among others, sensors and batteries, where large surface
areas and good electrical conductivity are sought. Along
these lines, the incorporation of graphene into gels formed
by short peptides (di- and tri-amino acids) as demonstrated by
Banerjee and coworkers offers an interesting route to incorpo-
rate biopolymers and eventually enzymes into graphene mate-
rials without denaturation.79 In these systems, the stabilization
of the graphene (reduced GO) flakes is proposed to result
from π-stacking between the terminal N-fluorenyl (Fmoc)
protecting groups of the oligopeptide and the graphene sur-
face. Indeed, similar gel-forming behavior was observed upon
replacing the Fmoc group with a pyrenyl moiety, which is well
known to bind to graphene via van der Waals interactions.80,81
The quenching of the pyrene fluorescence upon incorporation
of graphene is in line with pyrene’s involvement in stabiliz-
ing the graphene flakes and transmission electron microscope
(TEM) images show the presence of graphene flakes dispersed
inside the entangled nanofibrillar network (Figure 22.4). The
same authors further showed that a pyrene-appended trypto-
phan residue could form a hydrogel in the presence of GO,
and provoke the reduction of gold(III) into nanoparticles
through oxidation of the tryptophan moiety.82 Interestingly,
the morphology of the hydrogel showed the simultaneous
presence of sheet and fibrous structures, as well as metallic
nanoparticles, and the material possessed enhanced mechani-
cal strength with respect to the native hydrogel (compared to
the more common case in which the inclusion of graphene
Chemistry and Applications of Supramolecular Graphene Derivatives
(a)
0.5 μm
HR-TEM facility, IACS
FIGURE 22.4  TEM image of a hybrid organogel formed between graphene nanosheets and peptidic nanofibrils (a) and zoom of an area
showing the entangling of the fibrils around the graphene sheets (b). (Adhikari, B., Nanda, J. and Banerjee, A.: Pyrene-containing peptide-
based fluorescent organogels: Inclusion of graphene into the organogel. Chem. Eur. J. 2011. 17. 11488–96. Copyright Wiley-VCH Verlag
GmbH & Co. KGaA. Reproduced with permission.)
reduces the stability of the gel—this may be due to the use
of GO, which presents additional hydrogen-bonding interac-
tions on the surface and edges of the flakes). Furthermore,
the material possessed enhanced catalytic activity toward the
reduction of nitroaromatics, thanks to the presence of the gold
nanoparticles. Analogous results were obtained using GO and
either polyamines (e.g., spermine or spermidine),83 simple
amino acids (arginine, tryptophan, or histidine), or nucleo-
sides (adenosine, guanosine, or cytidine).84 In these examples,
the inclusion of gold nanoparticles also lead to the formation
of catalytically active hybrid organogels. Nanoparticles can
be ordered on a graphene plane through the use of a supramo-
lecular thin film, as demonstrated by Bai et al.85 Recent devel-
opments include the fabrication of amino acid-functionalized
GO gels that display aggregation-induced fluorescence.86
In addition to metallic nanoparticles, it is also possible to
include metal oxide nanoparticles within a graphene-based
organogel, as demonstrated by Ho and coworkers.87 The inclu-
sion of TiO2 material was achieved by predispersing GO
sheets, TiO2 nanorods, Au nanoparticle-loaded TiO2 nanorods,
and vitamin C (as a reduction agent for GO and as a gelling
agent) to obtain a homogeneous suspension that was kept at
55–90°C. Over time, the initial brown solution turned black
and aggregation of the reduced GO nanosheets and TiO2
nanorods led to the formation of a hybrid hydrogel. The mate-
rial, once isolated, was shown to be photoactive toward the
reduction of water through the sensitization of the TiO2 par-
ticles by graphene and gold nanoparticles. Under visible light
irradiation conditions, the authors were able to show that the
reduced GO—TiO2–Au@TiO2 system was ca. 4 times faster
at producing molecular hydrogen than the corresponding TiO2
nanorods alone.87 Another example of a photoactive graphene
gel system was reported by Lee et al., which functionalized the
residual carboxylic acid groups on reduced GO with azoben-
zoic acid via a diazonium-grafting procedure.88 The resulting
343
(b)
Gel nanofibers
Graphene
Nanosheets
0.2 μm
HR-TEM facility, IACS
material bound zinc(II) metal ions in water to form a hydro-
gel at 10 mg/mL concentration (1:1:1 metal ion/ligand/reduced
GO). The gel displayed blue fluorescence (λmax = 425 nm) and,
upon irradiation, underwent a morphological phase transition
that led to the formation of nanorods. The preparation of gels
and aerogels incorporating graphene and iron oxide (Fe3O4)
nanoparticles was reported by Chen et al.89
In an investigation of organogels obtained by the inclusion
of carbon nanostructures (fullerene C60, carbon nanotubes,
and reduced GO) into the gel network, Bhattacharya and col-
leagues evidenced synergistic effects resulting from the pres-
ence of specific combinations of carbon nanostrusctures.90
The experiments were performed using either a π-conjugated
tri-p-phenylenevinylene (TVP) or a saturated carboxamide
(C12CA) gelator (Figure 22.5). Gels obtained from TVP
in the presence of exfoliated graphene (from reduced GO),
fullerene C60, or single-walled carbon nanotubes possessed a
higher mechanical resistance (as determined from oscillatory
frequency sweep experiments) than gels formed from TVP
alone. Interestingly, the combination of exfoliated graphene
and single-walled carbon nanotubes led to a stabilization of
the gel structure that was not observed from the combination
of exfoliated graphene and fullerene. The synergy in promot-
ing gel stabilization observed between graphene and carbon
nanotubes was attributed to the propensity of TVP to undergo
both π-stacking interactions with the carbon nanostructures
as well as hydrogen bonding. In line with this hypothesis,
the same behavior was not observed for C12CA in which
π-stacking interactions are absent.
The reduction of GO in the presence of a non-
ionic Pluronic copolymer (poly[ethylene oxide]-block-
poly[propylene oxide]-block-poly-[ethylene oxide]) triblock
copolymer was shown by Zu and Han to lead to an aqueous
dispersion of reduced GO.91 In this system, the more hydro-
phobic propylene oxide segments bind to the surface of the
344 Graphene Science Handbook

50,000

OR 40,000
HO N OR
OR
30,000

G′ (Pa)
RO
RO N OH 20,000
RO
TVP (R = C15H33) 10,000

O 0
OH

60
60
1
N

EG

T
C
C

N
+
+

SW

SW

SW
+
H O

EG
1
1
C12CA

+
+
1

EG
1

60
C
+

+
1

EG
+
1
FIGURE 22.5  Chemical structure of organogelators TVP and C12CA and storage modulus (G′) of gels formed by TVP alone (10 mg/mL
in water) or in the presence of exfoliated graphene (EG), fullerene (C60), single-walled carbon nanotubes (SWNT), and mixtures of carbon
allotropes at 0.83 wt.%. (Samanta, S. K. et al.: Composites of graphene and other nanocarbons with organogelators assembled through supra-
molecular interactions. Chem. Eur. J. 2012. 18. 2890–901. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.)

reduced GO through van der Waals interactions, whereas the more abundant than the graphene-based organogels. This is
hydrophilic polyethylene oxide segments extend into the aque- partly a consequence of the inherent amphiphilicity in GO
ous phase and provide stabilization of the flakes. Upon addi- resulting from hydrophilic groups located preferentially on
tion of α-cyclodextrin (α-CD), a supramolecular organogel is the edges, which renders gelation an intrinsic property of the
obtained due to the formation of pseudorotaxane structures in material.93–96 Furthermore, in several examples, graphene gel-
which the polyethyleneoxide chains are threaded through the based materials were prepared by the reduction of the cor-
α-CD (Figure 22.6). The hydrogel thus obtained contained responding GO gel.76 Phenolic acids, which are abundant in
0.1 wt.% graphene and possessed a sol–gel transition temper- Nature, can be used to reduce GO to form a graphene aerogel
ature of 45°C and behavior typical of organogels, albeit with through a hydrothermal treatment.97 GO98 will form hydrogels
reduced stability and mechanical resilience when compared in the presence of aromatic polar amphiphiles99 or various
to reference samples without graphene. In a similar approach, polymers that interact with either the hydrophilic groups or
Liu et al. covalently grafted β-CD to reduced GO and used the remaining aromatic regions via π-stacking interactions,100
the inclusion of a diblock copolymer to induce gelation.92 including DNA.101 Direct gelation of numerous solvent–elec-
Although beyond the scope of this chapter, a short intro- trolyte systems was explored by Batabyal and coworkers
duction of gels incorporating GO follows, as these are much in view of preparing quasi-solid-state dye-sensitized solar

(a) OH (b)
OH OH
n

O
n

O
n

O O
HO O
O
O O O
O
O O
O
n

O OH
O O n
O O
n
HO O O
O n O
O
HO
n

O
O

OH

FIGURE 22.6  Proposed structure of the copolymer-coated graphene (a) and supramolecular graphene hydrogel (b). (Reprinted with
­permission from Zu, S.-Z. and Han, B.-H. Aqueous dispersion of graphene sheets stabilized by pluronic copolymers: Formation of supra-
molecular hydrogel. J. Phys. Chem. C 113: 13651–7. Copyright 2009 American Chemical Society.)
Chemistry and Applications of Supramolecular Graphene Derivatives
cells.102 It was shown that the I 2 /I3− electrolyte system in gel-
ated acetonitrile could be incorporated into the cells to attain
conversion efficiencies of 7.5%, on par or slightly better than
the corresponding solution-based control cells (η = 6.9%).
The chemical derivatization of GO further allows it to be
readily endowed with functionalities such as response to
stimuli including temperature or pH.103,104 The application of
a stimuli-sensitive GO gel toward controlled drug delivery,105
and the subcutaneous in vivo formation of a GO hydrogel in a
mouse triggered by temperature106 suggest that the full poten-
tial of these systems is yet to be explored.
22.4 SELF-ORGANIZATION OF
FUNCTIONALIZED GRAPHENE
DERIVATIVES
Graphene can spontaneously self-assemble to generate a vari-
ety of mesoscopic structures. For example, a slightly oxidized
form of graphene (formed via HNO3 treatment) formed within
carbon nanotubes can reorganize to yield tube-in-tube nano-
structures.107 Here, the treatment of graphitic nanoparticle
impurities contained inside the nanotubes using nitric acid
gives rise to small graphene sheets via an intercalation–exfo-
liation process, and also leads to their functionalization at the
sheet edges through the introduction of carboxylic acid or
hydroxyl groups. These modified graphene sheets then orga-
nize inside and outside the pristine carbon nanotubes via a
sulfuric acid-catalyzed esterification process, to form double
and triple-channel tube-in-tube nanostructures. Covalent
modification of the graphene surface with charged polymers
yields materials that can be assembled onto electrodes via
electrostatic interactions using layer-by-layer techniques.108
Owing to its large aromatic and hydrophobic plane, gra-
phene is able to give rise to complex supramolecular assem-
blies with various substrates, particularly those possessing
extended π-aromatic structures, which bind to its surface
to generate adlayers with a regular pattern. For instance,
hexafluorotribenzo[a,g,m]coronene with n-carbon alkyl chains
(FTBC-Cn, n = 4, 6, 8, 12) possessing a Janus-type “double-
concave” shape gives rise to highly oriented complex structures
on graphene.109 The structural dependence of the self-assem-
bled motifs with the molecular conformation of the alkyl chain
could be investigated by scanning tunneling microscopy aided
by density functional theory calculation. An interesting reverse
face “up–down” way is observed in FTBC-C4 assembly due to
the existence of hydrogen-bonding interactions (Figure 22.7).
With increasing alkyl chain length (from C4 to C12) and con-
sequently stronger van der Waals interactions, the molecules
no longer adopt the alternating “up–down” orientation and
organize into various adlayers possessing lamellar, hexagonal
honeycomb, and pseudohoneycomb structures.
Porphyrins and phthalocyanines bind efficiently to car-
bon nanostructures through π-stacking interactions.110,111 In
the case of graphene, this can be used as a means to induce
the exfoliation of graphite to directly form a graphene–phtha-
locyanine assembly.112 The stable graphene dispersions thus
obtained show that the electronic properties of the graphene
345
Liquid
b
Self-assembly
a on HOPG
Side view
FIGURE 22.7  Top and side views of the proposed structural
model for the ordered FTBC-C4 adlayer and schematic illustra-
tion of “up–down plates” representing the molecular orientation
due to hydrogen-bonding interactions (black dashed lines). (Chen,
Q. et al. Structural selection of graphene supramolecular assembly
oriented by molecular conformation and alkyl chain. Proc. Natl.
Acad. Sci. USA 105: 16849–54, Copyright 2008 National Academy
of Sciences, U.S.A.)
component are sensitive to the presence of the adsorbed phtha-
locyanine–oligophenylene–vinylene adduct. Interestingly,
the resulting material, once deposited onto a transparent
ITO (indium tin oxide) electrode, is able to generate a small
photocurrent upon illumination. Investigation of the photo-
induced properties using transient absorption spectroscopy
revealed that an electron transfer process occurs from the
photoexcited ZnPc acting as an electron donor to the gra-
phene electron acceptor. Similar electron transfer processes
were also observed in a covalent graphene–phthalocyanine
material which, upon excitation, affords a charge-separated
state within a few picoseconds that decays with a rate of ca.
3 × 109 s−1 in N-methyl-2-pyrrolidone (NMP).113 Direct exfo-
liation of graphite using a free-base porphyrin has also been
reported,114 although the stability of the chromophores during
the ultrasound treatment remains a significant concern. With
this in mind, an alternative route for anchoring sensitizers
on graphene via electrostatic interactions has been explored
by Guldi and coworkers.115 In this case, the integration of
the sensitizer by means of electrostatic interactions occurs
through the use of a positively charged, water-soluble pyrene
derivative as an anchoring group (Figure 22.8). The charged
pyrene component acts as a powerful exfoliating agent and
then interacts with a negatively charged porphyrin to promote
the assembly of the latter onto the graphene surface. Using a
layer-by-layer technique, the construction of a photoelectrode
by means of an electrostatic self-assembly onto a transparent
ITO electrode was demonstrated.
346 Graphene Science Handbook

graphene to construct a metal organic framework (MOF)

FIGURE 22.8  Schematic representation of a graphene architec-
ture using an immobilized cationic pyrene derivative to bind a nega-
tively charged porphyrin through electrostatic interactions. (Malig,
J. et al.: Integrating water-soluble graphene into porphyrin nanohy-
brids. Adv. Mater. 2012. 24. 800–5. Copyright Wiley-VCH Verlag
GmbH & Co. KGaA. Reproduced with permission.)
22.5 SUPRAMOLECULAR GRAPHENE
DERIVATIVES FOR DEVICE APPLICATIONS
Harnessing the electronic properties of graphene and reduced
GO for molecular device applications is a long-term princi-
pal objective of many studies involving their supramolecular
functionalization. Indeed, graphene has been proposed, on
a theoretical basis, to be a superior material for fabricating
nanogap junctions for single-molecule electronics.116 Early
studies rapidly evidenced that the supramolecular stabiliza-
tion of reduced GO using a pyrene–butyric acid conjugate
could lead to the formation of films that possessed high
conductivity (2 × 102 S/m).11 Nonetheless, examples of func-
tional graphene-based devices are rare, despite the increasing
interest in supramolecular electronic devices for sensing and
solar energy conversion.9,117 Examples of graphene/phthalo-
cyanine–poly(p-phenylene vinylene) (PPV) systems112,115 and
nanocomposite gels for hydrogen production87 and solid-state
dye-sensitized solar cells102 were described previously in
Sections 22.2 and 22.3, respectively. In another route to the
supramolecular porphyrin–graphene hybrid systems, Jahan
et al. used ancillary pyridine groups covalently grafted onto
in the presence of an iron(II) porphyrin derivative (Figure
22.9).118 The material thus obtained possessed good catalytic
activity for the four-electron reduction of oxygen reaction
in a fuel cell while being relatively inert toward methanol
oxidation.
Various approaches have been pursued to improve the effi-
ciency of solar energy conversion devices using graphene.
However, the direct introduction of graphene in the device
active layer generally results in a decline in device performance
or even internal short circuit of the device. AbdulAlmohsin
and Cui119 showed that the efficiency of a solid-state hybrid
organic–inorganic photovoltaic cell employing vertically
aligned zinc oxide nanowires grafted with porphyrins could
be significantly improved (from 0.09% to 0.4%) by the incor-
poration of graphene in the poly-3-hexylthiophene matrix
due to improved hole collection. To convert carbon dioxide
into formic acid, Yadav et  al.120 grafted a rhodium photo-
catalyst and an electron donor to form an ensemble capable
of regenerating nicotinamide adenine dinucleotide (NADH)
from NAD+. In the presence of a biological enzyme, formate
dehydrogenase, the system is capable of sensitizing, using vis-
ible light, the reduction of carbon dioxide into formic acid.
Vertical alignment of the graphene layers was also shown to
be important in preparing carbon-based films for energy stor-
age devices such as Li-ion batteries. Such an alignment could
be obtained through supramolecular interactions during the
spin-coating process of a liquid crystal precursor followed by
pyrolysis.121
As mentioned in the introduction, sensing is an attractive
target application for supramolecular graphene-based materi-
als as it potentially benefits from graphene’s extended surface
area and high charge-carrier mobility. These properties are
particularly well adapted to electrochemical sensing applica-
tions.122,123 Devices in this area are inherently supramolecular
when they employ reversible molecular interactions as a basis
for molecular recognition. Even in the absence of efficient elec-
tronic coupling to the graphene layer, it is possible to design
cost-effective turn-on sensors by making use of graphene’s
intrinsic ability to efficiently quench electronic excited states

(a) (c)
(f)
Fe (e)
N

O2

(b) (d)
4e–
H2O
N O H OH–

FIGURE 22.9  Reduced GO possessing ancillary styrylpyridine groups (b) is obtained by chemical modification of GO (a) and forms, in
the presence of a MOF (d) constructed from a tetracarboxylic acid porphyrin (c) and Fe(II) ions, a hybrid structure (e) that is catalytically
active in the four-electron reduction of oxygen reaction that occurs in fuel cells. The proposed structure of the hybrid material is shown in (f).
(Reprinted with permission from Jahan, M., Bao, Q. and Loh, K. P. Electrocatalytically active graphene–porphyrin MOF composite for
oxygen reduction reaction. J. Am. Chem. Soc. 134: 6707–13. Copyright 2012 American Chemical Society.)
Chemistry and Applications of Supramolecular Graphene Derivatives
ssDNA Dye
(a) (b)
Target
S ferricyanide, and methylviologen), as well as selected biomol-
GO HN N Oligo
= Carbon = Oxygen = Hydrogen FAM = H
COOH
O O OH
FIGURE 22.10  Binding of a labeled ss-DNA oligomer to GO (a)
efficiently quenches the fluorescent probe’s emission. The latter is
restored upon exposure to the target strand through the release of
the duplex triggered by the decrease in hydrophobic interactions
upon hybridization (b). (Lu, C.-H. et al.: A graphene platform for
sensing biomolecules. Angew. Chem. Int. Ed. 2009. 48. 4785–7.
Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced
with permission.)
generated chemically or by direct excitation.68,72,124,125 Thus,
Lu et al. exploited the ability of graphene and GO to bind ss-
DNA by using dye-labeled ss-DNA oligomers bound to GO as
a general platform for sensing ss-DNA.126 The binding to gra-
phene event efficiently extinguishes the probe strand’s emis-
sion, which is restored upon exposure to a complementary
strand. The driving force for sensing selectivity results from
hybridization of the probe strand, which considerably reduces
its propensity to bind to the GO surface through hydrophobic
interactions (Figure 22.10). Analogous results were obtained
with a binding agent for the minor groove in double-stranded
DNA,127 and extension of the system toward the detection of
proteins was achieved by the use of an aptamer sequence and
demonstrated for the detection of human thrombin, a pro-
tein linked to blood coagulation.126 Thanks to the aptamer’s
high-binding specificity and good signal-to-noise response of
turn-on fluorescent sensors in general, a lower detection limit
of 2 nM could be attained. In this respect, graphene and GO
offer a more affordable alternative to carbon nanotube sup-
ports that had been previously employed in such bioassays.128
Ultrasensitive aptamer-based sensing was also achieved in a
hybrid metal nanoparticle with a fullerene or graphene carbon
material.129 An investigation of binding of various ss-DNA
segments and double-stranded DNA onto graphene nanorib-
bons (prepared by the unzipping of single-walled carbon
nanotubes) evidenced high anisotropy in the electronic inter-
actions, suggesting that the DNA oligomers are ordered on the
graphene nanoribbons.130
The binding of receptors onto graphene has already been
partly covered in Section 22.2. The adsorption of covalently
modified graphene possessing molecular receptor units onto
electrodes is a convenient route to prepare electrochemi-
cal sensor devices. For example, an adamantane-functional-
ized enzyme (horseradish peroxidase) was supramolecularly
grafted onto a cyclodextrin-modified graphene material.131 The
supramolecular construct could then be immobilized onto an
electrode to produce an enzyme–electrode possessing a high
sensitivity toward H2O2 (detection limit of 100 nM) coupled
with good signal reproducibility. Electrodes modified with
347
cucubiturils (a molecular capsule possessing a hydrophobic
interior cavity) supported onto graphene were used for electro-
analytical sensing of various electroactive reagents (ferrocene,
ecules such as l-thyrosine in serum, at nanomolar concentra-
tions.132 Variations in electrochemical behavior with respect to
the solution suggested that the use of graphene imparted an
increase in electron mobility. Enzyme mimics of peroxidase
displaying enantioselectivity have recently been reported.133
Binding of osmium(II) complexes onto reduced GO using
pyrene–graphene interactions can be used as a technique to
quantify the electroactive surface available.134
The use of graphene to probe spin density in molecular
magnets is particularly promising in view of graphene’s large
surface area–single-layer construction and zero-bandgap elec-
tronic states. These can potentially allow a longer lifetime of
spin states in adsorbed magnetically active materials, while at
the same time providing a high coupling to the charge trans-
port properties of graphene. The combination of these proper-
ties is especially interesting for spintronic applications. This
aspect has been investigated from a theoretical perspective,135
and also demonstrated experimentally by Candini et al.136 The
latter used the supramolecular interactions between pyrene
and graphene to bind terbium phthalocyanines onto the sur-
face of an etched graphene flake onto which source and drain
electrodes (Ti/Pt) were deposited by electron beam lithog-
raphy (Figure 22.11). By measuring the electric conductiv-
ity through the graphene layer at different external magnetic
fields, it is possible to map out the magnetoconductivity signal
that evidences the expected uniaxial magnetic anisotropy of
the molecular magnets adsorbed onto graphene. In addition
to the structural variation of the molecular component, such
devices allow considerable tunability by adjusting the back-
gate voltage and applied magnetic field.
22.6 SUMMARY
The use of supramolecular interactions to tailor the proper-
ties of graphene and its derivatives represents a very attractive
solution to solve the conundrum of improving its mechanical
and chemical properties without sacrificing its attractive elec-
tronic properties. In this respect, the weak interactions that
govern supramolecular interactions (van der Waals, hydropho-
bic forces, and hydrogen bonding) allow the exploitation of the
large surface area developed by graphene flakes by increasing
the contact area between molecules. This improves the dis-
persibility of graphene without the necessity of chemically
modifying the aromatic plane (which would decrease the elec-
tronic properties). The weak interactions between graphene
and the adsorbed species can be exploited toward the design
of very sensitive chemical sensors that can, in the future, inte-
grate a diversity of chemical receptors and multiplex their out-
put in what is generally termed an artificial nose.137 For these
and other applications, the inclusion of modified graphene into
electronic devices is necessary. This can be advantageously
achieved through the use of noncovalent modification.
348 Graphene Science Handbook

(a) (b)

N
N
N N
N N
N
N

C6H13 Tb C6H13
C6H13
N N N
C6H13 N N C6H13
N N N C6H13
O
(CH2)4–pyrene

(c) (d)
200 nm

S D
ID S D

x
y

FIGURE 22.11  Structure of a single-molecule magnet (a) composed of a Tb phthalocyanine appended with a pyrene moiety for supramo-
lecular binding to the surface of graphene (b). Schematic (c) and false-color scanning electron microscope image (d) of a device prepared
from an etched graphene sheet onto which source and drain electrodes were deposited by electron beam lithography. Results show that
the charge transport through the graphene sheet is sensitive to external magnetic fields due to the presence of the adsorbed Tb complex.
(Reprinted with permission from Candini, A. et al. Graphene spintronic devices with molecular nanomagnets. Nano Lett. 11: 2634–9.
Copyright 2011 American Chemical Society.)

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olfaction: Sensors and applications. Talanta 124: 95–105.
23 Applications of Graphene
in Tissue Engineering
Eoin Murray, Brianna C. Thompson, and Gordon G. Wallace

CONTENTS
Abstract...................................................................................................................................................................................... 353
23.1 Tissue Engineering........................................................................................................................................................... 353
23.2 Biocompatibility............................................................................................................................................................... 354
23.2.1 Properties of Graphene Relevant to Biocompatibility.......................................................................................... 354
23.3 Use of Graphene for Tissue Engineering.......................................................................................................................... 357
23.3.1 Graphene-Only Structures.................................................................................................................................... 357
23.3.2 Graphene/Inorganic Structures............................................................................................................................ 357
23.3.3 Graphene/Polymer Composites............................................................................................................................ 359
23.4 Conclusion........................................................................................................................................................................ 360
References.................................................................................................................................................................................. 360

ABSTRACT made of appropriate materials with cells, chemical cues

Inclusion of carbonaceous components into materials for
tissue engineering has been shown to impart new physico-
chemical properties favorable for the control of growth and
biological function in cells. Research into the incorporation of
materials such as conducting polymers, carbon fibers, carbon
nanotubes, or diamond into biomaterials has led to enhance-
ments in the conductivity, mechanical properties, bulk and
surface functionality, and even introduced bioactive species
for cell–structure interfaces.
In recent years, graphene has been considered as an ideal
candidate for such purposes, due to its inherent physical,
mechanical, and conductive properties. Additionally, gra-
phene can be easily and inexpensively produced from graph-
ite in large quantities. Most importantly, it has been suggested
that the toxicity of graphene is lower than that of carbon nano-
tubes and other carbon materials, due to its unique composi-
tion and two-dimensional geometry.
Using a range of mechanical and chemical methods, gra-
phene has been successfully incorporated into biomaterials,
with the resulting graphene biomaterials having shown to retain
the biocompatibility, biodegradability, and processability of the
biomatrix but with conductivities and mechanical properties
enhanced by orders of magnitude. Similarly, the functionaliza-
tion of graphene nanosheets with biological factors has provided
a pathway to intimately integrate graphenes into biological sys-
tems. Here, we explore the applications of graphene in the devel-
opment of materials and structures for tissue engineering.
23.1  TISSUE ENGINEERING
The aim of tissue engineering is to repair or replace the dam-
aged or diseased tissue by combining a fabricated structure
(drugs, growth factors, or other endogenous signals), and
physical cues to encourage cells to develop into functional tis-
sues. The field of tissue engineering is a branch of biomateri-
als science, with an emphasis on providing the correct cues
to cells isolated from the patient using the developed scaf-
fold, and then reintroducing the construct into the patient to
develop in situ. The general process of tissue engineering is
illustrated in Figure 23.1.
The general tissue-engineering approach to the repair of
damaged tissues has developed to reduce the risk of immu-
nogenicity that is inherent in transplants of tissues or stem
cells from donors or in xenotransplantation. Treatment of the
patient with their own cells means that implant rejection is no
longer a risk and also provides the best chance for the develop-
ment of a “normal” tissue. Owing to the massive differences
between cell requirements in terms of the cues needed, the
development of purpose-built scaffolds for the regeneration of
different types of tissues is required. Scaffolds need different
properties for application in different parts of the body; so, the
application will determine not just the form factor, but also
the material properties required. Tissue-engineered implants
may be required to replace large blocks of an amorphous tis-
sue (such as muscle or fat), membranes (to replace internal
membranes or the skin), or may need a more fibrous form
(e.g., in engineering nerve fibers), as illustrated in Figure 23.2.
Different methods may be used to produce these structures,
such as casting, three-dimensional (3D) printing, freeze dry-
ing, electrospinning, wet spinning, extrusion, or lithography,
with the fabrication methods needed to change with the prop-
erties of the materials used. One requirement of materials
that are intended for implantation into humans that does not
change regardless of application is the requirement for bio-
compatibility of the material.

353
354
FIGURE 23.1  Tissue-engineering process: (1) Cells are isolated
from the patient. (2) A scaffold is constructed to provide an environ-
ment to encourage the development of cells into tissues. (3) Cells are
seeded onto the scaffold in vitro. The scaffold, containing the correct
physical, mechanical, chemical, and structural cues encourages cell
proliferation and/or differentiation, and the construct matures until
the nascent tissue is in the correct state. (4) The tissue-­engineered
material with cells is reimplanted into the patient, where the body
provides cues to develop into a fully functional and connected tissue.
Blocks
Membranes
Fibers
FIGURE 23.2  Examples of desirable form factors for tissue-
engineered structures. Blocks, which may be used to replace large
blocks of tissue, could be simple gels (left), lattices of gels, polymers
or ceramics (center), or freeze-dried structures with large porosity.
Membranes may be simple cast structures (left), lattices with large
pores (center), or mats made from nanofibers, such as the electros-
pun example shown on the right. Fibers may be simple tubes of gels
or hard plastics (left), coaxial tubes with combinations of materials
(center), or hollow conduits (right).
23.2 BIOCOMPATIBILITY
For any material that is to be used for tissue engineering,
the property of paramount importance is biocompatibility.
However, the term “biocompatibility” has a wide range of
definitions, from a material that does not kill cells in simple
laboratory tests to more comprehensive definitions incorpo-
rating many tests of different factors that are important for
not impeding biological systems. For materials that are to
be implanted into the body, a comprehensive set of require-
ments for biocompatibility are set out by the United States
Graphene Science Handbook
of America’s Food and Drugs Administration (USFDA),
which is summarized in Table 23.1. The Food and Drugs
Administration (FDA) outlines a clear set of tests that must
be performed before a device can be released to the mar-
ket for any medical application in the United States, and
this includes tests that a material must pass before it can be
implanted into the body for any purpose. The guidelines pro-
vided by the FDA are largely based on ISO10993 “Biological
Evaluation of Medical Devices” (ISO10993 1997) and the
document in which the FDA outlines their requirements is the
1995 Memorandum #G95-1 “Use of International Standard
ISO-10993, ‘Biological Evaluation of Medical Devices Part
1: Evaluation and Testing’” (Health 1995). However, with
revisions to the ISO10993 guidelines in 2009, the FDA has
recently (April 2013) released a draft-revised version of this
document, which, while similar, gives more detailed guide-
lines for the expected outcomes of tests and follow-up tests
for researchers to consider, more detail on treatments of pre-
viously approved materials, and updated definitions for more
novel materials, such as nanostructured materials or materials
that are polymerized in situ (Health 2013).
23.2.1 Properties of Graphene Relevant
to Biocompatibility
The broad range of geometries, chemistries, and physical
properties possible with graphene-type materials results in a
large number of variable properties relevant to their biocom-
patibility (Table 23.2). Here, we will discuss some of these
properties.
Dimensions: Graphene sheets vary in lateral size from
10 nm (Yang et al. 2011) to more than 10 ​µm that can have
a great influence on their cellular uptake and excretion (Yue
et al. 2012, Akhavan et al. 2013, Li et al. 2013). At the smaller
end of the size scale, graphene oxide (GO) has been shown
to have low cytotoxicity and high cellular uptake over an
extended time period and can be renally and fecally excreted
(Yang et al. 2011, Zhang et al. 2013). Cellular uptake of larger
graphene sheets, however, is poorly understood but recently, it
has been shown that GO sheets can undergo internalization by
receptor-mediated endocytosis with size-dependent efficien-
cies (Mu et al. 2012, Zhang et al. 2013) or phagocytosis (Yue
et al. 2012), with larger graphene sheets being less likely to
be taken up by cells. Larger GO sheets have also been shown
to undergo degradation by horse radish peroxidase (HRP) via
the formation of holes by oxidation of basal defects (Kotchey
et al. 2011), meaning that they may be able to be broken down
in the body, changing their biocompatibility profile.
Surface area: Owing to its atomic monolayer nature, the
theoretical maximum surface area of a pristine graphene sheet
is approximately 2625 ​m2/g. This is reduced with stacking
and agglomeration but is still an order of magnitude greater
than most other bionanomaterials and more than double that
of single-wall carbon nanotubes (CNTs). This extremely large
surface area has a considerable potential for surface interac-
tions with the biological media, particularly physical adsorp-
tion and catalytic chemical reactions, leading to a potential
Applications of Graphene in Tissue Engineering 355

TABLE 23.1
Biocompatibility Testing Standards Required by the USFDA for Approval of Implanted Medical Devices (or
Materials) with a Lifespan of More than 30 days in Humans (Based on 1995 Memorandum #G95-1 “Use of
International Standard ISO-10993, Biological Evaluation of Medical Devices Part 1: Evaluation and Testing”) for
Implantation into Bone/Tissue or into Areas in Direct Contact with the Circulatory System (Blood)
Test Name Test Summary Blood Bone/Tissue
Cytotoxicity Using cultured cells in vitro the effects of the material or extracts of the material on cell growth a a

and toxicity.
Sensitization Look for indicators of an allergic response against the material (or extracts) in animal models. a a

Genotoxicity Use mammalian and nonmammalian cell to look at DNA changes, gene mutations, and a a

chromosomal aberrations (changes in number or structure) caused by exposure to the material

(or extract).
Implantation The material is implanted into the relevant tissue or site in the body and the effects on the a a

pathology-surrounding tissues are inspected after a relevant period of time, to observe immune
response, tissue reactions, and material stability.
Irritation or intracutaneous Short-term exposure of the material (or extracts) to the eye, skin, or in subcutaneous injections a c

reactivity in an animal model to observe the local reaction of the tissue.

Systemic toxicity (acute) A single dose of the material (or extracts) is intravenously injected into an animal model and a c

adverse reactions (respiratory, digestive, circulatory, and pyrogenic) are monitored for more
than 24 h.
Subchronic toxicity An animal is dosed with single or multiple exposures to a material (or extract) and monitored a c

for between 24 h and 10% of the life span of the animal (e.g., 90 days in rats) (can be replaced
by chronic toxicity studies).
Chronic toxicity An animal is dosed with single or multiple exposures to a material (or extract) and monitored b b

for more than 10% of the life span of the animal (e.g., 90 days in rats).
Carcinogenicity Observation of tumor formation in animals that are implanted with the material for more than b b

10% of the life span of the animal (e.g., 90 days in rats).

a Required for initial evaluation.

b May be required for further evaluation.
c Are included in the draft proposal for future FDA guidelines (UCM348890) (April 2013).

for sequestration of nutrients or biomolecules important for
tissue function.
Surface chemistry: Even without further functionalization,
graphene can exhibit a wide variety of surface chemistries
(Figure 23.3). Pristine graphene, both mono- and few-layered
graphene, produced by techniques such as chemical vapor
deposition (CVD) is hydrophobic, atomically flat (although
may be crumpled), and generally chemically inert. On the
other hand, GO is atomically rough with basal and edge
defects created by the oxidation of graphite used to produce
it. These oxide, hydroxyl, and carboxyl sites provide hydro-
gen-bonding sites, electrostatic stabilization in solution and
subsequent hydrophilicity, and reaction sites for the chemi-
cal attachment of relevant biomolecules. However, the basal
defects also interrupt the sp2 conjugation of the sheet result-
ing in loss of conductivity. Reduction of GO by chemical,
mechanical, or thermal means (Li et  al. 2008) results in an
intermediate material (reduced graphene oxide, rGO). At its
best, rGO removes as many of the basal defects as possible
restoring the sp2 hybridization and conductivity while retain-
ing enough edge defects to maintain electrostatic stabiliza-
tion. The conductivity, number of reactive sites, and solubility
can be controlled in this manner.
Purity: Compared with other nanostructured carbon com-
pounds such as CNTs, graphene production usually results
in little or no contamination with residual catalysts or reac-
tive chemicals. CNT production gives rise to a number of
unwanted residues detrimental to healthy cell growth includ-
ing metal catalysts, carbon nanoparticles, and chemical resi-
dues. Graphene impurities tend to be graphite or in the case
of chemical oxidation/reduction, residual reductants usually
present themselves due to improper washing (Bussy et  al.
2013). Properly purified GO has been shown to not induce
significant cytotoxic responses either in vitro or in vivo
(Ali-Boucetta et al. 2013).
Mechanical properties: Matching the substrate mechani-
cal properties with the physiologically appropriate mechani-
cal properties of the tissue in question improves the efficacy
of tissue-engineering materials. The inherent elastic moduli
of the tissue vary from Pa for fat cells to MPa for the tendon
and articular cartilage and it has been shown that materials of
a similar modulus mimic the natural mechanical environment
(Levental et al. 2007). Graphene stiffnesses can be controlled
as they are inversely proportional to the number of layers and
are also dependent on the oxidation level, with GO exhibiting
an elastic moduli less than half of that calculated for a pristine
 356

TABLE 23.2
Biologically Relevant Material Properties of Carbon Materials Used in Tissue Engineering
Graphene GO/Reduced GO CNTs Carbon Fibers References
Size/shape • Controllable shape—flat sheet, ribbon, • Single or few sheets • Cylindrical • Fibers Ajayan and Tour (2007), Liet al. (2008), Yuan
etc. • Atomically rough or • Single-wall nanotube • µm to cm lengths et al. (2012), Yue et al. (2012), Akhavan et al.
• Single or few sheets possibly crumpled (SWNT) or multiwall • 5–8-µm diameters (2013), Bussy et al. (2013), Gambhir et al.
• Atomically flat or possibly crumpled • nm to µm lateral nanotube (MWNT) (2014), Yang et al. (2013)
• nm to µm lateral dimensions dimensions • nm to cm lengths
• Single- to multiatom thickness with a • nm-scale diameters
minimum of 0.33-nm interlayer spacing
Surface area 2625 ​m2/g decreases with stacking 800–2000 ​m2/g • SWNT—1315 m2/g 0.2–1 ​m2/g Li et al. (2008), Tang et al. (2012), Bussy et al.
• MWNT—100–700 m2/g (2013), Gambhir et al. (2014), Valentini et al.
Both reduce with bundling (2013), Wang et al. (2013), Zhang et al. (2013),
Zhang et al. (2013)
Surface Single or few molecular layer aromatic Incomplete sp2 hybridization Single or few molecular Lamellar polycondensed Li et al. (2008), Tang et al. (2012), Gambhir
chemistry structure with complete sp2 hybridization due to basal defects, edge layer aromatic structure hexagonal carbon with et al. (2014), Ku et al. (2013), Murray et al.
defects, and oxide groups with sp2 hybridization multiple surface (2015), Sayyar et al. (2013a,b, 2015), Valentini
allows solubilization and “active” sites usually et al. (2013), Wang et al. (2013), Zhang et al.
functionalization oxygen defects (2013), Zhang et al. (2013)
Impurities Metallic catalyst residues Graphite and chemical Chemical residues, Usually oxygen species Ali-Boucetta et al. (2013), Bussy et al. (2013),
from residues from oxidation and unconverted amorphous but also heteroatoms. Chowdhury et al. (2013), Ku et al. (2013)
synthesis reduction. Dependent on carbon, and metallic Unconverted polymeric
the washing regime and catalyst residues. precursors
preparation methods Dependent on preparation
methods
Mechanical Modulus of 1000 GPa becoming stiffer on Modulus of 380–470 GPa Modulus of 270–850 GPa Modulus of 100–400 Frank et al. (2007), Lee et al. (2008), Li et al.
properties stacking becoming stiffer on (in the axial direction) GPa (2008), Tang et al. (2012), Gambhiret et al.
stacking (2014), Valentini et al. (2013), Wang et al.
(2013), Zhang et al. (2013), Zhang et al. (2013)
Biodegradation Unknown Enzymatic degradation via Enzymatic degradation via Unknown possible Van de Velde and Kiekens (2002), Kotchey et al.
oxidation and subsequent oxidation and subsequent hydrolysis at defect (2011), Bussy et al. (2013)
holing holing and/or unzipping sites
Cellular uptake Phagocytosis and endocytosis Phagocytosis, endocytosis, Phagocytosis, Phagocytosis (possibly Liao et al. (2011), Sasidharan et al. (2011), Yang
and possibly membrane macropinocytosis, after surface treatment) et al. (2011), Zhang et al. (2011), Liu et al.
absorption at small sizes endocytosis, membrane (2012), Mu et al. (2012), Nguyen and Berry
dependent on surface adsorption, and piercing (2012), Zhang et al. (2012), Akhavan et al.
chemistry and dependent on surface (2013), Miao et al. (2013), Misra and
functionalization chemistry Chaudhari (2013), Sahni et al. (2013), Wang
et al. (2013), Yang et al. (2013)
Graphene Science Handbook
Applications of Graphene in Tissue Engineering
(a) (b) CO2H CO2H
HO2C
O O OH
HO2C
OH O O
HO2C
O O
HO2C
O O
HO2C
O O O HO
HO2C
OH O O O
HO2C
O O
HO2C
CO2H
CO2H
FIGURE 23.3  Chemical structure of (a) pristine graphene, (b) GO, and (c) rGO. Note the many basal defects of GO that are mostly
removed on reduction to rGO just leaving a number of edge defects. On the other hand, CVD-grown pristine graphene has complete sp2-
hybridized carbon with very few or no edge or basal defects. (d) A graphene composite with exfoliated graphene sheets (black) either
blended with the polymer matrix (dark gray) or covalently linked to the polymer chains (light gray).
graphene sheet (Liu et al. 2012). Graphene, GO, and rGO can
also be used as fillers in polymer composites to control the
mechanical properties of the polymer. In addition, single- and
few-layered graphene sheets have been shown not to affect
the elastic modulus when applied to the underlying polymer
tissue-engineering structures.
Electrical conductivity: While not vital for biocompatibil-
ity, electrical stimulation has been shown to be advantageous
for the growth of electroresponsive cells such as nerve and
muscle cells (Heo et al. 2011, Parket al. 2011, 2013). Recent
work has shown that under electrical stimulation, graphene
and graphene composites can increase neurite outgrowth
length of nerve cells in vivo (Sherrell et al. 2014).
23.3 USE OF GRAPHENE FOR
TISSUE ENGINEERING
The biocompatibility of graphene is obviously of huge impor-
tance in any potential use of the material for tissue-engi-
neering applications. In addition, the material must support
whatever processes the cells must go through to develop into
the final mature tissue. This might involve proliferation of
cells in the scaffold  in vitro and in vivo, migration of endog-
enous cells into the scaffold in vivo, differentiation of precur-
sor cells into mature tissues, or permission of angiogenesis
(the development of new blood vessels) to keep the mature
tissue connected to the circulatory system. These require-
ments will vary between different tissue-engineering appli-
cations—for example, nerve regeneration generally requires
softer materials, while regeneration of the bone requires very
stiff materials. Graphene has been considered for use for tis-
sue engineering for a wide range of tissue targets, as a stand-
alone material (Section 23.3.1), as a composite with inorganic
materials (Section 23.3.2), or as a composite with organic
materials (Section 23.3.3).
23.3.1 Graphene-Only Structures
Many of the remarkable properties reported about graphene
(particularly mechanical and electrical properties) are based
357
CO2H (c) COOH COOH COOH (d)
CO2H
CO2H
O
CO2H
HOOC
O O
CO2H COOH
CO2H
O
OH
CO2H
CO2H COOH COOH COOH
on the properties of unmodified, pristine single-layer gra-
phene. However, these pristine graphene sheets alone are
unlikely to provide a suitable substrate for a tissue-engineered
structure, due to their lack of strength, and inability to be han-
dled without a support or to be processed in solution. Several
studies have grown pristine graphene sheets and transferred
graphene onto other surfaces (tissue culture plastic, flexible
biodegradable polymers, silicon, etc.), often for explorations
of the ability of graphene to act as a muscle or nerve stimulat-
ing/recording electrode for in vitro or in vivo applications. GO
and rGO structures hold more promise than pristine graphene
for building implantable structures due to their ease of syn-
thesis on a large scale, increased processability, and chemical
functionality. This has allowed researchers to create 3D struc-
tures out of these materials alone, as well as coating surfaces
with the materials to explore their compatibility with various
cells and tissues, or exposing cultured cells or animals to GO/
rGO dispersions to assess their toxicity.
Literature relating to pristine (CVD-synthesized) gra-
phene, GO, or rGO for in vitro or in vivo applications and
investigations are summarized in Table 23.3 with a few groups
finding minor adverse effects both in vitro and in vivo (Lim
et al. 2011, Sasidharan et al. 2011, Wang et al. 2011, Zhang
et  al. 2011), while the vast majority found that graphene
showed good biocompatibility, or even enhanced biocompat-
ibility or bioactivity of substrates (Ali-Boucetta et  al. 2013,
Bendali et al. 2013, Ku and Park 2013, Li et al. 2013, Sherrell
et al. 2014). In general, papers reporting the biological effects
of graphene tend to focus on either material characterization
or biological response, complicating the interpretation of the
significance of results.
23.3.2 Graphene/Inorganic Structures
Graphene materials can also be used as minority fillers in
traditional biocompatible systems (organic and inorganic)
forming hybrid systems with superior properties for tissue-
engineering applications. For example, hydroxyapatite (HA)
is a calcium-phosphate-based inorganic material similar to the
biological apatite found in bone and teeth. HA has been found
358 Graphene Science Handbook

TABLE 23.3
Summary of Recent Literature Describing Nonchemically Modified Graphene, GO, and rGO Materials Suitable for
Tissue-Engineering Purposes In Vitro or In Vivo
Graphene Type Substrate Cell/Tissue Type References

IN VITRO
Pristine (CVD) Tissue culture polystyrene Primary mouse hippocampal cells Li et al. (2011)
Pristine (CVD) Permanox Primary rat cortical neurons Sahni et al. (2013)
Pristine (CVD) Glass and silicon/silicon Human neuroblastoma cell line SH-SY5Y Park et al. (2013)
dioxide surfaces
Pristine (CVD) PLA/PLGA biodegradable Rat PC-12 cells (neural differentiation model) Sherrell et al. (2014)
polymers
Pristine (CVD) Glass and sapphire Primary adult and neonatal retinal ganglion Bendali et al. (2013)
neurons
GO (and CNTs) Nil Human hepatoma HepG2 cells Yuan et al. (2012)
GO and rGO Aminated glass surfaces Mouse C2C12 myoblast cell line Ku and Park (2013)
rGO Glass Rat hippocampal neurons Kim et al. (2013)
Bilayer, thermally expanded graphite oxide, None Monkey kidney epithelial cells (Vero) Sasidharan et al.
and unmodified and carboxyl-functionalized (2011)
3D GO hydrogel Nil Human MG-63 osteosarcoma cell line Lim et al. (2011)
3D rGO hydrogel scaffold (reduced with Nil Nil Sui et al. (2011)
vitamin C)
Graphene aerogels (lyophilized, microwave- Nil Nil Hu et al. (2013)
treated GO hydrogels)
3D graphene “foam”– CVD-synthesized Nil Neural stem cells isolated from neonatal Li et al. (2013)
multilayer graphene mouse hippocampus
GO (modified Hummer’s method) Nil Human fibroblast (in vitro) and intravenous Wang et al. (2011)
injection into mice at 0.1–0.4 mg per mouse
(~6–25 mg/kg assuming 15-g mouse)

IN VIVO
GO Nil Intravenous injection into mice at 1 and 10 ​ Zhang et al. (2011)
mg/kg
Small (243-nm hydrodynamic radius) and large Nil Intravenous injection into mice at 1–10 ​mg/kg Liu et al. (2012)
(914 ​nm) GO
Well-characterized, purified, stable, and evenly Nil Intraperitoneal injections at 50 ​µg per mouse Ali-Boucetta et al.
dispersed GO in aqueous solutions (~2.5 ​mg/kg in a 20-g mouse) (2013)

TABLE 23.4
Summary of Recent Literature Describing Composite Materials Based on Inorganic Materials with GO and rGO
Suitable for Osteo-Tissue-Engineering Applications
Graphene Type Substrate Cell/Tissue Type References
GO (Hummer’s method) CaCO3 and HA Mouse osteoblast cell line (MC3T3-E1) Kim et al. (2011)
reduced to rGO by hydrazine
GO reduced to rGO with GO was functionalized with polydopamine, Mouse L-929 fibroblast cell line Liu et al. (2012)
polydopamine and then converted into rGO/HA
rGO HA formed in the presence of rGO, and Human osteoblast cells (HFOB 1.19 SV40 Liuet al. (2013)
subsequent plasma spark sintering transfected osteoblasts)
GO (and CNTs) Poly(methyl methacrylate) (PMMA)/HA Nil Goncalves et al.
bone cement (2012)
GO PLA/HA composites Nil Marques et al.
(2012)
GO (Hummer’s method) Electrospun PLA/HA composite membranes Mouse osteoblast cell line (MC3T3-E1) Ma et al. (2012)
rGO (hydrazine reduced) Sol–gel TiO2 Human AGS (gastric adenocarcinoma) and MG-63 Kandiah et al.
(osteosarcoma) cell lines, and Escherichia coli and (2014)
Staphylococcus aureus bacteria
Applications of Graphene in Tissue Engineering 359

to support the growth and osteoinduction of cultured cells,
and is the most widely used material in bone tissue engineer-
ing (Hench and Polak 2002, Li et al. 2007, Eom et al. 2012,
Melton et  al. 2012). However, its mechanical properties are
not sufficient to use for this application alone (Liuet al. 2013,
Wu et al. 2013). The addition of GO or rGO has been found to
improve the mechanical properties and even biocompatibility
and osteoinductive properties of inorganic materials, as docu-
mented in the literature summarized in Table 23.4.
23.3.3 Graphene/Polymer Composites
Despite many studies demonstrating the cytocompatibility
of graphene and GO (Table 23.3), much work has gone into

TABLE 23.5
Summary of Recent Literature Describing Polymer-Modified Graphene, GO, and rGO Composite Materials
Suitable for Tissue- Engineering Purposes In Vitro or In Vivo
Graphene Type Substrate Cell/Tissue Type References

IN VITRO
GO (Hummer’s method) and rGO Graphenes dispersed in polyethylene Mouse L-929 fibroblast cell line Wojtoniszak et al.
(glucose/hydrothermal reduction) glycol (PEG), PEG–polypropylene (2012)
glycol–PEG (Pluronic P123), or sodium
deoxycholate
GO Fibrin Human osteosarcoma (MG-63) and mouse Deepachitra et al.
fibroblast (NIH 3T3) cell lines (2013)
GO Poly(epsilon-caprolactone) (PCL) Nil (biomineralization tests) Wan and Chen (2011)
GO Poly(d, l-lactic-co-glycolic acid) (PLGA) Rat PC-12 cells (neural differentiation Yoon et al. (2011)
model)
GO PLGA Human epithelial (adenocarcinoma) cell Yoon et al. (2012)
line (HeLa)
rGO PCL Mouse L-929 fibroblast cell line rat PC-12 Sayyar et al. (2013a,b)
cells (neural differentiation model), and
mouse C2–C12 muscle cell line
GO and hydrothermally reduced Chitosan Red blood cells and human skin fibroblast Liao et al. (2011)
rGO cell line
Graphene produced by direct Chitosan Mouse L-929 fibroblast cell line Fan et al. (2010)
current arc discharge
GO Chitosan “Pre-osteoblasts” Depan et al. (2011)
GO Chitosan Mouse osteoblast cell line (MC3T3-E1) Depan and Misra
(2013)
rGO Chitosan/lactic acid Mouse L-929 fibroblast cell line Sayyar et al. (2015)
rGO N-fluorenyl-9-methoxycarbonyl (Fmoc) Nil Adhikari and Banerjee
protected synthetic dipeptide hydrogels (2011)
GO PVA Osteoblast/fibroblast—details not sufficient Zhang et al. (2011)
GO, expanded graphite, and CNTs Poly(methylmethacrylate) (PMMA), Nil Ramanathan et al.
poly(acrylonitrile) (PAN), and (2008)
poly(acrylic acid) (PAA)
GO “nanoribbons,” “nanoplatelets,” Polypropylene fumarate Nil Lalwani et al. (2013)
molybdenum nanoplatelets, and
CNTs
GO PVA (electrospun) Mouse osteoblast cell line (MC3T3-E1) Qi et al. (2013)
GO Silicone elastomers Osteoblast Girase et al. (2012)
Graphene nanoplatelets Ultra-high-molecular weight polyethylene Osteoblast cell line (insufficient detail) Lahiri et al. (2012)

IN VIVO
PEGylated nanographene sheets PEG Intravenous injection into mice at 20 mg/kg Yang et al. (2011)
Various sizes of GO and rGO with/ PEG Oral and intraperitoneal administration into Yang et al. (2013)
without PEGylated surface mice at 4 mg/kg dose
coatings
GO and PEG-grafted GO as well PEG Intravenous injections into mice at Miao et al. (2013)
as photosensitizer chlorin e6 and 80 mg/kg
drug doxorubicin
GO Pluronic Subcutaneous injection into mice Sahu et al. (2012)
360
modifying the surface chemistry by functionalization of gra-
phenes, either by covalent modification or by mixing of gra-
phenes into polymer systems. Polymers such as polyethylene
glycol, fibrin, and poloxamer copolymers have been shown to
reduce these hydrophobic interactions of graphene with cells
in vitro, and in vivo responses have been improved by reduc-
ing the hydrophobicity and aggregation of graphene. In addi-
tion to the modification of graphene to improved biological
interactions, polymers that have a known biocompatibility
have had their properties, and even bioactivity improved by
the addition of graphene. Polymers commonly used in tissue
engineering, such as polycaprolactone (PCL) (Coombes et al.
2002, Mota et al. 2013, Wang et al. 2013), polylactic/glycolic
acid (PLA, PLGA) (Cicek et al. 2013, Kim et al. 2013, Lanao
et al. 2013), and chitosan (Di Martino et al. 2005, Sanchez
et al. 2012, Kim et al. 2013, Mendonca et al. 2013, Sowjanya
et al. 2013) have all been reported to have enhanced proper-
ties (mechanical, conductive, biocompatibility, or bioactivity)
with the addition of graphene to make composite materials,
as reported in the literature summarized in Table 23.5.
While GO can form hydrogels alone (Xu et  al. 2010),
combining GO with known biocompatible hydrogel systems
can allow for enhanced control over the swelling, degrada-
tion, shape retention, and cellular adhesion of materials with
high water content, biocompatibility, and natural soft-tissue
properties (Zhu and Marchant 2011). Examples of chitosan,
polyvinylalcohol (PVA), PMMA, and pluronic GO/rGO com-
posites can be found in Table 23.5.
Imparting electrical conductivity into polymers or hydro-
gels by the addition of rGO or pristine graphene has impor-
tance in the engineering of excitable tissues such as nerve
and muscle, where electrical stimulation can improve the
growth of electroresponsive cells (Heo et al. 2011, Park et al.
2011).
Finally, blending with polymers can impart processability
to graphene/polymer composite materials that could never be
achieved in graphene alone. Several groups have used additive
fabrication techniques to create 3D scaffolds and structures
that allow investigation of biological interactions in 3D (such
as those shown in Figure 23.2) (Sayyar et al. 2013a,b, 2015).
This is an exciting development, combined with finding that
electrically conductive materials with controlled structures
can enhance neural and muscular outgrowth (Quigley et  al.
2009, 2012). The ability to tailor mechanical and conducting
properties of the scaffolds processed from GO and rGO com-
posites makes these materials the most promising for tissue-
engineering applications.
23.4 CONCLUSION
The use of graphene in tissue engineering is at a very early
stage of development, with commercialization of a number of
years in the future. However, the current studies in biocom-
patibility show a major promise as purified graphene with
the correct properties has minimal cytotoxicity or adverse
effects in vitro and in vivo and can indeed improve and direct
Graphene Science Handbook
cell differentiation and growth. Additionally, the mechani-
cal strength, capacity for chemical modification, and con-
ductivity of graphene certainly merit further investigations
as materials for tissue-engineering scaffolds but care must
be taken when selecting the size, composition, and chemis-
try of graphene to be used for any medical application. 3D
structures composed entirely of graphene have been made,
and show some potential for niche applications in tissue engi-
neering but it is likely that the increased processability and
versatility of graphene composites (with inorganic or organic
materials) will result in improved platforms for advanced
tissue-engineering applications with enhanced strength and
electrical properties.
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Zhang, L., Z. Wang, C. Xu, Y. Li, J. Gao, W. Wang, and Y. Liu.
2011. High strength graphene oxide/polyvinyl alcohol com-
posite hydrogels. Journal of Materials Chemistry 21(28):
10399–10406.
Zhang, X. Y., W. B. Hu, J. Li, L. Tao, and Y. Wei. 2012. A com-
parative study of cellular uptake and cytotoxicity of multi-
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Zhang, X. Y., J. L. Yin, C. Peng, W. Q. Hu, Z. Y. Zhu, W. X. Li, C.
H. Fan, and Q. Huang. 2011. Distribution and biocompatibility
studies of graphene oxide in mice after intravenous adminis-
tration. Carbon 49(3): 986–995.
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gel tissue-engineering scaffolds. Expert Review of Medical
Devices 8(5): 607–626.
 24 Graphene in Space
Domingo Aníbal García-Hernández and Franco Cataldo

CONTENTS
Abstract...................................................................................................................................................................................... 365
24.1 Introduction...................................................................................................................................................................... 365
24.2 Complex Compounds in Evolved Stars............................................................................................................................ 365
24.3 Discovery of Fullerenes and Graphene in Space.............................................................................................................. 366
24.4 Formation of Fullerenes, Graphene, and Molecular-Related Species in Space............................................................... 367
24.4.1 Photochemical Processing of HACs..................................................................................................................... 368
24.4.2 Photochemical Processing of Large PAHs........................................................................................................... 369
24.5 Composition and Structure of the Carriers of Unidentified Astronomical Features........................................................ 370
24.6 Other Fullerene and Graphene Structures in Space......................................................................................................... 371
24.6.1 Hydrogenated Fullerenes...................................................................................................................................... 372
24.6.2 Endohedral and Exohedral Fullerene Complexes................................................................................................ 372
24.6.3 Graphene Nanoribbons......................................................................................................................................... 373
24.7 Crossing the Boundaries between Astrochemistry and Several Fields
of Applied Research: Commercialization and Potential Applications............................................................................. 373
24.8 Summary.......................................................................................................................................................................... 374
References.................................................................................................................................................................................. 374

ABSTRACT species synthesized in space? What is the role of these mol-

One of the major challenges of present-day astrophysics and
astrochemistry is to understand the formation pathways of
complex organic molecules such as graphene and fullerenes in
space. Such complex compounds have been found on meteor-
ites and on Earth and their study may have important implica-
tions for the enrichment of the early solar system and possibly
on the origin of life on Earth. The recent and unexpected detec-
tion of fullerenes (C60 and C70) and graphene (possible planar
C24) around old stars such as our Sun indicates that these rela-
tively complex molecules may be ubiquitous in the interstellar
medium, playing an important role in many aspects of space
chemistry and physics. This raises the exciting possibility that
graphene and other carbon nanostructures could be widespread
in the Universe. The formation process of graphene in space
could be different to the production methods employed on
Earth and its astrochemical study extends well to other disci-
plines such as experimental physics and chemistry. By cross-
ing the boundaries of astrophysics, astrochemistry, and several
fields of applied research for technological development, it is
possible to study the formation route of graphene in space with
their potential applications in technology research and industry.
24.1 INTRODUCTION
One of the major challenges of present-day astrophysics and
astrochemistry is to understand the formation pathways of
complex organic molecules (e.g., fullerenes, graphene, and
polycyclic aromatic hydrocarbons) and inorganic solid-state
compounds in space. How are these complex carbon-based
ecules in circumstellar/interstellar chemistry and physics?
What is the composition and structure of the carriers of cer-
tain unidentified astronomical features widely observed in the
Universe? What other forms of carbon are present in space?
24.2 COMPLEX COMPOUNDS
IN EVOLVED STARS
Most of the stars (M < 8 solar masses, M☉) in the Universe end
their lives with a phase of a strong mass loss (up to 10−4–10−5 M☉/
yr) on the asymptotic giant branch (AGB) (Herwig 2005), just
before they form planetary nebulae (PNe). The strong mass loss
efficiently enriches the interstellar medium (ISM) with gas and
dust, and AGB stars are one of the main contributors to the
enrichment of the ISM where new stars and planets are born,
and thus to the chemical evolution of galaxies. A large variety
of organic species have been observed to emerge in the circum-
stellar environment of stars in the transition phase between
AGB stars and PNe, following the formation of gas-phase
molecules and inorganic solid-state compounds in the previ-
ous AGB phase. The structures of these complex compounds
are similar to the insoluble organic matter found in meteorites
and terrestrial planets, and their study has important implica-
tions for the enrichment of the early solar system and possibly
the origin of life on Earth; for example, fullerenes have been
found in meteorites carrying extraterrestrial gases, although
this result is highly controversial and still awaits confirmation.
Contrary to much more complex astronomical environ-
ments (e.g., the diffuse ISM, protoplanetary disks, reflection
nebulae, galaxies, etc.), the main advantages of studying the
365
366
circumstellar environment around stars evolving from the
AGB phase to the PNe stage lie in their well-determined
physical conditions (e.g., density, temperature, and radiation
background), the singleness of the systems (a single energy
source with a simple geometry), as well as the short chemical
timescales that are defined by the dynamical timescales (AGB
phase: 106 yr, proto-PNe stage: 103 yr, and PNe stage: 106 yr).
Thus, the well-defined conditions of these circumstellar envi-
ronments approximate a controlled laboratory as closely as
possible in space, providing severe constraints on any model of
gas-phase and solid-state chemistry and physics (Kwok 2004).
24.3 DISCOVERY OF FULLERENES
AND GRAPHENE IN SPACE
Fullerenes are highly resistant and stable tridimensional mol-
ecules formed exclusively by carbon atoms; the most common
fullerenes are C60 and C70 (see Figure 24.1). Fullerenes were
synthesized in the laboratory by H. Kroto and R. Smalley—
who received the 1996 Nobel Prize in Chemistry due to this
discovery—25 years ago. Fullerenes and fullerene-related mol-
ecules have attracted much attention since their discovery in the
laboratory (Kroto et al. 1985) due to their potential applications
in superconductor materials, optical devices, and medicine. In
the astrophysical context, these complex molecules may explain
certain unidentified astronomical features such as an intense
ultraviolet (UV) absorption band at 217 nm (e.g., Cataldo and
Iglesias-Groth 2009) and the so-called diffuse interstellar
bands (DIBs)—well-defined absorption bands observed in the
visible and near-infrared (IR) spectra of reddened stars and that
may be associated with large carbon-based molecules (see, e.g.,
Herbig 1995 for a review of the long-standing astrophysical
problem of the identification of the DIB carriers). The remark-
able stability of fullerenes against intense radiation, ionization,
etc. (e.g., Kroto 1987; Cataldo et al. 2009) reinforced the idea
FIGURE 24.1  Artistic impression of the C60 molecules found in a
PN (SMP SMC 16) of the small Magellanic Cloud. The Spitzer Space
Telescope detects the four IR bands (at 7.0, 8.5, 17.4, and 18.9 µm)
of neutral C60. (From Gabriel Pérez Díaz, Instituto de Astrofísica de
Canarias [IAC Multimedia Service].)
Graphene Science Handbook
that fullerenes could be present in the ISM with important
implications on interstellar/circumstellar chemistry and phys-
ics. Indeed, fullerenes were found on Earth (e.g., Buseck et al.
1992) and possibly on meteorites (e.g., Becker et al. 2000), but
the presence of fullerenes in astrophysical environments has
been a matter of debate until very recently, when the mid-IR
spectral signatures of the C60 and C70 ­fullerenes—the largest
and more complex molecules ever detected in space—were
unambiguously detected by the Spitzer Space Telescope in the
young PN Tc 1 (Cami et al. 2010). On the basis of the lack of
the classical unidentified infrared (UIR) emission bands (e.g.,
at 3.3, 6.2, 7.7, 8.6, and 11.3 µm) usually attributed to polycyclic
aromatic hydrocarbons (PAHs; e.g., Leger and Puget 1984; see
also Section 24.4), Cami et al. (2010) claimed that the region
of Tc 1 where fullerenes flourish was hydrogen deficient and
carbon rich; in agreement with the original laboratory stud-
ies on the formation of fullerenes (Kroto et al. 1985; de Vries
et al. 1993), which show that fullerenes are efficiently produced
under hydrogen-poor conditions in the laboratory. At the same
time, it was shown that fullerenes are efficiently formed in
H-rich circumstellar environments (García-Hernández et  al.
2010). In particular, C60 fullerenes were detected in conjunction
with UIR emission bands in several PNe (including Tc 1) with
normal hydrogen abundances (García-Hernández et al. 2010).
In addition, a key and independent test for the paradigm regard-
ing fullerene formation in space was offered by the Spitzer
Space Telescope observations of a complete sample of the
so-called R Coronae Borealis (RCB) stars (García-Hernández
et al. 2011b). This is because the hydrogen deficiency together
with the helium and carbon-rich characters of RCBs resem-
ble the experimental conditions on Earth, and may facilitate
the formation of fullerenes. The unexpected detection of C60
fullerene features together with UIR emission only in the two
least H-deficient (H-deficiency of only ~10–100) RCB stars
DY Cen and V854 Cen (García-Hernández et al. 2011b, but see
also García-Hernández et al. 2012a) confirmed the surprising
results obtained in PNe. This challenged our understanding
of the fullerene formation in space, indicating that, contrary
to the general expectation, efficient fullerene formation takes
place only in H-rich environments. Indeed, C60 fullerene-like
molecules have since then been detected in a variety of astro-
physical environments such as the ISM, post-AGB stars, Herbig
Ae/Be stars, and Young stellar objects (e.g., Sellgren et al. 2010;
Zhang and Kwok 2011; Roberts et  al. 2012). None of these
environments is hydrogen poor (see Table 24.1). In addition,
the Spitzer detection of C60 and C70 fullerenes was extended
to extragalactic sources such as PNe in the Magellanic Clouds
(García-Hernández et al. 2011a). These extragalactic fullerene
detections have permitted an accurate determination of the
C60 and C70 abundances (C60/C ~ 0.07% and C70/C ~ 0.03%)
in space for the first time. The quantitative determination of
fullerenes in space was possible thanks to the laboratory studies
that have established how the fullerene-IR bands shift in posi-
tion as a function of temperature as well as thanks to the deter-
mination of the integrated molar extinction coefficient and the
integrated molar absorptivity of each IR band (Iglesias-Groth
et al. 2011).
Graphene in Space 367

TABLE 24.1
Detections of Fullerenes (C60) and Graphene (Planar C24) in Several Space Environments Such as PNe, the ISM,
RCB Stars, Post-Asymptotic Giant Branch Stars (Post-AGBs), Young Stellar Objects (YSOs), and Herbig Ae/Be Stars
Herbig Ae/
PNe ISM RCBs Post-AGBs YSOs Be Stars
Fullerenes (C60) Yes Yes Yes Yes Yes Yes
Graphene (planar C24) Yes Yes No No No No
References Cami et al. (2010); Sellgren et al. García-Hernández Zhang and Kwok Roberts et al. Roberts et al.
García-Hernández (2010); Berné and et al. (2011b) (2011); Gielen (2012) (2012)
et al. (2010, Tielens (2012); et al. (2012)
2011a) Berné et al. (2013)

Interestingly, graphene (planar C24) has been detected for

the first time in some of these fullerene-containing PNe both
C60
in the Magellanic Clouds and in our own Galaxy (García-
C24
Hernández et al. 2011a, 2012b; see Figure 24.2). Planar C24 is 2
just a dehydrogenated coronene—a very stable molecule (in
the high vacuum of space, because on Earth, it is expected
to be extremely reactive)—and can be viewed as a small (arbitrary units)
SMC 24
fragment of a graphene sheet (or a graphene precursor).
Graphene instead, can be defined as a single planar layer of
1
sp2-hybridized carbon atoms with an almost infinite length
λFλ

and wideness in comparison to the dimensions of a single

carbon atom. Some of these fullerene-containing PNe dis-
play very unusual emission features at ~6.6, 9.8, and 20 µm LMC 02
(see Figure 24.3) coincident with the theoretical transitions
0
of planar C24. A definitive confirmation, however, has to wait
6 8 10 12 14 16 18 20 22
for laboratory-IR spectroscopy of C24, which is extremely
Wavelength (μm)
difficult due to the high reactivity of this molecule. More

FIGURE 24.3  Spitzer Space Telescope IR spectra of two fullerene-

and graphene-containing PNe (SMP SMC 24 and SMP LMC 02) in
the Magellanic Clouds. The IR band positions of neutral C60 (dashed
lines) and planar C24 (a small piece of graphene, dotted lines) are
marked and the IR spectra are displaced for clarity. (Adapted from
García-Hernández, D. A. et al. 2011a. Astrophys J 737:L30.)

recently, one of these unusual C24 -IR features has also been
detected in the ISM, in the reflection nebula NGC 7023
(Berné et  al. 2013) that is also known to harbor fullerene-
like molecules (see Table 24.1). Thus, current astronomical
observations indicate that fullerenes and graphene structures
are intimately related and that they likely follow a common
formation route in space.

FIGURE 24.2  Artist’s impression of the graphene fragments (pla-
nar C24) and fullerenes found in a PN. The detection of graphene
fragments and fullerenes around old stars as common as our Sun
suggests that these molecules and other allotropic forms of carbon
such as nanotubes, carbon onions, nanodiamonds, etc. may be wide-
spread in space. (From Gabriel Pérez Díaz, Instituto de Astrofísica
de Canarias [IAC Multimedia Service]; original image of the
Dumbbell-M27 Planetary Nebula [Daniel López—IAC].)
24.4 FORMATION OF FULLERENES,
GRAPHENE, AND MOLECULAR-
RELATED SPECIES IN SPACE
The formation process of fullerenes and graphene structures
in space is still unclear to date. Several fullerene formation
mechanisms have been proposed, the most notable ones
being: (i) the formation in H-poor environments (Goeres
368
and Sedlmayr 1992) is based on the laboratory synthesis of
a fullerenes that occurs when carbon vapor (e.g., generated
from a carbon arc) is quenched in a low-pressure helium
atmosphere <100 Torr; (ii) high-temperature formation in
C-rich environments (Jäger et  al. 2009); (iii) photochemical
processing of hydrogenated amorphous carbon grains (HACs;
García-Hernández et  al. 2010); and (iv) photochemical pro-
cessing of large PAHs (Berné and Tielens 2012).
The first two mechanisms prevent the formation of hydro-
genated species, something that seems to be difficult to
reconcile with astronomical observations. They invoke the
key role of carbon vapor, which is essentially constituted by
the diradical species C2. When C2 is quenched in an inert
atmosphere, a mixture of fullerenes are formed dominated
by C60 and C70. Under these conditions, fullerenes may rep-
resent a maximum of 10% of the carbon products derived
from the condensation of C2; all the remaining 90% is con-
stituted by carbon soot that could contain unusual structures
such as onion-like carbon (big fullerenes incorporating
smaller fullerenes inside the cage; see also Section 24.5.2),
and carbon black. Carbon black is essentially made of gra-
phene sheets of different sizes arranged in a turbostratic and
completely disordered manner. The resulting carbon black
is extremely rich in trapped free radicals and it is indeed a
paramagnetic solid that could contain up to 1021 free radicals
per gram. Thus, the graphene sheets of such carbon black can
be precisely described as very large PAHs without hydrogen
atoms (see Section 24.5.3) at the end of the sheet but with
dangling bonds (i.e., carbon-centered free radicals at the
extremities of the graphene sheet). Indeed, Cami et al. (2010)
claimed that the fullerenes they observed in the PN Tc 1 were
not in the gas phase but embedded in carbon soot, exactly as
it happens in the laboratory synthesis. In short, the condi-
tions that lead to the formation of fullerenes are the same
as those that lead to the formation of graphene sheets with
dangling bonds at the extremities. The fullerenes are closed
cages and do not have free radicals in their neutral state, the
opposite is true for a graphene sheet that is by definition a
polyradical. When the graphene sheets stack together (or
clump together) in a disordered manner, then a large part of
the graphene sheets inside the bulk of the particle have their
free radicals inaccessible to other atoms and remain perma-
nently stable and unsaturated. Only the graphene sheets that
are located externally to a given carbon black particle may
react with adventitious atoms or molecules, yielding hydro-
genated edges of the graphene sheets that correspond to the
PAHs. It is also important to underline that when C2 vapor
is quenched in a hydrogen atmosphere, it invariably yields
a mixture of PAHs because the extremities of the graphene
sheets are saturated by the hydrogen atoms and the reaction
of C2 vapor quenching in a hydrogen atmosphere hinders the
formation of fullerenes and also limits the formation of soot.
However, it could happen that under certain circumstances
of opportune-mixing ratios of He and H2, a series of parallel
reactions could occur simultaneously leading to fullerenes,
PAHs, and carbon soot (carbon black at the same time) (see
Cataldo and Pontier-Johnson 2002).
Graphene Science Handbook
The alternative top-down approaches involve the photo-
chemical processing of HACs and large PAHs as first pro-
posed by García-Hernández et al. (2010) and Berné and Tielens
(2012), respectively (see below). Currently, they remain as the
most promising fullerene/graphene synthesis routes in space.
Both formation scenarios are based on top-down chemical
models toward the most stable C60 and C70 fullerenes. These
top-down fullerene and graphene formation scenarios seem
to be quite different to the fullerene production methods usu-
ally employed on Earth. The terrestrial vaporization or com-
bustion synthesis routes to form fullerene-like species cannot
work in space due to the low gas densities in the astrophysical
environments; for example, in the laboratory, the main forma-
tion channel for C60 is the buildup from atomic carbon, C2,
small carbon clusters, and rings (e.g., Heath 1992).
24.4.1 Photochemical Processing of HACs
The most likely explanation for the simultaneous presence
of fullerenes, graphene, and UIR emission in the H-rich cir-
cumstellar envelopes of PNe is that these molecular species
may be formed from the destruction (e.g., as a consequence of
shocks or the UV radiation from the central star) of a carbo-
naceous compound with a mixture of aromatic and aliphatic
structures—for example, HACs—which is a major constitu-
ent in their circumstellar envelopes (García-Hernández et al.
2010, 2011a, 2012b). It is to be noted here that there are other
carbonaceous materials (e.g., coal) with a mixture of aro-
matic and aliphatic structures similar to HACs. For example,
the closest natural analogous of such a structure is probably
kerogen, which is a random array of aromatic rings and ali-
phatic chains with functional groups made up of H, N, O, and
S attached, which may contribute to the solid-state mid-IR
features detected in evolved stars (e.g., Papoular et al. 1996;
Cataldo et  al. 2004). The coexistence of a large variety of
molecular species such as HACs, PAH clusters, fullerenes,
and small dehydrogenated carbon clusters (planar C24 or gra-
phene precursors) in PNe with fullerenes strongly supports the
laboratory experiments carried out by Scott and colleagues in
the 1990s, which showed that the decomposition of HACs is
sequential with small dehydrogenated PAH molecules being
released first, followed by fullerenes and large PAH clusters
(Scott et  al. 1997a). This fullerene (and graphene) forma-
tion scenario is also suggested by the strong—and unique—­
spectral variations (in a timescale of just a few years) seen in
the IR spectrum of the fullerene-containing RCB star V854
Cen, which indicates that a significant fraction of the dust
grains in the envelope have evolved from HACs to complex
species such as PAHs and fullerene-like molecules (García-
Hernández et al. 2011b).
The recent works by Bernard-Salas et  al. (2012) and
Micelotta et  al. (2012) also suggest that fullerene formation
in PNe likely starts from HAC processing. Perhaps, the most
novel idea is introduced by Micelotta et al. (2012) who propose
that UV photolysis produces structural changes in the HAC
grains, forming three-dimensional (3D) hollow structures
or arophatic clusters (aromatic clusters linked by aliphatic
Graphene in Space 369

bridging groups). These arophatic clusters end up with a cage-
like, cup-like, or tube-like aspect, being curled-up or folded-
over graphene sheets. Further, UV-induced dehydrogenation
of these arophatic clusters may introduce pentagonal rings,
permitting the curvature of the structure into large fullerenic
cages that can shrink down to the most stable C60 and C70
fullerene configurations.
24.4.2 Photochemical Processing of Large PAHs
This fullerene formation route has been proposed to explain
the formation of fullerenes and graphene in the ISM (Berné
and Tielens 2012). These authors propose an alternative
top-down model where large PAHs (with ≅ 70 C atoms) are
converted into graphene and subsequently fullerenes, under
the action of UV photons from massive stars. A schematic
view of this alternative top-down fullerene and graphene
formation model is shown in Figure 24.4. Upon UV irra-
diation, graphene formation takes place through PAH pho-
tolysis. The expected dehydrogenation, fragmentation,
and isomerization can give rise to a rich organic chemis-
try, forming fullerenes, small cages, rings, and chains (see
Figure 24.4). Carbon loss followed by pentagonal defects
formation that induces curvature of the graphene sheet may
form fullerenes by migration of the pentagons (Figure 24.4).
Remarkably, planar molecules such as C20 –C30 are expected
to be formed by further graphene fragmentation. In NGC
7023, emission at 6.6 µm (attributed to planar C24 molecules)
is seen near the ionizing star (Berné et  al. 2013), suggest-
ing that the carrier is a photoproduct of PAHs. In this con-
text, the detection of the very stable planar C24 molecule in
the ISM is also consistent with the idea of fullerene pro-
duction from photochemical PAHs processing via graphene
formation.

(a) Dehydrogenation and fragmentation

Graphene PAH

Chain Ring Flat

C10 C20 C30

Isomerization
Tangled Random Open cage
cage C50
polycyclic

Closed cage

Fullerene
(stable)
C60 C70

(b)

FIGURE 24.4  Schematic representation of the top-down fullerene and graphene formation scenario proposed by Berné and Tielens
(2012). (a) Under UV irradiation, fully hydrogenated PAHs (at the top right side) in the ISM (injected by stars) experience dehydrogenation,
fragmentation, and isomerization. Graphene is expected to be formed near bright stars by UV photolysis, which preferentially destroys the
weakest H bonds (complete loss of H). Flats, rings, and chains may be formed by further fragmentation although this process competes with
isomerization to various types of stable intermediaries such as cages and fullerenes. (b) Schematic illustration of the proposed conversion of
graphene into the C60 fullerene. Graphene sheets (i.e., dehydrogenated PAHs) lose C atoms under the influence of UV photons, and pentago-
nal defects (marked with light gray C atoms) appear at the edges of the sheet. The pentagonal defects in the hexagonal network may induce
the curvature of the sheet; pentagons may migrate, allowing the C60 fullerene molecule to close. (Image courtesy of Berné, O. and Tielens
A. G. G. M. 2012. Proc Natl Acad Sci USA 109: 401–406.)
370
FIGURE 24.5  Scholl’s reaction applied to the synthesis of coro-
nene “star” heptamer and its possible transformation to a graphene
plate having a diameter of 26.4 Å. (Adapted from Cataldo, F. et al.
2011. Fullerenes Nanot Carbon Nanostruct 19:713–725.)
The presence of graphene structures (planar C24) in
astronomical sources with fullerenes is consistent with
both formation scenarios mentioned above. Both chemical
routes are not mutually exclusive; for example, yet to date,
it is not completely clear if large PAH-like structures (see,
e.g., Figure 24.5) may be released from the decomposition
of HACs. It seems that the HAC fullerene route is favored
in PNe while the PAH route may well be at play in the ISM.
This is because fullerenes and graphene have been detected
in PNe whose IR spectra are clearly dominated by aliphatic
carbon-rich dust (with only weak signatures of aromatic
PAH-like species), represented by broad emissions such as
those at 6–9, 10–15, and 25–35 µm (García-Hernández et al.
2010, 2011a, 2012b). The 6–9-µm feature can be attributed
to HACs, large PAH clusters, or very small carbon grains.
On the other hand, the broad 10–15-µm (centered at about
11.5 µm) and 25–35-µm emission (the so-called 30-µm fea-
ture) may be explained by HACs (Grishko et al. 2001). The
observed variability of these broad features is quite consis-
tent with the variable properties of HACs, which are able
to provide a wide range of different spectra (e.g., the rela-
tive strength and position of the IR features) depending on
their physical and chemical properties (e.g., size, shape, and
hydrogenation; Scott and Duley 1996; Scott et  al. 1997b;
Grishko et  al. 2001). The carriers of the broad 11.5- and
30-µm features (also the bump at 15–20 µm and possibly
the so-called 21- and 26-µm features; see Section 24.4)
are very likely related with other decomposition products
of HACs (e.g., fullerene and graphene precursors or inter-
mediate products not yet identified) but a definitive answer
requires further laboratory efforts. The identification of the
UIR’s carriers offers a clue to the question of fullerene and
graphene formation in space and can be made through mul-
tiwavelength laboratory spectroscopy of HACs (and similar
materials) and their decomposition products (e.g., fullerene
and graphene structures or intermediate products). Contrary
to the PNe, fullerenes and graphene in the ISM (e.g., in the
reflection nebula NGC 7023) are observed together with very
strong aromatic PAH-like IR features and with no broad
Graphene Science Handbook
spectral signatures of HAC-like materials. This simple fact
seems to be against the idea that fullerene formation in the
ISM starts from HAC photochemical processing. However, a
possible solution to the apparent lack of HAC-like materials
(e.g., lack of a broad 30-µm emission) around the reflection
nebula NGC 7023 may be related with the harsh conditions
in the ISM (more intense UV fields). The UV field from
massive stars is much stronger than in fullerene PNe and
can process/destroy the interstellar HAC grains completely;
for example, large PAH clusters are rapidly evaporated into
free-flying PAHs. This speculation may be supported by
the fact that in the laboratory, the broad 30-µm emission in
HAC samples is suppressed at high temperature (Grishko
et al. 2001); the hydrocarbon component responsible for this
emission seems to be removed from the HAC network. In
fullerene PNe, we probably see the biggest (non-processed)
and colder grains (HAC aggregates) in the outer parts of the
circumstellar shell, which are shielded from the UV field
from the central star.
24.5 COMPOSITION AND STRUCTURE OF
THE CARRIERS OF UNIDENTIFIED
ASTRONOMICAL FEATURES
The ubiquitous and yet-UIR emission bands (UIRs at ~3.3,
6.2, 7.7, 8.6, and 11.3 µm), now detected in a wide range
of interstellar, circumstellar, and extragalactic sources,
were first discovered by Gillett et  al. (1973). The features
at 3.3 and 11.3 µm are indicative of aromatic CH groups as
found in small gas-phase PAHs (sp2-bonded carbons) such
as coronene. Sellgren (1984) proposed a model, involving
non-­equilibrium emission from carbon nanoparticles sto-
chastically heated to high temperatures by the absorption of
individual photons from the interstellar radiation field and
the observed excitation temperature for emission at 3.3 µm
was consistent with the presence of emitters containing ~50
carbon atoms (the so-called “PAH model”). Thus, the PAH
model has been widely accepted by astronomers as the car-
riers of the UIRs (e.g., at ~3.3, 6.2, 7.7, 8.6, and 11.3 µm)
and “free-flying” gas-phase PAHs have been assumed to be
a major reservoir for carbon in the Universe. Yet, to date,
astronomical observations have failed to unambiguously
detect any specific PAH molecule in space (e.g., Tielens
2011); especially in the UV spectral range, where gas-phase
PAHs are expected to show strong transitions. In addition,
UIRs are still detected in circumstellar/interstellar regions
having little UV radiation (e.g., post-AGB stars and cool
RCB stars), implying that high-energy UV photons are not
required for the excitation of the UIR’s emitters (Kwok and
Zhang 2011). Interestingly, additional emission at 3.4 µm
characteristic of aliphatic hydrocarbons (sp3-bonded car-
bons) is usually observed in sources evolving from the AGB
to the PNe stage (e.g., Kwok et al. 2001) and in the diffuse
ISM. Absorption/emission at 3.3 µm together with 3.4-µm
emission indicates that this PAH-like (sp2-bonded carbons)
component is mixed with aliphatic hydrocarbons. Indeed,
Kwok and Zhang (2011) have very recently demonstrated
Graphene in Space
that the astronomical data are more consistent with the
carriers being amorphous carbon solids with a mixed aro-
matic–aliphatic structure. As we have mentioned above,
mixed aromatic/aliphatic compositions are commonly
found in HACs or similar carbonaceous compounds (e.g.,
coal and kerogen). In this framework, the recent findings
of the coexistence of a large variety of molecular species
in H-rich circumstellar environments is supportive of this
new model in which non-equilibrium IR emission occurs
from small solid particles containing aromatic, aliphatic,
fullerene, and graphene structures similar to that of HAC
dust as produced in several laboratory experiments (e.g.,
Scott et  al. 1997b; Hu et  al. 2006; Jäger et  al. 2011), with
important consequences for heating, charge balance, and
chemistry in the ISM. Indeed, Duley and Williams (2011)
have suggested a model for the heating of HAC dust via the
release of stored chemical energy that gives a natural expla-
nation for the astronomical emission at 3.3 µm and other
UIR wavelengths, relaxing the previous requirement that
only stochastically heated molecules of ~50-atom carbons
(or small gas-phase PAHs) can produce the UIR emissions.
More recently, Gadallah et al. (2013) found that the thermal
processing of HAC dust increases the diameters of the gra-
phene layers and the aromatic structures become dominant,
while the aliphatic structures are destroyed. The heated
HAC materials display the aromatic bands at 3.3 and 6.2 µm
observed in astronomical spectra.
Apart from the aromatic and aliphatic UIR features men-
tioned above, there is an interesting set of still unidentified
features located at 21, 26, and 30 μm and those are generally
observed in stars evolving from the AGB stage to the PNe
phase. The 21-μm feature is only observed in proto-PNe and
their characteristics suggest a solid-state carrier of a fragile
nature. Many different carriers of the 21-μm feature have
been proposed in the literature but it seems clear that the
carrier should be a carbonaceous compound. Hydrogenated
fullerenes, HAC, and nanodiamonds are some examples
among the proposed carbonaceous species. Amides (thiourea
or urea) as the carrier of the 21-μm emission are the more
recent and exotic proposal (Papoular 2011). However, the
30-μm feature, sometimes with the substructure at 26 μm,
is seen all the time from the AGB to the PNe stage with an
important fraction of the total energy output, indicating that
the carrier is very abundant in the circumstellar shell. As we
have mentioned before, Grishko et al. (2001) show that HACs
emit at 30 μm and the HAC identification can also explain the
21- and 26-μm features.
A coherent effort to investigate HACs and similar mate-
rials in a large spectral range with very different chemical
properties (size, shape, and hydrogenation) and at physical
conditions (temperatures and densities) relevant to circum-
stellar and interstellar environments undoubtedly will lead
to new discoveries in this unexplored field. For example, one
experimental way to verify the theory that fullerene and gra-
phene may derive from HACs or similar materials consists of
the laser ablation of these materials and the consequent mass
spectrometric analysis to search for fullerenes, graphene, and
371
other molecular-related species. Only a few and limited labo-
ratory studies on the decomposition of HACs have previously
been made (e.g., Scott et  al. 1997a), while for other carbon
materials (e.g., coal and kerogen), these studies are completely
lacking in the literature. The interest for coal arises from the
fact that a coal-type carbon material can be found in carbo-
naceous chondrites, and meteorite samples fallen on Earth.
The carbonaceous chondrites were formed at the epoch of
the early solar system formation 4.7 billion years ago. This
implies that carbon-based molecules were present around the
Sun at that time and the IR spectra of certain evolved stars and
other astronomical objects resemble that of coal (Papoular
et al. 1989).
The study of the structural/optical properties and labora-
tory spectra in a large spectral range (from the UV to the
far-IR) of several materials of astrochemical interest such as
HACs and similar aromatic/aliphatic materials (coal, kero-
gen, oil shales, bitumen, and heavy petroleum fractions) as
well as the corresponding decomposition products such as
fullerene- and graphene-related species would be very help-
ful in identifying the carriers of the “classical” UIR emis-
sion bands widely observed in the Universe and the still
unidentified 21-, 26-, and 30-µm features usually observed
in C-rich evolved stars. In addition, such laboratory studies
will shed light on the carriers of the DIBs and on the origin
of the interstellar UV bump, two long-standing problems
in astronomy. Some experimental and theoretical efforts
have been recently made in this direction. Gadallah et  al.
(2011) have experimentally studied the structural and opti-
cal properties of some nano-sized HAC materials in corre-
lation with UV processing. Interestingly, they find that the
graphene layers become longer in the UV-irradiated HAC
material, which shows a band coincident with the UV bump
at 217 nm. On the other hand, Papoular et al. (2013) find that
theoretical models (from first principles) of nanoparticles
made of stacks of graphene layers with a moderate structural
or chemical disorder can also reproduce the interstellar UV
bump. Remarkably, by introducing structural or chemical
disorder, these model graphene materials become similar to
the amorphous materials such as HAC and coal studied in
the laboratory.
24.6 OTHER FULLERENE AND GRAPHENE
STRUCTURES IN SPACE
The detection of fullerenes and graphene around old stars such
as our Sun indicates that these complex molecules are much
more common and abundant in circumstellar and interstellar
environments than was originally believed. It reinforces the
hypothesis that fullerenes, graphene, and molecular-related
species are ubiquitous in the ISM and they may play an impor-
tant role in many aspects, yet to be elucidated, of circumstel-
lar and interstellar chemistry and physics. This raises the
exciting possibility that other fullerenes and graphene struc-
tures (e.g., hydrogenated fullerenes, carbon onions, fullerene
adducts, and graphene nanoribbons) could be widespread in
the Universe (see Table 24.2).
372
TABLE 24.2
Examples of Fullerene and Graphene Molecular
Nanostructures That Could Be Present in Space
Aromatic/Aliphatic
Fullerene Related Graphene Related Nanostructures
Hydrogenated fullerenes Graphene nanoribbons Hydrogenated
Endohedral fullerenes Graphene oxide amorphous carbon
Fullerene adducts Schwarzites Kerogen
Nanotubes Coal
Petroleum fractions
24.6.1 Hydrogenated Fullerenes
Fullerenes are known to be highly reactive with atomic
hydrogen, the most abundant element in the Universe. In the
laboratory, when fullerenes are exposed to atomic hydrogen
(formed, e.g., by catalytic dissociation of molecular hydrogen
over metallic surfaces, Cataldo et al. 2009), and even by dis-
sociating hydrogen iodide (Cataldo and Iglesias-Groth 2010a),
they become easily hydrogenated with a high degree of hydro-
genation leading, for example, to C60H18, C60H36, and C70H38
(see, e.g., Iglesias-Groth et al. 2012). It is completely reason-
able to think that fullerenes must be converted into hydro-
genated fullerenes (fulleranes; Cataldo and Iglesias-Groth
2010b) when they react with atomic hydrogen. Even more
important is the fact that an equilibrium between the free
fullerenes and their hydrogenated counterparts should exist.
The atomic hydrogen forms fulleranes quite easily and the
UV radiation or the thermal processing of fulleranes leads
back to free fullerenes with the liberation of molecular hydro-
gen (Cataldo et al. 2009). This has prompted the study of the
spectra of fulleranes (with a hydrogen content higher or equal
to 18 H atoms) in the lab and the use of these spectra as refer-
ences to search for these molecules in space (e.g., Iglesias-
Groth et al. 2012). A challenge is to synthesize fullerenes with
a lower degree of hydrogen content, even C60H2. Indeed, one
of the predictions of the HAC’s chemical energy model is the
presence of fulleranes together with abundant H2 molecules in
fullerene-containing astronomical environments (Duley and
Williams 2011).
24.6.2 Endohedral and Exohedral
Fullerene Complexes
Larger fullerenes and fullerene-based molecules may form
from preexisting C60 (and C70) molecules (e.g., Dunk et  al.
2012), opening the possibility of forming a rich family of
fullerene-related molecules (endohedral and exohedral fuller-
ene complexes) such as carbon onions, metallofullerenes,
and fullerene adducts. Under the space conditions that yield
C60 (and C70) fullerene formation, endohedral and exohedral
fullerene complexes also spontaneously form and they should
be active astronomical molecules.
The first evidence for the presence of other more com-
plex fullerene structures such as carbon onions (multishell
Graphene Science Handbook
fullerenes or buckyonions such as C60@C240 and C60@C240@
C540) in space has been recently deduced from the special char-
acteristics of the DIBs toward PNe with fullerenes (García-
Hernández and Díaz-Luis 2013). This is suggested by the
unusually strong and broad DIB at 4428 Å in these sources.
Photoabsorption theoretical models of fullerenes bigger than
C60 (C80, C240, and C540) and carbon onions (such as C60@C240
and C60@C240@C540) display strong transitions around 4428 Å
(Iglesias-Groth 2007) and this DIB may be explained by the
transitions (superposition) of such large fullerenes and carbon
onions. Recent studies of the 4428-Å DIB also indicate the car-
rier to be very resistant, large, and compact neutral molecules
(van Loon et al. 2013). Examples of structures of some giant
fullerene molecules and their derivatives are shown in Figure
24.6. Furthermore, metal atoms and ions may also be trapped
inside the fullerene cages, forming endohedral metallofuller-
enes such as K@C60, Na@C60, Li@C60, and Rb@C60 (e.g., Lu
et al. 2012). Some of these transition metals are known to be
very abundant in the ISM (e.g., K, Na) while other elements
such as Li and Rb can be strongly overproduced in evolved
stars (e.g., during the AGB phase), as a consequence of com-
plex nucleosynthesis processes (e.g., García-Hernández et al.
2006, 2007), and subsequently expelled into space. Further
laboratory and theoretical efforts to understand and charac-
terize the encapsulation of fullerenes with other fullerenes
and metals will undoubtedly help to unambiguously confirm
their possible presence in space.
Other interesting molecules are the fullerene adducts with
PAHs or metals (exohedral fullerene complexes). The astro-
nomical observations have shown that the fullerenes may be
mixed with the carriers of the UIR emission (usually attrib-
uted to PAHs). It is expected that in these conditions, C60
fullerenes may form adducts with PAHs since it is already
known that the C60 fullerene, being a polyene, acts as a diene
FIGURE 24.6  Artist’s impression of complex fullerenes (carbon
onions or multishell fullerenes such as C60@C240 and C60@C240@
C540) produced by a PN and expelled into the ISM. The connec-
tion between these molecules and certain DIBs suggests that these
giant fullerene molecules and their derivatives could be common
in space and could hold the key to solving the mystery of the DIBs.
(From Gabriel Pérez Díaz, Instituto de Astrofísica de Canarias
[Multimedia Service]. Original image of the nebula NGC7822 [José
Francisco Hernández Cabrera—IAC].)
Graphene in Space
FIGURE 24.7  Scheme of the formation of a Diels–Alder adduct of C60 with anthracene, which is the simplest fullerene/PAH adduct. The
addition reaction of anthracene to C60 fullerene is schematized. Note that initially, anthracene forms a monoadduct (#5) but in an excess of
anthracene, a bis-adduct (#6) is obtained (see Komatsu et al. 1999). (Adapted from García-Hernández, D. A., Cataldo, F., and Manchado, A.
2013. Mon Not R Astron Soc 434:415–422.)
in Diels–Alder so that it forms adducts with PAHs having a
dienophilic character like, for instance, anthracene or penta-
cene. In Figure 24.7, the cycloaddition Diels–Alder reaction
of anthracene to the C60 fullerene is shown and it is also sche-
matized that initially, anthracene forms a monoadduct but in
an excess of anthracene, di- and polyadducts are obtained
(Komatsu et al. 1999). The addition reaction between fuller-
enes and PAHs is quite general. Fullerenes can react with a
single molecule of pentacene forming a fullerene–pentacene
monoadduct or fullerene adducts where pentacene binds two
fullerene molecules in cis and trans geometry, respectively.
Using another type of reaction other than the Diels–Alder, it
is possible to also add benzene and other PAHs (Hoke et al.
1994). These fullerene/PAH adducts may emit through the
same IR vibrational modes (e.g., as isolated C60 and C70)
being indistinguishable from C60 (and C70) on the basis of IR
spectra alone. Indeed, recent laboratory work demonstrates
that fullerene/PAH adducts—such as C60/anthracene Diels–
Alder adducts—display mid-IR features strikingly coincident
with those from C60 and C70 (García-Hernández et al. 2013).
The C60/anthracene adduct is just the most simple example
of a new family of fullerene/PAH molecules (e.g., fuller-
ene adducts with larger catacondensed PAHs such as C60/
pentacene or even adducts with pericondensed or very large
PAHs), which may be likely present in various astrophysical
environments.
Together with PAHs, the circumstellar environment of
evolved stars is characterized by the presence of polyenes
(Cernicharo 2004), which are special carbon chain mol-
ecules of acetylenic character, which form easily in a car-
bon arc and more generally in carbon plasmas. Polyenes are
commonly considered as the precursors of both fullerenes
and PAHs. The synthesis of fullerenes–polyenes is a com-
pletely new research field since the reaction between poly-
enes and fullerenes was not yet explored at all. Synthesis
of fullerene–polyene adducts could pass through the use of
the Diels–Alder reaction heating the reagents together or
using a photoinduced Diels–Alder reaction by stimulating
the reaction between polyenes and fullerene using UV radia-
tion. Similarly, other interesting adducts are those of fuller-
enes with certain transition metals (Balch and Olmstead
1998), which may be present in the circumstellar envelopes
of evolved stars such as AGB stars. As we have mentioned
before, this is because AGB stars are the principal nucleo-
synthesis sites of certain types of transition metals, including
iron and heavier neutron-rich elements.
373
24.6.3 Graphene Nanoribbons
The discovery of the isolation of graphene and the way to pre-
pare it was somewhat naive (Novoselov et al. 2004) and many
efforts have been developed to produce graphene in a chemi-
cal way. In reality, graphene is an ideal material because when
it is prepared, it tends to stack into layers with other graphene
sheets. Consequently, special tricks can be adopted to keep
the layers separated, for instance, with the aid of certain long
and polar molecules inserted between the layers of the gra-
phene sheets. Under these more real conditions, it is more
common to talk about graphene nanoribbons. A novel way
to reach graphene is through the synthesis of large and very
large PAHs (Cataldo et  al. 2011). Indeed, PAHs are already
small fragments of a graphene sheet but if we are able to create
larger and larger PAHs, then we could approach a graphene
sheet. The use of the Scholl reaction has made these very
large PAHs accessible that can now be studied thanks to the
easy access offered by the novel Cataldo’s synthetic approach
(Cataldo et al. 2011). Another success to the road toward gra-
phene through very large PAHs involves the synthesis of coro-
nene dimers (dicoronylene), trimers, and oligomers via the use
of special thermal annealing conditions (Cataldo et al. 2011;
Talyzin et al. 2011). An example of the results of this approach
is shown in Figure 24.5. These large and very large PAHs
are now accessible for all the necessary studies—for example,
with IR spectroscopy—to have standard reference spectra to
search for these molecules in space.
We would like to remark that apart from the fullerene and
graphene structures mentioned above, carbon may also adopt
other more exotic structures in the solid state. For example,
negative-curvature graphene (the so-called Schwarzites;
Phillips et al. 1992) has curvature induced by the presence of
seven- or eight-membered rings. Negative-curvature graphene
does not occur in pure form but only mixed with other carbon
species maxime in certain carbon blacks.
24.7 CROSSING THE BOUNDARIES
BETWEEN ASTROCHEMISTRY
AND SEVERAL FIELDS OF APPLIED
RESEARCH: COMMERCIALIZATION
AND POTENTIAL APPLICATIONS
The study of fullerenes and graphene in space has an inter-
disciplinary nature that crosses the boundaries between astro-
physics, astrochemistry, and several fields of applied research
374
for technological developments in the industry. The impact of
such a study not only extends to many different areas in astro-
physics such as carbon dust nucleation and the recycling of
matter in space, the formation of H2 (with its implications for
the baryonic matter in the Universe), but also to other disci-
plines such as physics and chemistry with their potential appli-
cations in technological research and industry. Fullerenes are
extremely relevant for technology research. They have poten-
tial applications in superconductor materials, optical devices,
and medicine. The properties of graphene (high electrical and
thermal conductivity, transparency, thinness, and the possi-
bility of developing materials 200 times stronger than steel)
have continued to raise expectations of graphene becoming
the material of the future with applications for the manufac-
ture of new materials and advanced electronic devices (e.g.,
faster computers, screens on electronic devices, solar panels,
etc.). According to the leading market research company BCC
Research, the first commercially significant sales of graphene
products are expected to develop before 2015 when the market
is projected to be as large as $67 million. Graphene structural
materials will account for 26.1% of the commercial market
($17.5 million) for graphene technologies by 2015. The gra-
phene market is expected to experience an ~60% compound
annual growth rate in the period 2015–2020, with capacitors
accounting for more than 50% of the market for graphene
technologies in 2020.
The new fullerene and graphene-related species such as
fullerene adducts and very large PAHs may find applications
in different fields ranging from electroluminescence devices
as antitumor agents, semiconductor devices, and photosensing
devices. Very large PAHs have liquid crystal and self-assem-
bly properties and have already found applications in organic
field-effect transistors, bulk heterojunction photovoltaic cells,
and organic light-emitting diodes. The studies of carbon mate-
rials (coal, oil shale, bitumen, and heavy petroleum fractions),
especially in pyrolysis and gas-phase spectroscopy, will add
further knowledge of the chemical structure of these materi-
als, which may have an impact on the more efficient industrial
utilization of these raw materials. Even hydrogenation studies
on amorphous carbon may pave the way for future surface
functionalization and possible application as an active filler
for rubber and plastics.
24.8 SUMMARY
In summary, the knowledge of the chemical route to form
fullerenes and graphene in space will be a major contribu-
tion to our current understanding of the formation of large
organic molecules and dust processing in space, with crucial
implications for several unsolved problems in astrophysics
and astrochemistry. Such complex organic molecules are
major constituents of planetary atmospheres and solar system
solid bodies such as asteroids, meteorites, and terrestrial plan-
ets and their study has important implications for the enrich-
ment of the early solar system. The detection of fullerene and
graphene molecular nanostructures in space has opened up a
new field of interdisciplinary research, involving astronomers,
Graphene Science Handbook
chemists, and physicists to unveil the role of fullerenes and
graphene structures in circumstellar and interstellar chemis-
try and physics. Finally, fullerenes seem to have been found
in meteorites carrying extraterrestrial helium. This finding, if
confirmed, may have important implications for the origin of
life on Earth.
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25 Graphene Materials in Energy
Storage Applications
Grzegorz Lota, Krzysztof Fic, Ilona Acznik, and Katarzyna Lota

CONTENTS
Abstract...................................................................................................................................................................................... 377
25.1 Introduction...................................................................................................................................................................... 377
25.2 Graphene as Electrode Material for High-Power Electrochemical Capacitors Operating in Aqueous Media................ 377
25.3 Graphene for High-Energy Electrochemical Capacitors Operating in Aprotic Media and Ionic Liquids....................... 379
25.4 Graphene for Li-Ion Batteries........................................................................................................................................... 380
25.5 Graphene-Based Composites for Hybrid Energy Storage Devices.................................................................................. 382
25.6 Graphene in Fuel Cell Applications................................................................................................................................. 384
25.7 Concluding Remarks and Perspectives............................................................................................................................. 385
References.................................................................................................................................................................................. 385

ABSTRACT 25.2 GRAPHENE AS ELECTRODE

The introductory part of this chapter discusses the general MATERIAL FOR HIGH-POWER
features of graphene materials, accounting its physical and ELECTROCHEMICAL CAPACITORS
electrical properties. A short review of recent energy stor- OPERATING IN AQUEOUS MEDIA
age devices is also presented. Special attention is devoted to
Among many other interesting electrochemical energy con-
electrochemical capacitors and graphene materials—includ-
version and storage systems, electrochemical capacitors, also
ing composites with transition metal oxides, electrically con-
called electrical double-layer capacitors (EDLCs) or superca-
ducting polymers—acting as electrodes, mainly due to their
pacitors, seem to be at the center of great interest. In the fol-
defective structure and suitable porosity. Critical discussion is
lowing text, a general overview of materials used is provided,
conducted for the application of graphene and its composites
based mainly on activated carbons and their composites with
in Li-ion battery technology; application of graphene in fuel
other materials. It should be noted that activated carbons are
cell electrodes, mainly as a catalyst support, is also discussed.
considered the disordered form of graphene layer, highly
The experimental data presented are revised with the data
defective and porous.
available in the most recent literature; however, some of them
Electrochemical capacitors have been recently considered
were obtained by the authors. Briefly, this chapter describes
as systems for fast and efficient energy storage because of
graphene materials in electrochemical application, with par-
their good cyclability, high power rates, and relatively low
ticular interest in energy conversion and storage systems.
price [1–3]. Unfortunately, unlike batteries, supercapacitors
suffer from moderate specific energy [4]; hence, there are a
25.1 INTRODUCTION lot of efforts devoted to improving this feature. Taking into
account that the energy of the electrochemical capacitor is
By considering the physical properties of graphene, one can
proportional to the accumulated charge Q or capacitance
conclude that graphene is completely different from other
value C and operational voltage U in square [5], one may eas-
forms of carbon—it is not only the thinnest ever known (only
ily conclude that the enhancement of energy performance has
one layer by definition) but also the strongest. This unique
to be realized by capacitance or preferably voltage increase
structure leads to unusual properties, for example, graphene is
[6]. The capacitance of an electrochemical capacitor is based
found to have excellent electronic transport properties. These
on the electrostatic attraction of ions at the electrode/electro-
properties hold great promise for applications in fields such
lyte interface dependent mainly on the surface area A acces-
as energy storage. In particular, these materials have electri-
sible for ion adsorption [7–11] as described by the formula
cal conductivities superior to typical graphitic carbon, rela-
tively high surface area, wide chemical tolerance, and a broad
electrochemical window that would be very advantageous for εr ⋅ ε0 ⋅ A (25.1)
C=
application in energy technologies. d

377
378 Graphene Science Handbook

where εr is the relative permittivity of the considered medium,
ε0 the permittivity of the “free” space between the capaci-
tor plates (basically attributed to the value for vacuum,
8.9 × 10−12 F/m), and d the thickness of the dielectric, for elec-
trochemical capacitors equal to the thickness of the electrical
double layer. Hence, materials with high specific surface area
with suitable porosity such as activated carbons in their vari-
ous forms [12–15] have been accepted as fundamental elec-
trode materials for electrochemical capacitors. Unfortunately,
even with a specific surface area of 2000 m2/g, these mate-
rials cannot provide a real capacitance higher than 200 F/g
[12,15] related with ion size and screening effect of the pore
walls, which is widely discussed elsewhere [16,17]. Additional
charge considered as the so-called pseudocapacitance might
be provided by faradaic reactions occurring in the system
upon the charging/discharging process. Usually, pseudoca-
pacitive properties are attributed to electrode materials under-
going the redox process during polarization such as transition
metal oxides [18,19], electrically conducting polymers [20–
23], transition metal nitrides [24,25], or heteroatom-enriched
carbon materials such as oxygen or nitrogen [26,27], where
the pseudocapacitance originates from the redox process of
functional groups present on the carbon surface accessible
for the protic electrolyte [28]. The major disadvantage of the
pseudocapacitive system is their redox-dependent solid-state
kinetics, aggravating power performance and cycle life. Many
groups have made a significant effort to develop electrode
materials and electrolytes for supercapacitor applications,
examples of which can be seen in Table 25.1.
Especially in the case of conducting polymers, where the
charge is accumulated through the volume of the whole mate-
rial, specific power is deteriorated. They might be doped and
dedoped in the n/p-type polymer configuration, such as p- and
n-dopable poly(3-arylthiopene), p-doped poly(pyrrole), poly(3-
methylthiophene), or poly(1,5-diaminoanthraquinone). Hence,
the reversible faradaic reactions (revealed as single peaks) can
be exploited as a source of additional capacitance but that type
of current response is typical for battery-like systems where
the increase of capacitance occurs only in a narrow voltage
range. A completely different behavior is observed for some
transition metal oxides, such as RuO2 and MnO2, where high
capacitance values are observed in the whole voltage range.
Electrochemical deposition of polymer on the surface of
carbon seems to be the most promising way to obtain satisfying
results in terms of capacitance enhancement. Unfortunately,
doping and dedoping process has a strong influence on the
shape of the electrode because of changes of the volume dur-
ing cycling. It is the main bottleneck of that kind of material,
furthermore, leading to its degradation by shrinking, swell-
ing, and cracking; hence, it aggravates the conductivity and
strongly limits the cyclability [2,37–39].
Transition metal nitrides due to their physical and chemi-
cal properties, for example, low electrical resistivity, seem
to be other good candidates for capacitance enhancement in
supercapacitors. One of the most known and widely inves-
tigated materials is vanadium nitride (VN) [25]. There are
many other described and reported synthesis methods of other
nitrides, such as titanium nitride (TiN) [40], niobium nitride
(NbN), and tantalum nitride (TaN) [41], which additionally
allow to use them in supercapacitor applications. However,
metal nitrides should be mixed with carbon material and
a very thin film of the composite needs to be deposited on
glass, silicon substrate, or nickel disk to avoid resistive behav-
ior, particularly when it is covered by a layer of metal oxide,
which has poor conductivity but can give additional contri-
bution of faradaic reactions due to different oxidation states

TABLE 25.1
Examples of Supercapacitors with Different Electrode Materials and Properties
Material Specific Capacitance (F/g) Energy Density Power Density Electrolyte References
Activated carbons 260 6 M KOH [11]
PANI doped with LiPF6 107 1 M Et4NBF4 in AN [20]
PEDOT 100 1 M H2SO4 [23]
Templated carbons with nitrogen content 164 20 Wh/kg 1 M TEABF4 in AN [26]
0.5 kW/kg
83 4 Wh/kg 1 M H2SO4
0.2 kW/kg
Activated carbon 400 2 M H2SO4 [29]
Hydrous ruthenium oxide 809 112 Wh/kg 1 M H2SO4 [30]
at 1.5 A/g
Manganese oxide film 337 2 M KCl [31]
Polyaniline nanowires 775 1 M H2SO4 [32]
PPy film 403 1 M H2SO4 [33]
281 1 M NaNO3
Fibrous carbon composite 154 4 M H2SO4 [34]
107 7 M KOH
Activated carbon 251 MeEt3NBF4 in AN [35]
236 MeEt3NBF4 in PC
Activated carbon 70 40 Wh/kg [(C6H13)3P(C14H29)][Tf2N] [36]
Graphene Materials in Energy Storage Applications
[2,42,43]. Another advantage is the fact that there is no need
for using noble metal current collectors because they usually
operate in an alkaline medium.
On the contrary, a novel approach for pseudocapacitance
phenomena was invented by exploiting electroactive species
such as iodide/iodine/iodate moieties [44,45] coming directly
from the electrolyte and giving tremendous capacitance for
positive electrode. The iodide-based system was further
improved by combining the electroactivity of iodides with
vanadium species [46]; both redox couples were conjugated
in one cell, separated by Nafion® 117 membrane, giving high
capacitance values and moderate specific power. Recently,
the redox activity of other species such as hydroquinone has
been investigated and reported [47,48]. The work concern-
ing the redox activity of substituted benzenes performed by
Frackowiak’s research group demonstrated the strong influ-
ence of hydroxyl group substitution as well as electrolyte pH
on their electrochemical activity and final capacitance val-
ues [49]. Additional capacitance in the case of hydroquinone
might be explained not only by faradaic reactions taking place
directly in the electrolyte solution but also as a consequence
of the grafting process. During electrochemical polarization,
hydroquinone dissolved in acidic medium (with the pres-
ence of protons) behaves as a redox-active electrolyte and can
generate functional groups on the surface of the carbon elec-
trode, able to undergo reversible redox reactions. It is a great
advantage over pseudocapacitance received directly from the
electrode material because the influence of poor diffusion and
electrolyte penetration into the electrode structure is signifi-
cantly reduced. This method is also more convenient than the
chemical generation of electroactive groups on the electrode
surface, for example, during the synthesis of the electrode
material. Furthermore, redox response (reversible peaks) can
also be observed in an alkaline medium because of strong
intramolecular hydrogen-bonding interactions between the
quinone and the hydroxyl groups. In a neutral electrolyte,
there is no redox activity because of the balance between pro-
tons and hydroxyl groups.
Apart from typical electroactivity of the species present in
the electrolytic solution, hydrogen electrosorption on negative
carbon electrode described elsewhere in the literature [50,51]
might result in capacitance enhancement. However, the con-
tribution of this process appears to be rather significant at
mild current regimes [52,53]. It is worth noting that hydrogen
electrosorption might also play an important role in terms of
operational voltage widening in aqueous solutions. This issue
will be discussed later in the chapter.
The aforementioned issues were related with capacitance
enhancement. As it was mentioned, the energy density of the
energy storage device also depends on the operational voltage
of the device. This feature is related to the applied electrolyte.
Aqueous systems (solutions of 1 mol/L H2SO4, 6 mol/L KOH,
1 mol/L Na2SO4, etc.) have a thermodynamic limit of 1.23 V,
given by the water decomposition process, but their great
advantage over other electrolytes (organic-based, ionic liquids)
is their high conductivity resulting in high power density, usu-
ally higher capacitance values, and relatively low cost because
379
of less-demanding assembling process. However, recent works
in this field demonstrated that the barrier of water decomposi-
tion could be overcome in the neutral electrolyte, especially
in 1 mol/L Li2SO4 by strong solvation effect of SO2− 4 anions
or Li+ cations [54], hydrogen electrosorption on negative elec-
trode [55], or mass balancing of the electrodes with unequal
capacitances [56] resulting in a capacitor voltage of up to 2.2 V.
To date, there is no full agreement concerning the origin of
the observed phenomenon as the experimental conditions and
examination protocols were slightly different in the referred
papers. The strong influence of the electrode material on the
electrolyte decomposition voltage cannot be neglected as well.
Hence, to achieve such extraordinary results for that kind of
aqueous electrolyte, it is necessary to use microporous acti-
vated carbon with significant contribution of mesopores; they
play a role of channels for big, slow, and strongly solvated ions
under their transport to micropores where charge accumula-
tion process takes place. As expected, other carbon materials
do not demonstrate such specific properties when operating in
lithium sulfate aqueous solution, probably because of lack of
suitable porosity (micropores/mesopores ratio).
25.3 GRAPHENE FOR HIGH-ENERGY
ELECTROCHEMICAL CAPACITORS
OPERATING IN APROTIC MEDIA
AND IONIC LIQUIDS
Application of organic electrolytes might result in maxi-
mum voltage as high as 3.0 V. Obviously, taking into account
energy dependence on the voltage, this is a great advantage for
organic electrolytes. The most commonly used solvents are
acetonitrile and propylene carbonate [35,36,57]. Acetonitrile
is used more often because it can dissolve larger amounts of
salts than other solvents. Unfortunately, it suffers from envi-
ronmental and toxic problems. Propylene carbonate-based
electrolytes are more environment friendly and demonstrate a
wider electrochemical window, an extended range of operat-
ing temperature, and good conductivity. As a source of ions,
organic salts such as tetraethylammonium tetrafluoroborate,
tetraethylphosphonium tetrafluoroborate, and triethylmethyl-
ammonium tetrafluoroborate (TEMABF4) have been reported
as commonly used for organic electrolytes. Regarding their
properties, it is well known that compounds with less sym-
metric structure are characterized by lower crystal-lattice
energy and increased solubility. Unfortunately, the water con-
tent in organic electrolytes has to be maintained below 5 ppm;
otherwise, the voltage will be remarkably reduced.
Apart from organic salts dissolved in acetonitrile or pro-
pylene carbonate, ionic liquids composed only of ions play
a significant role as electrolytes for high-voltage capacitors.
Low vapor pressure, high thermal and chemical stability, low
flammability, wide electrochemical window ranging from 2
to 5 V, typically about 4.5 V, as well as conductivity at the
level of 10 mS/cm [58,59] make them promising alternative
for conventional electrolytes [60]. The main ionic liquids con-
sidered for capacitor applications are based on imidazolium,
380 Graphene Science Handbook

pyrrolidinium cations and asymmetric, aliphatic quaternary

ammonium salts with anions such as tetrafluoroborate, tri-
fluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide,
bis(fluorosulfonyl)imide, and hexafluorophosphate [59,61].
Quaternary ammonium salts such as tetraalkylammonium
[R4N]+ and cyclic amines such as aromatic pyridinium, imid-
azolium and saturated piperidinium, and pyrrolidinium are
usually liquid at room temperature; hence, they can be eas-
ily applied as capacitor solvent-free electrolytes. Compounds
based on sulfonium [R3S]+ and phosphonium [R4P]+ cations
are also considered and reported in the literature [59,62]. The
problem of low conductivity of the ionic liquid electrolytes is
usually solved by their dilution with organic solvents (acetoni-
trile, propylene carbonate, or γ-butyrolactone).
Although porous carbon materials have high specific
surface area, the low conductivity of porous carbon materi-
als is limiting its application in high-power-density superca-
pacitors. Carbon nanotubes (CNTs) have excellent electrical
conductivity and high surface areas. However, CNT-based FIGURE 25.1  SEM images of (a) graphite and (b) graphite oxide
reduced at 800°C in N2 atmosphere (RGO).
supercapacitors have not met the expected performance; one
possible reason is probably due to the observed contact resis-
tance between the electrode and the current collector. Hence,
many studies have focused on the morphology of the carbon
materials to boost the performance of the capacitor, such as
growing CNTs directly on bulk metals to eliminate the con-
tact resistance. Graphene, with its one-atom-thick layer two-
dimensional structure is emerging as a unique-morphology
carbon material with potential for electrochemical energy
storage device applications due to its superb characteristics of
chemical stability, high electrical conductivity, and large sur-
face area. Recently, it has been accepted that graphene should
be a competitive material for supercapacitor application. In
contrast to the conventional high surface materials, the effec-
tive surface area of graphene materials as capacitor electrode
materials does not depend on the distribution of pores at solid
state, which is different from the current supercapacitors fab-
ricated with activated carbons and CNT. Obviously, the effec-
tive surface area of graphene materials should depend highly
on the layers, that is, single- or few-layered graphene with less FIGURE 25.2  TEM image of RGO.
agglomeration should be expected to exhibit higher effective
surface area and thus better supercapacitor performance.
As mentioned earlier, increasing energy demands have moti- graphene-based materials. One of the most important is
vated researchers since a long time to find alternative energy chemical exfoliation of graphite to graphene oxide (GO), fol-
sources. Obviously, the present state of the art on the market lowed by thermal reduction of GO to graphene. In Figures
seems to be quite interesting and offers various alternatives. 25.1 and 25.2, the structure and morphology of reduced gra-
However, there is no doubt that lithium-ion batteries (LIBs)— phene oxide (RGO) are shown.
because of excellent rechargeable characteristics, high specific
energy, as well as long cycle life—are the leaders in the group. 25.4  GRAPHENE FOR LI-ION BATTERIES
The properties of graphene-like materials such as great
electrical conductivity, profitable surface-to-volume ratio, Various electrode materials based on transition metal oxides
rather flexible nature, and good chemical stability make these are proposed for LIBs to benefit from higher capacities than
materials promising to build the electrodes, enriched with var- the recently used graphite. Indeed, these transition metal
ious metal and metal oxide nanoparticles for energy storage oxides are characterized by very high theoretical capacities but
applications. In such composites, graphene provides support dramatically low electrical conductivity. This feature strongly
for nanoparticles and prevents the volume expansion–contrac- restricts their successful application in LIBs. However, there
tion of nanoparticles during the charge and discharge process. are many efforts undertaken to make these materials more use-
Several effective methods have been developed to synthesize ful in that application. Mentioning manganese oxide that has an
Graphene Materials in Energy Storage Applications 381

electrical conductivity in the order of 10−7–10−8 S/cm, it is obvi-

ous that such conductivity value will limit its application, even TABLE 25.2
if specific capacity obtained is in the order of 400 mAh/g. On Graphene-Based Lithium-Ion Battery Materials and
the contrary, specific capacity of tin dioxide (tentatively good Properties
material for negative electrode, with a huge theoretical specific Current
capacitance of 780 mAh/g) in LIBs is affected by tin oxide Capacity Density
phase transformation and change of the material structure due Material (mAh/g) (mA/g) Cycles References
to reversible lithium ion insertion and extraction during the Pure graphite 372 – – –
charge–discharge cycles [63]. It has to be mentioned that there Graphite/graphene 690 186 ~60 [69]
is an important issue related with the electrochemical stability oxide
of electrode materials at various current densities related with Graphene Paper 180 100 ~100 [70]
their conductivity. Additionally, a significant decrease in cyclic Porous graphene 211 at ~100 [71]
performance also needs to be considered. Owing to such rea- 20°C
sons, other more conductive carbon materials need to be con- Graphene–TiO2 157 200 ~100 [72]
sidered and they usually play a role of conductivity-enhancing hybrid paper 122 2000 ~100
additives. Among others, CNTs [64–66] or simply carbon par- 40 wt.%-RGO/ 690 500 ~100 [73]
ticles [67] have been added to increase conductivity. Recently, Fe2O3
the most often used anode material—graphite—demonstrated MnO/graphene 706 500 ~100 [74]
rather low capacity (372 mA h/g) because of limited lithium- Silicon@graphene 969 1000 ~200 [75]
Fe2O3/graphene 963 100 ~30 [76]
ion storage sites within sp2 carbon hexahedrons. However, it
SnO2–graphene 594 100 ~50 [77]
has to be noted that even if the capacity of the anode is rela-
Graphene/Cu6Sn5 411 500 1600 [78]
tively low, there is no cathode that is able to host and provide
Carbon- 925 100 ~50 [79]
lithium even on the comparable order, to preserve the charge encapsulated
balance in the system. The possibility to increase lithium inter- CoFe2O4/graphene
calation during the charging process is the usage of the layered CuO/graphene 600 100 ~50 [80]
structure of graphene nanosheets. It has been reported [68] Mn3O4/N-doped 400 2000 ~25 [81]
that the enhanced specific capacity of these carbon-based elec- graphene
trodes through the interaction of graphene nanosheets with C60 Co3O4/graphene 801 21.12 ~30 [82]
and CNT, which facilitates the nanospace size for lithium-ion
intercalation, might be achieved. Higher reversible capacity
(up to 1050 mAh/g) and cyclic stability was also demonstrated dimethylformamide (DMF) and hydrothermal treatment for
in disordered graphene nanosheets; it seems that the pres- the reduction of GO to RGO have been demonstrated. The
ence of edge and vacancy defects in graphene sheets provides slow hydrolysis has shown uniform distribution of nanopar-
additional storage sites for Li ions; however, their reversibility ticles on RGO sheets, resulting in enhanced capacity at vari-
seems to be rather questionable. It has also been demonstrated ous current densities (Figure 25.3).
that the addition of the graphene-like materials to transition To avoid the aggregation and capacitance fading of
metal oxide might remarkably enhance the specific capacity nanoparticles during the charge–discharge cycles, a new
of the electrodes, especially at high discharge rate and might strategy of metal oxide particle encapsulation by graphene
improve the electrochemical stability for several cycles. The sheets was developed [84]. It has been realized through the
improvement is assumed to originate from features such as coassembly of negatively charged GO with positively charged
excellent electronic conductivity, high surface area, thermal oxide nanoparticles using electrostatic attraction. The resul-
and chemical stability, and mechanical flexibility of mono- tant composite demonstrated very high reversible capacity
layer graphene sheets. Briefly, flexible graphene sheets could (in the order of 1100 mA h/g in first 10 cycles) for graphene-
accommodate a large volume expansion of metal oxide during encapsulated Co3O4 and 1000 mA h/g after 130 cycles.
the charge–discharge process and prevent the pulverization of Owing to its carbonaceous origin, graphene is rather
the electrodes, leading to higher electrical conductivity of the hydrophobic and needs to be specially treated before further
electrode. Moreover, the high surface area of graphene might processing. The functionalization of hydrophobic graphene
facilitate lithium-ion intercalation. Recently, many groups have sheets before mixing with highly hydrophilic metal oxide
made a significant effort to develop LIBs with good cyclability, nanoparticles is another reasonable approach to form well-
especially using metal oxide nanoparticles with graphene-like dispersed metal oxide coating [85]. It seems that the use of
material composites, as can be seen in Table 25.2. These metal surfactants as wetting agents (especially anionic ones, such
oxide nanoparticles are usually grown on GO, deposited with as sodium dodecyl sulfate) helps in dispersing individual
sophisticated solution chemistry followed by hydrothermal, graphene sheets and in situ crystallization of metal oxide
thermal, or chemical reduction. particles.
Regarding preparation methods, in Reference 83, a simple In Reference 85, TiO2/RGO composites were prepared as
two-step solution-based method for Mn3O4 –grpahene hybrids materials for LIB electrodes using surfactant-assisted growth
using slow hydrolysis of their salts (manganese acetate) in of nanoparticles of TiO2 and demonstrated more than the
382 Graphene Science Handbook

(a) 3.0 (b) 3 800 mA/g 400 mA/g

1600 mA/g
2.5
Li+ discharge

Voltage (V)

Voltage (V)
2.0 2
1.5 40 mA/g
1.0 1
Li+ charge
0.5

0.0 0
0 400 800 1200 0 200 400 600 800
Capacity (mAh/g) Capacity (mAh/g)

(c) 1400 (d) 1400

1200 Mn3O4/Reduced GO Free Mn3O4
1200
1000 40 mA/g
Capacity (mAh/g)

1000

Capacity (mAh/g)
400 mA/g 400 mA/g
800 800
800 mA/g Discharge
600 600
1600 mA/g Charge
400 400 40 mA/g
Discharge
200 200
Charge
0 0
0 10 20 30 40 0 2 4 6 8 10
Cycle number Cycle number

FIGURE 25.3  Electrochemical characterizations of a half-cell composed of Mn3O4/RGO and Li electrode. The specific capacities are
based on the mass of Mn3O4 in the Mn3O4/RGO hybrid. (a) Charge and discharge curves of Mn3O4/RGO for the first cycle at a current density
of 40 mA/g. (b) Representative charge and discharge curves of Mn3O4/RGO at various current densities. (c) Capacity ­retention of Mn3O4/
RGO at various current densities. (d) Capacity retention of free Mn3O4 nanoparticles without graphene at a current density of 40 mA/g.
(Reprinted with permission from Wang, H. et al. Mn3O4-graphene hybrid as a highcapacity anode material for lithium ion batteries. Journal
of the American Chemical Society 132:13978–80. Copyright 2010 American Chemical Society.)

double specific capacity than control rutile TiO2 at a high dis-
charge rate of 30°C [85]. In Reference 86, the authors used
the ternary self-assembly approach to prepare well-controlled
and ordered metal oxide (SnO2, SiO2, NiO, and MnO2)/gra-
phene nanocomposites, which includes self-assembly of metal
oxides, surfactants, and graphene for LIB electrodes. The
high concentration of RGO (30–60 wt.%) with anionic sur-
factant has been used to build layered metal oxide–graphene
composite film electrolyte.
Considering titanium oxides and its graphene relatives,
the controlled growth of TiO2 on GO sheets was achieved by
limiting the rate of hydrolysis during synthesis without sur-
factants [87]. The TiO2–RGO composite also showed more
photocatalytic activity than a variety of other TiO2 materi-
als. Furthermore, the study is not limited to the inorganic
oxide particles–graphene composite. It has to be noted that
nitrogen-doped graphene was also investigated as an anode
material for LIBs [88].
25.5 GRAPHENE-BASED COMPOSITES FOR
HYBRID ENERGY STORAGE DEVICES
As mentioned, supercapacitors or ultracapacitors are energy
storage devices for short load cycle (power peak) applications.
Supercapacitors with very high power density, fast charge/
discharge ability without degradation, and fast release charac-
teristic make them ideal candidates for applications in mobile
electronic devices and hybrid electric vehicles (HEVs).
Briefly, energy stored in supercapacitors is due to the ion
adsorption at the electrode interface, which forms EDLCs, or
due to the electron transfer between the electrolyte and the
electrode through fast faradaic redox reactions (the so-called
pseudocapacitors). Several supercapacitor materials have been
studied to improve specific capacitance and power density.
Among others carbon-based materials such as activated car-
bons, carbon fibers and CNTs have been extensively investi-
gated as electrode material for EDL supercapacitors owing to
their good electrical conductivity, chemical and mechanical
stability, long cycle life, and highly modifiable nanostructures
[8,89–91]. Materials such as RuO2 and MnO2 and electrically
conducting polymers are promising for pseudocapacitors.
Various graphene-based supercapacitor materials are summa-
rized in Table 25.3.
The example of electrochemical characteristic obtained for
RGO after thermal reduction is shown in Figures 25.4 and
25.5.
As described earlier, supercapacitors store charge electro-
statically by the adsorption of ions onto electrodes character-
ized by highly accessible specific surface area. Therefore, a
high specific capacitance active electrode plays an important
Graphene Materials in Energy Storage Applications 383

TABLE 25.3
Graphene-Based Supercapacitor Materials and Properties
Material Specific Capacitance (F/g) Energy Density Power Density Electrolyte References
RGO 206 1 M H2SO4 [92]
Graphene/VO2 225 0.5 M K2SO4 [93]
Ruthenium oxide/graphene 479 20.28 Wh/kg 600 W/kg 0.5 M H2SO4 [94]
Graphene/MnO2 327.5 35.54 Wh/kg 1 M Na2SO4 [95]
63.9 kW/kg
Sulfonated graphene/polyaniline 676 1 M H2SO4 [96]
Graphene/Ni(OH)2 1247 6 M KOH [97]
Nitrogen-doped graphene 132 1 M H2SO4 [98]
Graphene/activated carbon 220 6 M KOH [99]
PPy/graphene nanosheets/rare earth ions 238 1 M H2SO4 [100]
Fe3O4/RGO 220 1 M KOH [101]
GO/single-walled carbon nanotubes 260 123 Wh/kg Ionic liquid (EMI-TFSI) [102]
CoO/graphene 139.5 3 M NaOH [103]
Carbon/graphene composite 273 6 M KOH [104]
Graphene/ZnO 109 1 M KCl [105]

250
380°C 600°C 800°C 0.8 100 mA/g
200 200 mA/g
1000 mA/g
150
0.6
100
C ( F/g)

50
U (V)

0.4
0

–50
0.2
–100

–150
0.0
–200
0.0 0.2 0.4 0.6 0.8 0 200 400 600 800
U (V) Time (s)

FIGURE 25.4  CV curves of graphite oxide reduced at different FIGURE 25.5  Galvanostatic curves of RGO (reduced at 380°C) at
temperatures. The aqueous 6 mol/L KOH solution was used as the different charge/discharge currents.
electrolyte. Scan rate: 1 mV/s.

role in efficient energy storage. Various forms of porous car-
bon such as CNTs [106–109], mesoporous carbon [110], acti-
vated carbons with well-developed microporosity and specific
surface area [38], as well as carbide-derived carbons (CDCs)
[111] have been reported as promising electrode materials
in this application. Recently, graphene-like materials, rather
than various forms of RGO, have been estimated as a tentative
candidate for supercapacitor electrodes because of their high
specific surface area (for graphene, theoretically 2675 m2/g),
good chemical and electrochemical stability, satisfying elec-
trical and thermal conductivity, high demonstrated capaci-
tance values and good charge propagation, as well as relatively
low cost [81,94,95,112–115]. Unfortunately, volumetric capac-
itance, because of graphene’s low density, is relatively low. On
the contrary, graphene-like materials demonstrated intrinsic
capacitance near 21 μF/cm2 that set a new upper limit for
capacitance [116]. It is accepted that the work of Ruoff and
his coworkers [112] has pioneered the application of chemi-
cally reduced graphene in supercapacitors. In this work, they
applied chemically RGO and its potential as an electrode
material for supercapacitors. It is also discussed that even
if the surface area was in the order of mesoporous carbons,
that is, about 700 m2/g, the electrode was not fully accessible
by the electrolyte. Supercapacitors built with these materials
demonstrated a specific capacitance of 135 F/g and 99 F/g in
aqueous KOH and organic electrolyte, respectively. Improved
capacitance (191 F/g, in KOH) was obtained after using micro-
wave power to expand GO layers and reduce the GO to RGO
(surface area close to 460 m2/g) [117]. In another work [113],
specific capacitance value of ~205 F/g for hydrazine RGO of
384
effective surface area of ~320 m2/g was achieved. Obviously,
there is no doubt that the surface area of graphene-like mate-
rials plays an important role and directly affects the overall
performance of the supercapacitors.
A main drawback of using graphene and RGO is the
agglomeration and restacking due to strong van der Waals
attraction between the neighboring sheets. Agglomerates
have reduced electrochemically available surface area, which
results in capacitance fading. Therefore, in some papers, an
effort to keep graphene sheets separated by the addition of
metal oxide nanoparticles [118] is presented. Metal oxides
such as RuO2, MnO2, polyaniline (PANI), and nanocompos-
ite with graphene have also been demonstrated for keeping
good capacitance along the current load. The approach of
exploiting nanoparticles to enhance the electrochemical per-
formance is a good indication of a positive and synergistic
effect of combining graphene sheets and nanoparticles. To be
more in depth with examples, in RuO2/graphene composite,
graphene sheets were well separated by RuO2 nanoparticles
that were attached through the oxygen-containing functional
groups on graphene surfaces. The composite exhibited a high
specific capacitance of 570 F/g for 38 wt.% RuO2 loading with
excellent electrochemical stability (98% retention after 1000
cycles) and high energy density (20 Wh/kg) at high power
density (10 kW/kg). However, it is worth noting that these
values were calculated as an estimation. Similarly, MnO2/GO
composite electrode had a capacitance of 216 F/g that is much
higher than that of individual graphite oxide (11 F/g due to its
nonporous character as well as quite resistive characteristic)
and bulk MnO2 (not more than 7 F/g, because of low specific
area) [119]. In Reference 120, MnO2/graphene high-voltage
asymmetric capacitor based on graphene as a negative elec-
trode and MnO2/graphene composite as a positive electrode,
which exhibited a superior energy density of 30 kW/kg and
a power density of 5 kW/kg at 7 Wh/kg, has been demon-
strated. Although the metal oxide–graphene nanocomposite
has shown great promise for supercapacitors and high-energy-
density capacitors, the high-energy-density supercapacitors
with high charge–discharge rates are still subjected to fur-
ther investigations. Recent study [121] reveals the graphene-
based supercapacitor that exhibits a specific energy density of
85 Wh/kg at room temperature and 136 Wh/kg at 80°C at a
very high current density of 1 A/g. These values are compara-
ble to Ni-metal hydride (40–100 W h/kg). It has been reported
that the mesoporous structure of the curved graphene sheet
is responsible for such improvement; the defected nature of
graphene sheets prevents restacking and allows to maintain
a large pore size (2–25 nm) and capacitance. Furthermore,
quick charge–discharge ability in seconds and minimal loss
of capacity or energy density could make it an ideal candidate
better than existing batteries, but more in-depth research is
needed to be undertaken.
Recently, graphene–polymer composites have also received
much attention owing to their flexibility, and superior capaci-
tance than existing carbon-polymer-based capacitors. Among
the various conductive polymers, PANI has been considered
the most promising conductive electrode material and studied
Graphene Science Handbook
remarkably with CNTs and carbon system [122–127]. A gra-
phene nanosheet–PANI composite was synthesized by in situ
polymerization [122]. The specific capacitance of 1046 F/g
was obtained at a low scan rate of 1 mV/s. It seems that con-
ductive graphene nanosheets provide more active sites for
nucleation of PANI and is homogeneously coated by PANI
nanoparticles on both sides, resulting in an energy density of
39 kW h/g at a power density of 70 kW/kg. Of course, these
values need to be confirmed on a larger scale. Graphene–
PANI composite papers were also prepared by in situ anodic
electropolymerization of polyaniline film on graphene papers
[128]. The flexible as-prepared composite papers combined
the high conductivity and flexibility properties of graphene
sheets with large capacitance polymer and showed a gravi-
metric capacitance of 233 F/g.
25.6 GRAPHENE IN FUEL CELL APPLICATIONS
Apart from LIBs and supercapacitors, some overview for fuel
cell systems needs to be considered. Fuel cells are recently
accepted as one of the most promising power sources for
mobile and stationary applications because of their mod-
erate energy conversion efficiency and ease of handling.
Unfortunately, the high price of Pt and Pt-based materials,
widely used for the fuel cell as catalysts, might exclude them
from wide commercial applications. Nowadays, graphene-
based materials have also been investigated in fuel cell appli-
cations [129–141]. Many researchers have made significant
effort to develop composite electrode materials for fuel cell
application, and examples can be seen in Table 25.4.
The proton exchange membrane (PEM) fuel cells proto-
type using graphene was developed [130]. For instance, Toray
papers modified with RGO/Pt composites as a cathode and
Pt-dispersed on carbon black as an anode was developed and
investigated with promising results. The performance of the
fuel cell was compared with unsupported Pt cathode PEM
and gave direction for further research.
The RGO/Pt-based fuel cell showed a maximum power of
161 mW/cm2 compared with 96 mW/cm2 for an unsupported
TABLE 25.4
Graphene-Based Materials for Fuel Cell
Type of Fuel Cell Material References
PEMFC Pt/graphene [131]
PEMFC Pt/graphene [132]
PEMFC Pt–graphene/MWCNT [133]
DMFC PtRu/graphene [134]
DMFC CuPt/graphene [135]
DEFC Ni/graphene [136]
Ni-Co/graphene
MFC MnO2/graphene [137]
MFC PPy/graphene oxide [138]
DBFC Pt/graphene [139]
DBFC Au/graphene [140]
Graphene Materials in Energy Storage Applications
Pt-based fuel cell. The role of graphene support not only max-
imized the availability of the electrocatalyst surface area for
efficient electron transfer but also provided better mass trans-
port of the reactants to play as an electrocatalyst.
Recently, a reasonable trend for combining biology and
electrochemistry, biological applications of GO/RGO, RGO-
based single-bacterium bio-device, label-free DNA sensor,
bacterial DNA/protein, and polyelectrolyte chemical transis-
tor has been reported [141]. It was reported that the GO sheets
are biocompatible without obvious toxicity and employed GO
for drug delivery [142]. One of the promising targeting meth-
ods is the use of magnetic particles loaded with drugs. Thus,
magnetic NPs with graphene composites have been used
in various areas of drug carrier and even in magnetic reso-
nance imaging (MRI) [143–146]. The magnetization curve
of GO–Fe3O4 composite was measured at room temperature
and showed a magnetic hysteresis loop of “S” line curve with
nearly zero value of the magnetic remanence. This might sug-
gest that GO–Fe3O4 exhibited a superparamagnetic behavior.
25.7 CONCLUDING REMARKS AND
PERSPECTIVES
Graphene promises to offer the best possible material proper-
ties in practically all applications. The main disciplines where
its superior properties can be utilized are bioengineering,
composite materials, energy technology, and nanotechnology.
The range of applications, including LCD touchscreens and
OLEDs, smart packaging, supercapacitors, LIBs, composites,
ITO replacement, sensors, logic and memory, etc. is wide.
BCC provides the first significant increase in sales of tech-
nology linked to graphene before 2015, at the level of $67 mil-
lion. It is expected to achieve a market value of $675 million
in 2020. The major part of graphene market (26%) after 2015
will belong to construction materials at a value of $17.5 mil-
lion while capacitors will be more than half of the graphene
technology market in 2020 [147].
Arora et  al. [148] showed, based on their investigations
on new high-technology small-to-medium-sized enterprises
(SME) focused on graphene in China, United Kingdom,
and United States, how the graphene path from discovery to
application is accelerated, although the graphene area is in
the early stage of commercialization. They found three main
pathways for SME to specialize in commercial chances: prod-
uct development, specialization in materials development, and
integration into existing product portfolios. A bright future of
all graphene applications is proved by the fact that not only
SME are interested in graphene technology, but a number
of multinationals, such as Intel and IBM in computing, Dow
Chemicals and BASF as suppliers of graphene, or Samsung in
consumer electronics, are players on a global market related
with research and development of graphene technology.
In general summary, it should be highlighted that graphene
and its derivatives demonstrate a tentative and promising appli-
cation in energy storage devices, especially in supercapaci-
tors, but to date, there is still much work to be done in the field
of material science to go toward real devices and commercial
385
application. However, there is a clear direction indicated by
the advancement and the motivating force for undertaking
such efforts. Actually, there is no lift to success—you have to
take the stairs; it should be the first consideration.
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 26 Applications of Graphene in
Fuel/Propellant Combustion
Bruce Chehroudi

CONTENTS
Abstract...................................................................................................................................................................................... 391
26.1 Nanostructured Materials in Fuels/Propellants................................................................................................................ 391
26.2 Graphene Oxide Applications in Fuels/Propellants......................................................................................................... 392
26.3 Commercialization Potential............................................................................................................................................ 395
26.4 Conclusions....................................................................................................................................................................... 395
References.................................................................................................................................................................................. 396

ABSTRACT
Use of nanostructured materials, in particular graphene, in the
combustion and ignition of fuels has recently shown promis-
ing results in enhancing the fuel burn rate and potential for
light-activated volumetrically distributed ignition. For exam-
ple, the addition of f­unctionalized graphene (FG) sheets to
nitromethane, has been demonstrated to act as a catalyst and
substantially increase the linear burning rate of the fuel. The
functionalization of graphene is considered a great opportu-
nity for tailor-made material with specific properties of inter-
est. For example, it consists of chemical functional groups such
as epoxides and hydroxides on the surface, and hydroxides and
carboxylates on the edges of the sheet. These oxygen-contain-
ing functionalities bring about catalytic properties for fuel
decomposition and other intermediate fragments during the
fuel oxidation process. The defect structures in the FG sheets
have also been shown to act as active sites. Such augmented
fuel thermal decomposition and its derivatives have been veri-
fied through the use of molecular dynamics (MD) simulations.
FG sheets are easily dispersible in many hydrocarbon fuels
and propellants with no need for surfactants and may also
offer a substantially higher surface area than other nanostruc-
tured materials such as metal oxides and carbon nanotubes.
Also, because FG is entirely oxidized in high temperature
combustion zones with virtually no additional residues other
than common combustion products, it can be viewed as a fuel
supplement, contributing towards energy d­ ensity. In this chap-
ter, applications of graphene oxides and FG sheets in the igni-
tion and combustion of fuels are briefly reviewed, highlighting
the potential, and future prospects of these materials.
26.1 NANOSTRUCTURED MATERIALS
IN FUELS/PROPELLANTS
Nanostructured materials have exhibited unusual and inter-
esting thermal, mechanical, electrical, and optical properties
ever since C60, carbon nanotubes (CNTs), graphene, and o­ thers
have been discovered or inexpensively synthesized. Many of
these properties have been used in a wide number of appli-
cations, for example as additives in structural materials, as
drug carriers in targeted cancer therapies, in high-resolution
displays, and many others, for example (see Gogotsi [2006],
De Volder et al. [2013], Liu et al. [2012a,b], and Barton et al.
[2011]). The use of nanostructured materials in the ignition
and combustion of fuels is one rapidly growing and important
application of nano-science and technology. The motivation
behind such usages are varied and range from enhanced per-
formance and efficiencies to the reduction of harmful pollut-
ants from fossil-fueled combustors for power generation or
propulsion systems. A large majority of the work in this area
pertains to the use of nanostructured metals and/or oxides or
oxyhydroxides, for example (see Mench et  al. [1998], Risha
et al. [2002, 2004, 2008], and Tyagl et al. [2008]).
Researchers so far reported a host of promising results
when metallic nanoparticles (e.g., aluminum) were used as
additives in fuels during laboratory experiments such as a
­significant increase in energy densities and enhanced reaction
rates. However, despite these initial exciting results, poten-
tial barriers emerged due to passive metal oxide layers on
nanoparticles and production of these oxides as additional by-
products of the combustion process which must be contained
for environmental and health reasons. For detailed coverage
and discussion of nano-metallic particles in the ignition and
combustion of fuels, readers should consult the references
previously mentioned and other citations herein.
Applications of nanostructured carbon and its allotropes in
ignition and combustion have recently been demonstrated and
are currently the subject of intense research throughout the
world. Because CNTs have been available since their discov-
ery by Sumio Lijima (1991), their applications for ignition and
combustion naturally came first. Many synthesis approaches
have been devised for CNTs which paved the way towards
systematic work in the use of CNTs with fuels or propellants
391
392
for combustion purposes. As an application example, Moy
et al. (2002) were granted a US patent filed in 2002 in which
they claimed that about 1% to about 15% by weight CNTs
added to fuels can enhance the burning rate and additionally
function as an antiknock additive in spark ignited engines.
At the nano scale, Choi et  al. (2010) demonstrated that
by coupling an exothermic chemical reaction of cyclotri-
methylene trinitramine (TNA), a military explosive, with a
multiwalled nanotube (MWCNT), or nanowire possessing
­
high axial thermal conductivity, a self-propagating reactive
wave can be driven along its length which simultaneously gen-
erated an electrical pulse of disproportionately high specific
power (thermopower wave). The specific electrical power gen-
erated exceeds that of lithium-ion batteries commercialized
for automotive and railway applications. This carbon-nano-
tube-guided combustion might be used for microthrusters
which have minute combustion engines used for purposes,
for example, such as maintaining relative microsatellite posi-
tions within a microsatellite array. The directed pressure wave
­provides a total impulse (per mass of TNA and MWCNT)
that is 4–100 times that of other proposed microthrusters
(see Aliev and Baughman [2010]).
Another demonstrated application of nanostructured mate-
rials is in diesel engines. For example (see the work by Basha
and Anand [2011]). They showed that a CNT-blended water-
diesel emulsion fuel (25 and 50 ppm CNT mass fraction)
delivered considerable enhancement in the brake thermal
efficiency and substantial reduction in harmful pollutants.
Recently, Tewari et al. (2013) showed that a blend of MWCNT
with biodiesel also delivered a significant enhancement in
brake thermal efficiency and considerable reduction in harm-
ful pollutants.
Use of nanostructured carbon have been successfully
employed for an innovative light-activated volumetrically
­distributed ignition of liquid sprays and gaseous fuel/air mix-
tures by Chehroudi et  al. (2009, 2010), Chehroudi (2011),
Chehroudi (2012a,b), and Chehroudi (2013). Chehroudi et al.
were the first to demonstrate the distributed ignition of dry
CNTs (with metal nanoparticle impurities) and their abilities
to ignite a host of liquid, gaseous, and solid fuels of inter-
est. Minimum ignition energy (MIE) of such single-walled
CNTs (SWCNTs) with an ordinary low-energy camera flash
was reported. Experiments were focused on effects of inci-
dent pulsed-light exposure duration and wavelength on MIE.
Chehroudi (2012b) also showed that lower energy-per-pulse
is needed to initiate ignition when shorter flash duration is
used. For example, at a flash duration of ~0.2 ms, it required
a 30–35 mJ/pulse to initiate the ignition of as-produced fluffy
samples in standard air, whereas at 7 ms duration, it needed
an 80–90 mJ/pulse to achieve the same result. Average inten-
sities between 10 to 150 W/cm2 were needed to bring about
the ignition of SWCNTs, being a factor of about 80 lower
than cases where laser (pulsed or CW) was used in coal par-
ticles. An important application of this work, first conceived
and proposed by Chehroudi, is in highly efficient, environ-
mentally clean, and homogeneously charged compression-
ignition (HCCI) combustion engines in which the heat release
Graphene Science Handbook
process starts by autoignition of the lean premixed fuel and
air ­mixture (see Chehroudi [2011]). In HCCI engines, good
control of the time when the autoignition occurs is critical
for successful engine operation. “Controlled” autoignition of
lean gaseous fuel and air mixture has already been demon-
strated in a constant-volume chamber (see Chehroudi [2011],
and Berkowitz and Oehlschlaeger [2011]).
26.2 GRAPHENE OXIDE APPLICATIONS
IN FUELS/PROPELLANTS
Graphene oxide (GO) is a new member of the nanostructured
material family and has certain unique features, one of which
is that it carries oxygen with itself (see Figure 26.1). Studies
in the use of FG foams for light-activated ignition is dis-
cussed in Chehroudi (2011). Interestingly, Cote et al. (2009)
were first to demonstrate the photothermal reduction (using
a Xenon flash) of GO indicating that it was rapid, clean, and
versatile. Figure 26.2 shows the initial results from the igni-
tion and combustion of GO. Here, the GO sample was placed
on a paper wetted with ethanol and ignited via a flash of light.
The ignition of the graphene material caused the subsequent
ignition of the vapor cloud in its neighborhood. After ignition,
the deoxygenated graphene sample grows larger due to per-
haps exfoliation. The minimum ignition energy required for
ignition of dry samples of GO foam was measured in between
1.2 to 1.7 J/pulse at pulse duration of about 1 ms. This was
found to be much higher than the 35–85 mJ/pulse measured
for SWCNTs (see Chehroudi [2011]). Although the solubility
of GO and its oxygen carrying features are attractive, such a
relatively large minimum ignition energy is troublesome for
ignition applications.
As far as the application of graphene in the combustion of
fuels and propellants is concerned, this is currently consid-
ered to be in its infancy stage. A pioneering work by Sabourin
et al. (2009) is the one to describe here. The idea and excite-
ment in the use of GO is that, many of the problems related
to utilization of nano-metallic particles mentioned earlier can
be resolved considering that the use of FG sheets which not
only catalyzes fuel combustion reactions but also eventually
participates energetically and is consumed without producing
residual particulates. Graphene sheets show many of the same
desirable properties of CNTs, such as high electrical conduc-
tivity and good mechanical properties, etc, but do not contain
significant quantities of metal particles that are used to cata-
lyze CNT growth. This is because the synthesis of functional-
ized GO (FGO) does not use metal-containing catalysts. The
FG sheets used by Sabourin et  al. (2009) contain chemical
OH
O OH
OH O
O
O OH
O
HO O
OH O OH
O
OH O
FIGURE 26.1  ​Molecular structure of a functionalized graphene
oxide sheet.
Applications of Graphene in Fuel/Propellant Combustion
(a) (b)
FIGURE 26.2  ​Ignition of a GO foam sample with an ordinary camera flash, (a) sample on a wetted paper, (b) 7 ms after ignition onset,
and (c) about 15 ms after the ignition. Image magnification is the same. (From Chehroudi, B., 2011. Recent Patents on Space Technology,
1, 2, 107–122 [16].)
functional groups such as hydroxides and carboxides on the
surface, and hydroxides and carboxylates on the edges . The
carbon/oxygen mole ratio range from two for GO to higher
values depending on the degree of chemical or thermal reduc-
tion of the FG sheet. This creates vacancies and topographical
defects in the FG sheet.
Additionally, FG sheets have a heat of combustion close
to aluminum and are easily dispersible in many hydro-
carbon fuels and propellants without the need of surfac-
tants and may have significantly higher surface area than
metal oxides. Also, graphene-based additives are most
likely burned in an oxygen containing environment at high
­temperatures and energetically contribute to the combus-
tion process without exhaust particulate matter or plume
signatures beyond that produced through the fuel combus-
tion products themselves. Existence of nucleophillic oxy-
gen-containing functionalities on the surfaces and edges of
the FG sheets is likely to provide catalytic behavior which
can stabilize or encourage reaction intermediates dur-
ing the combustion process. The ability to adjust the C/O
(carbon-to-oxygen) ratio also offers the opportunity to tune
solubility in a variety of liquid fuels. For example, the more
reduced versions should be more compatible with alkanes
and a higher oxygen-containing version is more compatible
with more polar and/or ionic hydrocarbons such as alcohols,
aldehydes, and ketones.
In an experiment to demonstrate the benefits of FG sheets,
Sabourin et  al. (2009) used liquid nitromethane (CH3NO2)
as a fuel and mixed it with FG sheets to examine the burn
rate enhancement in a circular cross-section combustion
tube. Nitromethane, on account of low oxygen content and
reactivity at low pressures, is both considered as a fuel and
a ­monopropellant for rocket applications. Four experiments
were conducted on four different mixtures containing pure
(neat) NM (nanosized metal), NM and nanosized aluminum
oxides, NM and porous nanosized SiO2, and NM and FG
sheet with C/O ratio of 22.
Sabourin et  al. (2009) showed that by mixing FG sheets
with NM, the ignition and combustion rates were substantially
enhanced over those achieved by other mixtures. Although the
burn rate was also increased by the addition of the nanoparti-
cles, there are advantages in the use of FG sheets. Use of CNT
393
(c)
was not considered in their studies due to concerns about
metal contamination in the CNTs which might affect combus-
tion catalysis attributed to nanotubes themselves. However,
nowadays SWCNTs with 95% or higher purity are available
and worth a comparative study. Nevertheless, compared to the
NM-only case, results by Sabourin et al. (2009) showed that
the ignition temperature of the NM-and-FGO mixture was
lowered and its burn rate significantly enhanced at low pres-
sures (~4 MPa). At higher pressures (>12 MPa), however, burn
rates for the neat NM and FG-sheet-doped NM converged and
minimal advantage was seen. Despite, addition of FG sheet
had made the burn rate less sensitive to pressure changes. This
is a positive feature especially in the context of propulsion
applications such as rocket motors where pressure instabilities
lead to reduced control and performance. It is possible that
addition of SWCNTs may bring about even more dramatic
results due to the additional nanoparticle catalysts they carry.
Some claims have already been made on burn rate enhance-
ment of CNTs in fuels, for example (see Moy et al. [2002]).
Everything else being the same, the nanostructured material
which provides a faster burn rate is of interest from the practi-
cal perspective.
The enhancement mechanism was thought to be increased
by heat transfer due to radiation and thermal conductivity.
Thermal conductivity is increased due to catalysis and the
nitric oxide and FG sheet oxidation reaction, both of which
reduce flame thicknesses at lower pressures. The presence of
particles within the liquid as well as those entrained within
the gas-phase reaction zone provide opportunities for both
radiation emitters and absorbers of thermal energy which do
not exist in the pure NM combustion process. Thermal con-
ductivity of single sheet graphene is quite high, being near
that measured for CNTs. Hence, the heat absorption capac-
ity for the FG-sheet-doped suspension is expected to be much
higher than that of the NM-alone mixture. Finally, the cata-
lytic activity at the defect sites were considered as another
important mechanism contributing to the enhanced burn
rate of the FG-sheet-doped NM. Although, several possible
chemical routes were discussed in Sabourin et  al. (2009),
it appears that formation of aci-anions (CH 2 NO2− ), a sub-
stance which has been identified as a sensitizing species in
the detonation of liquid nitromethane will be the most likely
394 Graphene Science Handbook

path (see Engelke et al. [1988a,b] and Engelke et al. [1986]). CH3NO2H
(a)
Note that the reduced FG sheet is known to contain signifi-
O
cant landscape defect structures. These defects can act as H H
the sites for free radical formation and stabilization, offering CH3NO2
Nitromethane C N O
mechanisms not present in the metal oxyhydroxides (which
H H
also have o­ xygen-containing functionalities). Finally, another
route p­ ossibly contributing to rapid burn rate was cited as
the reaction between NO (nitrogen oxide) and carbonaceous
materials, in this case the FG sheet. The exothermic reac-
tion between NO and carbon (having similar reaction rates as
O2-C reaction), studied intensively in the context of soot and
NOx reduction in engines, was thought more likely to have an O
effect on NM burning rates. H
In a follow-up study conducted by Liu et al. (2012a,b) at
CH3NO
Princeton University, they investigated the observed enhanced
thermal decomposition of the NM on FG sheet using ab ini-
tio molecular dynamics (AIMD) simulation. Although, sug-
gestions were earlier made by Sabourin et al. (2009) that the CH2NO
CHNO
catalytic reaction might be in play in the FG sheet and nitro-
methane reaction, it was impossible to determine the mecha-
nism using the available experimental techniques. Liu et al.
(b) H CH2NO
(2012a,b), using AIMD, showed that catalytic activity origi-
nates from lattice defect complexes within the graphene sheet, O
notably vacancies functionalized with O2-containing groups
such as hydroxyls, ethers, and carbonyls, and they provided
detailed mechanistic insight into the atomic-scale processes
leading to complete NM decomposition (see Figure 26.3).
In particular, their calculations showed that pristine gra-
phene interacts very weakly with NM, whereas hydroxyl or H
epoxy groups adsorbed on graphene can form H-bonds with
O
NM and consequently abstract H from NM with much lower CH2NO2–
barrier than required for the C-N bond scission. Note that,
this bond scission takes place in the initial stages of the gas- CH3NO2
eous NM decomposition without the presence of FG sheets.
Interestingly, they showed that while these processes facili- FIGURE 26.3  ​Shows the catalytic role that FG sheet plays in the
tate NM decomposition, they do not lead to “catalytic action” decomposition of nitromethane. (a) An example of a proton transfer
in which the original catalyst is regenerated at the end. This from a hydroxyl group on an FG sheet to a nitromethane molecule
regeneration process is shown in Figure 26.3. In fact, through forming a reactive intermediate is indicated. (b) The subsequent
AIMD calculations, they showed the evolution of the aci-ion regeneration of the hydroxyl group caused by a proton transfer from
population that appeared at the onset of the simulation and a nitromethane derivative to a carbonyl on the FG sheet is shown.
subsequently disappeared within ~2 ps after extinction of Other examples of proton transfer mechanisms are depicted below
the NM population, a behavior which interpreted that NM the sheet, representing a small set of potential reactions that take
place between FG sheet and nitromethane and FG sheet and NM
decomposition was initiated by catalytic production of aci-
derivatives. White and gray balls are hydrogen and carbon and light
ions. Figure 26.4 shows some of the proposed reactions in the black and dark black are oxygen and carbon, respectively as shown.
decomposition of NM in presence of the FG sheet. (From Liu, L.-M. et al., 2012b. Journal of American Chemical
Liu et  al. (2012a,b) also demonstrated that the reaction Society (JACS), 134, 19011–19016.)
rate decreases when NM density is reduced, roughly propor-
tional to the density. Although, they did not investigate the
effect of lower NM initial temperature, they indicated that it and strongly enhances the rate of successive relations. This
should reduce the burning rate dramatically. However, they property in conjunction with high dispersive and thermal
commented that at lower temperatures, the FG sheet should characteristics makes FG sheet a high-performing additive
play an even more important role in initiating the combus- for future propulsion systems. The basic mechanisms in play
tion as the heterogeneous reaction promoted by the FG sheet was associated with the highly defective regions which form
has a significantly lower activation barrier than the alternative in FG sheet during the thermal reduction of GO. Finally, the
homogeneous reactions. The key conclusions were that gra- concentration of these defects increases with an increase in
phene with carbon vacancies is an effective catalyst for NM the C/O ratio provided that thermal annealing is prevented
combustion and that FG sheet initiates the NM decomposition through process temperature control methods.
Applications of Graphene in Fuel/Propellant Combustion
NM on FGS CH3NO2H+
Quickly undergo
CH2NO2– additional reactions
Aci-ions
CH3NO
CH2NO2H–
Typical intermediate
+ NM
+ Other
intermediates
CH2ONO2H
CH2O
FIGURE 26.4  ​Complex flow of reactions for the nitromethane in presence of FG sheet is summarized.
Although, this is not considered as a use of graphene in
fuels/propellants for burn-rate enhancement, chemically
modified graphene as GO has been recognized as a prom-
ising flame retarding nanoadditive in polymers, for example
(see Higginbotham et  al. [2009]). However, according to
early reports, it can be easily decomposed with ignition upon
application of heat. Reduction of GO has been recognized
as highly exothermic, about 10 times the energy of the heat
input. The reduction reaction can be triggered at one end of
the GO film by hot soldering iron (~400°C) where the reac-
tion rapidly propagates through the whole film as shown by
Shi and Li (2011). The obtained reduced-GO was reported
very stable and no carbon combustion occurred after expos-
ing clean reduced-GO to a flame which is in good agreement
with the flame retardancy of GO. However, it is important to
note that the thermal stability of the reduced-GO significantly
decreases in the presence of alkali impurities such as potas-
sium salts. For example, self-propagating carbon combustion
is observed when reduced-GO is exposed to a flame in the
presence of even a small amount of KOH salts, perhaps due
to the canalization effect from the alkali metal. In addition,
GO solids containing potassium ions becomes highly flam-
mable in clear contrast to the expected good thermal stability
of pristine GO. Kim et al. (2010) also showed that GO strips
after extensive purification are flame retardant. Unfortunately,
the typical chemical exfoliation process for production of GO
sheets involves using oxidants such as KMnO4 or NaNO3.
Hence extensive removal of residual salts after chemical exfo-
liation is essentially important if GO or reduced-GO materials
395
OH
H2O
on FGS
CH2NO
Very reactive
O from NM
or another
intermediate
CH2ONO
Unstable
Decomposes
HNO2 CH2O NO
Oxidizes
CO, CO2, H2O
are to be used as flame retardants. Past research efforts are
summarized and discussed in Table 26.1.
26.3 ​COMMERCIALIZATION POTENTIAL
Although at this time, no serious ignition and combustion
related commercialization of the observations discussed here
is in process, the great potential of CNTs and graphene for
ignition and combustion enhancements should be perceivable/
possible. One reason that it is not yet so is that more research
and development activities are needed. Another ­reason is the
high price of the graphene at this stage of knowledge devel-
opment and manufacturing technology, despite the small
amounts used in these studies. The other issue is related to
potential health and environmental impacts of such nano-
structured materials, if beyond a yet-to-be-determined limit
amount escapes the combustion process and ends up in the
atmosphere. Although most studies indicated that the carbon
nanostructures burn during the combustion process, their
concentrations in the exhaust of the combustion systems in
which they are used are to be investigated.
26.4 ​CONCLUSIONS
Use of functionalized GO in fuels and propellants is considered
at its early stages of growth. However, initial results showed
great potential for future applications, particularly in the igni-
tion process and for burn-rate enhancement of their subsequent
combustion. Preliminary results from the light-activated fuel
396
TABLE 26.1
Applications of CNTs and Graphene in Ignition and
Combustion
Material
Researchers Used Application
Moy et al. (2002) CNTs 1%–15% by weight added to fuels
enhanced burning rate and acted
as ani-knock in SI engines
Choi et al. (2010) MWCNTs TNA (an explosive) and
MWCNTs creats a self-
propagating reactive wave which
generates high specific power
electricity
Aliev and Baughman CNTs CNT-guided combustion was
(2010) proposed as providing thrust for
microthrusters
Basha and Anand CNTs CNT-blended water-diesel
(2011) emulsion fuel was demonstrated
to deliver enhanced engine
thermal efficiency and reduction
of pollutants
Tewari et al. (2013) MWCNTs MWCNTs blended with biodiesel
showed enanced engine thermal
efficiency and reduction in
emission of pollutants
Chehroudi et al. SWCNTs Demonstrated light-activated
(2009, 2010), volumetrically distributed
Chehroudi (2011, ignition of liquid sprays and
2012a,b, 2013) gaseous fuel/air mixtures with
applications for rockets and
HCCI engines
Cote et al. (2009) GO First to demonsterate
photothermal reduction (with
Xenon flash). It was rapid, clean,
and versatile
Chehroudi (2011) GO Light-activated ignition of fuels
Sabourin et al. FG sheets Used nitromethane mixed with
(2009) FGO and demonstrated the
ignition and combustion rates
were substantially enhanced
over other nanostructured
material/fuel mixtures and at low
pressures (~4 MPa)
Liu et al (2012a,b) FG sheets Using AIMD simulation, showed
that catalytic activity originates
from lattice defect complexes
within graphene sheet
Higginbotham et al. Chemically Potential as flame retardant in
(2009) modified polymers
graphene
Shi and Li (2011) Reduced-GO No carbon combustion seen after
exposing clean reduced-GO to a
flame indicating flame
retardancy of GO. However,
even small addition of alkali
impurity such as
potassium salt reverses the
flame retardancy
Graphene Science Handbook
ignition with GO showed potential in volumetrically distrib-
uted ignition strategy, although comparatively higher ­ignition
energies, with respect to the as-produced CNTs, is an area
that needs improvement. Mixing FG sheets with nitromethane
showed substantial burn-rate enhancement at low pressures, a
result that is likely to be carried when other fuels/propellants
are tested in future. AIMD of the decomposition of nitrometh-
ane on FG sheets suggested catalytic reaction pathways aided
by structural defects in the graphene sheets where they were
functionalized on the surface, as hydroxides and carboxides.
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 27 Fabrication of Graphene-Based Porous
Materials and Their Applications
in Environmental Fields
Zhu-Yin Sui, Ding Zhou, and Bao-Hang Han

CONTENTS
Abstract...................................................................................................................................................................................... 399
27.1 Introduction...................................................................................................................................................................... 399
27.2 Preparation of Graphene-Based Porous Materials........................................................................................................... 400
27.2.1 Cross-Linking Method......................................................................................................................................... 400
27.2.1.1 Covalent Cross-Linking Method........................................................................................................... 400
27.2.1.2 Noncovalent Cross-Linking Method..................................................................................................... 402
27.2.2 In Situ Reduction Method..................................................................................................................................... 405
27.2.3 Chemical Activation Method................................................................................................................................ 406
27.2.4 Template-Directing Method................................................................................................................................. 408
27.3 Potential Applications........................................................................................................................................................410
27.3.1 Adsorption of Gases..............................................................................................................................................410
27.3.1.1 Hydrogen Adsorption..............................................................................................................................410
27.3.1.2 Carbon Dioxide Adsorption....................................................................................................................411
27.3.1.3 Ammonia Adsorption.............................................................................................................................413
27.3.1.4 Reactive Gas Adsorption........................................................................................................................413
27.3.2 Adsorption of Organic Dyes..................................................................................................................................414
27.4 Conclusion.........................................................................................................................................................................415
References...................................................................................................................................................................................415

ABSTRACT
Graphene, a two-dimensional single-layer sheet of sp -hybrid-
ized conjugated carbon lattice, has attracted intense interest
for its potential in various applications such as hydrogen stor-
age, carbon capture, and electrode material in electrochemical
energy devices. Graphene oxide sheets generally prepared by
the chemical exfoliation of graphite, possessing various reac-
tive functional groups such as hydroxyl, epoxy, and carbox-
ylic groups, are a vital building block to fabricate functional
porous materials. Graphene-based porous materials have
been prepared by various methods such as the cross-linking
method, in situ reduction method, chemical activation, and
template-directing method. The as-prepared graphene-based
porous materials show improved or excellent performance in
various fields. In this chapter, we will summarize the prepara-
tion of graphene-based porous materials, and their applica-
tions in the adsorption of gas and organic dyes. Furthermore,
graphene-based porous materials can be scaled up for practi-
cal application in the future due to their facile preparation,
low cost, and excellent adsorption performance.
27.1 INTRODUCTION
2 Graphene, a kind of two-dimensional (2D) carbon material,
has become a famous star for scientists in different fields
because of its appealing features such as large specific sur-
face area, high electric conductivity, excellent chemical sta-
bility, and potentially low manufacturing cost. Andre Geim,
Konstantin Novoselov, and their collaborators obtained exfo-
liated graphene for the first time in 2004.1 This discovery led
to Geim and Novoselov sharing the Nobel Prize in Physics
in 2010, and to a boom in the amount of research articles
related to graphene.2 Although perfect graphene with high
flexibility, large aspect ratio, and negligible thickness exhib-
its excellent charge mobility, chemical stability, mechanical
robustness, and high electrical conductivity,3 it is not an ideal
building block to construct functional materials due to dif-
ficulties in synthesis and poor processability. So far, many
other routes have been developed and achieved to prepare
graphene, including chemical vapor deposition (CVD),4 epi-
taxial growth on an insulator,5 bottom-up synthesis of gra-
phene from organic molecules,6 and chemical reduction of

399
400 Graphene Science Handbook

Graphene-based porous materials, which are a collection

TABLE 27.1 of graphene-related materials with porous structure, have
Advantages and Disadvantages of Several Methods attracted increasing attention in recent years. These gra-
to Prepare Graphene phene-based porous materials generally possess low density
and highly porous structures, which enable easy access and
Methods Advantages Disadvantages References
diffusion of ions and molecules through the porous structures.
Mechanical Low cost, less Low yield and [1]
Furthermore, these graphene-based porous materials possess
exfoliation of defects, excellent difficulty in
highly oriented charge mobility, preparing in a
large accessible surface area, which is important for achieving
pyrolytic high chemical large scale the maximum functionality of graphene-based porous materi-
graphite stability, and als. So far, scientists have found a great amount of promising
mechanical applications such as energy storage and conversion, cataly-
robustness sis, sensors, oil adsorption, and wastewater treatment.11–15 In
Epitaxial High quality and High raw material [5] this chapter, we will summarize the preparation of graphene-
growth on SiC graphene sheets and equipment based porous materials, and their applications in the adsorp-
with large size costs, high tion of gas and organic dyes.
growth
temperature
CVD High-quality, mass High cost [4] 27.2 PREPARATION OF GRAPHENE-
production, and BASED POROUS MATERIALS
graphene sheets
with large size
So far, various methods have been used to prepare graphene-
Chemical Large-scale Many defects, [7] based porous materials, as summarized below. For example,
reduction of production and poor mechanical these porous materials can be fabricated through the cross-
exfoliated low cost and electrical linking method via the interaction between graphene or GO
graphite oxide properties sheets and various kinds of inorganic or organic species, that
is, inorganic nanoparticles, polymers, biomolecules, and metal
ions. In addition, some other methods such as in situ reduction
exfoliated graphite oxide.7 Table 27.1 shows the advantages method, chemical activation, and template-­directing method
and disadvantages of several methods to prepare graphene. have also been used to produce graphene-based porous mate-
In these methods, chemical reduction of exfoliated graph- rials with special performance.
ite oxide is considered to be a common method to prepare
graphene on a large scale.7 A great amount of reductants
27.2.1 Cross-Linking Method
such as sodium borohydride, hydrazine, hydroquinone,
l-ascorbic acid, and aqueous alkaline solution have been Various kinds of graphene-based porous materials have been
applied to reduce graphene oxide (GO).8,9 Graphite oxide fabricated through the cross-linking method. The cross-­
can be typically prepared by reacting graphite powder with linking method used in the process of preparation of gra-
a strong oxidant such as KMnO4 in concentrated sulfuric phene-based porous materials can be divided into two types:
acid.8 Exfoliated graphite oxide sheets, termed GO sheets, the covalent cross-linking method and the noncovalent cross-
that can be obtained from exfoliation of oxidized graphene linking method.
sheets to form stable and single-layer suspensions in water
and other common polar solvents, possess various reactive 27.2.1.1  Covalent Cross-Linking Method
functional groups such as hydroxyl, epoxy, and carboxylic For the covalent cross-linking method, bi- or multifunctional
groups on their basal plane and edge.8 Therefore, GO could molecules are used as cross-linkers, in which the functional
be considered as an amphiphilic macromolecule composed groups can react with the oxygen-containing groups and the
of the hydrophobic aromatic domain and hydrophilic oxygen- carbon skeletons. For example, graphene-based hybrid porous
containing groups functionalized domain. It is well known materials were constructed by Zhang et  al. via the cross-­
that the oxygen-containing groups of GO sheets could be linking method through the reaction of organic diisocyanates
easily removed during the process of reduction of GO; how- with GO sheets. Figure 27.1 shows the formation process of
ever, the irreversible agglomeration also happens due to the the hybrid porous materials, in which the GO sheets are linked
increase in the π–π stacking interaction and van der Waals using the reaction of their hydroxyl and carboxyl groups on
forces between graphene sheets.7 The aggregation of gra- both sides with isocyanato groups. They reported the as-made
phene sheets will hamper the rapid mass transport, reduce porous materials possess a much enlarged Brunauer–Emmett–
the surface area, and consequently impact the performance Teller (BET) specific surface area (168 m2 g−1) compared with
of the as-prepared materials. In order to solve this problem the powdery GO (23 m2 g−1). The improved specific surface
and explore further advanced applications, the preparation of area could be due to the fact that the rigid organic diisocya-
graphene-based porous materials such as hydrogels, aerogels, nates acting as nanoscale spaces effectively limit the face-to-
and macroporous film, which usually possess high surface face stacking between GO sheets and hinder the aggregation
area and large porosity, is needed.10 of the sheets.16
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields 401

HOOC HOOC
HO OH O
COOH

HOOC OH
OH
COOH

NCO

NCO

HOOC HOOC
HO OH O
COOH
OH

HN O
O
O NH
HO
HOOC O
HOOC NH
O
O
NH NH
COOH
HOOC O O OH
O HOOC O
N OH
O OH
COOH H
OH
OH COOH
HOOC

NCO
NCO
NCO

or

NCO
NCO
NCO

FIGURE 27.1  Schematic illustration of the construction of graphite oxide hybrid porous materials (GHPMs) through cross-linking GO
sheets with organic diisocyanates. (Reprinted from Carbon, 47 (13), Zhang, D.-D.; Zu, S.-Z.; Han, B.-H., Inorganic–organic hybrid porous
materials based on graphite oxide sheets, 2993–3000, Copyright 2009, with permission from Elsevier.)

Burress et  al. synthesized porous GO framework (GOF)
materials by using the well-known reactivity between dibo-
ronic acid and hydroxyl groups of GO layers as shown in
Figure 27.2. They also reported that the as-prepared GOF
structures have tunable pore widths, volumes, and binding
sites depending on the linkers chosen.17 In a similar study,
Srinivas et al. reported the synthesis of porous GOFs by react-
ing GO sheets with various linear boronic acid pillaring units
in a solvothermal condition. The porous structures were also
constructed through boronate-ester formation as a result of
B–O bonding between boronic acids and oxygenated groups
of the GO sheets. Furthermore, the as-made porous materials
exhibit higher BET specific surface area (about 470 m2 g−1)
compared to that of GO (10 m2 g−1).18
The versatile functionalization of graphene with organic
molecules allows it to act as building block in constructing
metal–organic framework (MOF) hybrids or other porous
materials. Jahan et al. reported that benzoic acid-functional-
ized graphene (BFG) can act as a structure-directing template
in influencing the crystal growth of MOF.19 MOF nanowire
on BFG was fabricated as shown in Figure 27.3. In addition,
they indicated that the as-made hybrid material possesses a
BET specific surface area of 810 m2 g−1. Table 27.2 shows the
porous properties of some graphene-based porous materials
402 Graphene Science Handbook

(a)
Azeotropic
R R
OH HO removal O
B B
+ of water
R″ R″
–2H2O
OH HO R′ O
R′ Boronic ester

(b) OH
O Solvothermal
synthesis in
methanol at
OH OH O + 80°C
OH OH O –nH2O

O OH OH
GOF

FIGURE 27.2  Representations of (a) boronic ester and (b) GOF formation. Idealized GOF materials proposed in this study consist of GO
layers connected by benzenediboronic acid pillars. (Burress, J. W. et al.: Graphene oxide framework materials: Theoretical predictions and
experimental results. Angew. Chem. Int. Ed. 2010. 49 (47). 8902–8904. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with
permission.)

(220)

BFG

MOF

Nanowire

MOF/BFG

FIGURE 27.3  Schematic of proposed bonding between functionalized graphene and MOF via –COOH groups. (Reprinted with permis-
sion from Jahan, M. et al. Structure-directing role of graphene in the synthesis of metal–organic framework nanowire. J. Am. Chem. Soc.
132 (41): 14487–14495. Copyright 2010. American Chemical Society.)

prepared through the covalent cross-linking method. From
Table 27.2, we can find that the as-prepared graphene-based
porous materials through the covalent cross-linking method
possess high porosity, which plays an important role in the
fields of energy and environment.
27.2.1.2  Noncovalent Cross-Linking Method
For the noncovalent cross-linking method, various interac-
tions, including hydrogen bonding, π–π stacking, hydrophobic
interaction, electrostatic interaction, ion coordination, and
chemisorption, can perform as the driving forces for the for-
mation of graphene-based porous materials.
Cheng et  al. demonstrated a facile method to construct
GO-based hydrogels and organogels through the supramolecu-
lar self-assembly of amphiphilic molecules, which possess a
polar carbohydrate headgroup attached to a nonpolar pyrene
group. They indicated that the driving forces for the gelation pro-
cess could be ascribed to π–π stacking and hydrogen bonding
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields 403

interaction between GO sheets and the glycoconjugate-based

TABLE 27.2 gelators in both aqueous and organic solutions (Figure 27.4).23
Porous Properties of Some Graphene-Based Porous GO/DNA composite hydrogels with high mechanical strength,
Materials Prepared through Covalent Cross-Linking excellent environment stability, and high adsorption for dye
Method have been developed by Xu et  al. through a novel and facile
three-dimensional (3D) self-assembly method. The typical
Specific Surface Pore Volume
GO/DNA hydrogels can be prepared by mixing GO dispersion
Namea Area (m2 g−1) (cm3 g−1) References
and the aqueous solution of double-stranded DNA followed by
GHPM 168 0.37 [16]
heating the homogeneous mixture at 90°C for 5 min (Figure
GOF 470 – [17]
27.5a). During the heating process, the double-stranded DNA
PGF-1 825 0.74 [20]
was unwound to single-stranded DNA, which can bridge
GOBIN 920 0.40 [21]
adjacent GO sheets via strong noncovalent interactions. They
GTCF 440 0.34 [22]
indicated that the prepared hydrogels have a well-defined and
“–” Represents that the value is not given in the reference. interconnected 3D porous network as seen from scanning elec-
a The abbreviation of the as-prepared graphene-based porous materials is tron microscopy (SEM) image of their freeze-dried samples
given according to the original references. (Figure  27.5b and c). The pore diameters range from submi-
crometer to several micrometers.24 Zu et al. employed triblock

Self-assembly

Py1b
Hydrogen bond

GO

Self-assembly

FIGURE 27.4  Proposed structure of the formation of the GO hybrid hydrogel. (Reprinted with permission from Cheng, Q.-Y. et al.
Supramolecular self-assembly induced graphene oxide based hydrogels and organogels. Langmuir 28 (5): 3005–3010. Copyright 2012
American Chemical Society.)
404 Graphene Science Handbook

adsorbed with the hydrophilic PEO chains extend into water.

(a)
90°C
5 min
(b) (c)
5 μm 2 μm
FIGURE 27.5  Photographs of the formation of GO/DNA self-
assembled hydrogel (a); SEM images with low (b) and high (c) magnifi-
cations of GO/DNA self-assembled hydrogel interior microstructures.
(Reprinted with permission from Xu, Y. X. et al. Three-dimensional
self-assembly of graphene oxide and DNA into multifunctional
hydrogels. ACS Nano 4 (12): 7358–7362. Copyright 2010 American
Chemical Society.)
copolymer (poly(ethylene oxide)-block-poly(propylene oxide)-
block-poly-(ethylene oxide), PEO-b-PPO-b-PEO) as the sta-
bilizer for chemically exfoliated graphite oxide. The triblock
copolymer is an amphiphilic polymer containing hydrophobic
PPO and hydrophilic PEO segments. The aromatic area of
graphene or GO is hydrophobic, on which the PPO segments
Therefore, the dispersibility of graphene or RGO increased.
Furthermore, supramolecular hydrogel could be formed after
the addition of α-cyclodextrins, owing to the penetration of
PEO chains into the cyclodextrin cavities. 25
Graphene-based porous materials can be fabricated by
incorporating inorganic species between graphene sheets or
GO sheets such as inorganic nanoparticles and metal ions.
Many types of inorganic nanoparticles have been deposited
on graphene sheets, thus severing as the spacer in the hybrid
materials such as metal,26–28 metal oxides,29,30 polyoxometa-
lates (POMs),31,32 and quantum dots.33,34 In the hybrid system
of graphene–nanoparticle composites, inorganic nanoparti-
cles incorporated between graphene sheets effectively reduce
the aggregation between graphene sheets35; thus porous mate-
rials with a large surface area and even improved properties
could be fabricated.36 Zhou et al. reported a simple and effec-
tive method to prepare graphene-based nanoporous materials
with a large specific surface area by utilizing the interaction
between graphene sheets and POM nanoparticles.31 POM is a
kind of well-known cluster with a polynuclear metal-oxo struc-
ture37 and is considered a versatile inorganic building block for
fabrication of functional hybrid materials. Figure 27.6 shows
the schematic illustration of graphene–POM hybrid porous
materials. In this approach, the mixture of GO and POM is
homogeneous because both of them possess negative charge.
After the addition of hydrazine into the mixture, the graphene
sheets obtained from the reduction of GO are assembled with
POM through the driving force of chemisorption interaction
into 3D porous structures.

OH –OOC OH
OH
OH HO O
O COO–
HO
COO– COO– Hydrazine hydrate

Peroxide

o-GPOM POM HPB GPOM

FIGURE 27.6  Scheme of the formation process of GPOM and o-GPOM. (Zhou, D.; Han, B.-H.: Graphene-based nanoporous materials
assembled by mediation of polyoxometalate nanoparticles. Adv. Funct. Mater. 2010. 20 (16). 2717–2722. Copyright Wiley-VCH Verlag
GmbH & Co. KGaA. Reproduced with permission.)
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields
It was reported that a variety of metal ions can induce
the gelation of aqueous GO dispersion and the formation
of 3D porous materials owing to ion coordination between
the metal ions and oxygen-containing groups of GO sheets.
Bai et al. proposed that monovalent ions (e.g., K+, Li+, and
Ag+) cannot induce GO gelation, whereas divalent and tri-
valent ions (e.g., Ca2+, Mg2+, Cu2+, Pb2+, Cr3+, and Fe3+) can
promote the formation of GO hydrogels due to the strong
cross-­linking abilities resulting from the large coordination
stability constants between metal ions and hydroxyl and
carboxyl groups on GO sheets, as shown in Figure 27.7a.
The 3D network structure of the as-made hydrogels can be
clearly observed from the SEM images (Figure 27.7c) and
their morphology is similar to that of the lyophilized GO
dispersion (Figure 27.7b).38 Although many multivalent ions
can promote the gelation of GO, gelation time of GO sheets
is too short (usually only several seconds). It is very hard
to control the reaction process of the mixture and obtain
uniform hydrogels. Therefore, it is quite necessary to find
a method to prepare uniform GO hydrogels. Huang et  al.
designed a facile method to fabricate a uniform GO hydrogel
in a well-controlled way. In this method, glucono-δ-lactone
(GDL) is used as a hydrogel promoter to make the uniform
GO hydrogel. The hydrolysis product of GDL is gluconic
acid, which can decrease the pH value of the solution. They
showed that multivalent metal ions (e.g., La3+, Co2+, and Ni2+)
can assemble GO sheets into 3D porous structures with the
help of the hydrolysis product of GDL.39
(a)
1 2 3 4 5 6 7 8 9
(b) (c)
FIGURE 27.7  Photographs (a) of aqueous GO dispersions mixed
with different cross-linkers (1. 20 mM Li+; 2. 20 mM K+; 3. 20 mM
Ag+; 4. 15 mM Mg2+; 5. 9 mM Ca2+; 6. 3 mM Cu2+; 7. 3 mM Pb2+;
8. 3 mM Cr3+; 9. 3 mM Fe3+), SEM images of lyophilized GO dis-
persion (b) and (c) GO/Ca2+ hydrogel with 9 mM Ca2+. CGO = 5 mg
mL −1, and scale bar = 10 µm. (Reprinted with permission from Bai,
H. et al. On the gelation of graphene oxide. J. Phys. Chem. C 115
(13): 5545–5551. Copyright 2011 American Chemical Society.)
405
27.2.2  In Situ Reduction Method
GO and chemically reduced GO (RGO) (also called graphene
in this chapter) are favorable building blocks to construct
graphene-based porous materials. Recently, it has been found
that GO can be reduced to graphene and simultaneously
assembled in situ into a 3D macrostructure of the graphene
under a certain reducing environment, as shown below. The
3D porous graphene materials prepared by this method usu-
ally have pore sizes ranging from submicrometers to several
micrometers.
Hydrothermal routes have been extensively employed to
prepare graphene-based porous materials. Supercritical water
can play the role of reducing agent in hydrothermal conditions
and behaves like a fluid with strong electrolytic solvent power,
high diffusion coefficient, and dielectric constant that can be
comparable with that of polar organic molecules. In addition,
its physiochemical properties can be varied widely with pres-
sure and temperature.40 Shi et al. reported the synthesis of gra-
phene hydrogels by hydrothermal reduction of aqueous GO
dispersion for the first time. The typical graphene hydrogel
can be easily prepared by heating 2 mg mL −1 of homogeneous
aqueous GO dispersion sealed in a Teflon-lined autoclave at
180°C for 12 h (Figure 27.8a) and the obtained hydrogels with
high water content possess excellent electrical and mechanical
properties. In graphene hydrogel, the partial restacking in the
graphene sheets can create large out-of-plane pores and makes
it a well-defined and interconnected 3D porous network, as
(a) (b)
GO SGH
Before After 5 μm
(c) (d)
1 μm 500 nm
FIGURE 27.8  (a) Photographs of a homogeneous aqueous GO
dispersion (2 mg mL−1) before and after hydrothermal reduction at
180°C for 12 h; (b–d) SEM images with different magnifications of
the self-assembled graphene hydrogel (SGH) interior microstructures.
(Reprinted with permission from Xu, Y. X. et al. Self-assembled gra-
phene hydrogel via a one-step hydrothermal process. ACS Nano 4 (7):
4324–4330. Copyright 2010 American Chemical Society.)
406
shown in the SEM image of its freeze-dried sample (Figure
27.8b through d). In addition, they indicated that the as-made
graphene hydrogels exhibit a high specific capacitance of 160
F g−1 (1 A g−1).41
In addition to the synthesis of graphene hydrogels, gra-
phene-based porous composite materials can also be easily
prepared through hydrothermal reaction. For example, Au/
graphene hydrogel has been prepared by Li et al. through the
self-assembly of Au/graphene sheets under hydrothermal con-
ditions.42 Chen et al. reported the fabrication of a hierarchically
porous graphene–nickel hydroxide (hGN) hybrid hydrogel by
the hydrothermal treatment of a mixture of holey GO (hG)
and Ni(NO3)2 (Figure 27.9a). SEM images (Figure  27.9b)
reveal the large out-of-plane macropores in hGN, ranging
from several to tens of micrometers. In addition, the in-plane
pores of hGN can be observed by its high-resolution transmis-
sion electron microscope (TEM) images (Figure 27.9c and d),
which show the presence of mesopores of several nanometers
to tens of nanometers on the graphene sheets.43
Various reductants have also been applied to synthesize
graphene-based porous materials. Zhang et  al. reported the
fabrication of mechanically strong and electrically conductive
graphene aerogels obtained from either supercritical drying
or freeze drying of hydrogel precursors synthesized from the
reduction of GO with l-ascorbic acid. The as-prepared gra-
phene aerogel shows light weight (12–96 mg cm−3), high BET
specific surface area (512 m2 g−1), and large volume (2.5 cm3
g−1).9 Wang et  al. reported a green and mild method for the
synthesis of 3D structure of graphene. The porous graphene
materials were prepared based on the chemical reduction of
(a)
Ni(NO3)2
150°C
hG hGN
(c)
0.2 μm
FIGURE 27.9  Photographs of the formation of hGN (a), SEM images of freeze-dried hGN (b), and TEM images of hGN, showing that
the hybrid contains holey graphene sheets and Ni(OH)2 particles (c and d). (Chen, S. et al.: Hybrid hydrogels of porous graphene and nickel
hydroxide as advanced supercapacitor materials. Chem. Eur. J. 2013. 19 (22). 7118–7124. Copyright Wiley-VCH Verlag GmbH & Co. KGaA.
Reproduced with permission.)
Graphene Science Handbook
GO with the aid of a range of natural phenolic acids and self-
assembly of graphene sheets.44 Cong et al. reported a one-step
fabrication of macroscopic multifunctional graphene-based
hydrogels with robust interconnected networks using ferrous
ions as a reducing agent (Figure 27.10a, b).45 They demon-
strated that during the self-assembly of GO sheets, metal
oxide nanoparticles such as α-FeOOH nanorods and mag-
netic Fe3O4 nanoparticles are simultaneously deposited on
GO sheets. The as-prepared graphene hydrogel containing
about 96 wt% water exhibits a well-defined and intercon-
nected 3D network microstructure as shown in Figure 27.10c.
More interestingly, a large number of nanoparticles are homo-
geneously enwrapped in the graphene sheets seen from a mag-
nified SEM image (Figure 27.10d). In addition to l-­ascorbic
acid and natural phenolic acids, and ferrous ions, there are
many other reductants (NaHSO3, Na2S, HI, etc.) that can be
used to prepare graphene-based porous materials with high
porosity.46 Table 27.3 shows the characteristics of graphene-
based porous materials prepared through the reduction of GO
by using various reductants. It is believed that the formation
of 3D macrostructure of graphene sheets is due to the restored
conjugated domains and diminishing oxygenated groups,
which results in an increase in hydrophobic and π–π stacking
among the sheets.9,41,44
27.2.3 Chemical Activation Method
Chemical activation is a widely used method to prepare
activated carbons with many interesting properties such as
high specific surface area, good thermal stability, excellent
(b)
3 μm
20 μm
(d)
0.5 μm
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields 407

(a) (b)

Scale-up
0.5 h 1h 1.5 h 2.5 h 6h
100 times

(c) (d)

5 μm 200 nm

FIGURE 27.10  Photographs of the time-dependent formation process of the hydrogels with GO dispersions in the presence of FeSO4 (a),
Photograph of the scale-up synthesis of hydrogels (b), low- and high-magnified SEM images of the freeze-dried graphene/FeOOH hydrogel
(c and d). (Reprinted with permission from Cong, H. P. et al. Macroscopic multifunctional graphene-based hydrogels and aerogels by a metal
ion induced self-assembly process. ACS Nano 6 (3): 2693–2703. Copyright 2012 American Chemical Society.)

hydrophobic character, and high adsorption capacity for gas the chemical activation method. The new porous carbon mate-
storage. Compared with physical activation methods such as rial was prepared by the chemical activation of microwave-
using carbon dioxide or steam as gasifying agents, chemi- exfoliated graphite oxide (MEGO) and can be used as an
cal activation has been extensively applied to prepare porous electrode material in a supercapacitor. The activation process
materials due to its various advantages, for example, higher was carried out by treatment of MEGO with KOH. The acti-
yields, lower operating temperatures, and less activation time. vation temperature and KOH/MEGO ratio play an impor-
So far, many groups have utilized the chemical activation tant role in the synthesis process of porous carbon materials.
method to fabricated graphene-based porous materials. Furthermore, they showed that the as-prepared porous materi-
To the best of our knowledge, Ruoff et al. synthesized gra- als with high specific surface area and electrical conductiv-
phene-based porous materials with high BET specific surface ity enable supercapacitors with high energy storage capacity.51
area (3100 m2 g−1), high electrical conductivity (~500 S m−1), Zhang et  al. synthesized highly porous 3D graphene-based
and low oxygen and hydrogen content for the first time through bulk materials prepared from in situ hydrothermal polymeriza-
tion/carbonization of the mixture of cheap biomass or industry
carbon sources with GO and subsequent chemical activation
(Figure 27.11). They indicated the resulting graphene-based
TABLE 27.3
porous materials at the bulk scale exhibit ultrahigh BET spe-
Characteristics of Graphene-Based Porous Materials
cific surface area (3523 m2 g−1) and excellent bulk conductiv-
Prepared with Different Reductants ity (up to 303 S m−1). Meanwhile, they demonstrated that the
Specific Electrical obtained porous materials exhibit excellent performance for
Surface Area Conductivity supercapacitors in various electrolyte systems.52
Reductants (m2 g−1) (S m−1) References In addition to possessing excellent electrochemical perfor-
l-Ascorbic acid 512 63 [9] mance, graphene-based porous materials obtained from the
Dopamine 310 – [47] chemical activation method also exhibit excellent adsorption
NaHSO3 – 17 [46] capacity for various gases. Chandra et al. reported the fabri-
Na2S – 7 [46] cation of N-doped porous carbon with high specific surface
HI – 110 [46] area via chemical activation of polypyrrole functionalized
Gallic acid 299 34 [44] graphene sheets. The polypyrrole functionalized graphene
Gentisic acid 109 18 [44] sheets were prepared via chemical polymerization of pyrrole
Protocatechuic acid 140 13 [44] in GO dispersion using ammonium persulfate followed by
Mercaptoacetic acid – 54 [48]
reduction using hydrazine. They indicated that the as-made
Vanillic acid 184 23 [44]
N-doped porous materials exhibit adsorption selectivity to
Ferulic acid 347 25 [44]
carbon dioxide (4.3 mmol g−1) over nitrogen (0.27 mmol g−1)
Hydrazine 620 – [49]
at 298 K.53 Srinivas et  al. reported the synthesis of a range
l-Glutathione 315 2 [50]
of high surface area porous carbons from GO precursor with
“–” Represents that the value is not given in the reference. KOH chemical activation. They showed that the activation
temperature and GO to KOH ratio have a great effect on the
408 Graphene Science Handbook

Biomass Polymer

or
Hydrothermal Activation
+ Carbonization

Porous 3D
GO sheets Intermediate product
Graphene-based material

FIGURE 27.11  Schematic illustration of the simple and green process of synthesizing porous 3D graphene-based materials. (Reprinted
by permission from Macmillan Publishers Ltd. Sci. Rep., Zhang, L. et al. Porous 3D graphene-based bulk materials with exceptional high
surface area and excellent conductivity for supercapacitors. 3, copyright 2013.)

surface area and pore volume. The specific surface area, pore 27.2.4 Template-Directing Method
volume, and pore size distribution are tunable with KOH con-
centration and activation. It is reported that the optimum acti- Template-directing methods have been employed to fabri-
vation condition is found to be 800°C and 1:9 GO to KOH cate 3D graphene-based porous materials such as the emul-
ratio to obtain a porous material with the highest BET spe- sion technique,59 breath-figure method,60 and CVD,61,62 as
cific surface area (1900 m2 g−1) and the maximum total pore shown below. Guo et  al. reported the fabrication of hollow
volume (1.65 cm3 g−1). In addition, they also indicated that the GO spheres via a water-in-oil emulsion technique using the
as-prepared porous materials exhibit excellent adsorption for aqueous ammonia core as a soft template. The authors indi-
carbon dioxide and methane, making them very promising cated that the aqueous ammonia plays an important role in the
solid adsorbents for gas adsorption applications due to their formation of the soft template and the self-assembly of GO
low-cost production, tunable pore size/volume, easy synthe- sheets around the template. They proposed that GO sheets
sis, and high chemical stability.54 could be self-assembled into shells of microspheres through
Therefore, chemical activation is a useful method to pre- hydrogen bonds around water templates and a shell structure
pare graphene-based porous materials. Table 27.4 shows was formed around the soft template with the removal of
the porous properties of graphene-based porous materials aqueous ammonia. In addition, they indicated that the heat-
prepared through the chemical activation method. These treated GO spheres exhibit an enhanced cycle and rate perfor-
graphene-based porous materials prepared by this method mance compared with artificial graphite due to high electrical
commonly possess high specific surface area and large pore performance of graphene as well as the porous graphene
volume, which could be beneficial to various applications shells.59 The breath-figure method is a straightforward proce-
such as supercapacitors, hydrogen adsorption, carbon dioxide dure for the fabrication of large-area porous polymer films.63
capture, and so on. It can also be employed to prepare graphene-based porous
materials. Lee et al. reported the self-assembly of chemically
modified graphene platelets into mechanically flexible, mac-
TABLE 27.4 roporous carbon films via the breath-figure method.60 Owing
Porous Properties of Some Graphene-Based Porous to difficulty in dispersing GO sheets into organic solvent,
polymer-grafted GO sheets were first synthesized. Then, they
Materials Prepared through Chemical Activation
cast the dispersion onto a suitable substrate and exposed the
Method synthesized dispersion to a stream of humid air. The mac-
Specific Surface Pore Volume roporous film of polymer-grafted GO can be obtained after
Namea Area (m2 g−1) (cm3 g−1) References endothermic evaporation of the volatile organic solvent and
a-MEGO 3100 2.14 [51] subsequent drying as shown in Figure 27.12a. Upon pyrolysis,
GOF 470 – [17] a mechanically flexible and robust macroporous film compris-
PF16G-HA 3523 – [52] ing RGO sheets can be prepared. In addition, they indicated
a-NDC 1588 0.75 [53] that the as-made porous film also shows a few closely packed
GODCsol-800 1894 1.60 [54] macroporous structure and reveals an open porous morphol-
asMEG-O 3290 – [55] ogy (Figure 27.12b, c).
NG8 1336 0.68 [56] As discussed above, chemically derived graphene sheets
PIG8 936 0.52 [57] have been extensively applied to prepare graphene-based
GHTC-a 1646 0.82 [58]
porous materials due to the ease of preparation and process-
“–” Represents that the value is not given in the reference. ing. However, these as-made materials show low electrical
a The abbreviation of the as-prepared graphene-based porous materials is conductivity owing to severe structural defects in the gra-
given according to the original references. phene sheets during the exfoliation and reduction processes.
CVD is a common method to prepare highly conductive
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields 409

(a) Humid air flow
(b) (c)
2 μm 2 μm
FIGURE 27.12  Procedure for the self-assembly of RGO into mac-
roporous carbon films (a). Plane-view (b) and (c) 60°-tilted SEM
images of an RGO film. (Lee, S. H. et al.: Three-dimensional self-
assembly of graphene oxide platelets into mechanically flexible
macroporous carbon films. Angew. Chem. Int. Ed. 2010. 49 (52).
10084–10088. Copyright Wiley-VCH Verlag GmbH & Co. KGaA.
Reproduced with permission.)
graphene. Recently, CVD has been extensively used to pre-
pare graphene-based porous materials with high electrical
conductivity. Chen et al. reported a general strategy for the
synthesis of macroscopic 3D graphene foam using template-
directed CVD. They chose nickel (Ni) foam as a template
for the growth of graphene foams due to the porous struc-
ture with an interconnected 3D scaffold of nickel. In brief,
carbon was introduced into the nickel foam by decomposing
methane at 1000°C under ambient pressure. After the CVD
growth, the entire Ni foam surface was fully covered by a
continuous graphene film. They deposited a thin layer of
poly(methylmethacrylate) (PMMA) on the surface of the
graphene films as a support to prevent the graphene net-
work from collapsing during Ni etching. Graphene foams
can be obtained after carefully removing the PMMA layer
by hot acetone. The as-made graphene foams possess an
outstanding electrical conductivity due to the high quality
of the graphene sheets and their perfect connection in three
dimensions. In addition, they also demonstrated that gra-
phene foam/poly(dimethylsiloxane) composites exhibit great
potential for flexible, foldable, and stretchable conductors.61
Cao et al. also prepared 3D graphene foam by the template-
directed method using Ni foam as a sacrificial template.
They used ethanol as the carbon source to prepare graphene
networks (Figure 27.13a). Compared to other CVD pro-
cesses that use explosive carbon sources (e.g., methane), it is
safe and cheap to apply ethanol as the carbon source. After
removal of the Ni foam, the graphene sheets can replicate
the 3D network and porous structure of Ni foam, as shown
in Figure 27.13b, c.62
In the above-mentioned several reports using template-
directing methods to prepare porous materials, these as-made
porous materials with pore size generally limited in microm-
eter range have been obtained. However, fabrication of gra-
phene-based nanoporous materials, especially with pore size
smaller than 50 nm (mesopores) is needed, which may open
new application possibilities in various fields. Huang et  al.
synthesized nanoporous graphene foams (NGFs) with con-
trollable pore size (30–120 nm) and ultra-high pore volumes
(~4.3 cm3 g−1) through the hydrophobic interaction driven
hard templating approach. They chose methyl group grafted

(a)
Ethanol-CVD

Ni foam 3D graphene networks

(b) (c)

500 μm 200 μm

FIGURE 27.13  Schematic illustration of the synthesis of 3D graphene networks on Ni foam by ethanol-CVD (a), SEM images of 3D gra-
phene networks grown on Ni foam after CVD (b), and 3D graphene networks after removal of Ni foam (c). (Reprinted from Cao, X. et al.:
Preparation of novel 3D graphene networks for supercapacitor applications. Small. 2011. 7 (22). 3163–3168. Copyright Wiley-VCH Verlag
GmbH & Co. KGaA. Reproduced with permission.)
410 Graphene Science Handbook

: –CH3 modified silica sphere Graphene oxide

I Assembly

II

Calcination/HF
etching

NGFs GO/silica spheres composite

FIGURE 27.14  Schematic illustrations of the formation process of the NGFs. (I) The self-assembly occurs between GO sheets and hydro-
phobic silica templates and (II) calcination and silica etching to produce NGFs. (Huang, X. D. et al.: Functional nanoporous graphene foams
with controlled pore sizes. Adv. Mater. 2012. 24 (32). 4419–4423. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with
permission.)

silica spheres with a hydrophobic surface and uniform size as
the hard template. It is well known that GO sheets possess a
hydrophobic nature. The silica templates and GO sheets can
form lamellar-like structures (silica spheres wrapped between
GO sheets) when the silica spheres are mixed with GO sheets
in a neutral aqueous solution. The nanoporous foams com-
prising RGO sheets can be prepared by calcining the as-made
composites obtained in the first assembly step under atmo-
sphere to reduce GO sheets into graphene followed by hydro-
fluoric acid (HF) etching to remove silicas (Figure 27.14).64
27.3  POTENTIAL APPLICATIONS
Graphene-based materials, as a result of distinct structural
and electric properties, are being increasingly investigated
for their potential applications in traditional fields such as
supercapacitors, lithium ion batteries, solar cells, and fuel
cells. The high electrical conductivity enables these gra-
phene-based materials exhibit excellent electrochemical per-
formances. More recently, a number of new application areas
have emerged due to graphene-based porous materials pos-
sessing other excellent properties such as high surface area
and large porosity.
Environmental pollution by water-soluble toxic pollut-
ants and noxious greenhouse gases is causing great concern
around the world. There has been a great interest in the devel-
opment of new adsorbents. Recently, graphene-based porous
materials have attracted extensive attention due to their excel-
lent properties such as high surface area, tunable pore size,
large porosity, and various functional groups. In this part,
we will present a brief review of some work using graphene-
based porous materials as adsorbents in the adsorption of gas
and organic dyes.
27.3.1  Adsorption of Gases
Graphene, like other carbon-based materials, is light and
cheap in comparison to other solid-state gas adsorbents.
Meanwhile, graphene-based porous materials also possess
high specific surface area and chemical stability. Therefore,
graphene-based porous materials are good choices for the
adsorption and storage of various gases.
27.3.1.1  Hydrogen Adsorption
In the race to develop the next generation of clean fuel, hydro-
gen is one of the main contenders. Hydrogen storage is one of
the main issues for the development of fuel cell electric vehicles
before hydrogen can become a widespread energy source in prac-
tical applications. Scientists around the world are trying to find
safe, economic, practical, and convenient methods for hydrogen
storage. At present, a lot of porous materials have been used as
adsorbents for hydrogen storage, for example, zeolites, MOFs,
and microporous carbon.65–70 The basic requirements of hydro-
gen storage materials are large surface area and high porosity.71
Graphene has recently attracted attention as a promising storage
medium. Graphene-based porous materials are a new type of
hydrogen storage materials due to their highly porous structure,
large surface area, light weight, and high stability.
Theoretical calculations have predicted that regular or irreg-
ular combinations of sp3-bonded carbon atoms and graphene
fragments are favorable to the adsorption of hydrogen.72 Many
groups have explored the promising application of graphene and
its derivatives in the field of hydrogen storage. Srinivas et al.
showed that chemically reduced graphene obtained from the
reduction of a colloidal suspension of exfoliated graphite oxide
can store hydrogen. The as-made materials with a BET spe-
cific surface area of 640 m2 g−1 exhibited a hydrogen adsorption
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields
1.2
1.0
H2 uptake (wt%)
0.8
9
0.6
Qst (kJ mol–1)
7 0.0
0.4
5
0.2
0.0 0.4
H2 (wt%)
0.0
0 2 4 6
P (bar)
FIGURE 27.15  Hydrogen uptake isotherms at various tem-
peratures. Inset: Isosteric heat of adsorption as a function of gas
uptake. (Burress, J. W. et al.: Graphene oxide framework materials:
Theoretical predictions and experimental results. Angew. Chem. Int.
Ed. 2010. 49 (47). 8902–8904. Copyright Wiley-VCH Verlag GmbH
& Co. KGaA. Reproduced with permission.)
capacity of 1.2 and 0.1 wt% at 77 and 298 K, respectively.73
GO sheet is also a useful building block to construct porous
materials for hydrogen adsorption. Calculations carried out by
Burress et  al. showed that GOF has a potential for hydrogen
storage. GOFs were prepared through the well-known reaction
between boronic acids and hydroxyl groups of GO sheets, and
the as-made porous materials possess a BET specific surface
area of 470 m2 g−1. They predicted that the GOF can theoreti-
cally achieve a hydrogen uptake of ca. 6.1 wt% at 77 K and
1 bar. However, the as-made GOF exhibited a hydrogen uptake
of 1.0 wt% at 1 bar (Figure 27.15).17 In a similar way, Srinivas
et al. reported detailed synthesis of porous GOFs by reacting
GO sheets with linear boronic acid pillaring units in a solvo-
thermal reaction. They showed that the obtained framework
pillared by 1,4-phenyldiboronic acid had a maximum adsorp-
tion capacity of 1.2 wt% for hydrogen at 77 K and 10 bar.18
Zhou et al. reported a kind of graphene-based nanoporous
material prepared through assembling graphene sheets medi-
ated through POM nanoparticles. They used POM nanopar-
ticles as the spacer to increase the distance between graphene
sheets in order to fabricate 3D graphene-POM (GPOM) with
large specific surface area and high porosity. They reported
that the as-prepared graphene-based hybrid material pos-
sesses a specific area of 680 m2 g−1. The GPOM can be oxided
into o-GPOM due to the redox ability of the POM. The as-
made graphene-based nanoporous material exhibits excellent
adsorption capacity for hydrogen and the hydrogen uptake can
increase from 0.8 wt% of GPOM to 1.3 wt% of o-GPOM by
tuning the redox state of the POM, as shown in Figure 27.16,
indicating that the GPOM exhibits a controllable hydrogen
adsorption–desorption capacity.31
411
1.4
77 K 1.2 o-GPOM
Hydrogen uptake (wt%)
1.0
87 K 0.8
GPOM
0.6
0.4
0.2
0 200 400 600 800
Absolute pressure (mmHg)
0.8
FIGURE 27.16  Hydrogen uptake isotherms of GPOM (squares)
and o-GPOM (triangles) performed at 77 K. 1 mmHg = 1.33 × 102
8 Pa. (Zu, S.-Z.; Han, B.-H.: Aqueous dispersion of graphene
sheets stabilized by pluronic copolymers: Formation of supramo-
lecular hydrogel. J. Phys. Chem. C. 2009. 113 (31). 13651–13657.
Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced
with permission.)
Recently, MOFs have been considered to be promising
hydrogen storage media as MOFs exhibit high surface area and
tunable pore size. Graphene-based MOFs have been reported
by several groups due to their high porosity, adsorption capac-
ity for specific gases, and electric properties.19,74,75 Liu et al.
reported the preparation of hybrid composites (denoted as CG)
based on Cu–BTC [Cu3(BTC)2(H2O)3; BTC = benzene-1,3,5-
tricarboxylate] and GO layers with different percentages of
GO. They found that the nano-sized and well-dispersed Cu–
BTC induced by the incorporation of GO greatly improves
the hydrogen storage performance of the composites. The
as-made materials exhibit about a 30% increase in hydrogen
storage capacity (from 2.81 wt% of Cu–BTC to 3.58 wt% of
CG-9 at 77 K and 42 atm).74
Although graphene-based porous materials exhibit huge
potential in hydrogen storage, the adsorption capacity of these
porous materials for hydrogen is still extremely limited due to
their surface area being much lower than the theoretically pre-
dicted value for pristine graphene. In addition, many groups
have reported that the introduction of metal could enhance
hydrogen uptake capacity. Lee et al. demonstrated that indi-
vidually dispersed calcium-decorated graphene-based nano-
structures could serve as a high-capacity hydrogen storage
medium using the first-principles method. The Ca-decorated
zigzag graphene nanoribbon was calculated to be 5 wt%
under ambient conditions.76 Du et  al. reported theoretical
predictions that Li-decorated porous graphene is potentially
capable of adsorbing hydrogen up to 12 wt%. Therefore, in
order to further improve the hydrogen uptake capacity of gra-
phene-based porous materials, the introduction of metal into
graphene-based porous materials is also needed.
27.3.1.2  Carbon Dioxide Adsorption
The current scientific community is extensively involved in
developing novel materials for environmental applications.
412
Removal of carbon dioxide from the atmosphere is one of
the most important applications. The accumulation of carbon
dioxide in the atmosphere is responsible for climate change.
Therefore, the capture and storage of carbon dioxide at low
cost are very important for achieving substantial reduction.
Currently, there have been some new technologies adopted
for carbon dioxide adsorption. For example, the aqueous
amine technology and simple ammonia solution method are
employed for absorption in industry by chemisorptive forma-
tion of N–C bonded carbamate (bonding energies, ~100 kJ
mol−1), which has shown many advantages over other state-
of-the-art carbon dioxide capture technologies.77 However,
this technology requires high energy for recycling and suffers
from a corrosion problem. Adsorption on solid adsorbents is
considered to be one of the promising methods for efficient
adsorption of carbon dioxide. Recently, graphene-based
porous materials have been adopted as solid adsorbents for
carbon dioxide adsorption.
It is well known that carbon dioxide is slightly acidic,
and the basicity of adsorbents in surface chemistry plays an
important role in the adsorption capacity of carbon dioxide.
It is reported that the introduction of basic sites could greatly
enhance carbon dioxide adsorption performance. Different
groups have prepared graphene-based porous materials with
basic character for carbon dioxide adsorption. Yang et  al.
reported the preparation of graphene-based porous silica
sheets impregnated with polyethyleneimine (PEI).78 In this
work, they demonstrated that graphene-based mesoporous sil-
ica (G-silica) can serve as an efficient carrier support for PEI
(denoted as PEI/G-silica) via a nanocasting technology. The
as-prepared PEI/G-silica sheets show excellent carbon diox-
ide adsorption behavior due to their thin nature, high amine
density, and high heat conductivity. As shown in Figure 27.17a
and b, PEI/G-silica sheets exhibit a very stable adsorption/­
desorption cycle performance with a high adsorption capacity
of 171 mg g−1 at 75°C and 1 atm. However, PEI/silica sheets
show evident adsorption capacity decay for carbon dioxide
(a) 100
PEI/G-silica sheets
80
Concentration of CO2 (%)
60
40
20
0 0
0 300 600 900
Time (min)
FIGURE 27.17  (a) Carbon dioxide adsorption/desorption curves of PEI/G-silica sheets (flue gases: 15% carbon dioxide+85% nitrogen;
adsorption temperature: 75°C; desorption temperature: 120°C). (b) Cycle performance of PEI/G-silica and PEI/silica sheets (adsorption tem-
perature: 75°C; desorption temperature: 120°C). (Yang, S. et al.: Graphene-based porous silica sheets impregnated with polyethyleneimine for
superior CO2 capture. Adv. Mater. 2013. 25 (15). 2130–2134. Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.)
Graphene Science Handbook
capture during the cycle processes. Elements such as nitrogen,
oxygen, and sulfur can also increase the basic character in
carbonaceous materials. Chandra et al. reported that N-doped
porous carbon could be produced via the chemical activa-
tion of the polypyrrole–graphene composite.53 The polypyr-
role–graphene composite activated at 600°C possessed a
maximum carbon dioxide adsorption capacity (4.3 mmol
g−1) at 25°C and 1 bar. They also showed that the as-made
porous materials could be used for selective adsorption of
carbon dioxide over nitrogen. Metal oxides with basic sites
can be used as adsorbent for carbon dioxide adsorption. Many
kinds of metal oxides exhibit excellent performance for car-
bon dioxide adsorption such as manganese oxide and calcium
oxide. Zhou et  al. prepared graphene–Mn3O4 hybrid porous
materials by a hydrothermal reaction of the aqueous disper-
sion of MnO(OH)2 and GO. The synthesis of Mn3O4 and the
reduction of GO could proceed simultaneously. The as-made
hybrid porous materials exhibit a maximum carbon dioxide
adsorption capacity of about 11 wt% at 273 K and 1 bar. They
showed that two main factors could affect the carbon dioxide
adsorption capacity, the surface area and basic sites.79
Besides the introduction of basic sites, the specific surface
area and the porosity of the adsorbents can also increase the
carbon dioxide adsorption capacity. Srinivas et  al. reported
the synthesis of a range of graphene-derived porous carbon
with high surface area through chemical activation with KOH
from thermally exfoliated GO and solvothermally RGO pre-
cursors.54 They showed that the porous materials activated at
800°C show maximum adsorption capacities for both carbon
dioxide and methane gas. The high adsorption capacity could
be ascribed to the porous nature of the samples as well as
the high surface area. Ning et  al. reported the synthesis of
porous graphene with nanomeshes by a CVD method using
porous MgO layers as a template. The porous graphene pos-
sesses a high BET specific surface area of 2038 m2 g−1 and
micropores of approximately 1 nm. They showed that the as-
made porous material can be a promising material for carbon
(b) 200
180 PEI/G-silica PEI/silica
160
CO2 adsorbed (mg g–1)
140
120
100
80
60
40
20
1200 1500 2 4 6 8 10 12 14 16 18 20
Cycle number
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields 413

dioxide adsorption (36.5 mmol g−1 at 274 K and 3.1 MPa). GO foams by unidirectional freeze-drying technology. They
They proposed that the good performance in gas adsorption showed that the as-made porous materials possess a high
could be attributed to its porous structure and large corruga- adsorption capacity for SO2 and convert it to SO3; meanwhile,
tions. In addition, they also showed that the as-made porous the GO foams themselves can be reduced and turn black.
material is selective for the adsorption of carbon dioxide over They also compared the aqueous GO suspensions and the
methane and hydrogen.80 Liu et  al. reported the preparation GO foams for the adsorption of SO2. The results indicate that
of GO@Cu-based MOF porous composites containing nano- the redox reaction between GO and SO2 is more rapid and
sized and well-dispersed Cu–BTC crystallites on the layers of effective in GO suspensions.84 Huang et al. reported chemi-
GO. They indicated that the composites exhibit about a 30% cally cross-linked 3D GO aerogels with large specific surface
increase in carbon dioxide storage capacity (from 6.39 mmol area and outstanding mechanical performance. These aero-
g−1 of Cu–BTC to 8.26 mmol g−1 of CG-9 at 273 K and 1 atm). gels are fabricated by assembling 2D GO sheets into uniform,
The enhanced carbon dioxide adsorption capacity could be 3D hydrogel networks followed by supercritical fluid drying.
attributed to the increased micropore volumes and BET spe- They also indicated that the as-made aerogels possess super-
cific surface area of the composites.74 high chemical activity toward reactive gases such as H2S, HI,
Wood et al. used density functional theory calculations to and SO2.85 Table 27.5 displays the gas adsorption capacities of
determine the effect of chemical functionalization on gas the as-prepared graphene-based porous materials. These data
binding to exposed edges within model zigzag graphene indicate that graphene-based porous materials possess great
nanoribbons. The authors showed that the presence of polar potential in the fields of gas adsorption.
groups (COOH, NO2, H2PO3, and NH2) is beneficial to
enhancing carbon dioxide adsorption capacity, making the
edges potentially viable binding sites in materials with high TABLE 27.5
concentrations of edge carbons.81 This result has important Gas Adsorption Capacities of the As-Prepared
implications for improving carbon dioxide uptake in gra- Graphene-Based Porous Materials
phene-based porous materials that are known to have high Specific
quantities of edge carbons. Surface Area Gas Adsorption
Namea (m2 g−1) Capacity References
27.3.1.3  Ammonia Adsorption
GOF 470 1.0 wt% (hydrogen, 77 K [17]
GO consists of distorted graphene layers bearing carbonyl, and 1 bar)
hydroxyl, and epoxy groups on the basal planes as well as Graphene 640 1.2 wt% (hydrogen, 77 K [73]
carboxylic groups on the edges of the carbon sheets, which powder and 1 bar)
have strong interaction with the ammonia. Composites of the o-GPOM 680 1.3 wt% (hydrogen, 77 K [31]
MOF-5 and GO with different ratios of the two components and 1 bar)
are prepared and tested as ammonia absorbent under dry PGFs 825 1.2 wt% (hydrogen, 77 K [20]
conditions. Owing to the synergy of the large surface area of and 1 bar)
MOF-5 and the acidic groups on GO, the GO−MOF-5 materi- GOBIN 920 1.2 wt% (hydrogen, 77 K [21]
als show good performance as ammonia adsorbents, and the and 1 bar)
adsorption capacity of the composites increases with increas- a-NDC 1588 18.9 wt% (carbon dioxide, [53]
298 K and 1 bar)
ing GO content and is always higher than that of MOF-5.75,82
PIG6 534 13.2 wt% (carbon dioxide, [57]
POM, which is also a heteropolyacid, has strong Brønsted
298 K and 1 bar)
acidity, and the reaction of POM with ammonia results in the
GMNO-4 541 11.4 wt% (carbon dioxide, [79]
formation of ammonium salt. Adsorbents for ammonia were 273 K and 1 bar)
prepared by modifications of graphite oxide with the addition CG-9 1532 36.3 wt% (carbon dioxide, [74]
of a polymer followed by impregnation with either one of two 273 K and 1 bar)
different POM clusters, tungstophosphoric acid (H3PW12O40) NG8 1336 25.5 wt% (carbon dioxide, [56]
and molybdophosphoric acid (H3PMo12O40). In the hybrid 273 K and 1 bar)
material, ammonia is retained on the surface via interac- PGFs 825 7.2 wt% (carbon dioxide, [20]
tions with graphite oxide functional groups or with the POM 273 K and 1 bar)
clusters. The high acidity of those POMs combined with the GTCF 440 11.7 wt% (carbon dioxide, [22]
functionalities and acidity of graphite oxide are expected to 273 K and 1 bar)
initiate strong interactions with ammonia.83 GOBIN 920 14.2 wt% (carbon dioxide, [21]
273 K and 1 bar)
27.3.1.4  Reactive Gas Adsorption GODCsol-800 1894 72.1 wt% (carbon dioxide, [54]
300 K and 20 bar)
Graphene-based porous materials can also be utilized as
adsorbents for reactive gas adsorption such as SO2, H2S, and “–” Represents that the value is not given in the reference.
HI. Chemical bond formation could occur between functional a The abbreviation of the as-prepared graphene-based porous materials is

groups of the as-prepared porous materials and reactive gas given according to original references.
during the adsorption process. Long et  al. prepared porous
414
27.3.2  Adsorption of Organic Dyes
Toxic chemical dyes are frequently used in the textile, print-
ing, and paper industries. Dye wastewater has become a big
problem and attracts extensive concern around the world.
Adsorption is considered to be an effective method to solve
this problem. Adsorption is a surface phenomenon, where
pollutants are adsorbed on the surface of the adsorbent. Many
factors can affect the adsorption capacity of adsorbent such as
temperature, concentration of pollutants, contact time, nature
of the adsorbate and adsorbent, and pH value.86 Carbon-based
materials have been used as adsorbents for wastewater treat-
ment, such as activated carbon87 and carbon nanotubes.88,89
Recently, graphene-based porous materials have been widely
used for the adsorption of organic dyes due to their large sur-
face area, pore volume, and presence of surface functional
groups in these materials.
Tiwari et  al. reported the preparation of 3D RGO-based
hydrogels by the reduction of GO using sodium ascorbate.90
They showed that graphene sheets can be self-assembled into
a well-defined and interconnected 3D porous network through
strong van der Waals and π–π interactions. In addition, they
also indicated that the 3D RGO-based hydrogels show excel-
lent removal capabilities for MB (~100%) and RhB (~97%)
due to adsorption through strong π–π stacking and anion–
cation interactions. Sui et al. prepared carbon nanotube–gra-
phene hybrid aerogels by supercritical carbon dioxide drying
of their hydrogel precursors. Carbon nanotube–graphene
hybrid hydrogels can be fabricated from heating the aqueous
GO dispersion and carbon nanotubes with vitamin C with-
out stirring. They employed two kinds of carbon nanotubes,
pristine multiwalled carbon nanotubes (MWCNTs) and acid
treated multiwalled CNTs (c-MWCNTs). The as-made aero-
gels exhibit promising performance in the removal of organic
dyes. They showed that the graphene–c-MWCNT hybrid aero-
gel possesses a larger adsorption capacity than the graphene–
MWCNT hybrid aerogel for three basic dyes (methylene blue,
rhodamin B, and fuchsin) because the graphene–c-MWCNT
hybrid aerogel has higher oxygen content, which is favorable
(a) 2.5
0h
12 h
Percentage of dye removal
2.0
24 h
1.5
Absorbance
1.0
0.5
0.0
400 500 600
Wavelength (nm)
FIGURE 27.18  (a) Absorption spectra of aqueous basic fuchsine solution on the top of hydrogel. (b) Percentages of dye removal by the
hydrogel at different times; the inset shows the digital images of dye removal (at 0, 12, and 24 h from left to right). (Reprinted with per-
mission from Cheng, Q.-Y. et al. Supramolecular self-assembly induced graphene oxide based hydrogels and organogels. Langmuir 28 (5):
3005–3010. Copyright 2012 American Chemical Society.)
Graphene Science Handbook
to the electrostatic interaction between the hybrid aerogel and
positively charged basic dyes.91 Li et al. reported the prepa-
ration of calcium alginate immobilized GO composites.
They indicated that the as-made composites exhibit excellent
adsorption capacity for methylene blue and the maximum
adsorption capacity obtained from the Langmuir isotherm
equation is 181.8 mg g−1. In addition, they also investigated
the effects of pH, contact time, temperature, and dosage on
the adsorption properties of methylene blue onto calcium
alginate immobilized GO composites. Cheng et al. reported
the synthesis of 3D GO-based gel networks through the self-
assembly of a series of amphiphilic molecules. They stud-
ied the adsorption capacity of the obtained supramolecular
hydrogel using basic fuchsine as the model dye. They showed
the as-made hydrogel exhibits good adsorption capacity for
basic fuchsine and about 96% of the dye can be adsorbed by
the hydrogel (Figure 27.18a and b). This is because GO hydro-
gels show negative charges, which exhibit high affinity to the
positively charged dye molecules.23
Gao et al. presented a one-step method to prepare polydo-
pamine-modified graphene hydrogel (PDA-GH). In the work,
PDA is expected to be the active site for synthetic dyes and other
organic pollutants through electrostatic or hydrogen bonding
interactions. They found that the as-prepared PDA-GH exhib-
its improved adsorption capacities toward rhodamine B com-
pared with the hydrothermally synthesized graphene hydrogel
(HT-GH). Figure 27.19a shows the adsorption of rhodamine B
at different initial concentrations at room temperature. They
showed that PDA-GH possesses a higher maximum adsorp-
tion capacity for rhodamine B (207.1 mg g−1) than HT-GH
(148.4 mg g−1). In addition, they found that PDA-GH exhibits
high adsorption capacities for rhodamine B without signifi-
cant decline after 10 repeated adsorption and desorption treat-
ments using ethanol as the desorption agent (Figure 27.19b).92
Xu et al. prepared multifunctional hydrogels through the 3D
self-assembly of GO sheets and DNA. They chose safranine
O as a model dye and studied the adsorption capacity of the
as-prepared graphene-based hydrogels. The results indicate
(b)
100
80
60
40
20
0
0 5 10 15 20 25
Time (h)
Fabrication of Graphene-Based Porous Materials and Their Applications in Environmental Fields 415

(a) (b)
Rhodamine B PDA-GH Rhodamine B
200 200 PDA-GH

qe (mg g–1)

qe (mg g–1)
HT-GH
100 100 HT-GH

0 0
0 200 400 600 0 2 4 6 8 10
Ce (mg L–1) Cycle number

FIGURE 27.19  Adsorption behaviors of rhodamine B on PDA-GH and HT-GH: (a) adsorption isotherm plots and curving fitting by
Langmuir (dot line) and Freundlich (solid line) models of rhodamine B on PDA-GH and HT-GH, and (b) adsorption capacities of PDA-GH
and HT-GH as a function of repeated adsorption–desorption cycles for the removal of rhodamine B. (Reprinted with permission from Gao,
H. et al. Mussel-inspired synthesis of polydopamine-functionalized graphene hydrogel as reusable adsorbents for water purification. ACS
Appl. Mater. Interfaces 5 (2): 425–432. Copyright 2013 American Chemical Society.)

that the obtained hydrogels possess a high adsorption capacity
(960 mg g−1) and 100% of the dye can be adsorbed after 24 h.
They considered that the high adsorption performance is par-
tially ascribed to the strong electrostatic interactions between
positively charged safranine O and negatively charged GO as
well as DNA. In addition, the porous structure of hydrogel
and abundant conjugated domains of GO also play an impor-
tant role in increasing the contact opportunity and affinity of
dye molecules on GO sheets.24
It is reported that these 3D porous materials are more effi-
cient absorbents for organic pollutants than 2D graphene mate-
rials, because they inhibit the restacking problem that often
occurs during the formation of RGO materials.89 Therefore,
graphene-based porous materials have promising application
in solving the problem of dye wastewater pollution.
27.4 CONCLUSION
As we have illustrated in this chapter, there are many meth-
ods for preparing graphene-based porous materials, including
the cross-linking method, in situ reduction method, chemical
activation, and template-directing method. The large surface
area, high stability, and environmentally friendly nature of
these porous materials make them potential candidates for
various applications such as hydrogen adsorption, carbon
dioxide gas capture, and reactive gas adsorption, as has been
demonstrated in this chapter.
Substantial progress has been made in the synthesis, char-
acterization, and application of graphene-based porous mate-
rials over recent years. Special attention has been paid to the
use of graphene-based porous materials at large scale and
low cost in an environmentally friendly way, and to improv-
ing the performance of these porous materials to make the
production commercial. However, the actual application of
graphene-based porous materials is virtually untapped. In
the near future, researchers from all over the world will con-
tinue their work on graphene-based porous materials, and
the scientific and technological innovations they bring for-
ward could have a great effect in this area and bring about
important applications of graphene-based porous materials in
the adsorption of gas and organic dyes.
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418 Graphene Science Handbook

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g raphene oxide-based hydrogels for the efficient cap-
­ Mussel-inspired synthesis of polydopamine-functionalized
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173–182. tion. ACS Appl. Mater. Interfaces 5 (2): 425–432.
 28 Graphene New Energy Material

Hongying Hou, Xianxi Liu, and Jinhui Peng

CONTENTS
Abstract.......................................................................................................................................................................................419
28.1 Preface...............................................................................................................................................................................419
28.2 Graphene for Lithium-Ion Batteries................................................................................................................................. 420
28.2.1 Graphene Anode Active Materials....................................................................................................................... 421
28.2.2 Graphene-Based Hybrid Anode Materials........................................................................................................... 422
28.2.3 Graphene-Based Cathode Active Materials......................................................................................................... 424
28.2.4 Graphene-Based Current Collector...................................................................................................................... 425
28.3 Graphene for Fuel Cells.................................................................................................................................................... 425
28.3.1 Graphene-Based Catalyst Support........................................................................................................................ 426
28.3.2 Graphene-Based Catalyst in Alkaline or Neutral Medium.................................................................................. 429
28.3.3 Graphene-Based Polymer Electrolyte Membrane for Fuel Cells......................................................................... 429
28.4 Conclusions and Prospects............................................................................................................................................... 430
Acknowledgments...................................................................................................................................................................... 430
References.................................................................................................................................................................................. 430

ABSTRACT boom of new alternative energies. Owing to the continuing

During the next decades, the world’s energy system may radi-
cally change with higher energy consumption by cleaner and
more efficient methods. Fundamental and applied research
about materials and processes, involved in each stage of the
energy-generating chain (storage, distribution, and use), will
be pivotal in facing this global challenge in a cleaner, safer,
more efficient, and economical way. As continuously being
pursued, integration in size and maximization in performance
will dominate the development trend of the next genera-
tion of power sources, which can be motivated and provoked
by the emerging of new-energy materials and technologies.
Graphene, a new two-dimensional member of the carbon fam-
ily, possesses extraordinary properties, including the highest
electron conductivity and mechanical strength as well as high
hydrogen storage, etc., among all current materials and it is
highly expected to be a promising potential energy material to
improve the performances of various power sources. Since its
successful availability by mechanical exfoliation in the lab in
2004, great progress has been made in the energy field with
graphene as an active material. In this chapter, the state-of-the-
art developments in graphene’s applications for clean energy
systems including lithium-ion batteries and fuel cells especially
within 1–2 years are summarized and reviewed. Furthermore,
the corresponding prospects in the future are also outlined.
28.1 PREFACE
The irreversible depletion of available fossil resources on the
planet is growing rapidly, which has aroused the development
efforts of numerous scientists around the world, the recent
years have witnessed the vigorous progress in some new
alternative energies and technologies on the basis of the suc-
cessful development of new materials and new functions of
old materials. For example, carbon family materials, con-
sisting of a single carbon element in different microscopic
structures, have contributed substantially to the success-
ful developments and exploitations of various energies and
technologies, as listed in Table 28.1. Typically, active carbon
powders are used to increase the electronic conductivity of
electrode active materials or directly act as active materi-
als within many energy storage and conversion devices [1].
More specifically, it is well known that the safety issues of the
Li-ion battery (LIB) was successfully resolved in 1991 owing
to multilayered graphite with the capacity of safe insertion/
extraction Li+, thus opening the door to commercial applica-
tion in a large scale [2]. Thereafter, football-shaped fullerenes
and carbon nanotubes (CNT) also attracted a great deal of
attention in the field of new energy owing to their own excel-
lent functions [3–5]. Recently, flexible graphene, the new-
est member of the carbon family, consisting of sp2-bonded
­carbon atoms into a two-­dimensional (2D) honeycomb lattice,
exhibited a wide and promising application in energy-related
devices [6–10]. In theory, graphene is a perfect single atomic
nanosheet (Figure 28.1) [11,12]. In fact, there are usually some
planar or edge defects in graphene nanosheet as well. Such
a unique microstructure endows graphene with some excel-
lent unique features, including ultrahigh electron conduc-
tivity (106 S cm−1), surface area (2630 m2 g−1), mechanical

419
420 Graphene Science Handbook

store and release electricity energy in many cycles, thus better

TABLE 28.1
Carbon Materials in Various Energies and Technologies
Carbon Materials Roles in Energy-Related Devices References
Active carbon Electrode materials in capacitor [1]
Graphite Electrode active materials in Li-ion [2]
battery
Carbon nanotubes Catalyst support in fuel cell [3]
Carbon nanotubes Conductive agent in Li-ion battery [4]
Fullerene Catalyst support in direct methanol [5]
fuel cell
Graphene Anode materials or conductive agent [6,7]
in Li-ion battery
Graphene Catalyst or support in fuel cell [8,9]
Graphene Hole or electron transporting material [10]
FIGURE 28.1  Ball–stick model of perfect graphene structure.
(Reprinted with permission from Katsnelson, M. I., Fasolino, A.
Graphene as a prototype crystalline membrane. Acc. Chem. Res.
46:97–105. Copyright 2013 American Chemical Society.)
properties (breaking strength of 40 N m−1 and 1.0 TPa of
Young’s modulus), low optical absorbance (2.3%) and density
(<1 g cm−3), and unusual flexibility [13–15]. Consequently,
graphene becomes a kind of newly emerging multifunctional
material for varied energy storage and conversion systems
such as fuel cells [16,17], LIBs [18,19], lithium–O2 batteries
[20–22], capacitors [23,24], sensors [25], solar cells [26,27], as
well as gas separation [28]. Besides successful experimental
preparation of graphene by mechanical exfoliation in 2004,
other methods including epitaxial growth, electrochemi-
cal exfoliation, chemical vapor deposition (CVD), etc. have
also been developed for producing graphene [29–31], which
provided the material guarantee for more intensive investi-
gations of graphene in terms of both experiment and theory.
Subsequent wide and intensive investigations of graphene for
the varied energy-related devices were triggered and reported,
and some review articles about graphene were also published
[32–34]. In this chapter, state-of-the-art advances especially
in the recent 1 or 2 years in the area of graphene’s applications
for LIBs and fuel cells are detailed and summarized.
28.2  GRAPHENE FOR LITHIUM-ION BATTERIES
LIBs, first commercialized in 1991 by Sony Corporation, are
currently one of the most popular rechargeable battery tech-
nologies around the world, because LIB can conveniently
meeting the need of consumer’s fast lifestyles and remedying
the uncertainty and randomness of wind and solar energies
[35]. Generally, LIB consist of three essential parts: Li+ inser-
tion/extraction anode, Li+ insertion/extraction cathode, and
nonaqueous electrolyte containing lithium salts, in which Li+
can shuttle back and forth between the anode and the cath-
ode. Since the safe operation problem was resolved in 1991 by
replacing the lithium metal anode with graphite carbon, LIB
rapidly captured most of the portable electron devices mar-
ket and enabled the wireless revolution of cell phones, laptop
computers, digital cameras, and iPads. Obviously, graphite
made a substantial contribution to the successful commer-
cialization of LIB owing to its well-defined layered structure
for Li+ intercalation, low operating potential, and remarkable
interfacial stability. The nature and microstructure of elec-
trode materials are crucial not only for energy and power den-
sity but also for safety and cycle life of the batteries. Later,
owing to the low theoretical capacity and unsatisfactory rate
performances of commercialized graphite anodes, continuing
efforts were made to promote the emerging of new materials
and technologies for LIB with higher rate capacity and longer
cycle life. As a result, various substitution materials have been
developed and the range of LIB in the market has also been
further extended to electrical vehicles. For example, inexpen-
sive and easily accessible carbon-supported elementary sub-
stances (Si, Ag, Sn, P25), sulfides (SnS2), oxides (CuO, SnO2,
V2O5, Fe2O3, TiO2, SiO2), lithium titanate or lithium stannate,
etc. were intensively studied as the anode active materials,
whereas LiFePO4, LiMnO4, LiNiO2, S, etc. were successfully
developed as the cathode active materials. Correspondingly,
three lithium storage mechanisms in the anode have been
also explored: (i) insertion/extraction for graphite, TiO2, and
Li4Ti5O12, in which Li+ can be reversibly inserted/extracted
without obvious structure damage [36]; (ii) alloying/dealloying
for Ag, Si, and Sn, in which 4.4 Li can be alloyed with a large
volume expansion during alloying, and then recovered to pris-
tine phases with partial pulverization during dealloying [37];
(iii) conversion reactions, where active materials partially or
completely decompose into metals and lithium oxides or salts
along with lithiation and recover to the original phase upon
delithiation, such as MmXn compounds (M = Fe, Co, Ni, etc.,
whereas X = O, S, etc.), especially transition-metal oxides
[38–40]. However, although these alternative anode materi-
als possess their respective highlights such as high theoretical
capacity, rate capacity, or high cyclability, these advantages
may be offset by poor electronic and ionic conductivity, big
volume change, aggregating, or dissolution of active com-
ponents. Recently, focusing on these problems, new multi-
functional graphene nanosheets with high surface area and
intrinsically superior electronic conductivity shed new light
on the development of LIB. It is highly expected that graphene
and its derivatives can meet the requirements by buffering the
volume change, anchoring the active nanoparticles, and allow-
ing for fast ion diffusion as well as electron transport. In the
case of its application for LIB, multifunctional graphene can
directly act as anode active materials, hybrid anode active
New Energy Material
TABLE 28.2
Roles of Graphene in Li-Ion Battery
Graphene’s
Role in LIB First Discharge Capacity
Anode 1079 mAh g−1@40 mA g−1
Anode 977 mAh g−1@300 mA g−1
Hybrid anode 937.7 mAh g−1@1000 mA g−1
Cathode additive 166 mAh g−1@0.2C
Cathode additive 153 mAh g−1@1C
Current collector 899 mAh g−1@50 mA g−1
materials, conductive additives in the cathode materials as
well as current collectors, as shown in Table 28.2.
28.2.1 Graphene Anode Active Materials
Based on the successful application of graphite for LIB, it is
naturally and easily expected that graphene can directly replace
traditional graphite as anode active materials for improved per-
formances of LIB. So, Yoo et al. [47] tested the performance of
pristine graphene nanosheet anodes in LIBs for the first time and
demonstrated low specific capacities of only about 540 mAh g−1.
Later, Fahiman et al. also studied the performance of graphene
nanoribbons with extremely high first cycle discharge capacity
but poor coulombic efficiency [48]. One of the possible reasons
for this poor performance was confirmed to be the use of a
nonconducting polymer binder in the sample preparation [49].
Thereafter, rapid developments of graphene as anode in LIBs
were reported, and enhanced capacity and electrochemical
performances were also achieved [31,50–55]. However, for the
moment, it is not very clear about the origin of enhanced capaci-
ties and electrochemical performances for graphene anode
materials in LIB, and there is still the controversy about the rela-
tionship between the enhanced capacity and microstructure of
­graphene. Most studies attributed the enhancement in the capac-
ity of graphene materials to its unusual large surface area and
larger d-spacing than the graphite anode, which is proposed to
provide more active sites to accommodate higher Li uptake than
LiC6. In fact, it was also first pointed out in 2009 that enhanced
capacity was neither fully determined by d-spacing of graphene-
based materials nor affected by structure integrity; and the sur-
face structure defects could result in solid-electrolyte interphase
(SEI) formation and extra Li-ion trapping, whereas the inner and
edge structure defects could lead to reversible capacity [56]. This
point was also confirmed in terms of experiment and theory
[57]. Recently, Kuo et al. [58] also indicated that the enhanced
capacity was associated with a specific functional group within
graphene other than larger surface area or structure defects.
More specially, the capacity at a potential higher than 1.5 V was
predominantly attributed to phenol groups, whereas the capacity
derived from the redox couple at 1.1 V resulted from cyclic edge
ether groups. Other functional groups, such as carboxyl, lactone,
and carbonyl, did not result in reversible lithiation/delithiation
processes [59]. It seems that intensive investigations should be
421
Cyclic
Number Retention References
50 93%@40 mA g−1 [41]
15 46.6%@300 mA g−1 [42]
50 69.5%@1000 mA g−1 [43]
50 98%@0.2C [44]
100 95%@1C [45]
20 64.5%@50 mA g−1 [46]
further carried out in order to clarify the more authoritative and
more accurate enhancement mechanism of graphene. Maybe,
the enhanced performance resulted from the co-­contribution
of multiple factors as mentioned above owing to a synergistic
effect.
In addition, the unique superiorities of graphene easily
disappeared owing to restacking via strong π–π interaction
between the nanosheets, and some planar- and edge-defects of
graphene nanosheets also made the measured electronic con-
ductivity deviate from the theoretical value while facilitating
the ionic diffusion. Therefore, it is very important and highly
desirable to keep 2D graphene nanosheets physically separate
and carefully control the number of defects for a compromise
between ionic and electronic conductivity [60,61]. Besides
making efforts to prepare graphene nanosheets with moderate
defects by optimizing and controlling the experiment condi-
tions, the doping and functionalizing of graphene nanosheets
were also paid more attention [62,63]. For instance, it was
reported that a very high capacity of 199 and 235 mAh g−1 can
be obtained for N-doped graphene anode and B-doped gra-
phene anode at 25 A g−1 (about 30 s to full charge), respectively,
attributing to rapid Li+ absorption and diffusion and electron
transport induced by the unique 2D structure, d­ isordered sur-
face morphology, heteroatomic defects, larger intersheet dis-
tance, and electrical conductivity of the doped graphene [63].
Similarly, Wang et al. [64] also made similar attempts to simul-
taneously achieve high power and large energy capacity of LIB
at a fast rate by ­benefitting from the synergistic effect of the
structure and doping of N atom. The obtained novel electrodes
can deliver a high-power ­density of 116 kW kg−1, whereas the
energy density can remain as high as 322 Wh kg−1 at 80 A g−1
(only 10 s to full charge). Furthermore, the optimized electrodes
exhibited long-cycling capability without significant capacity
loss for 3000 cycles. Cai et al. [18] achieved super-high capacity
(1123 mAh g−1 at a current density of 50 mA g−1) of graphene
anodes for LIB by doping high loading (7.04%) of nitrogen
with pyridine. More significantly, even at an extremely high
current density of 20 A g−1, a highly stable capacity of about
241 mAh g−1 could still be obtained. It was claimed that such
an electrochemical performance ranked the highest among
those ­previously reported N-doped graphene sheets. The 2D
structure, d­ isordered surface morphology, high N-loading, and
the existence of pyridinic nitrogen atoms were proposed to be
422 Graphene Science Handbook

(a)
Mesopores
Li+ insertion Li+

Li+ extraction
Edges

(b) (c) 1000

3.5
1C

Specific capacity (mAh g–1)

20C 10C 5C 1C 0.5C 0.1C
3.0 800
E (V) vs. Li/Li+

2.5
600
2.0
1.5 400
20C
1.0 200
Charging
0.5 Discharging
0
0.0 0 20 40 60 80 100
0 400 800 1200 1600 2000
Cycle number
(d) Specific capacity (mAh g –1) (e)
1200 2000

Specific capacity (mAh g –1)

Specific capacity (mAh g–1)

This work
1000
1600
800 1C
2C
1200
600 5C
ref. (1)
800
400 10C ref. (2)
20C ref. (12)
400 ref. (1)
200

0 0
0 5 10 15 20 25 0.6 0.9 1.2 1.5 1.8 2.1
Cycle number ID/IG

FIGURE 28.2  (a) Discharge (Li+ insertion) and charge (Li+ extraction) processes of the porous graphene electrode, meaning that Li ion
can be very easily inserted and extracted through the pores. (b) Galvanostatic charge/discharge curves of the porous graphene electrode at
0.1–20C. (c) Cycling performances of the porous graphene electrodes at 1C and 20C. (d) Rate performances of the porous graphene electrode
at different current densities. (e) Relationship between the intensity of D peak/intensity of G peak (ID/IG) in Raman spectrum of graphene
and the capacity of various reported graphene, including the present work. The cited graphene materials consist of many defects such as
edges, vacancies, and topological defects. (Reprinted from Carbon, 60, Fan, Z. et al., Porous graphene networks as high performance anode
materials for lithium ion batteries, 558–561, Copyright 2013, with permission from Elsevier.)

responsible for an excellent electrochemical performance, indi-
cating that high-level N-doped graphene sheets could be a prom-
ising anode material for high-performance LIB. Nevertheless,
Fan et al. [65] recently achieved a higher reversible capacity of
1718 mAh g−1 at 0.1C, excellent high rate capability, and cycling
stability for LIB only with bare graphene containing mesopores
and edges as anode, which was obtained by CVD using porous
MgO sheets as the template (Figure 28.2). The CVD induced
porous structure of graphene may play an important role in the
excellent behavior of graphene. Obviously, both the heteroatom
doping and controllable microstructure of graphene are benefi-
cial strategies to maintain the desired electrochemical perfor-
mance of graphene.
28.2.2 Graphene-Based Hybrid Anode Materials
As mentioned above, prior to the emergence of graphene,
graphite was the most mature anode material for LIB. In addi-
tion, there have been some candidates of anode active materi-
als such as carbon-based materials (fullerene C60, CNT, etc.),
high-capacity metal (oxides or sulfides), spinel lithium tita-
nate with long cycle life, and so on. These anode materials
exhibited their respective superiorities. Therefore, the syner-
gistic effects of various components make the idea of com-
bination preferable [66,67]. For example, the carbon matrix
can provide electrical conductivity, mechanical support, and
the structure stability by accommodating the volume expan-
sion and from preventing the disintegration or aggregation of
the metal (oxides) particles, whereas the second active phase
can contribute to high capacity as well as cyclability of the
anode. On the basis of combination conception, various gra-
phene-based hybrid anode materials such as graphene/graph-
ite [68], graphene/metal [69–73], graphene metal nitrides [74],
graphene/metal oxides (graphene/TiO2 [75–78], graphene/
SnO2 [79–84], graphene/iron oxide [85–91,89],  ­ graphene/
manganese oxide [92,93], graphene/MoO3 [94], gra-
phene/CeO2 [95], ­ graphene/CuO [96,97], graphene/V2O5
[98,99], graphene/Co3O4 [100,101]), graphene/lithium salts
(Li4Ti5O12 or Li2SnO3) [102,103,104], graphene/metal sulfides
[105,106,107], graphene/P25 [108], and graphene/Si [109–113]
New Energy Material 423

TABLE 28.3
Performances of Li-Ion Battery with Graphene-Based Hybrid Anodes
Cyclic
Hybrid Anodes First Discharge Capacity Number Retention References
Ag/graphene 1015 mAh g−1@0.1C 50 64%@1C [69]
Sn/graphene 1129 mAh g−1@0.05C 25 46%@0.05C [70]
TiO2/graphene 260 mAh g−1@0.18C 300 84%@0.8C [75]
SnO/graphene 1306 mAh g−1@100 mA g−1 50 45.5%@100 mA g−1 [80]
Fe2O3/graphene 1500 mAh g−1@50 mA g−1 50 74.4@50m mA g−1 [85]
Fe3O4/graphene 1250 mAh g−1@100 mA g−1 50 86.4%@100 mA g−1 [90]
V2O5/graphene 245 mAh g−1@100 mA g−1 300 89%@100 mA g−1 [98]
Li4Ti5O12/graphene 106.4@20C 300 94%@20C [103]
P25/graphene 319@0.5C 50 89%@0.5C [108]
Si/graphene 1297 mAh g−1@0.2C 50 92.7%@0.2C [110]

have been reported in the literature, and some corresponding
performances were listed in Table 28.3. Compared with cor-
responding single-component anode materials without gra-
phene, hybrid materials exhibited enhanced electrochemical
performance because of synergistic effects. Nevertheless, the
undefined structure of graphene-based nanocomposites and
the inhomogeneous insertion of metals (oxides) in the gra-
phene matrix usually result in a decrease of the electrochemi-
cal performance, including the reversible capacity and cycle
stability [114,115]. Therefore, fabrication of graphene-based
hybrid materials with well-defined structures remains an
important goal [116,117]. Furthermore, it is preferable to com-
bine different components in good order. As shown in Figure
28.3, six structural models were proposed [118] to describe the
combination method of graphene-based composite materials:
(a) anchored model: nanoparticles are anchored on graphene
surfaces; (b) core–shell model: nanoparticles are wrapped
by graphene; (c) encapsulated model: nanoparticles are
encapsulated in graphene; (d) sandwich-like model: nanopar-
ticles are squeezed between two graphene layers; (e) layered
model: alternative layers of nanoparticles and graphene; and
(f) mixed model: nanoparticles and graphene are mechani-
cally mixed with graphene forming a conductive networking
among the active nanoparticles.
For example, Si is regarded as one of the most promising
anode materials for next-generation LIBs, but usually exhib-
its poor cycling stability owing to the low intrinsic electrical
conductivity and huge volume change induced by the alloying
reaction with Li metal [119,120]. Zhu et al. designed and fabri-
cated a graphene/Si composite with core–shell structure. As a
result, the as-prepared graphene/Si composite anode delivered
a reversible capacity of 1648 mAh g−1 with an initial coulom-
bic efficiency as high as 80%. Moreover, capacity remained
1335 mAh g−1 after 80 cycles at a current of 200 mA g−1,
showing significantly improved electrochemical performance
in terms of rate capability and cyclic stability [121]. Wu et al.

(a) (b) (c)

(d) (e) (f )

Graphene nanosheet Metal oxide article

FIGURE 28.3  Schematic of structural models of graphene-based composites: (a) anchored model; (b) core–shell model; (c) encapsulated
model; (d) sandwich-like model; (e) layered model; and (f) mixed model. (Reprinted from Nano Energy, 1, Wu, Z. S. et al., Graphene/metal
oxide composite electrode materials for energy storage, 107–131, Copyright 2012, with permission from Elsevier.)
424
synthesized hybrid anode material of graphene anchoring
Co3O4 nanoparticles, and the resultant Co3O4/graphene com-
posite exhibited a large reversible capacity (935 mAh g−1 after
30 cycles), excellent cyclic performance, high coulombic
efficiency (above 98%), and good rate capability, highlight-
ing the advantages of anchoring Co3O4 nanoparticles onto
graphene nanosheets [122]. In addition, MnO2/graphene and
Zn2SnO4/graphene with layered structures [123,124], gra-
phene anchored ZnFe2O4 [125], sandwich-like Si/graphene
[126], Fe2O3/graphene with core–shell structure [127,128],
etc. were also experimentally prepared, and they exhibited
satisfying electrochemical behaviors in the anode of LIB as
expected. However, for the moment, there is still no substan-
tial data evidence to support that one of the structural mod-
els provides larger charge capacity or rate capability than
­others. For example, the core–shell structure for a graphene/
CeO2 composite anode showed a reversible capacity of 1100
mAh g−1 in the first 10 cycles and stable cycle performance,
retaining a capacity of ~1000 mAh g−1 after 130 cycles, which
is three times higher than that of a commercial graphite elec-
trode (~300 mAh g−1) [129]. The obtained results are similar
to those of graphene/iron oxide with nanoribbon structure
fabricated even by the same research group and by different
fabrication strategy [130]. Evidently, multiple factors jointly
determined the final electrochemical performance of compos-
ite anode materials and resulted in the difficulty of parallel
and accurate comparison among these combining models.
In addition, functionalized graphene was also used as
a participant in a hybrid anode. Usually, the introduction of
the third component such as CNT, carbon cloth, or heteroatom
(N, B, etc.) was the icing on the cake [131–134]. Chen et al.
designed and fabricated Fe2O3–CNT–graphene hybrid mate-
rials by CVD, and the obtained ternary materials exhibited a
high specific capacity of 984 mAh g−1 with a superior cyclic
stability and high rate capability to single and binary anode
materials under the same conditions possibly owing to the
synergistic effect of the various components [135]. Likewise,
three-dimensional (3D) flower-shaped VO2 was anchored on
N-doped graphene nanosheets by a single-step hydrothermal
reaction within a mixture of ammonium vanadate and colloi-
dal dispersion of graphite oxide, and the desired performances
were achieved [136]. A ternary anode also seems better than
a binary or single one owing to the synergistic effect of the
components in the other literature [137].
28.2.3 Graphene-Based Cathode Active Materials
Compared with wide and intensive investigations about the
applications of graphene nanosheets for LIB anodes, multi-
functional graphene has only recently been implemented as an
electron conducting additive for LIB cathodes [138,139]. It is
known that electronic and ionic conductivity play a vital role
in the normal operation of energy-related devices, which deter-
mines the electrochemical performance such as the output
power density and capacity. In the case of cathode materials
in LIB, several classic active materials are LiCoO2, LiMn2O4,
LiFePO4, LiNiO2, Li3V2(PO4)3, transition metal fluorides as
Graphene Science Handbook
well as sulfur and selenium, etc., which possess various micro-
structures with interspaces allowing for lithium-ion insertion/
extraction. Particularly, sulfur has high expectations as cathode
active materials compared with others owing to its numerous
appealing advantages such as high theoretical specific capacity
(1675 mAh g−1, based on the complete reactions of sulfur with
lithium metal to form Li2S), high theoretical specific energy
(2500 Wh kg−1, with a Li electrode), environmental benignity,
and abundant and cheap sulfur resources [140–142]. However,
the intrinsic low electronic conductivity of these cathode mate-
rials also offsets these advantages and hinders to some degree
the full realization of their high theoretical capacities. For
example, the orders of magnitude of electronic conductivity of
LiCoO2, LiMn2O4, Li3V2(PO4)3, LiFePO4, and sulfur are 10−4
[143], 10−6 [144], 10−7 [145], 10−9 [146], and 10−30 S cm−1[147],
respectively, which make it impossible to only use single active
materials owing to high inner resistance. The available as-
reported strategies modifying the conductivity included dop-
ing, coating, modifying the porous size and the morphology of
cathode active materials, and adding conductive agents (car-
bon-based powders, conducting polymers). Conventionally,
carbon black, acetylene black, or active carbon powders are
added into the cathode active materials to enhance conduc-
tivity. However, only the outer surface can effectively contact
with the active particles, that is, only the outer surface con-
tributes to the electrical conductivity of the material [148].
Obviously, in principle, alternative carbon materials with
higher surface area as well as simultaneous conductivity are
preferred. Graphene, possessing an extremely high surface/
mass ratio and sp2-bonded carbon atoms arranged in a hex-
agonal 2D lattice, could be a suitable candidate conductive
agent for LIB cathodes. Therefore, graphene nanosheets are
expected to meet the multiple requirements of high ionic and
electronic conductivity, short Li+ diffusion pathway, and uni-
form distribution of active materials. It was reported that the
experimental combination of graphene with cathode active
materials (LiFePO4, LiF, S, Li3V2(PO4)3, etc.) for LIB was
also achieved [149–153]. For example, the demand for power
sources for electric vehicles and hybrid electric vehicles with
high specific energy has brought immense interest in the appli-
cation of LiFePO4 for LIB cathode material; however, poor
electronic conductivity is a challenge to high rate capacity and
cyclic stability prior to the commercialization of LIB cathodes
[154,155]. For this purpose, graphene-wrapped LiFePO4 was
designed and fabricated for LIB, and the effect of graphene
wrapping on the performance of LiFePO4 was also evaluated.
Results suggested that a partial graphene wrapping was pre-
ferred to full wrapping, attributing this to a balance between
increased electron transport and fast ion diffusion, because
full graphene wrapping possibly isolated LiFePO4 from the
electrolyte and retarded ion diffusion. This indicated that
steric hindrance for ion diffusion should be also considered
simultaneously with electron transport during the constructing
of a carbon coating layer [156].
In the case of another example, graphene-anchored nano-
crystalline LiMn2O4 was synthesized via the solvo-ther-
mal method. As shown in Figure 28.4, LiMn2O4/graphene
New Energy Material
–200
(c)
–150
(d)
Zim (Ohm)
–100 (b)
(a)
–50
0
0 100 200 300 400
Zre (Ohm)
FIGURE 28.4  Nyquist plots of the pristine spinel LiMn2O4 nano-
crystals of (a) prepared with formaldehyde (circles) and (b) prepared
with isobutyraldehyde (triangles), and their nanocomposites with
graphene nanosheets (c) prepared with formaldehyde (squares) and
(d) prepared with isobutyraldehyde (diamonds). (Reprinted from
Electrochim. Acta, 92, Jo, K. et al., Remarkable enhancement of the
electrode performance of nanocrystalline LiMn2O4 via solvother-
mally-assisted immobilization on reduced graphene oxide nanosheets,
188–196, Copyright 2013, with permission from Elsevier.)
nanocomposites displayed smaller radius for the first semi-
circle in the Nyquist plots, indicating the improvement of Li+
diffusion on the surface of lithium manganate compared with
pristine spinel LiMn2O4. Correspondingly, the composite
cathode materials resulted in remarkable improvement of the
electrode performance of LiMn2O4 nanocrystals attributing to
the enhanced ionic and electronic conductivity [157]. In addi-
tion, the graphene additive can also inhibit Mn2+ dissolution
from the cathode into the electrolyte [158]. In principle, the
combining model between cathode active materials and gra-
phene can also follow the six models of hybrid anode materi-
als, as mentioned above.
Analogous to the well-known Li/S battery [159],
an electrochemical reaction of 2Li+ with one Se atom
(2Li+ + Se + 2e− = Li2Se) gives rise to a large specific theo-
retical capacity of 678 Ah kg−1 at around 2.4 V, resulting in
1627 Wh kg−1 of theoretical specific energy. Attracted by such
a high energy density, Kundu et  al. explored the feasibility
of selenium nanofibers and their composites with polypyr-
role and graphene for LIB cathodes [160]. As a result, both
conductive graphene and polypyrrole did promote electro-
chemical performance compared to trigonal selenium fibers
in terms of different aspects. More specifically, polypyrrole
minimized the polarization between charge and discharge
voltage, whereas graphene wrapping of Se fibers resulted in a
higher specific capacity at moderate current.
As discussed above, graphene is beneficial to the ionic and
electronic conductivity of cathode materials for LIB. However,
the effects of the loading of graphene on the electrochemical
performance of the cathode cannot be neglected. In fact, too
high a graphene concentration can also hinder the migration
425
of lithium ions in the cathode. For example, only 5% gra-
phene in LiFePO4 can greatly reduce the contact resistance
among LiFePO4 nanoparticles, and dramatically enhance the
electrical conductivity and electrochemical performances of
the cathode [161]. Furthermore, a composite conductive agent
consisting of graphene and a coating layer of carbon is better
than single graphene or carbon coating [155,159]. Although
graphene appears to be one of the best electron conducting
additives owing to its high electron conductivity and large
specific surface area, external assistances are still necessary,
that is, synergistic effects among various factors are preferred
to a single effect, and this point is consistent with the situation
of the anode of LIB.
500
28.2.4 Graphene-Based Current Collector
The current collector, an inactive accessory to collect the cur-
rent generating from the battery, is typically made up of alu-
minum, copper, or stainless-steel foil. It usually accounts for
about 15%–20% by weight and 10%–15% by cost of a battery,
and thus low specific weight is desirable in an inactive current
collector for high energy density in the premise of ensuring
the normal working of the battery. In addition, gradual cor-
rosion of the current collector will also adversely affect the
lifetime and safety owing to the increasing internal resistance
and passivation of active materials [162]. Therefore, lighter
and more anticorrosive materials are more preferred. Based
on this analysis, Prabakar et al. [163] improved the resistance
of Al foil to the corrosion by coating the graphene oxides
(GOs). Compared with bare Al foil, LIB with GO-coated Al
foil manifested a greater capacity with improved cyclability
during the charge/discharge test, and with less open circuit
voltage decline during the self-discharge test. In principle,
a metal-free battery possesses superior advantages to a con-
ventional battery, such as high energy density, low cost,
high safety, eco-friendliness and sustainability, and it is of
great practical significance. The availability of conductive
polymer and graphene nanosheets with ultrahigh electronic
conductivity makes it possible to assemble a metal-free bat-
tery. Recently, Wang et  al. [164] reported an experimental
example: a metal-free lithium/sulfur battery with graphene-
coated polyethylene terephthalate film as current collector
was assembled, in which graphene acted as the conductor,
while the polymer offered the mechanical and soft support.
During the self-discharge test, the decrease in the discharge
capacity was only less than 1% after 30 days storage at room
temperature. More recently, the MoS2 anode with graphene
paper as current collector other than conventional metal was
reported, indicating that the initial discharge capacity was as
high as 899 mAh g−1 and the coulombic efficiency of 97% was
also high enough [46].
28.3  GRAPHENE FOR FUEL CELLS
Fuel cells are new and friendly energy conversion systems, by
which chemical energy within the fuels and oxidants can be
directly converted into electrical energy with higher efficiency
426
(about 40%–60%) than an inner combustion machine owing
to the absence of limitation of the Carnot cycle. Among the
existing fuel cell technologies, the polymer electrolyte mem-
brane fuel cell (PEMFC), direct alcohol fuel cell (DAFC), and
microbial fuel cell (MFC) attract more attention owing to their
many merits, one of which is the operation temperature close
to ambient temperature [165–167]. In the case of DAFC with
alcohols (methanol, ethanol, etc.) as the fuel, it has been iden-
tified as a promising candidate to compete with conventional
batteries for powering portable electronic devices owing to its
compact and eco-friendly system, high efficiency, portability,
and so on [168,169]. For the moment, most of the achieve-
ments about PEMFC, DAFC, and MFC are based on the
noble and scarce Pt-based catalyst for sluggish electrochemi-
cal reaction of fuel and oxidant in the electrodes. Especially
for DAFC, Pt loading is as high as 3–4 mg cm−2. In addi-
tion, high fuel permeability resulted in mixed potentials in
the cathode. As for MFC, it can convert the metabolic energy
of organic wastes into electricity through the use of microor-
ganisms; however, for the moment, its efficiency is still poor
owing to the poor activity of the catalyst. Although a Pt-based
catalyst is the most effective electro-catalyst in fuel cells, it
still faces difficulty with respect to the mass marketing of fuel
cells for commercial applications, such as its susceptibility to
time-dependent drift and carbon monoxide deactivation, slow
electron transfer kinetics, high costs, limited source, and poor
durability. Multifunctional graphene nanosheets with unique
desirable structure features are also considered as a promising
key to resolve these problems in fuel cells. Recently, inten-
sive efforts in reducing or even wholly replacing Pt catalysts
in fuel cells have led to the rapid development of new gra-
phene-based electrocatalysts for electrochemical reactions.
Functionalized graphene materials have been used as either
cheap metal-free catalysts or the catalyst support with out-
standing performance. According to the roles of graphene in
fuel cells, the corresponding applications for fuel cells can be
classified into three kinds: (i) acting as the catalyst support in
acid and alkaline fuel cells [170,171]; (ii) directly serving as
the catalyst in alkaline medium in order to improve the activ-
ity of a Pt-free or metal-free catalyst for electrochemical reac-
tion or acting as the catalyst in neutral medium for modifying
the electron transfer rate at the bacteria/electrode interface or
oxygen reduction reaction in MFC [172–177]; and (iii) serv-
ing as reinforcement of the mechanical property of the poly-
mer electrolyte membrane while maintaining essential proton
conductivity as much as possible [178].
28.3.1 Graphene-Based Catalyst Support
As a promising alternative power for portable electronic
devices, DAFC has been extensively investigated and signifi-
cant progress has been made. However, the corresponding
widespread application is still hindered by several techni-
cal and economical barriers: sluggish dynamics for electro-
chemical reactions in the electrodes (especially for methanol
oxidation reaction), serious CO poisoning of the Pt catalyst
in the anode, and high cost because of high loading of the
Graphene Science Handbook
noble metal Pt. Therefore, decreasing the loading of the Pt
catalyst as much as possible must be pursued prior to the wide
commercial application of DAFC. As for PEMFC, the slower
dynamics of O2 in the cathode than that of H2 in the anode
are still a rate-determining step even with the most efficient
Pt catalyst, and thus slow down its pace of progress. Keeping
these problems in mind, periodical progress in decreasing
Pt loading while maintaining high electro-catalyst activity
has been made by changing from initial pure Pt black into
carbon-supported Pt nanoparticles for more available active
sites exposed to the fuel without sacrificing the cell perfor-
mance. Varied carbon powders (such as carbon black, carbon
ribbon, carbon fibers, CNT, and so on) were usually used as
the support of the Pt-based catalyst in order to enhance the
active sites and the efficiency of the Pt catalyst, and thus to
decrease the loading of Pt and the material cost of fuel cells
[179–181]. However, the performance degradation resulting
from carbon support loss during the durable operation of the
fuel cell remains a puzzling problem [182]. In addition, the
surface area of this carbon support is not high enough, and the
inner surface area is still unavailable to catalyst nanoparticles.
Therefore, it is desirable to find a better support to efficiently
disperse catalyst particles. New multifunctional graphene was
expected to be a more promising and efficient catalyst support
than the other conventional carbon powders, because of its
unique properties: ultrahigh surface area and ultrahigh elec-
tron conductivity. Till now, there have been many publica-
tions about Pt or non-Pt catalyst anchored on graphene-based
­support for fuel cells [183–215].
Generally, controllable morphology, high dispersion, small
particle size, and low loading of Pt catalyst particles were pur-
sued to enhance the performance of fuel cells. For example,
a highly crystalline flower-like Pt/graphene catalyst was pre-
pared by pulse electrochemical deposition, and used as an
anode catalyst for the hydrogen oxidation reaction of PEMFC.
The corresponding single cell exhibited the lowest inner
resistance and the highest peak power density at 75C [186].
Kakaei et  al. prepared highly dispersed Pt nanoparticles on
graphene by ionic-liquid-assisted electrochemical exfoliation
and sodium borohydride reduction, and the as-synthesized
graphene-supported Pt catalyst exhibited higher stability and
high catalyst activity for the oxygen reduction reaction than
commercial Pt/C, as shown in Figure 28.5 [190]. Also, the
graphene-supported Pt catalyst was prepared for the ethanol
oxidization reaction [191]. Compared with the commercial
Johnson Matthey (JM) 20% Pt/C electrode, the as-prepared
catalyst exhibited higher electrochemical activity, durability,
and stronger tolerance to poisoning species.
Figure 28.6 shows that ultrafine Pt nanoparticles were
highly dispersed on the surface of graphene nanosheets [216].
Furthermore, a single-atom Pt catalyst anchored on the gra-
phene nanosheets was also achieved through atomic layer depo-
sition, which exhibited 10 times greater catalytic activity over
that of the state-of-the-art commercial Pt/C catalyst [217,218].
In the case of decrease in the loading of the precious Pt cat-
alyst, Pascone et al. [219] designed and fabricated a graphene-
supported Pt-free iron catalyst, and the in situ durability test
New Energy Material
30
Pt/graphene
Pt/C
25
20
I (mA cm–2)
15
10
5
0 Time (h)
0 100 200 300 400 500 600 700 800
Time (s)
FIGURE 28.5  Chronoamperometric response during the oxidiza-
tion of methanol (1 M) on Pt/graphene and Pt/C electrode at peak
potentials in 0.5 M H2SO4. (Reprinted from J. Power Sources, 225,
Kakaei, K., Zhiani, M., A new method for manufacturing gra-
phene and electrochemical characteristic of graphene-supported Pt
nanoparticles in methanol oxidation, 356–363, Copyright 2013, with
permission from Elsevier.)
for 100 h of a fuel cell with a Pt-free iron-based catalyst for
the oxygen reduction reaction in acid medium was achieved
for the first time, as shown in Figure 28.7. The  satisfying
results were attributed into the high electronic conductivity
and durable resistance of graphene support to the corrosion.
The graphene-supported Pt-free Pd catalyst for methanol
oxidation reaction in alkaline medium was also synthesized.
Hsieh et al. fabricated graphene-supported Pd by the method
of pulse microwave-assisted polyol synthesis. The single cell
FIGURE 28.6  Transmission electron microscope (TEM) image
of highly dispersed Pt nanoparticles on transparent graphene
nanosheets. (Reprinted from Electrochem. Commun., 13, Park, S.
et al., Design of graphene sheets-supported Pt catalyst layer in PEM
fuel cells, 258–261, Copyright 2011, with permission from Elsevier.)
427
Stability test
250
200
Current (mA)
150
100
50
0
0 10 20 30 40 50 60 70 80 90 100
900 1000
FIGURE 28.7  Measured current over time at an applied voltage of
500 mV. (Reprinted from Catal. Today, 211, Pascone, P., Berk, D.,
Meunier, J., A stable and active iron catalyst supported on graphene
nano-flakes for the oxygen reduction reaction in polymer electro-
lyte membrane fuel cells, 162–167, Copyright 2013, with permission
from Elsevier.)
with Pd/graphene as anode catalysts exhibits a maximal power
density of 1.75 kW g−1 at 75C, attributing to good dispersibil-
ity of Pd nanoparticles on the graphene surface [220]. It was
also reported that the ternary catalyst of Pd/MnO2/graphene
exhibited higher catalytic activity and better stability than Pd/
graphene [221].
Urea is considered a stable, nontoxic, and nonflammable
hydrogen carrier for hydrogen production and fuel cells, and
its electrochemical oxidation has been used as an effective
approach for hydrogen production. An inexpensive graphene-
supported Ni catalyst for the electrochemical oxidization of
urea was prepared [222]. Likewise, owing to the large active
surface area of graphene sheets and the synergistic contribu-
tion of nickel and graphene sheets, the graphene-supported
Ni catalyst exhibited higher activity and efficiency than
­unsupported Ni.
As we know, graphene is produced from the exfoliation
of graphite by mechanical, chemical, or electrochemical
methods. Monolayered graphene sheet tends to irreversibly
agglomerate and re-form multilayered graphite through strong
π–π stacking and van der Waals interaction. Since most of its
unique properties are only associated with individual sheets,
it is highly important to prevent graphene sheets from re-
aggregation. How to keep its unique structure and make good
use of these unique functions of graphene are also challenges
that bring a new focus. Functionalization and modification of
graphene support were explored by doping nitrogen, boron,
polyelectrolyte, CNTs, carbon cloth, carbon black, Si, MnO2,
and so on, possibly due to the synergistic effect between vari-
ous components [223–234]. Theoretical calculation revealed
that doping of Si into the graphene make it easier for the
oxygen reduction reaction by decreasing the barrier and the
­endothermicity [231].
For instance, Vulcan carbon powders were introduced into
graphene as a nano-sized spacer (in Figure 28.8) [232], and
the obtained composite was used as the support of a PtRu
428
PtRu
Vulcan carbon
Graphene
FIGURE 28.8  Scheme of PtRu catalyst supported on Vulcan carbon powders and graphene nanosheets. (Reprinted from J. Power Sources,
222, Woo, S. et al., Enhanced electrocatalysis of PtRu onto graphene separated by Vulcan carbon spacer, 261–266, Copyright 2013, with
permission from Elsevier.)
catalyst for PEMFC. Such a composite structure resulted in
more triple-phase boundaries available for electrochemical
reaction and better mass transport in the catalyst layer and
thus higher electrochemical activity and utilization efficiency
of the noble metal Pt.
In another example, a 3D network of graphene was
constructed by growing on CNT in Figure 28.9, and the
obtained composite exhibited very high electrical conductiv-
ity (144.4 S cm−1) as well as electrochemically active surface
area (77.4 m2 g−1). Correspondingly, the single cell with this
composite-supported Pt as anode catalyst also showed satisfy-
ing performance [233].
Chemically method-induced defects in graphene usually
make it suffer from the problem of low electronic conductivity.
Theoretical and experimental studies have revealed that nitro-
gen, sulfur, or boron doping of graphene can modify the physi-
cal/chemical properties of graphene [234–238]. Therefore,
heteroatom (N, B, P, or S) doped graphene was investigated in
order to enhance the electrical properties. Doping of graphene
with heteroatoms can be achieved by either in situ doping dur-
ing the nanocarbon synthesis or posttreatment with hetero-
atom-containing precursors such as NH3. Posttreatment often
leads to the functionalization only on the surface, whereas in
situ doping can incorporate heteroatoms into the entire gra-
phene homogeneously. Heteroatom dopants in graphene can
cause electron modulation to provide desirable electronic
structures for catalytic process. It was reported that triangular
O N
O
OH
OH
O OH
O N
Graphene-CNT
Composite (G-CNT)
FIGURE 28.9  Scheme of 3D network of hybrid support of gra-
phene nanosheets with CNT. (Reprinted from Energy, 53, Jhan, J.
et al., Three-dimensional network of graphene grown with carbon
nanotubes as carbon support for fuel cells, 282–287, Copyright
2013, with permission from Elsevier.)
Graphene Science Handbook
O
HOOC
OH
HOOC
OH
HOOC OH
PtRu/Graphene–Vulcan carbon
palladium nanoparticles were supported on N-doped gra-
phene, in which N-doping enhanced the binding energy
between the graphene sheets and Pd catalyst and prevented the
loss of catalyst nanoparticles from graphene support and from
subsequent agglomeration [239]. In addition, doping-induced
spin redistribution also played an important role in regulat-
ing the activities of the oxygen reduction reaction [10]. More
intensively, in order to understand the roles of various nitrogen
states in electrocatalysis, Zhang et al. synthesized amino-func-
tionalized graphene and explored the roles of various nitro-
gen states in oxygen reduction reaction. X-ray photoelectron
spectroscopic (XPS) analysis revealed that there were several
nitrogen states: the pyridinic N, pyrrolic N, g­ raphitic N, and
amino group in the amino-­functionalized graphene structure,
as shown in Figure 28.10. The results showed that graphitic-N
and amino-N decided the onset potential and electron transfer
number in oxygen reduction reaction, whereas the total con-
tent of ­graphitic-N and ­pyridinic-N were responsible for the
enhanced oxygen reduction current density [240].
In conclusion, the graphene support with high surface
area provided more anchoring sites and better dispersibility
for nanoparticle catalysts, which is beneficial to the improve-
ment of the activity and efficiency of the catalysts. Also, the
Pyridinic N
Pyrrolic N
Graphitic N
OH
H2N
NH2
Amino N N N HN
HN
N
H2N N OH
N
O
NH2
FIGURE 28.10  Schematic illustration of nitrogen states in amino-
functionalized graphene. (Reprinted from Nano Energy, 2, Zhang,
C. et al., Synthesis of amino-functionalized graphene as metal-free
catalyst and exploration of the roles of various nitrogen states in
oxygen reduction reaction, 88–97, Copyright 2013, with permission
from Elsevier.)
New Energy Material
adulteration and modification make the unique structure and
superiority of the graphene more stable.
28.3.2 Graphene-Based Catalyst in Alkaline
or Neutral Medium
It was reported that an alkaline medium can allow for fast
kinetics of electrode reaction in fuel cells and expand the
selective window of electrochemical catalysts. Non-Pt, even
metal-free catalysts, can also be correspondingly electro-cat-
alytic active in alkaline fuel cells [241–243]. Metal-free cata-
lysts have received much attention because of their increasing
electro-catalytic activity in oxygen reduction reaction, long-
term stability, and tolerance to interfering substances for alka-
line fuel cells, indicating great potential for substitution of
Pt-based catalysts in fuel cells (FCs) [240–247]. Heteroatom-
doped graphene nanosheets or CNT are typical metal-free
catalysts [248–250]. The corresponding mechanism was
also explored. Raman and XPS measurements indicated that
nitrogen atoms introduced into graphene sheets can accept the
electrons from graphene nanosheets via intermolecular charge
transfer. The resultant positively charged graphene can inter-
fere in the charge transfer of the oxygen reduction reaction.
For example, Wang et al. designed and fabricated metal-free
catalyst–poly(diallyldimethylammonium chloride) (PDDA)
functionalized graphene for the oxygen reduction reaction in
alkaline fuel cells. The positively charged graphene exhib-
ited remarkable electrocatalytic activity toward the oxygen
reduction reaction with better fuel selectivity, tolerance to
CO poisoning, and long-term stability than that of the com-
mercially available Pt/C electrode [251]. When functionalized
with tridodecylmethylammonium chloride, graphene can also
exhibit electrocatalytic activity and be used as a metal-free
catalyst for oxygen reduction reaction in fuel cells, with the
results of long-term operational stability as well as tolerance
to methanol and ethanol via a four-electron pathway in alka-
line medium [252].
More recently, a graphene-based metal-free catalyst for
electrochemical reaction in neutral medium of MFC was also
investigated. MFC can directly convert chemical energy into
electrical energy via electrochemical-active microorganisms,
and thus have great potential application for simultaneous
waste water treatment, implantation power, as well as energy
recovery [167,253]. Oxygen is an ideal electron acceptor for
MFC cathodes owing to its high oxidation potential, its acces-
sibility in the ambient environment, and its being clean prod-
uct. However, the poor power density of MFCs remains one of
the main obstacles for their practical applications due to slow
electron transfer in the electrodes. Besides Pt-based catalysts,
nanostructured materials, possessing excellent electron trans-
fer characteristics with a high ratio of surface area to volume,
have been widely used in MFCs to facilitate electron transfer
[254]. Although there have been some investigations about
graphene-based catalysts in neutral medium for MFCs due to
their achieving fast electron transfer between active materi-
als and electrodes, these are still in their infancy compared
with those about typical fuel cells, and only small amounts
429
of the corresponding reports are available in the literature
[255–257].
For example, the power density of 1390 mW cm−2 of MFC
was achieved by using graphene/polyaniline nanocomplex as
anode, because high conductivity and large specific surface
area greatly improved the charge transfer efficiency and the
bacterial biofilm loading [258]. Zhuang et al. proposed a new
way to fabricate 3D graphene/biofilm composites for MFC.
Electrochemical studies showed that graphene–biocathode
possessed greater catalytic activity toward cathode oxygen
reduction, faster electron transfer kinetics, and smaller inter-
nal resistance [259].
28.3.3 Graphene-Based Polymer Electrolyte
Membrane for Fuel Cells
Flexible and soft GO nanosheets, a precursor of graphene, are
usually manufactured by exfoliating multilayered graphite
into one or a few nanosheets of oxidized graphene via acid
intercalation, oxidation, and subsequent physical agitation
typically by sonication [260]. Finally, flexible graphene can be
obtained by the reduction of GO. This approach is relatively
simple and easy for mass production compared with other
methods. In fact, graphene still contains oxygen-containing
groups, such as epoxy and hydroxyl groups at the basal plane,
carbonyl and carboxylic groups at the edges, but much lower
than that of GO. These oxygen-containing groups can signifi-
cantly affect electrical conductivity. For example, graphene
with poor oxygen-containing groups has higher electronic
conductivity, whereas rich oxygen-containing groups decrease
the electrical conductivity to different degrees. Typically,
GO is not an electrical conductor but an ionic conductor. In
addition, GO can also act as the barrier for fuel permeabil-
ity and reinforcement to improve the mechanical strength of
the polymer. Based on this analysis, composite membranes
containing GO for PEMFC in both acid and alkaline media
were designed and fabricated [178,261–265]. For exam-
ple, in order to prohibit methanol crossover of the Nafion®
membrane, Lin et  al. [266] prepared GO paper laminated
with Nafion membrane. The obtained composite membrane
exhibited higher selectivity (the ratio of proton conductivity
to methanol permeability) than Nafion115, and thus, it was
superior to the pristine Nafion115 in DMFC with 8 M metha-
nol as fuel. Sulfonated poly (ether ether ketone) (SPEEK) is
well known to be an inexpensive promising alternative can-
didate to Nafion membrane for PEMFC. However, there still
exists a conflict between high sulfonation of degree and poor
mechanical property for SPEEK [267,268]. Therefore, sulfo-
nated GO was introduced into the SPEEK matrix for better
overall performances such as satisfying proton conductivity,
high mechanical property, low fuel permeability, as well as
low cost [269,270]. In addition, a hybrid membrane contain-
ing graphene nanosheets and poly (vinyl alcohol) (PVA) for
alkaline DMFC was also designed, and the transport property
of the hybrid membrane was explored. The results suggested
that graphene nanosheets were uniformly dispersed, resulting
in continuous, well-connected, and tortuous ionic channels.
430
Only 0.7 wt% graphene in the PVA matrix resulted in 126%
improvement in ionic conductivity and 55% reduction in
methanol permeability, whereas 1.4 wt% graphene enhanced
the adhesion of the nano-filler matrix, giving an increase of
73% in the tensile strength.
28.4  CONCLUSIONS AND PROSPECTS
Flexible graphene, a newly emerging multifunctional carbon
material, possesses many miraculous and unique superior
qualities to other materials. It is highly expected to resolve
current problems in various energy-related storage and con-
version devices. Extensive efforts were made to explore the
feasibility of these expectations in terms of experiment and
theory. Fortunately, some desired results were obtained,
implying that graphene and its derivatives can shed new light
on improved performance, as expected. Multifunctional gra-
phene-based materials can not only efficiently disperse active
nanoparticles, but also directly act as active materials, which
are attributed to their ultrahigh surface area, fast ­electron
transfer in the electrodes, as well as excellent mechanical
property.
The miraculous properties of graphene are closely asso-
ciated with its unique 2D structure; therefore, it is crucial
to maintain its microstructure and avoid the aggregation
of nanosheets as much as possible. Heteroatom-doping and
functionalization are usual strategies.
There is still controversy on planar or edge defects in gra-
phene nanosheets: on the one hand, these defects can make
the measured electronic conductivity deviate from the theo-
retical value; on the other hand, they can also facilitate the
ionic diffusion, and offer more surface active sites to anchor
the nanoparticles and heteroatoms on graphene nanosheets by
covalent or noncovalent methods. In fact, the requirements of
energy devices are usually multiscaled. For example, in the
case of support, both high electronic conductivity and high
ionic conductivity are preferable; as for the polymer, it is
desirable that graphene possesses low electronic conductivity
with as high ionic conductivity as possible. Therefore, these
defects provide more space to tailor the overall performances
for different applications, and careful control is necessary
for different situations. Also, the promoting mechanism of
­graphene-based materials is not very clear, so intensive inves-
tigations of graphene are still necessary in terms of both
­theory and experiment for better multiapplications.
It is still premature to synthesize graphene in bulk for dif-
ferent applications, and the various related issues are better
resolved prior to commercialization and application in large
scale.
ACKNOWLEDGMENTS
We are grateful for financial support from The National
Natural Science Foundation of China (51363011), the
Scientific Research Foundation for the Returned Overseas
Chinese Scholars, State Education Ministry in China (6488-
20130039), the Program of High-Level Introduced Talent of
Graphene Science Handbook
Yunnan Province (10978125), Yunnan Project of Training
Talent (1418425), and the Project of Key Discipline (14078232).
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29 Potential Applications of Graphene in
Polymer Electrolyte Membrane Fuel Cell
Avijit Ghosh and Anil Verma

CONTENTS
Abstract...................................................................................................................................................................................... 439
29.1 Introduction...................................................................................................................................................................... 439
29.2 PEMFC and Associated Issues......................................................................................................................................... 440
29.3 Graphene: A Potential Candidate for Various Components of PEMFC.......................................................................... 442
29.3.1 Graphene in Bipolar Plate..................................................................................................................................... 442
29.3.1.1 Different Type of Materials for Bipolar Plate........................................................................................ 443
29.3.1.2 Carbon–Polymer Composite Bipolar Plate............................................................................................ 444
29.3.1.3 Graphene Reinforced Carbon–Polymer Composite Bipolar Plate........................................................ 447
29.3.2 Graphene as an Electrocatalyst Support............................................................................................................... 450
29.3.2.1 Synthesis of Graphene Supported Metal Electrocatalyst...................................................................... 452
29.3.2.2 Properties of Graphene Supported Metal Electocatalyst for Fuel Cell................................................. 453
29.3.2.3 Performance of PEMFC Using Graphene as an Elctrocatalyst Support............................................... 456
29.3.3 Graphene in Polymer Electrolyte......................................................................................................................... 456
29.3.4 Graphene in Microporous Layer........................................................................................................................... 456
29.4 Summary.......................................................................................................................................................................... 456
Acknowledgment....................................................................................................................................................................... 457
References.................................................................................................................................................................................. 457

ABSTRACT
The polymer electrolyte membrane fuel cell (PEMFC) is one
of the most promising, clean, and high efficiency energy con-
version devices. The carbon, due to its unique electrical and
structural properties, is one of the key materials in PEMFC.
Carbon is used to develop the composite bipolar plate, cata-
lyst support material, microporous layer, and gas diffusion
layer (GDL). The different form of carbon materials such as
graphite, carbon black, carbon fiber, and carbon nanotube
has been widely chosen by many researchers for develop-
ment of PEMFC components. Moreover, the establishment
of graphene nanomaterial opened up new avenues to be used
in PEMFC components. The graphene being investigated as
reinforcement into the composite bipolar plate to improve the
electrical conductivity, particularly through plane according
to U.S. Department of Energy (U.S. DoE) target properties.
The graphene supported platinum catalyst is investigated to
develop highly stable and high electrochemical activity in
PEMFC environment. Recently, it is reported that the rein-
forcement of graphene into solid polymer electrolyte increases
the PEMFC performance significantly. It can also be used to
develop the microporous layer (MPL) on the electrode sur-
faces of membrane side for uniform distribution of the fuel
and oxidant over catalyst layer. This chapter presents state-
of-art use of graphene in PEMFC component along with a
description of the different carbon materials currently being
used and their ability to meet the requirements. The chapter
discusses composite bipolar plate and electrocatalyst support
using graphene along with the possible future usages of gra-
phene in MPL and GDL.
29.1 INTRODUCTION
The International Energy Outlook in 2013 estimated that
the global energy consumption might increase around 35%
by 2040 from its current usage of 89 million barrels per day.
The present energy demand of the world is primarily met by
the conventional fuel resources. However, the present world
energy scenario reveals that within the next few decades, the
world would face a severe shortage of the present conven-
tional fuel resources. Moreover, the uses of fossil fuel pose
unwanted side effects to the environment such as emission
of toxic and greenhouse gases [1]. Therefore, owing to the
probable shortage of the conventional fuels, scientists and
technologists are in search of non-conventional sources and
efficient energy conversion devices. There are various non-
conventional energy sources, and much research work is
being carried out worldwide to make the technologies eco-
nomically viable. In this aspect, the fuel cell is found to be one
of the most stringent and promising power conversion devices
in future [2]. Fuel cells are basically galvanic cells, which
directly convert the chemical energy of a fuel into the electri-
cal energy. Polymer electrolyte membrane fuel cell (PEMFC)
439
440 Graphene Science Handbook

is one of the fuel cells that operate at low temperature and
is found suitable for stationary and automotive applications
owing to its attractive features such as relatively low operat-
ing temperature, convenient fuel supply, longer lifetime, high
power density, and its modularity [3]. However, the feasibil-
ity of PEMFC, against conventional technologies, requires
that it should undergo significant miniaturization along with
low cost while achieving higher power densities in variable
load conditions [4]. For example, the cost of automotive fuel
cells should be competitive with today’s internal combustion
engines for successful commercialization. Considering the
high volume production of fuel cell stack, the U.S. DoE esti-
mated that the cost is reduced by 65%, that is, from $275 kW−1
in 2002 to $73 kW−1 in 2008. The DoE’s cost target for com-
mercialization of a fuel cell system in 2010 was $45 kW−1 for
a production volume of 500,000 units. Moreover, this target
was divided into the fuel cell stack ($30 kW−1) and the sup-
porting balance of plant ($15 kW−1). However, the ultimate
goal for replacing the internal combustion engine by 2017 is
$30 kW−1 [5]. New material development, stack technology
innovation, and system optimization are the drivers to achieve
the cost target.
29.2  PEMFC AND ASSOCIATED ISSUES
PEMFC is one of the challenging energy conversion devices
for transportation and distributed power generation systems
owing to its attractive features such as high power density,
modularity, solid state construction, low operating tempera-
ture, longer lifetime, minimal emissions, quick startup, negli-
gible noise, and high chemical to electrical energy conversion
efficiency. The PEMFC may generate power in the range of
Watt to kilowatts. The major application of PEMFC is focused
on transportation, because of its potential impact on the envi-
ronment such as the control of greenhouse emission. Figure
29.1 shows a schematic representation of a single PEMFC
(Figure 29.1a), whereas Figure 29.1b shows the exploded view
of a PEMFC stack (two single cells in series). It can be seen in
Figure 29.1 that PEMFC mainly consists of anode and cath-
ode compartments separated by a proton exchange membrane

Load
(a)

e– e–
Inlet, O2
Inlet, H2 e–
H2 H+ e– O2

H2 e– e– O2
H+
Monopolar plate
Monopolar plate

H2 O2
End plate

End plate

H2 e– e– O2
Anode H+ Cathode
H2 e– O2

H2 H+ e– O2

Outlet, H2 e– O2

e– H+ Outlet, water,
unused H2 H2 e– O2
and unused O2
Carbon paper Carbon paper
Microporous layer Microporous layer
Anode Pt catalyst layer Cathode Pt catalyst layer
Proton exchange membrane

MEA Bipolar plate MEA

(b)
Inlet, H2
Inlet, O2
H2 O2 H2 O2

H2 O2 H2 O2
Monopolar plate

Monopolar plate

O2 O2
End plate

H2 H2

Cathode
End plate

H2 O2 H2 O2
Anode
H2 O2 H2 O2

H2 O2 H2 O2

Outlet, H2 O2 H2 O2 Outlet, water,

unused H2 H2 O2 H2 O2 and unused O2

Carbon paper Carbon paper

Microporous layer Microporous layer
Catalyst layer Catalyst layer
Proton exchange membrane

FIGURE 29.1  Schematic of (a) single-cell PEMFC and (b) an exploded view of a PEMFC stack (two unit cells in series).
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell 441

(PEM). Both the compartments have similar components like 300

monopolar plate/bipolar plate, carbon paper, and micropo- 275 $· kW–1 Initial estimation
Balance of plant (assembly and testing)
rous layer (MPL) on which the catalyst is coated. The anode 250 Stack

Fuel cell system cost ($ ·kW–1)

and cathode, both comprising of carbon paper, MPL, cata-
lyst layer, along with PEM is known as a membrane electrode
assembly (MEA) as shown in Figure 29.1b. It may be noted
that the bipolar plate accommodates both fuel and oxidant as
well as connects the single cells in series. Many cells may
be stacked with the help of a bipolar plate for higher power
output. The anode, which provides an interface to the fuel
(generally H2) and the electrolyte, catalyzes the fuel oxidation
reaction, and provides a path through which free electrons are
conducted to the load via external circuit. The cathode pro-
vides an interface to the oxidant (generally O2) and the elec-
trolyte catalyzes the oxygen reduction reaction (ORR). The
electrolyte provides a conductive path to the protons and acts
as a separator between anode and cathode compartment to
prevent the mixing of hydrogen and oxygen, thus preventing
direct combustion.
The basic principle of PEMFC is that the H2 and O2 elec-
trochemically react to produce water, electricity, and heat.
The hydrogen gas is supplied to the anode side of the PEMFC,
where H2 molecule splits into two protons (H+) and two elec-
trons (e−) in the presence of Pt catalyst as shown in Equation
29.1. The monopolar plates provide a pathway through which
the generated electrons are conducted to the cathode via
external circuit through a load. Protons generated at the anode
migrate to the cathode through the PEM. At the cathode, the
protons, electrons, and oxygen react as per Equation 29.2 to
form water, and heat is also generated being an exothermic
reaction. The overall reaction is shown in Equation 29.3.
The electrochemical reactions in a PEMFC are shown as
follows:
Anode reaction: H 2 → 2H + + 2e − (29.1)
1 (Pt/C). The carbon paper and the MPL contain carbon. Thus,
Cathode reaction: O2 + 2H + + 2e − → H 2O (29.2)
2 it can be understood that carbon not only highly contributes to
Target 2017
200
150
100 47 $·kW–1
30 $ ·kW–1
50
0
2002 2006 2007 2008 2009 2010 2011 2012 2017
FIGURE 29.2  Projected cost of an 80 kW PEMFC system consider-
ing high volume manufacturing (500,000/year). (From J. Spendelow
and M. Jacos, Fuel cell transportation cost analysis, preliminary
results:presentation at the U.S. DOE hydrogen and fuel cells program
annual merit review and peer evaluation, http://www.hydrogen.energy.
gov/pdfs/12020_fuel_cell_system_cost_2012.pdf, 2012.)
Figure 29.2 shows the timeline of PEMFC system cost
along with the target cost to be achieved by 2017 [10]. The
fuel cell system cost involves stack cost as well as the cost
for the balance of plant. It is targeted to achieve $30 kW−1 by
2017 considering 80 kW PEMFC stack with a production of
500,000 units per year. This cost reduction would be achieved
by advances in the science and technology using efficient and
durable fuel cell components.
As discussed earlier, the PEMFC stack mainly consists of
bipolar plates and MEA. The cost analysis of the components
of a PEMFC is shown in Figure 29.3. It may be noted that vari-
ous components in the above list contain carbon in some form
or the other. Present research pattern of bipolar plate is focused
on carbon composites (graphite, carbon fiber (CF), carbon
black (CB), etc), whereas platinum catalyst is supported on CB

1 Membrane Others
Overall reaction: H 2 + O2 → H 2O + Energy + Heat (29.3) 7%
2 12% Bipolar
plate
38%
PEMFC exhibits good energy efficiency and higher power
Catalyst
density per unit volume. However, the high costs of noble (Pt)
metal catalyst, polymer electrolyte membrane, control sys- 11%
tem, as well as lack of efficient bipolar plate are the main
constraints for the worldwide commercialization of PEMFC
[6–8]. In addition, less durability of carbon-supported Pt
catalyst also hinders long-term operations [9]. Moreover, a
single-cell does not generate any useful power and therefore,
single-cell needs to be stacked. It is worth mentioning that Electrodes
though the fuel cells generate high currents but are very low 32%
voltage sources. Therefore, to have a useful voltage output,
the single-cell PEMFCs need to be stacked in series, which FIGURE 29.3  PEMFC stack cost analysis. (From S.K. Kamarudin
generate the requirement of the efficient bipolar plate. et al., Journal of Power Sources, 157, 2006, 641–649.)
442 Graphene Science Handbook

materials have been investigated in recent past for the devel-

TABLE 29.1 opment of efficient PEMFC components, based on physical
PEMFC Components and Associated Major Issues and electrochemical properties. In particular, electrical con-
[15–21] ductivity and excellent chemical stability in acidic and redox
environment are a few of the most important requirements. It
PEMFC Components Major Issues
is reported that carbon in the form of its different allotropes is
Bipolar plate High corrosion; low electrical conductivity;
extremely attractive for use in the PEMFC components such
low mechanical strength; and high ICR
Electrocatalyst support Low specific surface area; low electrical
as bipolar plate, microporous layer, gas diffusion layer (GDL),
conductivity; and low durability and catalyst support, owing to its high electrical conductiv-
Solid polymer electrolyte Low ionic conductivity; low mechanical ity and electrochemical stability in PEMFC [22]. Moreover,
strength; and low durability the establishment of graphene nanomaterial has attracted the
Microporous layer Low electrical conductivity research focus owing to its unique properties.
Graphene (GP) is one of the most exciting nanomaterials
being explored during recent years, not only out of academic
interest but also for its potential applications. Graphene is an
atomically thin sp2 hybridized two-dimensional (2D) sheet of
800
a carbon atom, packed in a hexagonal lattice structure with a
700 carbon–carbon distance of 0.142 nm. The graphene is recog-
Number of journal articles

600
500
400
300
200
100
0 bon atoms that contribute to a delocalized network of electrons
1990 1995 2000 2005
Year
FIGURE 29.4  Number of journal articles published on PEMFC.
(From http://www.scopus.com, Search: polymer electrolyte mem-
brane fuel cell, May, 2013.)
the weight and volume of the PEMFC but also greatly influ-
ences the performance of the PEMFC [11]. From Figure 29.3, it
can be seen that the bipolar plate is the most costly component
contributing to around 38% PEMFC stack cost after electrodes
(MPL on carbon paper). Moreover, the bipolar plate is the
heaviest component of the PEMFC stack having 80% weight
of the stack [12,13]. Table 29.1 summarizes various required
properties of the PEMFC composite material. Therefore, the
researchers are attracted to study the materials used in the man-
ufacturing of the bipolar plate, catalyst support, microporous
layer, and carbon paper. The pressing need to overcome the
issues of PEMFC has driven the exponential growth and inter-
est in the field of PEMFC as shown in Figure 29.4 [14].
The current status of the different types of carbonaceous
components used in PEMFC is discussed in the subsequent
section.
29.3 GRAPHENE: A POTENTIAL CANDIDATE
FOR VARIOUS COMPONENTS OF PEMFC
The material selection plays a pivotal role in the performance
of a fuel cell as discussed in the earlier sections. A number of
nized as the basic building block of all graphitic materials such
as three-dimensional-graphite, one-dimensional (1D)-carbon
nanotube (CNT), and 0D-fullerene [23,24]. Initially, the exis-
tence of 2D crystal was assumed to be thermodynamically
unstable. However, in 2004, Geim and Novoselov [25] estab-
lished single layer 2D crystal from graphite using Scotch tape
method. The carbon atoms in the graphene crystal lattice are
bonded together with σ bonds, and one π electron (owing to
delocalized pz orbital) is freely suspended to each of the car-
2010 2015 [26]. This distinct structure of graphene has received consid-
erable attention because of its fascinating properties including
very high theoretical surface area (around 2630 m2 g−1) [27],
highest electrical conductivity (around 106 S cm−1) [25], very
good mechanical strength (100–200 times stronger than steel),
inherent flexibility, high aspect ratio, and unique basal plane
structure [23,25,28]. Therefore, the graphene has attracted a
great deal of attention in a variety of applications including
fuel cell components [1,29–33].
Following subsections provide the present research and
development status of various components of PEMFC that
use carbon and its allotropes and have the potential to use
graphene.
29.3.1 Graphene in Bipolar Plate
The bipolar plate is one of the vital components of PEMFC,
which accounts for 80% of the total weight, around 90% of
the total volume, and also consumes around 38% of total cost
of the PEMFC stack [34,35]. The various functions of the
bipolar plates of a PEMFC stack are to [36]
1. Support the MEA
2. Distribute the fuel and oxidant over the active elec-
trode surface
3. Facilitate water management within the cell
4. Prevent leakage of reactant gases and coolant
5. Carry current away from the cells
6. Dissipate the generated heat from the cells
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell 443

metal bipolar plate is the other option, which may exhibit high
TABLE 29.2 electrical conductivity, excellent mechanical strength, high
​Stringent Target Properties for Bipolar Plates in PEMFC thermal conductivity, easy flow channels processability, and
Application [30,37,39,40] high hydrogen gas impermeability. Different types of metal,
metal-alloy, and metal foam have been studied for possible
DoE or Plug
Required Properties Units Power Target
replacement of pure graphite bipolar plates. They include
aluminum, stainless steel, titanium, nickel, copper, and their
Density g cm−3 <2
alloys [43–45]. However, metals are susceptible to corrosion
In-plane electrical conductivity and S cm−1 >100
upon exposure to harsh acidic, humid, and redox environment
through-plane electrical conductivity
of fuel cell at about 80°C [46,47]. The degradation of the fuel
Flexural strength MPa >59a
cell may start by catalyst poisoning and membrane contami-
Deflection at mid-span % 3–5
nation due to leaching of the metal ions from the bipolar plate
Thermal conductivity W m−1 K−1 >10
[45]. To overcome the corrosion issue, a protective layer was
Hydrogen permeability (at 80°C and cm3 cm−2 s−1 <2 × 10−6
3 atm)
coated on the metal surface to resist the corrosion in acidic
Scleroscope shore hardness C-type >40a
PEMFC environment [47]. It should be ensured that the elec-
Corrosion current density μA cm −2 <1
trical conductivity of the coated metal bipolar plate should
Interfacial contact resistance mΩ cm2 <10
not be much compromised. In addition, the coating must be
Durability with cycling H >5000
adhered well to the metal surface. However, this protective
layer increases the surface resistivity of the metal bipolar
a Plug power Inc. plate due to the formation of micro-pores and micro-cracks in
the coating layer by uneven thermal expansion between metal
and coating layers [45,48–51].
To meet the above functions, the bipolar plate should have Considering the above issues, it was felt that there was
several properties including [35] a need to find alternative material to fulfill the stringent
requirements of the PEMFC bipolar plate. In this concern,
1. High through-plane as well as in-plane electrical the carbon–polymer composite bipolar plate is being stud-
conductivity ied extensively to replace the pristine graphite and metal/or
2. Good mechanical strength coated metal bipolar plate [15–21]. Table 29.3 summarizes the
3. High thermal conductivity advantages and disadvantages of different materials, which
4. Low hydrogen permeability are commonly being investigated for the development of
5. Excellent electrochemical stability bipolar plate. It can be seen that the carbon–polymer com-
6. Low interfacial contact resistance (ICR) posite bipolar plates show high corrosion resistance as com-
7. High durability pared to metal and good mechanical strength as compared
8. Easy processability for designing flow field to pure graphite along with moderate electrical conductivity.
Therefore, the carbon–polymer composite bipolar plate is
Therefore, many agencies have given benchmarks for extensively used as a bipolar plate for PEMFC. Figure 29.5
bipolar plate properties. Table 29.2 shows the stringent tar-
get properties form the benchmarks provided by the DoE and
Plug Power Inc. [30,37–39]. The above stringent targets can TABLE 29.3
only be achieved using suitable materials for the bipolar plate.
​Common Materials for Bipolar Plate and Their
29.3.1.1  Different Type of Materials for Bipolar Plate Advantages and Disadvantages [15–21]
Different type of materials, including graphite, metal sheet, Materials Advantages Disadvantages
coated metal, and carbon–polymer composite, have been Pure graphite High electrical Low mechanical strength
introduced for the development of bipolar plates. However, conductivity High H2 permeability
developing suitable bipolar plate, which can satisfy all the Good corrosion resistance Difficult machining of flow
stringent target properties is still in progress. Pure graphite is field
the most common material used to develop bipolar plates. The Metal High electrical High corrosion
graphite bipolar plates have very good corrosion resistance, conductivity High ICR
High mechanical strength High density (more weight)
excellent chemical stability, good electrical conductivity, and
Coated metal High electrical conductivity Uneven thermal expansion
high thermal conductivity. However, the main limitation of
High mechanical strength High density
graphite bipolar plate is its brittleness, which poses difficulty
Carbon–polymer High corrosion resistance Long processing time
in machining the flow channels in the plate for the reactant composite Good mechanical strength
flow [41]. In addition, cutting and machining of the flow chan- Moderate electrical
nels is time-consuming and costly, owing to the brittleness of conductivity
graphite. In view of all these issues, pure graphite may not be Low ICR
suitable for automobile and portable devices [42]. Therefore,
444 Graphene Science Handbook

Carbon-polymer composite bipolar plate

Carbon reinforcement Polymer matrix

Natural Expanded Carbon Carbon Carbon Graphene

graphite graphite black fiber nanotube (GP)
(NG) (EG) (CB) (CF) (CNT)

Thermosets Thermoplastic

Poly (vinylidene fluoride) poly (arylenedisulfide) Polypropylene Polyethylene

(PVDF) (PDS) (PP) (PE)

Novolac phenol formaldehyde resin Resol formaldehyde resin Vinyl ester resin Epoxy
(NPFR) (RPFR) (VER)

FIGURE 29.5  Classification of carbon–polymer composite bipolar plate materials. (From V. Mehta and J.S. Cooper, Journal of Power
Sources, 114, 2003, 32–53; A. Hermann, T. Chaudhuri, and P. Spagnol, International Journal of Hydrogen Energy, 30, 2005, 1297–1302.)

shows the different types of additives, reinforcements, and
matrix, which are commonly used for the development of
carbon–polymer composite bipolar plate [34,47,52]. Natural
graphite (NG) or synthetic graphite (SG) or expanded graph-
ite (EG) is commonly used as a primary reinforcement for the
polymer composite bipolar plate. The critical primary rein-
forcement to matrix ratio should be around 60–75 vol.% or
25–40 wt.% to maintain proper dispersion of reinforcement
into the polymer matrix [30]. Moreover, the different types of
additives such as CB, CF, CNT, and GP are introduced into
the primary reinforcement/polymer matrix to tune the electri-
cal and mechanical properties of the composite bipolar plate
in order to achieve the stringent benchmark [30,37,53–57].
It has been seen that combining NG with the additives such
as CB, CF, and CNT show an effective way to develop the
carbon–polymer composite with higher electrical and good
mechanical properties [34,58,59]. Generally, thermosetting or
thermoplastic polymer is used for the development of carbon–
polymer composite bipolar plate as a matrix.
The composite bipolar plates are usually prepared by com-
pression molding and injection molding techniques. One of
the main advantages of these preparation techniques is that
the flow channels can be prepared in situ in the bipolar plate
at the time of compression/injection molding thus, eliminat-
ing the cost associated with the machining steps. The injec-
tion molding method is preferred for large-scale production of
carbon composite bipolar plate using thermoplastic resin due
to short processing time, automated production, and accurate
size [60]. However, it has some disadvantages such as exces-
sive mold wear for high viscosity of the materials, limited
flow ability, and poor through-plane electrical conductivity of
the composite due to flow-induced orientation of the continu-
ous fillers [61]. In this regard, compression molding may be a
good choice for the development of composite bipolar plates
due its high accuracy, higher electrical conductivity, good
thermal conductivity, and high filler loadings handling capa-
bilities [54,62–64]. However, compression molding technique
has slow output as compared to injection molding technique.
The subsequent section will discuss on recent advances of
carbon–polymer composite bipolar plate for PEMFC applica-
tion [21,41,65,66].
29.3.1.2  Carbon–Polymer Composite Bipolar Plate
NG is used as reinforcement along with different matrix
[64,67,68]. Kuan et  al. prepared the composite bipolar plate
by mixing bulk molding compound (BMC) and NG using
compression molding technique [67]. Different proportions of
the BMC and NG were used, and the optimum performance
of the developed composite bipolar plate was found at 75%
NG content (mean size 177 µm) and 25% BMC. The in-plane
electrical conductivity and flexural strength were found to be
114 S cm−1 and 31.25 MPa, respectively. However, it may be
noted that the flexural strength is quite low as compared to
the target values shown in Table 29.2. Moreover, the through-
plane electrical conductivity of the developed composite bipo-
lar plate is not reported. Yin et  al. optimized the operating
preparation parameters and composition of NG/NPFR com-
posite. They have studied molding temperature and molding
time on the electrical and mechanical properties of the com-
posite bipolar plate and studied the effect of NPFR content
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell
[64]. It was found that the electrical conductivity of the com-
posite decreased initially up to 220°C and 45 min of molding
time. Thereafter, with a further increase in the molding tem-
perature and time, the electrical conductivity achieved max-
ima for molding temperature of 240°C and a molding time of
1 h. However, the electrical conductivity decreased with fur-
ther increase in temperature and molding time. The optimum
temperature and time of the compression molding was uti-
lized to fabricate composites of various composition of NG/
NPFR. The flexural strength of the above composites also fol-
lowed the same trend for molding temperature and time. The
best in-plane electrical conductivity and flexural strength was
found for NG/NPFR 85/15 (wt.%) composite were 142 S cm−1
and 61.6 MPa, respectively. However, the other properties of
the composite were not reported. The effect of graphite par-
ticle size (mean size 75 and 150 µm) and its content on the
properties of NG/polymer composite bipolar plate was studied
by Kang et al. [68]. The through-plane electrical conductiv-
ity of the optimum composite NG/RPFR 80/20 (wt.%) was
reported as 31.1 and 39.1 S cm−1 using average NG particle
sizes of 75 and 150 µm, respectively, which was significantly
lower than DoE target. Moreover, the air permeability of the
optimum composites was around 1.7 × 10−5 cm3 cm−2 s−1 and
7.6 × 10−5 cm3 cm−2 s−1 for average NG particle sizes of 75 and
150 µm, respectively, which was quite high in comparison
to the stringent target benchmark for hydrogen permeability
(Table 29.2). It was found that only the use of graphite might
not be suitable to improve the various properties of the com-
posite bipolar plate.
Various literatures report the use of NG, EG, CB, CF, along
with the resin matrix for the development of composite bipo-
lar plate [15,55,69]. For example, Dhakate et  al. along with
Lee et al. reported similar electrical and mechanical behavior
of CB/NG/NPFR and CB/NG/epoxy composites, respectively
[65,70]. The optimum CB content was found to be 20% [70]
as compared to 5% [65]. These differences arise from intrin-
sic electrical properties, and from morphology-related issues
of both graphite and CB particles [41]. It is reported that the
properties, particularly conductivities of the NG/polymer and
EG/polymer [61,71] composites may be benefitted from the
addition of small CB content. It is also reported that CF are
the primary source of mechanical strength for carbon–poly-
mer composite bipolar plate [30].
Table 29.4 shows the comparison of some of the recent and
past literature data on the properties of carbon–polymer com-
posite bipolar plates. It can be seen that the in-plane electrical
conductivity of the composite bipolar plate was extensively
studied, but through-plane electrical conductivity was not
reported extensively. The through-plane electrical conductiv-
ity for bipolar plate is more important than in-plane electri-
cal conductivity, as the electrons are collected by the plate
at the anode side and transported through the bipolar plate
to cathode side (other side of the bipolar plate) in a fuel cell
stack. It is obvious that the electrical conductivity and flexural
strength are the most important properties among the other
stringent benchmarks. Therefore, research is going on to
increase the mechanical strength and electrical conductivities
445
(particularly through-plane) of the carbon–polymer compos-
ite bipolar plate using different types of carbon nanofillers.
In the other words, it is difficult to obtain simultaneous high
electrical conductivity and high mechanical strength, for the
same reinforcement in the composite bipolar plate [21,72].
Polymer matrix distributes the various stresses/loads
throughout the composite (NG/polymer) and provides the
mechanical strength. However, the achievement of the higher
mechanical strength is adversely accompanied by the reduc-
tion of electrical conductivity. Therefore, balancing these
two properties along with the properties is one of the main
­challenges in the research of PEMFC bipolar plate. Moreover,
the pathway to reach high power density is closely related
to the ohmic losses within the PEMFC stack. In this regards,
the optimization of the electrical conductivity of the compos-
ite bipolar plate plays a leading role thereby demanding many
efforts to the development of highly conductive ­materials.
A  common approach reported to improve the electrical
conductivity and mechanical strength is to reinforce minor
amount of highly conductive carbon nanofillers into the NG/
polymer composites. In this concern, researchers and scien-
tists studied carbon nanomaterial, which may overcome these
problems. Among the various reinforcements single-walled
CNT, multi-walled CNT (MWCNT), and graphene have
attracted considerable attention as potential candidates for
fabricating multi-fillers reinforced efficient carbon–polymer
composite bipolar plate.
It is found that in general, the reinforcement loadings
fall in 60%–75% to reach adequate electrical conductivity
by the polymer composite bipolar plate [21]. However, there
is a lack of polymer matrix to fill all the interstices among
graphite particles at high carbon filler loadings. Therefore, the
mechanical strength of highly reinforced carbon composite
bipolar plate is insufficient as well as susceptible to hydrogen
permeability [41,54,77]. The CNTs are used as reinforcement
for polymer composite to increase the mechanical properties.
As an example, the tensile strength of the pure epoxy bipolar
plate can be increased by 159% (89.1–231.5 MPa) using CNT/
epoxy 16.5/83.5 (wt.%) composite bipolar plate [78]. Although
the in-plane electrical conductivity of the CNT/epoxy com-
posite achieved the DoE target (Table 29.2) but other target
properties including the through-plane electrical conductiv-
ity were not reported. Moreover, it is reported that the high
aspect ratio of CNT has the tendency to agglomerate at higher
loadings into the polymer matrix, which may decrease the
properties of the CNT/polymer composite [52]. Therefore,
CNT can be used as a low loading additive in the NG/polymer
composite to improve the electrical and mechanical proper-
ties [75,79–81].
An investigation by Lee et  al. [65] was conducted on
the electrical and mechanical properties of a compression
molded SG/polymer composite bipolar plate reinforced with
different additives such as CB, MWCNT, or CF. They have
found that the optimum in-plane electrical conductivity of
254.7 S cm−1 was achieved for 73 vol.% SG, 25 vol.% epoxy,
and 2 vol.% of MWCNT, which is 105% higher than SG/
epoxy composite with the same amount of conducting filler
 446

TABLE 29.4
Properties of the Carbon–Polymer Composite Bipolar Plate Reported in Literatures in Recent Past
Electrical Conductivity (S cm−1) Interfacial Corrosion Hydrogen
Composite Bipolar Plate Developed Flexural Deflection Contact Current Permeability Thermal
Using Compression Molding Density Strength at Mid-span Resistance Density (×10−10 conductivity
Technique (g cm−3) In-plane Through-plane (MPa) (%) (mΩ cm2) (µA cm−2) cm3 cm−2 s−1) (W m−1 K−1) References

NG/NPFR 85/15 vol.% N/A 142 N/A N/A N/A N/A N/A N/A N/A [64]
CF/NG/PVDF 6/70/24 wt.% N/A 292 32 60 N/A N/A N/A N/A N/A [35]
EG/NG/NPFR 7.5/67.5/25 wt.% 1.85 250 N/A 50 N/A N/A N/A N/A N/A [73]
CNT/NG/NPFR 3/82/15 wt.% N/A 145.2 N/A 68.6 N/A N/A N/A N/A N/A [74]
PP:24w;NG:76w;CNT: 4 phr N/A 548 N/A 32.6 N/A N/A N/A N/A N/A [75]
CF/NG/Epoxy 7/68/25 vol.% N/A 240 N/A 67 N/A N/A N/A N/A N/A [65]
CNT/NG/NPFR 1/64/35 vol.% 1.78 178 30 56 N/A N/A N/A N/A 50 [52]
CF/CB/NG/NPFR 5/5/60/30 vol.% 1.81 286 92 55.28 5.2 N/A 0.99 11.11 128.26 [55,76]
CNT/NG/VER 0.5 phr/70/30 wt.% N/A 261.1 N/A 45 N/A N/A N/A N/A 27.3 [48]
NG/RPFR 80/20 wt.% N/A 324.7 31.1 41.9 N/A N/A N/A 7.6 × 104 N/A [68]
(air permeability)
NG/BMC 80/20 wt.% N/A 167 35.2 N/A N/A N/A N/A N/A N/A [19]
CF/EG/NG/NPFR 5/5/40/50 wt.% N/A 1518 76 84 N/A N/A N/A N/A N/A [20]
CF/EG/NG/NPFR 10/5/45/40 wt.% N/A 101 N/A 74 N/A 9 at 1.5 MPa N/A No leakage detected 9.6 [57]
CF/SG/NG/NPFR 10/10/45/35 vol.% N/A 125 N/A 40 N/A N/A N/A N/A N/A [59]

Note: N/A, not available.

Graphene Science Handbook
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell
(75/25 vol.%). This may be attributed to the high aspect ratio
of MWCNT, which formed good conducting path as well as
connected the graphite particles. The flexural strength of
the MWCNT/SG/epoxy composite was found to be 48 MPa,
which was also 83% higher that SG/epoxy composite. It was
shown that the electrical conductivity of MWCNT rein-
forced composite bipolar plate decreased with the increased
content of MWCNT beyond 2%. It may be due to the clus-
ter formation of MWCNTs at higher loading due to lack of
polymer matrix in the composite resulting incomplete bind-
ing during the molding process. Thus, the generated voids
acted as an insulator and reduced the electrical conductiv-
ity [82]. However, the through-plane electrical conductivity
of the MWCNT reinforced composite bipolar plate was not
reported. Later, Dhakate et  al. [52] reported a similar ben-
eficial effect of MWCNTs in forming additional conducting
paths in MWCNT/NG/NPFR composite. The through-plane
electrical conductivity of the optimum MWCNT/NG/NPFR
1/35/64 (vol.%) composite was 30 S cm−1, which was around
233% higher than without MWCNT reinforced composite
bipolar plate. The in-plane electrical conductivity, flexural
strength, and thermal conductivity of the optimum compos-
ite was increased by 106%, 25%, and 100%, respectively,
due to the reinforcement of 1% MWCNT into the NG/NPFR
composite as compared to without MWCNT composite bipo-
lar plate. This significant improvement can be attributed to
the MWCNTs, which were oriented in all directions and
having a higher value of intrinsic thermal conductivity and
mechanical strength. Moreover, the MWCNT oriented in the
z-direction (through-plane) facilitate pathway for electrical
conduction and heat transfer along the composite. It was seen
that though the various polymer matrices and carbon rein-
forcements were used in the studies, the composite bipolar
plates could not achieve the required properties set in Table
29.2, or the properties were not reported. Moreover, it can
also be seen that many of the other crucial properties of the
composite bipolar plate have not been studied thoroughly.
The hydrogen permeability, corrosion resistance, contact
resistance, and thermal conductivity are the foremost prop-
erties among them. Therefore, the research is going on to
improve the overall properties of the composite bipolar plate.
Graphene can be a potential reinforcement into the poly-
mer composite bipolar plates owing to attractive electrical
and mechanical properties as compared to CNTs. Table 29.5
TABLE 29.5
Properties of Different Carbon Materials [52,83–85]
Properties Units NG
Density g cm−3 2.26
Electrical conductivity S cm−1 ~104
Thermal conductivity W m−1 K−1 500 (in-plane)
6 (through-plane)
Specific surface area m2 g−1 10
Fracture strength GPa ~10−1
447
shows the comparison of the different carbon material prop-
erties, which are usually being under investigation for the
preparation of efficient composite bipolar plate. It can be seen
that the electrical, mechanical, and physical properties of the
GP is significantly high as compared to other carbon materi-
als. The specific surface area is around 10 times higher than
CNT, which is one of the most important and desired proper-
ties for various components of a PEMFC. Furthermore, it can
be dispersed uniformly into the polymer matrix without any
entanglement with suitable treatment [30].
29.3.1.3 Graphene Reinforced Carbon–Polymer
Composite Bipolar Plate
The GP nanoparticles exhibit low percolation threshold in
GP/polymer composites, typically in the range of 0.1%–2%,
depending on the dispersion in the polymer and employed pro-
cessing conditions. The GP nanoparticles affect the behavior
of the surrounding polymer matrix and improve the electrical
and mechanical strength at lower filler content [86–88]. The
GP content at percolation threshold (0.1 vol.%), the electrical
conductivity of the GP/polystyrene composite was around
0.001 S cm−1 [27]. This electrical conductivity is sufficient for
many electrical applications, but it is not suitable for the bipo-
lar plate. Moreover, it is reported that the electrical conductiv-
ity of the polymer nanocomposite can further be increased by
increasing the GP content beyond percolation threshold value
[30]. Song et al. patented a process on the development of GP/
polymer composite using 15 wt.% GP. They have reported that
the GP/polymer 15/85 (wt.%) nanocomposite exhibits in-plane
and through-plane electrical conductivities around 100 and
20 S cm−1, respectively [89]. Thus, GP nanomaterial may also
be reinforced in high content to improve the properties of the
polymer composite.
Recently, the GP/polyphenylene sulfide nanocomposite
with high loading of GP nanoparticles was prepared by Jiang
et al. [72]. They found that the in-plane electrical conductivity
increased with the increased GP content. However, the con-
ductivity was still below the DoE target even at 60 wt.% GP
content. It indicates that using GP as the single conductive
filler may not be able to provide enough conductive pathways
for the desired electrical conductivity. It may be due to the
presence of polymer matrix in the micro-pores and/or micro-
gaps between GP particles, which impede through the elec-
tron electrical conductivity in the composite.
CB CF CNT GP
1.12 1.76 1.33 >1
~102 ~103 ~104 ~106
174 10.46 (in-plane) 3000 5000
70 (through-plane)
254 12 400 2630
~10−2 1.87 45 124
448 Graphene Science Handbook

It is often reported that the carbon–polymer composite
bipolar plates should be comprised of more than one type of
conductive reinforcement to achieve the desired properties
of the bipolar plate, where NG may be commonly used as a
primary reinforcement (Table 29.4). The interactions between
reinforcements are determinant for the bulk electrical behav-
ior of the polymer composite. The major problem in the poly-
mer composite is a thin insulating layer that often forms by
polymer resin around the conductive fillers and by decreasing
the effective electrical conductive pathway along the filler par-
ticles. Therefore, the NG/polymer composite requires micro
and/or nano-fillers to increase the conductivity of the com-
posite. One key issue to solve this problem is to reinforce one
or more appropriate conductive fillers (NG and/or CB and/or
CF and/or EG and/or CNTs, and/or GP) that could implement
excellent electrical and mechanical properties at relative low
filler loadings [10,55,66,81,90].
It is found that the in-plane electrical conductivity of the
NG/VER 70/30 (wt.%) composite was increased by 67.7% due
to the reinforcement of 0.5 phr MWCNT content. However,
the in-plane electrical conductivity of the same composite was
increased by 83.9% due to the reinforcement of only 0.2 phr
GP content. On the other hand, the flexural strength of the
NG/VER composite bipolar plate was improved by 60.7%
and 75.7% due to reinforcement of MWCNT (0.5 phr) and
GP (0.2 phr), respectively. Therefore, it is understood that the
GP is much effective than MWCNT for not only improving
the electrical conductivity but also the mechanical strength
of the polymer composite bipolar plate [48]. The in-plane
electrical conductivity of the MWCNT reinforced composite
bipolar plate decreases at higher loading of MWCNT (beyond
0.5 phr). This can be attributed from the fact that the forma-
tion of local clusters due to lack of compatibility between
MWCNT and polymer matrix increase the resistance between
the clusters for electron migration, thus causing decreased in-
plane electrical conductivity. However, the effect of GP con-
tent on the NG/VER composite was not studied. Moreover,
the PEMFC fuel cell performance in terms of power density
was improved by using different composite bipolar plates,
whereas the other parameters were kept same. The fuel cell
power density using NG/VER nanocomposite bipolar plate
was enhanced around 21.2% and 16.9% for the incorporation
of 0.2 phr GP and 0.5 phr MWCNT, respectively [48].
Therefore, it is obvious that GP can be more favorable
reinforcement into the NG/polymer composite than MWCNT,
which is attributed from the difference in the intrinsic prop-
erties of GP and MWCNT (Table 29.5). However, they have
not reported the through-plane electrical conductivity of the
GP-reinforced NG/VER composite bipolar plate. The flex-
ural strength of the GP (0.2 phr) reinforced NG/VER com-
posite bipolar plate was found to be 49.2 MPa, which is far
below the stringent target (Table 29.2). The comparisons of
the properties of GP reinforced composite bipolar plates are
summarized in Table 29.6. It can be seen that the CF/CB/NG/
polymer composite bipolar plate exhibits better electrical and
mechanical properties as compared to GP (0.2 phr) reinforced
NG/polymer composite bipolar plate. Therefore, there is a
need to study the effect of GP content on the electrical and
mechanical properties of the CF/CB/NG/polymer composite
bipolar plate.
In this regard, exhaustive and systematic study, which
explains the effects of each of these carbon conductive fill-
ers (reinforcements and additives) on the final composite, was
conducted by several researchers using various matrices. The
final composites were prepared by compression molding and
cured at required curing temperatures to obtain composite
bipolar plates [18,65,69]. Figure 29.6 shows the schematic
representation of the development of NG/polymer compos-
ite using a different type of additives such as CB, CF, and
GP. It was observed that the NG/polymer composite bipolar
plate with an optimized combination was able to achieve the
desired in-plane and through-plane electrical conductivities
(Table 29.6) [76]. However, the flexural strength (31.99 MPa)
and deflection at mid-span (2.85%) of the optimum NG/RPFR

TABLE 29.6
Comparison of Graphene Reinforced Polymer Composite Reported in Various Literatures
GP/NG/VER CB/NG/ CF/CB/NG/ GP/CF/CB/NG/
GP/PDS 0.2 phr/70/30 NG/RPFR RPFR RPFR RPFR
Properties 60/40 (%) (%) 75/25 (%) 5/70/25 (%) 5/5/65/25 (%) 1/5/5/64/25 (%)
Density (g cm−3) N/A N/A N/A 1.845 1.81 1.804
In-plane electrical conductivity (S cm−1) 188 286.4 363.4 424.96 415.05 435.31
Through-plane electrical conductivity (S cm−1) N/A N/A 103.3 115.71 99.70 130.17
Flexural strength (MPa) 31.24 49.2 31.99 45.97 54.23 57.28
Deflection at mid-span (%) N/A N/A 2.85 3.03 5.2 5.85
Interfacial contact resistance (mΩ cm2) N/A N/A N/A N/A N/A N/A
Corrosion current density (µA cm−2) N/A N/A 0.1052 0.157 0.997 0.998
Hydrogen permeability (×10−10 cm3 cm−2 s−1) N/A N/A N/A 7.06 9.51 7.15
Thermal conductivity (W m−1 K−1) N/A 27.2 N/A 135.71 145.3 145.9
Scleroscope shore hardness (C-type) N/A N/A N/A 50 66 N/A
References [91] [48] [92] [66,76]
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell
Polymer
matrix
and
acetone
Mixing
Final composite
The powder form of
composite mixture in a mold
FIGURE 29.6  Schematic representation of the mixing of additives/reinforcement/polymer for the carbon–polymer composite bipolar
plate.
75/25 (vol.%) composite was significantly lower as compared
to the benchmark. Moreover, the through-plane electri-
cal conductivity (103.30 S cm−1) of the above optimum NG/
RPFR composite reached the target, which is required to be
increased for better fuel cell stack performance.
Therefore, shortfall in the required properties (Table 29.2)
may be achieved by replacing some of the NG with the other
relevant additives without much compromising the other
properties including density, corrosion current, and hydrogen
permeability [76]. For example, the high through-plane con-
ductivity was achieved by introducing spherical conductive
particles between the flaky graphite particles and the mechan-
ical strengths by the fibrous conductive material. Therefore,
CB and/or CF were used not only to increase the mechanical
strength but also to increase the in-plane and through-plane
electrical conductivities of the composite [76]. It can be noted
that the in-plane electrical conductivity, through-plane electri-
cal conductivity, flexural strength, and deflection at mid-span
of the CB/NG/RPFR composite was increased by around 17%,
12%, 43%, and 34%, respectively, due to reinforcement of 5%
CB at the expense of NG in the NG/RPFR 75/25 vol.% com-
posite. This improvement in the properties of the composite
bipolar plate is attributed to positive synergetic effect between
NG and CB. The synergetic effect can be explained in terms
of formation of an electrical bridge between two neighbor-
ing NG flakes. As the CB content increases, they may not be
fully coated with the polymer resin due to high surface area
of the CB as compared to NG, leading to decreased electri-
cal and mechanical performance of the composite. However,
flexural strength and through-plane electrical conductivity
of the above composite (CB/NG/RPFR 5/70/25 vol.%) were
449
NG CB
Mixing Mixing
Mixing GP Mixing CF
below the benchmark. To further improve the mechanical and
electrical properties of the above CB/NG/RPFR composite,
the CF was reinforced into the CB/NG/RPFR composite at
the expanse of NG content. The in-plane and through-plane
electrical conductivity of the optimum composite CF/CB/NG/
RPFR 5/5/65/25 (vol.%) bipolar plate were slightly reduced
to 415.09 and 99.70 S cm−1, respectively, as compared to CB/
NG/RPFR 5/70/25 (vol.%). However, the flexural strength and
deflection at mid-span of the composite were significantly
improved (55.28 MPa and 5.2%) as compared to the CB/NG/
RPFR 5/70/25 (vol.%).
Figure 29.7a and b show the scanning electron microscope
(SEM) of the optimum composite bipolar plates with CB and/
or CF reinforced NG/polymer composite [18]. It is clearly
visible that the CB particles help to increase the electrical
conducting path by occupying the gap between NG–NG and/
or NG–CF. Moreover, from Table 29.6, it can be seen that
the overall properties of the CF/CB/NG/polymer are signifi-
cantly higher as compared to the GP/polymer and GP/NG/
polymer composite. The through-plane electrical conductiv-
ity and flexural strength of optimized composite (without
GP), CF/CB/NG/RPFR 5/5/65/25, is edge below the stringent
benchmark. Therefore, graphene was used as low loading
additive to increase the electrical and mechanical properties
of the CF/CB/NG/RPFR composite [66]. It can be seen in
Table 29.6 that the incorporation of graphene in the above-
optimized composite improved the electrical and mechanical
properties. It is found that 1% GP content at the expense of
NG in the above-mentioned optimized composite increased
the in-plane electrical conductivity, through-plane electri-
cal conductivity, and flexural strength of the composite from
450 Graphene Science Handbook

(a) (b)
NG

NG

CF

CB CB

10 μm
EHT = 15.00 kV WD = 13 mm Mag = 1.00 KX Signal A = SE1 10 μm*
EHT = 10.00 kV Mag = 1.43 KX Signal A = SE1 WD = 16 mm

(c) (d)
NG
NG

CB
CF
GP

GP CF

CB

10 μm EHT = 18.00 kV Mag = 1.00 KX 10 μm EHT = 5.00 kV Mag = 2.00 KX

CIF-IITG CIF-IITG
WD = 4.8 mm Signal A = InLens WD = 1.9 mm Signal A = InLens

FIGURE 29.7  SEM images of bipolar plate: (a) CB/NG/polymer; (b) CF/CB/NG/polymer. (From B.K. Kakati, D. Sathiyamoorthy, and
A. Verma, International Journal of Hydrogen Energy, 35, 2010, 4185–4194.) (c and d) GP/CF/CB/NG/polymer at different magnifications
(unpublished).

415.05 to 435.31 S cm−1, 99.07 to 130.17 S cm−1, and 54.23 to
57.28 MPa, respectively. Moreover, the corrosion current den-
sity of the composite bipolar plate was not affected due to
the incorporation of the GP content (Table 29.6). Figure 29.7c
and d show representative SEM images of a GP/CF/CB/NG/
polymer 1/5/5/64/25 vol.% composite bipolar plate at different
magnifications. It is observed that the reinforcements are well
bonded within the composite and as a result, the properties
of the above composite were increased significantly (Table
29.6). However, our research group found the ICR of the opti-
mized GP/CB/CF/NG/polymer composite bipolar plate as
14.4 mΩ cm2 at 2 MPa applied pressure (unpublished).
Figure 29.8 shows the maximum power densities of
PEMFC for four different sets of carbon–polymer composites
bipolar plates with and without GP [48,66,92]. It can be seen
that the GP content in the bipolar plate increases the perfor-
mance of the fuel cell significantly. In almost all the cases,
the maximum gain in the power density is about 10% as com-
pared to without GP reinforced composite bipolar plate. The
gain in the power density is due to the increased electrical
conductivity and reduced contact resistance [93]. The gra-
phene reinforced composite bipolar plate (GP/CF/CB/NG/
RPFR 1/5/5/64/25) meets almost all the stringent benchmark
shown in Table 29.6.
It may be noted that inexpensive raw materials were used
for the development of the above composite. However, the cost
analysis was not performed by the authors. Moreover, there is
further scope to study the effect of graphene content on other
properties of the composite bipolar plate.
The beginning of the chapter discusses that the graphene
can be used in various components of the PEMFC. The
subsequent sections discuss the role of graphene as an elec-
trocatalyst support, as a constituent of the MPL as well as
reinforcement into the electrolyte of PEMFC.
29.3.2 Graphene as an Electrocatalyst Support
The electrocatalyst plays a vital role in the performance of
PEMFC stack. High electrocatalytic activity is necessary for
efficient performance of the fuel cell. In this concern, the
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell 451

1.0
a: MWCNT/NG/VER 0.5phr/70/30%
of Pt electrocatalyst [94–97]. Generally, the requirements
0.9 a′: GP/NG/VER 0.2phr/70/30% for catalyst support material are [95] (i) high surface area to
b: CF/CB/NG/VER 5/5/65/25%
0.8 b′: GP/CF/CB/NG/VER 1/5/5/64/25% improve the dispersion of the metal electrocatalyst, (ii) high
Power density (W· cm–2)

c: CF/CB/NG/NPFR 5/5/60/30% electrical conductivity to provide low ohmic resistance [98],

0.7 c′: GP/CF/CB/NG/NPFR 1/5/5/59/30%
d: CF/CB/NG/RPFR 5/5/65/25%
0.6 d′: GP/CF/CB/NG/RPFR 1/5/5/64/25%
0.5
a
0.4 a′
0.3 b as a support material for Pt and Pt-alloy nanoparticles in
0.2
b′
c
c′ d CB as a support for the PEMFC catalyst is easily oxidized
0.1 d′
0.0
[40] [85] [84] [65]
Reference
Operating conditions
[40]: Pt loadings (anode: 0.3 mg·cm–2; cathode: 0.5 mg·cm–2); Cell temperature:
70°C; H2 flow rate: 100 sccm; O2 flow rate: 250 sccm
[65, 84, 85]: Pt loadings (anode: 0.5 mg·cm–2; cathode: 1 mg·cm–2); Cell temperature:
50°C H2 flow rate: 0.5 lpm; O2 flow rate: 1 lpm
FIGURE 29.8  Comparison of power density reported in various
literatures with and without graphene reinforced composite bipolar
plate.
research work is going on to develop highly durable, highly
efficient, and cost effective catalyst for PEMFC applications.
For example, the U.S. DoE has set target for PEMFC dura-
bility as 5000 h for car applications, 20,000 h for bus appli-
cations, and 40,000 h for stationary applications, which are
about two times more than the presently achieved durability
[10]. The failure of any of the components limits the durability
of the fuel cell. Therefore, in this section, durability and the
performance of electrocatalyst are being discussed.
Commonly, platinum is used as an active electrocatalyst in
PEMFC for not only hydrogen electrooxidation at the anode
but also for oxygen electroreduction at the cathode. However,
the use of bulk platinum (noble metal) does not yield good
performance of the PEMFC due to low surface area per unit
weight of platinum. Moreover, due to the limited natural
resource, the cost of Pt noble metal is gradually increasing
with time [33]. It is thus necessary to reduce the Pt loading by
increasing the surface area of the platinum per unit weight.
Therefore, Pt nanoparticles are dispersed on supporting mate-
rial to increase the active electrochemical surface area (ESA)
(iii) long-term electrochemical stability under fuel cell oper-
ating conditions, and (iv) good interaction between support
material and metal catalyst.
Commonly, CB (Vulcan XC-72) is commercially used
PEMFC application [99,100]. However, it is reported that the
as compared to graphitized form of carbon at higher poten-
tial (greater than 0.8 V versus standard hydrogen electrode)
[101,102]. Moreover, it is well-known that the corrosion of CB
increases due to the presence of Pt nanoparticles, which leads
to detachment of Pt from the support and agglomeration of the
Pt nanoparticles [103] as shown in Figure 29.9. The agglom-
eration results in lowering the active ESA over the time [104].
Moreover, during the preparation of catalyst layer on the
electrode surface, around 30% of the catalyst either does not
form triple phase boundary (TPB) or the Pt catalyst depos-
its into the deep cracks of the CB, resulting in lower catalyst
activity than expected [33]. Figure 29.10 shows the schematic
representation of TPB in the catalyst layer, where catalyst,
ionomer, and reactant are simultaneously present for the elec-
trochemical reaction and transport of ion and electrons apart
from reactant and byproduct. Owing to the above-stated prob-
lems, graphene is being exploited as a promising candidate
for fuel cell electrocatalyst support due to its high corrosion
resistance, attractive basal plane structure with high electrical
conductivity, and high surface area [32,94,95,105–111].
It may be noted that thermochemically synthesized
graphene does not have very good interaction with the Pt
nanoparticles [94]. Therefore, functionalization of graphene
is required to enhance the interaction of Pt with the gra-
phene. Moreover, it is well-known that graphene sheets,
which have high specific surface area, unless well separated
from each other, tend to form irreversible agglomerates or
even restack to form graphite through strong π–π staking
and van der Waals interactions [98]. Therefore, numerous
research efforts have been made to exploit the unique fea-
tures of graphene and functionalized graphene (FGP) to
develop fuel cell electrocatalyst with enhanced activity and
increased durability.

Catalyst degradation
over prolonged
operation of PEMFC

Metal
agglomeration

Metal (Pt or Pt alloy)

Carbon black support Carbon black support Metal detachment
from the support

FIGURE 29.9  Schematic of M/C (M: Pt, Pt-alloy) catalyst degradation process.
452 Graphene Science Handbook

Triple phase
boundary (TPB)
Gas pores
Carbon support
Pt 2e–
H2

Nafion
2H+ + 2e– 2H+

FIGURE 29.10  TPB of an electrocatalyst in PEMFC.

29.3.2.1 Synthesis of Graphene Supported
Metal Electrocatalyst
Different types of synthesis methods such as impregnation
method [112], colloidal method [113], ethylene glycol reduc-
tion method [114], green electrochemical method [96], sono-
chemical method [115], and sputtering [116] method have been
reported for the preparation of Pt electrocatalyst supported on
carbon-based materials. The above methods can be catego-
rized into two groups such as physical and chemical method
[117]. The physical methods are atomization of Pt in vacuum
by thermal evaporation or sputtering on the support, whereas
the chemical methods are used to form neutral Pt atom on the
support by reducing Pt ions. It is also reported that support
material, particle size, and dispersion of the Pt nanoparticles
on the support materials can strongly affect the utilization of
the catalyst and its electrocatalytic activity in PEMFC. In this
concern, chemical methods have the significant advantages
due to ease in controlling the size, shape, and composition as
compared to physical methods [117,118].
However, it may be noted that as-synthesized graphene
does not have very good interaction with Pt nanoparticles.
Moreover, the FGP may have better interaction than as-syn-
thesized graphene [119]. The presence of functional groups
such as carboxyl (─COOH), hydroxyl (─OH), ether (─O─),
and carbonyl (─C═O) on the graphene surface are respon-
sible for physico-chemical adsorption of the Pt on the sup-
port. In addition, the functional groups on the graphene help
to provide the hydrophilicity, which help in the efficient dis-
persion of the electrocatalyst during the electrode ink prepa-
ration. Functionalization of the graphene [100,105,107,120] is
usually done by different chemicals such as poly (diallyldi-
methylammonium chloride) (PDDA) [95,121], citric acid [94],
and nitrogen-doped graphene (N-GP) [122,123]. Figure 29.11
shows the schematic representation of the synthesis of GP,

(1) (2)

HO
C
NG
GrO GP

(3)
C

HO

HO C
HO

HO
HO C
HO
HO
C

OH HO HO
HO

HO C
(5) (4) HO
C
C

OH
OH

C
OH

C C
C HO C HO HO
C

C
C

HO
FGP + Pt precursor FGP
Pt/FGP

: GP sheets; : Pt precursor; : Pt particle

FIGURE 29.11  Synthesize of Pt/FGP electrocatalyst: (1) oxidation of NG to graphite oxide (GrO); (2) thermal exfoliation of GO to form
GP nanosheets; (3) chemical functionalization of GP nanosheets to FGP; (4) addition of Pt precursor to FGP slurry; and (5) Pt/FGP electro-
catalyst formation through NaBH4 reduction.
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell
functionalized (FGP), and platinum supported on FGP (Pt/
FGP) [99,106].
29.3.2.2 Properties of Graphene Supported
Metal Electocatalyst for Fuel Cell
Electrochemical properties of the graphene-supported cata-
lyst were evaluated by many researchers for fuel cell appli-
cation. ESA is one of the important characteristics of the
electrocatalyst. The ESA is usually done by cyclic voltam-
metry (CV) using hydrogen adsorption/desorption (HAD) on
the Pt/GP electrocatalyst. Figure 29.12 shows a representative
cyclic voltammogram of HAD using Pt electrocatalyst. The
forward and reverse peaks (Figure 29.12) in the voltammo-
gram show the hydrogen desorption and adsorption peaks on
the Pt catalyst surface [94]. The ESA can be determined using
Equation 29.4, where 210 µC cm−2 Pt is a constant for charge
(qPt) adsorption by polycrystalline Pt surface [112].
ESA (m 2 × g −1Pt )
q Pt (µC × cm −2 Pt )
= (29.4)
   210 (µC × cm −2 Pt) × Pt loading (g Pt × m −2 )
The shaded area in Figure 29.12 shows the charge asso-
ciated with the hydrogen adsorption on Pt, which can be
found out by integrating the hydrogen adsorption peak in the
potential range of 0.05–0.4 V [standard hydrogen electrode
(SHE)] for evaluating the ESA [124]. The specific double layer
capacitance was reported to be 40 and 8 µF cm−2 for Pt and
CB, respectively [102,125]. However, since the capacitance
is a function of potential, the double layer does not behave
as an ideal capacitor. Moreover, the non-faradic or capacitive
current generated due to charging/discharging the electrical
double layer capacitance of electrode/electrolyte interface.
Non-faradic current involves charge accumulation but not
chemical reactions or charge transfer. The electrical charge
associated with double layer charging must be considered for
e–
0.015
H +
+
Pt +
0.010
Current density (A·cm–2)
0.005 Double layer charge
0.000
–0.005
orptio
–0.010 Pt-H Ads
–0.015 qPt
–0.020
0.05 0.10 0.15 0.20 0.25
Potential (V/SHE)
FIGURE 29.12  Representative cyclic voltammogram of PEMFC
electrocatalyst showing HAD in H2SO4 solution.
453
the analysis to avoid ­overestimating the charge attributed to
the electrocatalytic activity [126].
The electrocatalytic activity of the supported Pt catalyst
depends on the presence of nano-sized (around 1–5 nm) Pt
particles on the support material [127]. Table 29.7 shows
various properties of graphene supported Pt electrocatalyst.
Significant improvement in the electrocatalytic activities is
observed, when GP is used instead of CNT and CB as cata-
lyst supports [94,106]. Moreover, the FGP showed even bet-
ter electrochemical activity as well as fuel cell performance.
On comparison of the electrochemical activities of the Pt/
GP with Pt/C catalyst, the ESA of Pt/GP is found to be
44.6 m2 g−1 Pt, which is higher than the commercial catalyst
Pt/C (30.1 m2 g−1) [106]. The higher ESA of Pt/GP is attrib-
uted to the high surface area of GP, better interaction between
Pt and GP nanoparticles, the good charge transport property
of GP sheets, and easy loading of noble metal nanoparticles
on GP surface. Another example of high ESA for the Pt/GP
catalysts with 40, 60, and 80 wt.% Pt loading was reported as
53, 51, and 36 m2 g−1, respectively, whereas the ESA of com-
mercial Pt/C (40 wt.%) was around 26 m2 g−1 Pt. The Pt par-
ticle size of the Pt/GP catalysts is found to be around 3 nm
[100]. The TEM images of the Pt/GP catalyst with different
Pt loadings are shown in Figure 29.13. It can be seen that the
Pt nanoparticles are highly dispersed even at high Pt loadings
(60 wt.%). However, at 80% loading, the Pt nanoparticles show
significant agglomeration. Generally, well dispersed high Pt
loading on the CB support is very difficult to obtain, because
the Pt nanoparticles tend to sinter due to weak interactions
between Pt nanoparticles and low surface area carbon sup-
port [96]. ESA mainly depends on the dispersion of Pt on the
support materials and the size of Pt particles. Pt/GP catalysts
exhibit much higher stability and enhanced current density as
compared to Pt/C catalyst even for methanol oxidation reac-
tion (MOR) analyzed by CV analysis [96,100,101,128–131].
However, it is reported that the electrocatalytic activities of
GP-based Pt catalysts can further be improved using func-
tionalization of GP particles.
In this regards, Pt/FGP catalyst is prepared and activity as
well as stability toward electrochemical ORR of the GP-based
electrocatalyst are evaluated [107]. The Pt/FGP (20 wt.%)
shows an initial ESA of 108 m2 g−1 Pt, which decreases to
67.6 m2 g−1 Pt after 5000 cycles of CV operation. It has also
been reported that beyond the 5000 cycles the Pt particle
size of the Pt/FGP catalyst increases from 2.5 to 5.5 nm. On
the other hand, the Pt particle size of the commercial Pt/C
increases from 2.8 to 6.9 nm after 5000 cycles of CV analy-
n sis. However, the smaller Pt particle size in Pt/FGP catalyst is
required for high ESA and ORR activity of electrocatalysts. In
an another study, a severe degradation (49.2%) of Pt/GP cata-
lyst is found as compared to PDDA functionalized Pt/FGP
(22.1%) after 3000 cycles of CV analysis using ORR [121].
0.30 0.35 0.40 However, it is reported that PDDA FGP support improves the
dispersion of Pt nanoparticles as well as stabilizes GP sheets
against restacking during the reaction [132].
On the other hand, the N-GP was found to be an effec-
tive way to improve the anchoring sites as well as to better
454 Graphene Science Handbook

TABLE 29.7
Properties of Graphene or FGP Supported Electrocatalysts
Pt Particle
Size (nm)/ Electro­ Electrocatalytic Activity of Comparison of Single-Cell
Electro­ Loading ESA chemical Comparison with Other As Anode PEMFC/DMFC Performance
catalyst (wt.%) (m2 g−1) Analysis Catalyst or Cathode with Other Catalyst References
Pt/GP 5–6/45 44.6 HAD; MOR Pt/GP > Pt/C N/A N/A [106]
Pt/FGP 3.5/20 N/A HAD; ORR Pt/FGP > Pt/CNT > Pt/C N/A N/A [95]
Pt/GP–CNT 2–2.4/20 127.78 HAD Pt/(GP–CNT) > Pt/GP > N/A N/A [133]
Pt/CNT > Pt/C
Pt/FGP 2/20 108 HAD; ORR Pt/FGP > Pt/C N/A N/A [107]
Pt/GP 2.9/70 N/A ORR Pt/GP > Pt/C Cathode Pt/GP > Pt/C [132]
Pt/GP 3.5/40 65 HAD; ORR Pt/GP > PtCo/GP > PtCr Cathode Pt/GP > Pt–Co > GP > Pt–Cr [134]
Pt/GP 2–3/20 24.01 HAD Pt/GP > Pt/C N/A N/A [135]
Pt/GP 1.8/40 53 MOR Pt/GP > Pt/C N/A N/A [100]
Pt/GP 2.4/20 81.8 N/A N/A N/A N/A [89]
Pt/GP–CB 2–6/20 N/A HAD Pt/GP–CB > Pt/C Cathode Pt/GP–CB > Pt/C > Pt/G [136]
Pt/GP 5–8/20 N/A HAD; ORR Pt/GP > Pt/C N/A N/A [137]
Pt/GP 3–5/10 N/A ORR Pt/GP > Pt/C N/A N/A [128]
Pt/FGP 1.95/~40 N/A HAD; ORR Pt/FGP > Pd–Pt/GP > Pt/GP N/A N/A [121]
Pt/FGP 4/20 57.93 HAD; ORR Pt/FGP > Pt/GP > Pt/C Both Pt/FGP > Pt/GP > Pt/C [94]
Pt/GP 2–4/N/A N/A MOR Pt/GP > Pt/C N/A N/A [138]

(a) (b)

50 50
Particle content (%)
Particle content (%)

40 40
30 30
20 20
10 10

20 nm 0
1 2 3 4 5 6 7
20 nm 0
1 2 3 4 5 6 7
Particle size (nm) Particle size (nm)

(c) (d)

50 50
Particle content (%)

Particle content (%)

40 40
30 30
20 20
10 10
20 nm 0 1 2 3 4 5 6 7 20 nm 0 1 2 3 4 5 6 7
Particle size (nm) Particle size (nm)

FIGURE 29.13  TEM images of (a) Pt/C (40 wt.%); (b) Pt/GP (40 wt.%); (c) Pt/GP (60 wt.%); and (d) Pt/GP (80 wt.%) electrocatalysts as
well as the particle size distributions of the Pt nanoparticles. (Reprinted from Langmuir, 25, C. Shan et al., Water-soluble graphene cova-
lently functionalized by biocompatible poly-l-lysine, 12030–12033, Copyright 2009, with permission from Elsevier.)
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell
exploitation of the electrochemical activity of the Pt particles
[139]. The dispersion of Pt nanoparticles on N-GP support
was better than on GP support. Moreover, the MOR cur-
rent density using CV analysis of Pt/N-GP was three times
higher than the commercial Pt/C catalyst. Similarly, the four
times higher MOR current density using CV analysis was
observed for Pt/GP (0.12 mA cm−2) as compared to Pt/C
(0.03 mA cm−2) [110].
The similar electrochemical behavior for the citric acid
FGP supported Pt catalyst is found by Ghosh et al. [94]. The
smaller Pt particle size and better dispersion of Pt particles
on FGP support were observed as compared to without FGP
support and on CB. The ESA for hydrogen adsorption on
Pt/C, Pt/GP, and Pt/FGP were determined as 40, 53.76, and
57.93 m2 g−1 Pt, respectively. Thus, as compared to commer-
cial Pt/C catalyst, the ESA of Pt/G and Pt/FG was found to be
higher than 34.9% and 44.8%, respectively. Moreover, the sta-
bility of the catalysts was measured after 500 and 1000 scan
cycles of the HAD using CV analysis. It was found that the
decrease in forward peak current density was nearly the same
after 500 cycles. However, after 1000 cycles, the decrease in
the forward peak current density was only 12.37% and 8.84%
for Pt/GP and Pt/FGP as compared to Pt/C (17.45%) [94].
Another alternative procedure against functionalization
was reported to prevent the staking of GP sheets, in which
the CNT was used along with GP as catalyst support for Pt
catalyst [133]. The 1D CNTs act as nano-spacer between 2D
graphene nanosheets to effectively inhibit the face-to-face
stacking and/or agglomeration of GP layers. The ESA of the
Pt/C, Pt/CNT, Pt/GP, and Pt/GP/CNT was found to be 43.63,
51.46, 94.06, and 127.78 m2 g−1 Pt, respectively. In addition,
the incorporation of CNT also improves the pathway for mass
transfer of the chemical reactants and products and works as
an electrical bridge between the GP sheets. The representative
electrochemical properties of Pt/GP and Pt/FGP electrocata-
lysts are summarized in Table 29.7.
Recently, the supported Pt-alloy electrocatalysts were found
to be more electrochemically active due to their enhanced
catalytic properties relative to individual carbon-supported Pt
electrocatalyst [134]. Amongst the many Pt-alloy, Pt–Co and
Pt–Cr were found to be more efficient to enhance the ORR
activity at low overpotential [134]. The ESA of the Pt-alloy
catalysts was found to be 65, 57, and 55 m2 g−1 Pt for Pt/GP,
Pt3Co/GP, and Pt3Cr/GP catalysts, respectively. Moreover, it
was found that the ORR activity of the Pt3Co/GP and Pt3Cr/
GP catalyst was 3–4 times higher than that of Pt/GP cata-
lyst. The overpotential for ORR of the Pt–M/GP (M: metal) is
45–70 mV less than the Pt/GP. The durability of the graphene
supported Pt, Pt3Co/GP, and Pt3Cr/GP catalyst was conducted
using ORR analysis. The marginal degradation was observed
in ORR activity using CV after 500 cycles of Pt/GP, Pt3Co/
GP, and Pt3Cr/GP catalyst, which was within 5%. Therefore,
the graphene as catalyst support for Pt-alloy can also improve
the electrochemical activities and stability of the catalyst. In
addition, the graphene-based Pt electrocatalyst enhance the
carbon monoxide (CO) tolerance as compared to commer-
cial Pt/C catalyst, which is one of the most important desired
455
properties of PEMFC hydrogen fuel cell electrocatalyst. It is
well-known that the major source of hydrogen as fuel is steam
reforming of hydrocarbons [140]. The hydrogen gas obtained
by steam reforming process generally contains trace amount
[141] of CO, which was easily adsorbed irreversibly on the
surface of Pt and thus, poison the PEMFC anode electrocata-
lyst. Therefore, the high CO tolerance of the electrocatalyst is
required for the hydrogen fuel cell [110,135]. Pt/GP catalyst
is evaluated for the CO stripping analysis and compared with
commercial Pt/C catalyst and it is found that the CO adsorp-
tion rate of Pt/GP is significantly (about 40 times) lower than
Pt/C catalyst [110]. In their further studies, a more significant
support effect is observed in the presence of H2 and 500 ppm
CO mixture for Pt/GP, Pt/C, and Pt–Ru/C catalysts and com-
pared the performance using pure hydrogen gas [135]. The
hydrogen oxidation reaction (HOR) activity of the Pt/GP in
H2 + CO mixture was found to be 52% of pure H2. In contrast,
the electrocatalytic activity exhibited by Pt/C was around 11%
of the pure H2. In comparison, Pt–Ru/C that is well-known
CO tolerant catalyst, maintained electrocatalytic activity up
to 45% (of pure H2) under a mixture of 500 ppm CO and H2.
It was found that the catalytic activity toward CO tolerance of
Pt/GP was significantly superior as compared to Pt/C and that
the substrate carbon material altered the catalytic properties
of the Pt for the PEMFC. The two possible reasons attributed
to the excellent CO tolerance for HOR activity of the Pt/GP
catalyst are the presence of sub-nano-Pt cluster on the gra-
phene surface, which promoted CO tolerance, and the modifi-
cation of the Pt electronic structure by graphene support.
Therefore, to minimize the CO poisoning on the Pt sur-
face, various GP supported bimetallic nanoparticles such
as Pt–Pd, Pt–Au, Au–Pd, Pd–Ru, Fe–Pt, and Pt–Ag, sig-
nificantly attracted researchers due to their enhanced cata-
lytic activity relative to individual Pt-based nanoparticles
[97,129,134,142–145]. It can be seen that the enhanced elec-
trochemical activities were observed for both MOR and etha-
nol oxidation reaction with Pt–Ru/GP catalyst as compared
to Pt/C [129]. Moreover, the adsorption of CO species on the
surface of Pt particles was greatly reduced due to the introduc-
tion of Ru metal into the Pt/GP catalyst. Furthermore, ternary
metal alloy catalysts also attracted the scientific community
due to their superior electrocatalytic activities and stability
than single and bimetallic catalysts [109]. It is reported that
the Pt–Pd–Au/GP catalyst provides higher electrocatalytic
performance with reduced overpotentials as compared to GP
supported single metallic and bimetallic catalyst.
Graphene is being evaluated not only as a catalyst sup-
port but has also attracted significant attention as a metal free
electrocatalyst for fuel cell applications. Significantly, higher
ORR activity was found using metal free N-GP as compared
to commercial Pt/C catalyst [146]. The current research work
indicated that the GP and its derivatives doped with other
heteroatoms such as boron-doped, phosphorous-doped, and
sulfur-doped could also enhance ORR electrocatalytic activi-
ties [147–149]. More recently, boron and nitrogen doped GP
(BN-GP) was synthesized for electrochemical ORR activ-
ity. It was observed that the electrocatalytic activities of
456
metal-free BN-GP catalyst were better than the commercial
Pt/C catalyst [150].
It can be seen that the graphene and FGP supported Pt,
and/or Pt-alloy electrocatalyst show superior catalytic activi-
ties as compared to Pt/C and Pt/MWCNT [151] for PEMFC
applications. However, from the practical point of view, the
fuel cell test is the ultimate evaluation criterion for the sup-
ported electrocatalyst. Therefore, the following section will
discuss the PEMFC performance using graphene-supported
electrocatalyst including metal free GP catalyst in single-cell
PEMFC.
29.3.2.3 Performance of PEMFC Using Graphene
as an Elctrocatalyst Support
Although the enhanced electrochemical properties have been
observed on graphene-based metal electrocatalysts, but that
were based on half-cell electrochemical tests. Therefore,
there is a need to evaluate graphene-supported metal electro-
catalysts in PEMFC. However, only a few research works are
reported in which the performance of the PEMFC is evalu-
ated using graphene as a catalyst support. For example, Seger
and Kamat reported a single-cell PEMFC performance using
Pt/GP or Pt catalyst at the cathode, whereas at the anode
commercial Pt/C was used. They have reported that the Pt/
GP showed a maximum power density of 0.161 W cm−2 as
compared to 0.091 W cm−2 for an unsupported Pt catalyst
[152]. The similar kind of support effect was reported, where
graphene supported electrocatalyst was evaluated only as the
cathode catalyst for PEMFC [123,132,134]. Recently, Ghosh
et al. [94] reported the single-cell PEMFC performance using
Pt/GP and Pt/FGP at anode as well as cathode and the perfor-
mance was compared with the commercial Pt/C. Figure 29.14
shows the polarization and power density curves of single-cell
PEMFC using Pt/FGP, Pt/GP, and Pt/C electrocatalysts. The
maximum power density using Pt/C, Pt/GP, and Pt/FGP were
obtained as 0.314, 0.426, and 0.455 W cm−2, respectively. The
1.0 Pt/FG
Pt/G
Pt/C
0.8
Cell voltage (V)
0.6
0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Current density (A· cm–2)
FIGURE 29.14  PEMFC performance using Pt/FGP, Pt/GP, and
Pt/C electrocatalysts at both the electrode. (A. Ghosh, A. Verma.:
Graphene and functionalized graphene supported platinum catalyst
for PEMFC. Fuel Cells. 2014. 14. 259–265. Copyright Wiley-VCH
Verlag GmbH & Co. KGaA. Reproduced with permission.)
Graphene Science Handbook
better dispersion of the Pt on GP or FGP and higher ESA of
the electrocatalysts were the probable reasons for achieving
higher performance in the PEMFC.
29.3.3 Graphene in Polymer Electrolyte
It is interesting to note that recently quite a few literatures have
reported the use of graphene oxide (GO) in a conventional
nafion membrane in PEMFC [153–156]. The incorporation
of GO in the electrolyte increases the ionic conductivity and
mechanical strength of the GO/nafion and GO/polyethylene
oxide nanocomposite for PEMFC applications. The ionic con-
ductivity of the GO/nafion 10/90 (wt.%) was found to be around
four times higher than recast nafion [155]. Moreover, the GO
and sulfonated GO (SGO) were used in polybenzimidazole to
increase the temperature tolerance of recast nafion membrane.
It was found that the above composite nafion membrane was
stable up to 175°C and showed satisfactory performance when
used in the PEMFC [40,157]. The single cell PEMFC perfor-
mance of the GO/nafion nanocomposite increases significantly
as compared to recast nafion [40,91,154,155].
29.3.4 Graphene in Microporous Layer
The MPL shown in Figure 29.1 is one of the critical compo-
nents of MEA [136,158]. The MPL is deposited on the GDL.
The GDL is typically a carbon-based microporous substrate
in the form of carbon paper or carbon cloth. The MPL along
with the GDL provides a physical support to the catalyst layer
as well as conducting path for the electron to reach up to the
bipolar plate or current collector. Commonly, MPL consists
of CB powder, hydrophilic, and hydrophobicity agent, and
the composition depends on whether the MPL is on anode
or cathode side of the GDL. The function of MPL is to pro-
vide uniform pore structure for better gas distribution on
the catalyst layer, water removal to avoid flooding, and also
minimize electric contact resistance with the adjacent catalyst
0.5 layer. Therefore, MPL should have high electrical conductiv-
ity, crack free surface morphology, high oxidative stability,
and balanced hydrophilicity/hydrophobicity [159,160]. It is
0.4
expected that using graphene along with the CB would pro-
Power density (W ·cm–2)
vide higher electrical conductivity as compared to the car-
0.3 bon-based MPL. In this concern, the properties of graphene
nanomaterial may be a potential candidate instead of CB.
0.2 However, hardly any literature reports the use of graphene as
MPL. Therefore, there is a need to study on GP for potential
application in GDL in PEMFC.
0.1
0.0 29.4 SUMMARY
1.4
The development of graphene has opened up many possibili-
ties to be used in various applications due to its extraordinary
properties. The use of graphene in energy conversion devices
such as fuel cell is being explored in full extent. The pres-
ent state-of-art of PEMFC is not competitive enough to pen-
etrate the market due to various challenges. These challenges
include high cost, low performance as well as durability issues
Potential Applications of Graphene in Polymer Electrolyte Membrane Fuel Cell
of various components. Carbon is used in many components
of PEMFC such as composite bipolar plate, microporous
layer, electrolyte, and catalyst support material. The different
forms of carbon material such as graphite, CB, CF, and CNT
are widely studied for the PEMFC components. This chap-
ter has shown the intensive research findings on graphene on
the fuel cell components, where graphene is being evaluated.
Moreover, the use of graphene in the possible components of
PEMFC was also discussed.
It has been found that incorporation of graphene in bipolar
plate improves the performance by great extent, especially,
electrical conductivity. The systematic approach to replace a
small part of NG in the composite by CB, CF, and GP has
achieved a suitable carbon–polymer composite bipolar plate.
The bipolar plate with the composition of GP/CF/CB/NG/
polymer 1/5/5/64/25 achieved all the stringent properties
required, except the flexural strength, which was edge behind
the required value (57.28 MPa against 59 MPa). However, fur-
ther study may be conducted to improve the flexural strength
probably by incorporating the CF suitably. Even the use of
graphene in the polymer electrolyte membrane has also been
tested.
Although enhanced properties have been observed using
graphene-based components, but most of their applica-
tions are limited to the laboratory. Therefore, much work is
needed to be carried out to find a general, economic, and
effective method of fabricating the components for industrial
application.
ACKNOWLEDGMENT
The authors gratefully acknowledge the financial sup-
port given for this work by the Council of Scientific and
Industrial Research (Sanction number: 22[0498]/10/EMR-II),
Government of India.
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 Nanoscience & Technology Aliofkhazraei
Ali
Milne

GRAPHENE SCIENCE HANDBOOK Ozkan

Mitura

GRAPHENE
Gervasoni
Applications and Industrialization

SCIENCE

GRAPHENE SCIENCE HANDBOOK

Applications and Industrialization
“This is a very good and excellent book on graphene material which is not only useful for researchers but also for students...
This hand book is devoted to different applications of graphene materials in different fields...”
—Dr. Noorunnisa Khanam Patan, Center for Advanced Materials, Qatar University

HANDBOOK
“Graphene Science Handbook: Applications and Industrialization is a comprehensive collection of the most recent
advances on diverse areas of graphene science and development. The book has recognized editors and as such attracted high
quality authors for chapters. The chapters have their own independent structures that allow the readers to read and use
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recommend this book as a good reference that covers both basic and advanced topics regarding graphene.”
—Professor Kourosh Kalantar-Zadeh, Royal Melbourne Institute of Technology (RMIT), Australia

Applications and
“Many practical applications utilize not only graphene’s electronic properties and optical transparency but also its extremely
high thermal conductivity, mechanical strength and flexibility, tunable electron density, excellent current-carrying capacity,
and ultimate surface-to-volume ratio. The present volume provides a scope of applications in sensors and nanodevices that
use one or several unique material characteristics of graphene.”
—Dr. Alexander A. Balandin, University of California Presidential Chair Professor

“I am confident in the materials … The wide scope of information covered, and the qualifications of the contributors
projects a positive image of the potential quality of the publication.”
Industrialization
—Albert V. Tamashausky, Asbury Carbons Inc.

“This book is a result of an impressive project to collect views from experts in every aspect of graphene science. All popular
topics in the research of this impressive material are covered. This is the best and most complete presentation that has been
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“…this set of volumes represents a complete handbook showing the state of the art of science and technology related with
graphene. This set of books is written by great specialists and competent experts. For someone who works in this field, this
set of volumes is an essential reference for the characterization and application of graphene.” EDITED BY
—Dr. Alex Axelevitch, Holon Institute of Technology (HIT)
Mahmood Aliofkhazraei • Nasar Ali
William I. Milne • Cengiz S. Ozkan
Stanislaw Mitura • Juana L. Gervasoni
K20508
ISBN: 978-1-4665-9133-2
90000

9 781466 591332

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