Review

Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX pubs.acs.org/jced

Graphene and Graphene Oxide-Based Composites for Removal of

Organic Pollutants: A Review
Kirti Thakur† and Balasubramanian Kandasubramanian*,‡
†
Department of Atomic and Molecular Physics, Manipal Academy of Higher Education (MAHE), Manipal, 576104, India
‡
Nano Surface Texturing Lab, Department of Metallurgical and Materials Engineering, Defence Institute of Advanced Technology
(DU), Ministry of Defence, Girinagar, Pune 411025, India

ABSTRACT: Graphene, graphene oxide (GO), and their composites have

been prominently utilized for wastewater purification because of their
adsorption, oxidation, and catalytic properties. Graphene and GO and its
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composites naturally have significant pore volume, high conductivity, rich

surface chemistry, and an exceptionally large aspect ratio which make it
favorable for adsorption and catalysis of organic pollutants from wastewater.
The sheet-like, resonating, polyaromatic π-system of graphene subsidiaries
play a significant role in π−π interactions, hydrogen bonding, and/or
electrostatic interactions with organic pollutants that include dyes,
pharmaceutical waste, and agricultural and industrial effluents whose base
structure consists of notably reactive unsaturated aromatic rings and
oxygen-rich functional groups. The adsorption capacities of pollutants have
been widely researched and catalogued by considering the adsorption
J. Chem. Eng. Data

isotherm (Langmuir, Freundlich, Temkin, DR model) they fit, the kinetic

models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion) they follow, the parameters that affect the
process (pH, temperature, etc.) and the reusability of the adsorbent. The photocatalytic efficiency has been anthologized with
the viewpoint of the radicals being involved in photocatalysis and the light source used for the process. This review focuses on
adsorption, advanced oxidation, and catalysis of various emerging organic pollutants using graphene subsidiaries, graphene-
based composites, and hybrids; proves their efficacy as multifunctional materials for the expulsion of toxic aqueous phase
pollutants; and presents new prospects for designing advanced water treatment strategies.

1. INTRODUCTION structures was based on the melting point depression

Graphene, an sp2 hybridized, hexagonally arranged, covalently
bonded chain of polycyclic aromatic hydrocarbon arranged in a
single sheet of atomic thickness in a honeycomb crystal lattice
with a unit cell of two carbon atoms has unique properties
owing to its structural and chemical morphology such as high
surface to volume ratio,1 excellent transparency,2−5 unmatched
conductivity,6,7 and high mechanical strength.8 Thus graphene
attracted worldwide attention from various researchers and can
be assessed by its application in varied fields of science and
engineering such as biosensors,9,10 fuel cells,11,12 electro-
magnetic shielding,13 aerospace applications,14,15 energy
storage devices,11,16 photonic17,18 and electronic devices as
nanoantennas,19 sound transducers,20,21 organic light emitting
diodes,22,23 protective coatings,24,25 integrated circuits,26,27
biomedical devices,28,29 and contamination purification in
wastewater management.12,30,31
We discuss thoroughly the exceptional properties and wide
applicability of graphene inadvertently ignoring that the mere
existence of 2D crystals was considered implausible.32 Laudau
and Peierls both argued the thermodynamic instability of 2D
nanocrystals and individually reported their theory deeming
2D structures as non- existent and were further experimentally
supported by Mermin.33−35 The unstable nature of the 2D
experienced because of a large difference in the surface volume
proportionality, and thus the structures struggle to exist in the
nanometre regime.12,36,37 The intercalation and exfoliation of
graphite with the help of nitric and sulfuric acid by German
scientist Schafhaeutl in 184038 and the reduction of the
intercalated layers using potassium chlorate by a British
scientist, Brodie, resulted in the formation of first graphene
oxide layers on graphite in 1962.39 Boehm and Clauss further
reduced the graphene oxide layers with the help of hydrazine
and hydroxyl amine to form reduced GO and coined the term
“graphene”40−42 In 2004, Novoselov and Geim mechanically
stripped graphene using a scotch tape method for electric field
effect studies which led to them receiving the Nobel Prize in
2010.6,12,43
Historically, activated carbon has been a conventional
adsorbent for waste water treatment (WWT)44,45 due to its
versatility, benign nature, and wide applicability but falls short
due to high regeneration cost and chemical rigidness.46 The
need for a better carbon-based alternative is satisfied by
Received: November 9, 2018
Accepted: February 1, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.8b01057

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Figure 1. Structure of (a) graphene and (b) graphene oxide.
graphene because apart from being carbonaceous it has a vast
surface area by virtue of its planar sheet-like morphology. The
existence of few layered graphene (FLG) also enhances its
adsorption capabilities due to interlayer adsorption.47 Graphe-
ne’s polyaromatic π-system which readily reacts with the
aromatic rings of organic entities in water by either π−π
stacking interactions48 or strong hydrophobic effect49 make
them highly efficient adsorbent materials and have been
successful in eradicating pollutants such as naphthalene, 1-
naphthyl-amine, aspirin, and dyes50 such as Rhodamine B
(RhB),51 methylene blue (MB),52,53 etc. The hydrophobic
nature of graphene makes it nondispersible in water and thus
the applicability of graphene, in its pure form, is limited for
decontamination purposes. The use of graphene is thus either
supported by or in the form of composites that render it
useable.48 The properties offered by the graphene skeleton
have been further enhanced by oxidizing it to graphene oxide
that contains substantial oxygen functional groups such as
carboxyl, carbonyl, epoxy, and hydroxyl, which provide it with
a negative charge and make it hydrophilic.54,55 Further
functionalization of graphene and graphene oxide lead to
surface modification and can be tuned to be reactant specific
for various organic entities. The large number of oxygen-based
functionalities affects its conductivity, and GO has an
electrically insulating reputation.56 The reduction of graphene
oxide does not form pristine graphene, instead, it forms
reduced graphene oxide (rGO) that has a carbon to oxygen
ratio to 246:1 when a comparison is made with GO(2:1).57
Thus, rGO can be considered as an intermediate of graphene
and GO although its π−π interactions with organic effluents
are augmented more than both of its associates and thus makes
it advantageous for the removal of organic effluents efficiently
from wastewater.58 The structure of graphene and graphene
oxide can be visualized in Figure 1.
The oxygen functional groups present on GO also
participate in redox reactions and transform various pollutants
into environment friendly and degradable form. This
eliminates the issue of disposing of waste matter as is in the
case of adsorption. The radical-based oxidation processes also
termed as advanced oxidation processes (AOP) directly
transform the organic entities to innocuous entities which
are compatible with the environment and include various
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minerals, less toxic fragments of carbon-based pollutants, and
neutral entities such as water and carbon dioxide.59 Graphene-
based materials are known to generate hydroxyl and sulfate
radicals that undergo oxidation to eliminate aromatic hydro-
carbons successfully.60 Photocatalysis is also a part of the
advanced oxidation process and has been effective in the
degradation of various organic entities by graphene-based
materials and their composites.61 Photoelectrocatalysis,62
ozonization,63 etc. of organic pollutants has also been reported
for organic effluent elimination.64−67 Reduction by graphene is
also reported and processes such as photoreduction and
chemical reduction form important processes for enhancing
wastewater remediation.68,69
This review provides a systematic anthology of graphene-
based materials in effective wastewater treatment technology.
In today’s scenario, efficient water purification systems are
desired and hence many technologies are being developed after
scrutinizing their practicality, affordability, and durability. To
maximize the removal of pollutants from graphene, first we
need to understand the morphology of the pollutants with
which the graphene composite interacts and the intricacies of
these interactions. Hence in the following sections an
understanding of the structure of pollutants and graphene,
their possible interaction mechanism, thermodynamics and
kinetics of the said interactions, and catalytic efficiency of some
of the designed composites have been discussed. The review
focuses on graphene as a state of the art and establishes that its
prominence in organic effluent eradication is colossal and
cannot be overlooked for designing effective wastewater
treatment strategies.
2. NECESSITY OF GRAPHENE-BASED ORGANIC
EFFLUENT ERADICATION
Aromatic organic compounds are those compounds that have
one or more than one unsaturated cyclic carbon chain in the
whole molecule. Their negative biological impact is a source of
concern in reference to their removal from the water system.
The toxicity of these compounds can be established by studies
that classify them as carcinogens, mutagens, teratogens, and
render them genotoxic and immunotoxic.70−72 Hence they
pose a great threat to aquatic life due to bioaccumulation and
biomagnification and hamper the food chain because of their
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characteristic lipophilic property.73,74 Because of their high
affinity toward water owing to the hydrogen bonds and π ring
structures, aromatic hydrocarbons are more toxic than aliphatic
hydrocarbons with almost the same number of carbon
atoms.75,76 Polycyclic aromatic hydrocarbons (PAHs) are a
class of hydrocarbons that are made up of carbon and
hydrogen arranged in repeated ring structures. They are
noncharged and nonpolar molecules formed from various
processes such as burning of petroleum products, incomplete
combustion of biomass, coal mining, etc.77 PAHs have harmful
effects on human health and are known to cause skin, blood,
bladder, and liver cancer78,79 and cardiovascular diseases.80
Monocyclic aromatic hydrocarbons such as toluene, xylene,
benzene, etc. are also harmful to the human population as they
affect the central nervous system and hamper its activity.81
They are largely excreted from industry due to improper
disposal of waste, leaks, and accidents, etc. Other organic
compounds such as bisphenol A (BPA), phenols, benzene,
biphenyls, toluene, ethylbenzene, xylenes, anthracene, pyrene,
phenanthrene, and fluoranthene are a few of the organic
pollutants that have been hampering the aquatic environment
and pose a threat to human wellbeing.82,83 Pharmaceutical
wastes are also organic pollutants that have adverse effects on
the environment and on human health as they have been
designed for biocompatibility. Drugs such as aspirin,
acetaminophen, dorzalamide, ketoprofen, and ciprofloxacin
can cause adverse effects in humans as they have been designed
for uptake by the human body.84 These compounds are very
hard to eliminate and biodegrade even at low concentrations.
Another class of aromatic hydrocarbons widely found polluting
the environment are dyes and pigments such as methylene blue
(MB), methyl orange (MO), reactive black, etc. that are
difficult to remove from the environment and cause disruption
in the photosynthetic process of aquatic plants by changing the
color of water, thereby blocking sunlight causing an imbalance
in the whole aquatic ecosystem.85 Some of the structures of
these pollutants have been shown in Figure 2 and their
aromatic structures can be easily observed. Adsorption,
advanced oxidation, and photocatalysis have been used to
remove the organic pollutants from harming the environment
and graphene-based materials have been proven to be highly
efficient for wastewater remediation.86,87
Figure 2. Structure of some of the (a) pharmaceutical pollutants, (b)
dye pollutants, (c) other organic entities.
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Graphene-based remediation of organic pollutants from
wastewater is extensively investigated and catalogued.76 The
various combination of graphene with other metallic or
nonmetallic entities create new composites or enhance the
effectiveness of the existing materials for adsorption, oxidation,
or catalysis of the pollutants such that they disintegrate into
harmless constituents or are easily separated by techniques
such as filtration, magnetic separation, or a simple solvent
wash. The ability of graphene-based composites to individually
separate a plethora of pollutants makes it a promising
candidate for overcoming the drawbacks of existing wastewater
technology.88,89
The inept existing WWT strategies and the need for novel
ways to eliminate organic effluent has steered us toward
graphene since it has been extensively studied that graphene-
based materials show enhanced usability in adsorption,90,91
advanced oxidation52,92 and catalysis93,94 for the removal of a
multitude of organic pollutants. These include polyaromatic
hydrocarbons (PAH) and their derivatives, dyes,95,96 pesti-
cides,97 and pharmaceutical waste such as antibiotics98 and
other organic entities generated during the manufacturing
processes of various industries. Graphene modified with
functional groups or enhanced by forming a polymer and
nanobased composites accentuate these properties of graphene
materials and provide extra support and stability thus providing
major advantages in effective WWT.99,100 Therefore, it is
essential to understand the ways graphene interacts with other
moieties. This is discussed in the next section.
3. INTERACTIONS OF GRAPHENE
The remarkable properties of graphene are highly dependent
on its availability as a single layer. If the layers are in close
vicinity to each other graphene tends to agglomerate or restack
like graphite owing to the π−π interactions between the
graphene layers and its properties are somewhat impaired.101
When dispersed in water, graphene, due to its hydrophobic
nature may or may not agglomerate but does not remain
suspended due to the absence of any electronegativity
difference in the planar carbon lamella. This agglomerating
behavior of graphene can be reduced by attaching smaller
molecules or polymers which are either hydrophilic and/or
hydrophobic to the graphene sheets. These functional groups
inhibit the agglomeration of graphene layers either by
immensely polar interactions or by their bulky nature and
also aid in the dispersion of graphene in water or any other
polar or nonpolar solvent enhancing its usability. The reactions
involved in functionalization not only signify the trans-
formation of graphene sheets for applicability in water
dispersion but also incorporate how graphene or its
subsidiaries interact when aromatic molecules are in close
proximity. Hence these interactions form the foundation of
wastewater treatment technology and signify how organic
pollutants react with functionalized or nonfunctionalized
graphene systems. GO and rGO being hydrophilic also
undergo functionalization to enhance the properties offered
by the graphene backbone and tune them according to their
use. The GO surface is rich in oxygen functional groups such
as hydroxyl, epoxide, diol, carboxyl, etc. that modify the van
der Waals interactions. Although the aromaticity of graphene is
lost due to utilization of π electrons in covalent bonding of
these oxy groups on graphene skeleton, the presence of
carboxyl, carbonyl etc. groups at the edge make them highly
soluble and dispersible in water.
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The interactions of graphene with other moieties for its
functionalization can either be covalent, noncovalent, or a
combination of both. Depending on the type of interaction the
molecules either disturb the hybridization of graphene from sp2
to sp3 disrupting its aromatic nature or follow a more versatile
non- covalent approach preserving the aromaticity of the
lamella. The apperception of these interactions is imperative as
they alter the chemistry of graphene and its subsidiaries and
assist us in designing better graphene-based materials for
specific applications. Therefore, a detailed study of these
interactions of graphene and its subsidiaries with other organic
entities is essential to enhance their attributes and usability.
3.1. Covalent Functionalization. The functionalization
that is associated with the transformation of some of the sp2
hybrid carbon of graphene to sp3 hybridization by sharing of
the delocalized electrons is known as covalent functionalization
and results in the loss of aromaticity.102 Graphene can be
functionalized by nucleophilic substitution, electrophilic
addition, condensation, and addition reactions.
3.1.1. Nucleophilic Substitution (SN) Reaction. The
reactions in which an electron-rich nucleophile is attracted to
an electrophile, that is, a positively charged atom and replaces a
leaving group are known as nucleophilic substitution
reactions.103,104 These kinds of reaction are possible in
graphene that has defects or GO and rGO layers as they
have electron-rich groups.
A representative case is the functionalization of GO by
substituting it with amine groups that attack the epoxy group
on the GO surface. The lone nitrogen pair renders it as a
nucleophile, and the reaction takes place at room temperature.
Not only amine but also amino acids and amine terminated
biomolecules, etc. have also been used to functionalize
graphene.105−107 One of the methods of amine group
substitution is by using ammonia and ethylene glycol as
solvent and nitrogen as precursor. The formation of rGO-NH2
at relatively low temperature by the solvo-thermal method was
achieved, and hydroxyl, epoxide, and carboxyl groups
containing oxygen functionalities such as lactones, anhydrides,
etc. were obtained on the graphene skeleton via nucleophilic
substitution of carboxyl and epoxide group with ammonia
radicals.108 The addition of amino groups provides graphene
with excellent complexing properties that can be used in
various applications. Tetrafluoroterephthalonitrile (TFT) or
decafluorobiphenyl (DFB) were linked to GO sheets via an
aromatic SN reaction and resulted in porous GO. The pore
size and surface area were observed to have considerably
increased and thus this material acted as adsorbents for specific
pharmaceutical effluents such as carbamazepine, paracetamol,
ibuprofen, sulfadiazine, sulfamethoxazole, and phenacetin.109
Ethylenediamine-N,N-disuccinic acid (EDDS) was used to
reduce GO and was used to eradicate tetracycline from
aqueous media. Epoxide was removed from GO by
protonation by hydronium ion followed by nucleophilic
substitution for ring opening that formed an intermediate
with the hydroxyl group. The hydroxyl group was removed via
dehydration followed by deprotonation, and sp2 hybridization
was restored110
3.1.2. Condensation Reaction. In the condensation
reaction, the combination of two molecules lowers the
entropy102 and yields some other small molecule as byproducts
such as water, ammonia, acetic acid, or hydrogen sulfide.
Graphene undergoes this transformation with isocyanates, di-
isocyanates,111 and amine compounds and forms compounds
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such as amide and carbamate that functionalize via ester
linkages.112 Chitosan-modified graphene is also formed by this
mechanism for which the amine group of chitosan and
carboxyl group of GO react. This has been used in the removal
of several organic pollutants such as dorzalamide and
hydroquinone, and dyes such as methylene blue, and has
good aqueous solubility and biocompatibility. The esterifica-
tion of carboxyl and hydroxyl groups of β-cyclodextrin (β-CD)
is also used to functionalize graphene.113 β-CD forms hybrids
with graphene and other entities such as Fe2O3 that enhance
its magnetic character and helps in removal of dyes such as
brilliant green and MB.114 Polyvinyl acetate (PVA) is also used
for formation of ester linkages for surface modification of
GO.115 Amide bond formation in amine functionalized
porphyrin (TPP-NH2) enhances the solubility and constancy
of graphene subsidiaries in organic and aqueous phases.116 An
ion exchange material, sulfanilic acid functionalized GO has
been prepared, and amide bond formation takes place between
amine group of sulfanilic acid and carboxylic group of GO.117
3.1.3. Electrophilic Substitution (SE) Reaction. When the
hydrogen atom is replaced by an electrophilic entity the
reaction is called an electrophilic substitution reaction.
Graphene has hydrogen atoms on its edges, and they can be
easily replaced by other functional groups.
GO decorated with oxidized functional groups is highly
affected by the hydroxyl radical that possesses the dual nature
of being able to oxidize and participate in electrophilic
addition. The Fenton reaction is a method to degrade aromatic
compound in water by a highly selective hydroxyl radical. The
GO can either provide the hydroxyl radical or the radical can
be utilized to breakdown the graphene sheets. Other entities
such as para-nitro aniline,118 aryl diazonium salt,119,120 4-
bromo-aniline,121 ferrocene,122 methyl-2-pyrrolidone,123 and
polystyrene124 have also been used to functionalize graphene
composites via electrophilic substitution.
3.1.4. Addition Reaction. Addition reactions are responsible
for forming larger molecules by a combination of two smaller
molecules and are devoid of any byproducts. Khatri and group
reported an aza Michael reaction125 that involves the addition
of an amine to the β position of an α,β-unsaturated carbonyl
and nitrile106,126 compound of graphene to give a β-amino
carbonyls and nitriles127 as products with an aqueous
dispersion of GO. This reaction had a high catalytic activity
with reaction times as low as 5−10 min. Another example is
the formation of a GO-based polymer nanocomposite
incorporated with polydopamine and poly(sodium p-styrene-
sulfonate) hydrate (GO-PDA-PSPSH) in which the addition of
PSPSH and GO-PDA took place via Michael addition. These
nanocomposites showed great results for the removal of
methylene blue dye from wastewater.128
3.2. Noncovalent Functionalization. Noncovalent func-
tionalization refers to all the types of bonding that do not
involve sharing electrons but are based solely on the
interactions based on the charges of the moieties.29,129 π -π
bonding, electrostatic attraction, and hydrogen bonding, etc.
are few of the noncovalent interactions that graphene-based
materials are involved in for functionalization or other
applications.102 Usually π−π interactions happen with organic
molecules and polymers with extensive π systems while van der
Waals forces are formed between graphene and GO with the
same type of characteristics as for π−π interactions but the
functionalizing entities should have a hydrophobic character.29
The oxygen functionalities on the surface and edges of GO
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induce ionic interactions and hydrogen-bond formation. These
noncovalent bonds do not interfere with the π system of the
graphene-based materials, and hence the properties offered by
unique sp2 hybrid planar structure is maintained.29
The π−π interactions are formed between entities that have
extended π systems and a compatible geometry. The planar
graphene readily interacts with other aromatic planar
molecules. This ability is reduced in rGO and GO and the
π−π interactions thus formed are weaker than that formed by
graphene. Other interactions such as hydrogen-bond formation
and electrostatic interactions take place due to electro-
negativity differences between reacting molecules and their
proximity, respectively. These have been depicted in Figure 3
Figure 3. Noncovalent interactions of GO.
and can be well understood from these figures. The adsorption
of organic compounds on carbon-based graphene materials
depends on several interactions such as hydrophobic
interaction, H-bonding, electrostatic interplay, pore-filling
mechanism, or a combination of these.130
A study which explained the interactions with graphene and
MB gives an example as to how the adsorption process takes
place. SMFS and DFT simulations have been systematically
and quantitatively investigated and the nanomechanical
interactions have been understood. While most of the studies
focus on electrostatic and π−π interactions, this study proves
that the epoxy on the GO surface participates in most binding
events. The activation Gibbs Energy of bond dissociation is
(ΔG) −4.61 kcal mol−1.131 This also explains the unfavorable
removal of anionic AOCs by GO. This can be visualized in
Figure 4.
These interactions play a major role in the eradication of
pollutants using graphene. While the covalent bonds are
mainly formed when the formation of the composites takes
place, the weaker noncovalent bond forms the locus of
separation of pollutants as they are mainly involved in
adsorption following the mechanical separation of pollutants
or their catalysis. The mechanical separation and catalysis
require the pollutants to be separable with minimum amount
of energy which is evident in the noncovalent bond breakage.
A study of the interactions of graphene and their pollutants
revealed that most of the organic pollutants interact via
noncovalent bonds as evident in Tables 2 and 3. The study of
interactions leads the way to analyze the adsorption process
with a view of thermodynamics and kinetics that further
establish the kind of interactions between the said adsorbate
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Figure 4. SMFS and DFT simulations to determine the interactions
between (a) MB/graphene, (b) MB/epoxy graphene, (c) MB/un-
ionized carbonyl-graphene, (d) MB/ionized carbonyl graphene.131
Symbols: gray, carbon; white, hydrogen; red, oxygen; blue, nitrogen;
yellow, sulfur.
(organic pollutants) and the adsorbent (graphene-based
materials).
4. GRAPHENE-BASED ADSORPTION OF ORGANIC
POLLUTANTS
In 1881, German physicist Heinrich Kayser conferred the term
“adsorption”132 which according to IUPAC is defined as
“increase in the concentration of a substance at the interface of
a condensed surface and a liquid or gaseous layer owing to the
operation of surface forces”, that is, the adherence of atoms or
molecules onto a surface as a result of surface energy. The
adsorption process mainly involves the atoms on the surface
whose bonding efficiency is not fulfilled as they are not wholly
surrounded by the constituents of the adsorbent and hence
have the ability to attract the adsorbate. This involves a
multitude of interactions in accordance with the adsorbate (the
species getting adsorbed) and the adsorbent (the surface for
adsorption) and includes attractive forces such as electrostatic
interactions, van der Waals forces, or stronger covalent or
hydrogen bonding.133 Adsorption is a surface phenomenon
and that involves a superficial interaction of molecules and is
used in various applications such as chromatographic
techniques,134 purification of sugar,135 the cleaning mechanism
of soaps and detergents,136 and removal of metallic and
nonmetallic pollutants from water.74,137−139 In water treat-
ment, adsorption has played a vital role, and activated carbon is
still being used as a primitive adsorbent. Because pharmaceut-
icals were designed to be compatible with human anatomy,57,84
the waste generated from these materials is highly toxic. In
controlled doses and for particular ailments the dosage of
pharmaceutics is helpful but when present in the environment
they pose a threat as their consumption can have adverse
effects. Dyes and other organic pollutants such as herbicides
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and pesticides are removed by adsorption since antiquity and
graphene-based materials are used to efficiently adsorb dyes
and widely used in wastewater treatment technology.140,141
The need to understand the basic requirement for a material
to be an adsorbent is extremely necessary to analyze the
adsorption process. The materials generally used as adsorbents
must have a large surface area, minute pore diameters, high
thermal stability, and the ability to withstand abrasion.142 In
industry, adsorbents are classified into three categories based
on the constituents of the adsorbents. Oxygen-containing
compounds such as silica gel143−145 are hydrophilic and polar;
hence, the interactions between the water molecule and the
pollutants are enhanced. Carbon-based materials such as
activated carbon44,135 are hydrophobic and nonpolar and
have innumerable pores that offer a larger surface area that
ameliorates the adsorption process as pollutants get adsorbed
in the pores. Another category of compounds utilized for
adsorption are polymer-based compounds, and they have a mix
of polar and nonpolar entities in a porous polymer matrix and
have been used widely for organic pollutant adsorption.138,146
Graphene-based materials have a carbon base and are oxidized
to form GO and rGO and form polymer composites,147 metal
ceramics,148 hybrids,149 or are wrapped,150 encapsulated,151
sandwiched,148,152 or mixed with other materials to synthesize
high performance adsorbents which can revolutionize existing
water treatment technologies.
Adsorption has been an effective tool in the removal of
heavy metals, dyes, pharmaceutics, herbicides, pesticides, and
other toxic elements from the aqueous media. For the study of
adsorption dynamics, a detailed study of activation energy and
parameters, change in Gibbs free energy, enthalpy, and entropy
is essential. These parameters are critical to predict the
performance and mechanism of the adsorption process and
provide us with tools for characterization and optimization of
the adsorption mechanism involved. The parameter that a
thermodynamic isotherm conveys about a reaction is the
spontaneity or the thermal requirement of a system, that is, the
reaction is endothermic or exothermic. Considering an
example in which GO and rGO separately form a complex
with sodium alginate, the former graphene derivative displays
an exothermic process while the latter displays an endothermic
nature.153 The amount of adsorbate adsorbed as a function of
temperature and adsorbent concentration is determined by a
simple adsorption isotherm that is expressed by the equation
(Co − C t)V
qt =
m (1)
−1
where qt (mg g ) is the amount of adsorbate per mass unit of
adsorbent at time t, V is the volume of the solution (L), Co and
Ct (mg L−1) are the concentration of adsorbate at initial time
and at time “t”, respectively, and m is the mass of adsorbent
(g).154 But this was proposed without considering complex
systems, that is, when more than one reaction parameter
changes at the same time. In 1894, Freundlich isotherm was
proposed that gave the best fit for a gaseous adsorption but
lacked in several parameters.4 Then in 1916, Irving Langmuir
proposed a model which came to be widely accepted although
it did not consider all parameters affecting rate of adsorption.2
The establishment of a relationship between the different
adsorption parameters and adsorption isotherm is thus
essential to get any meaningful information.
Gibbs free energy along with entropy and enthalpy give
details about spontaneity of a given reaction at a certain
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temperature. When the adsorbate and the adsorbent have been
contacted long enough equilibrium is established and is
described by the adsorption isotherms. The free energy of the
adsorption process is related to the equilibrium constant by the
Van’t Hoff equation:
ΔG 0 = −RT ln KD (2)
−1 −1
where R is the ideal gas constant (8.314 J mol K ), and T is
temperature (K), ΔG0 is Gibb’s free energy change (kJ mol−1)
and KD is the single point or linear sorption distribution
coefficient and is expressed as
Ca
KD =
Ce (3)
where Ca is the equilibrium adsorbate concentration on the
adsorbent (mg L−1) and Ce is the equilibrium adsorbate
concentration in the solution (mg L−1).155 So, we can conclude
that if we can determine the adsorption isotherm of a process
we can deduce other thermodynamic parameters that can
enhance the adsorption capacity. The adsorption state
describes the final state of the system but reaction dynamics
is not governed only by the initial and the final state but also by
the reaction pathway that is explained by kinetics. The
understanding of the reaction timeline helps to control the
reaction parameters and thus the overall thermodynamic
considerations of the system can be influenced. A detailed
study of the possibility of reactions between an organic
pollutant (adsorbate) and graphene-based materials (adsorb-
ent) has been described in this section, and to utilize that
knowledge we need to further understand the thermodynamics
and kinetics of the reaction mechanism.
The need for an ideal adsorption system with which to
compare the given adsorbent materials on the basis of
adsorption parameters and quantitative analysis of their
adsorption capacity for varied conditions is of utmost
importance.156 Hence it is crucial to establish a standard for
the adsorption equilibrium for analyzing the given adsorption
system for their efficiency.157 These equilibrium correlations
are established by adsorption isotherms that can be used to
validate the interaction of pollutants with the adsorbent
materials and help in establishing adsorption mechanisms,
enhancing adsorption capacities, tuning the surface attribute
and help in designing competent adsorption systems.5,158
The standard for adsorption was determined by mathemat-
ical expressions159 specified for adsorption of a pollutant from
the aqueous phase to the adsorbent, that is, graphene-based
materials and is governed by various parameters such as pH,
temperature, and other entities present in the media, etc., and
tools developed for this specific purpose have been used to
determine the mechanism of adsorption, its affinity toward
pollutants, and the effect of the change in environment of the
pollutants while being adsorbed on graphene-based materials.
Thermodynamics and kinetic models are some of these tools
which augment the understanding of the adsorption process.
When an adsorbate is in contact with an adsorbent for
specific amount of time it undergoes a dynamic adsorption
desorption process that defines a state of equilibrium.160 The
physicochemical parameters explaining the thermodynamics
are represented by mathematical models and can be expressed
graphically.161 Several models have been proposed that
consider different parameters for the adsorption process. The
best fit of adsorption data in any of the models describes the
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Review

Table 1. Linear and Nonlinear Forms of Adsorption Isotherm

adsorption isotherm nonlinear form linear form reference
One-Parameter Isotherm
Henry Adsorption constant qe = KHECe 1
Two-Parameter Isotherms
KLCe q
Langmuir qe = qo qe = qo + e 2−5
1 + KLCe KLCe
1
Freundlich qe = KFC1/n
e log qe = log KF + log Ce 2,3,158
n
Dubinin−Radushkevich isotherm qe = (qs) exp(− kadε 2) ln qe = ln qs − kadε 2 5,162,163
RT RT RT
Temkin qe = ln A TCe qe = ln a T + ln Ce 157,164,165
bT bT bT
ij θ yz
logjjjj zzzz = log KFH + nFH log(1 − θ)
θ
k Co {
Flory−Huggins = KFH(1 − θ)nFH 166
Co

ij C yz
Three Parameter Isotherms

lnjjjjKR e zzzz = g ln Ce + ln aR
j q z
CeKR

k e{
Redlich Peterson Isotherm qe = 167
1 + CepaR

ij K yz
n ln Ce = −lnjjjj S zzzz + ln(aS)
jq z
(K sCe n)

k e{
Sips qe = 168
1 + (asCe n)

K TCe qe 1
Toth qe = ln = ln Ce − ln(a T + Ce) 169
a TCe1/ t KT t
ACen 1 1 B
Koble Karrigan qe = = + 170
1 + BCen qe ACen A
qsbK Ce
Khan qe = 171
(1 + bK Ce)μ K
qMRPKRPCe
Radke Prausnitz qe = 172
(1 + KRPCe)MRP

isotherm of the system. There have been many isotherm
models established on different factors and utilized for removal
of pollutants from aqueous media.138 Some of these isotherms
have been stated in Table 1.
The thermodynamic isotherms determine the final state of
the system but to understand the changes in chemical
properties with respect to time, the kinetics of the system
needs to be studied. The kinetics helps us to determine the rate
controlling mechanism such as mass transport and chemical
reactivity.173−175 The pseudo-first-order,176,177 pseudo-second-
order,65,178 Elovich,179 and intraparticle diffusion are some of
the kinetic models that have been determined for graphene-
based systems.
Adsorption is affected by the interfacial atmosphere, and
hence surface area, nature, and initial concentration, pH,180,181
temperature,182,183 and interfering substances play an im-
portant part in the adsorption process. The extent of
adsorption is directly proportional to the surface area and
requires the adsorbent to be finely divided and porous as more
adsorption is achieved per unit weight.184,185 Graphene has a
sheet-like structure and both sides are available for
adsorption,186,187 but due to other chemical properties
graphene is more advanced than activated carbon for the
adsorption process.
The physicochemical nature of both adsorbate and
adsorbent affect both the rate and capacity of adsorption.184,188
The solubility,189 molecular size of adsorbate with respect to
adsorbent, 190 delocalized electrons, polar entities, and
proximity of the adsorbate and adsorbent all contribute to
G DOI: 10.1021/acs.jced.8b01057
the process of adsorption and can be exemplified by a
cellulose/GO composite as increase in adsorption capacity
from 245.7 to 451.2 mg g−1 was observed when the
concentration of MB increased from 100 to 220 mg L−1 at
318 K.191 A pH increase from 3 to 7 resulted in the increase in
adsorption capacity from 28.5 to 542 mg g−1 in the adsorption
of MB by GO at 293 K. This was attributed to the greater
affinity of H+ ions to the GO surface than the MB molecule. At
pH 9, hydrolysis of GO took place hence the adsorption ceased
to exist. MB was also affected by the high pH as a result of
stepwise demethylation.192 The effect of temperature was
evident in the case of cellulose/GO fibers that signify an
endothermic process as the adsorption capacity increases from
419.09 to 451.18 mg g−1 when temperature is increased from
278 to 313 K.191 The polydopamine-coated layer of GO had a
negative enthalpy value which concluded that the reaction was
exothermic.193 The concentration of organic and inorganic
compounds other than the pollutant in consideration strongly
influences the adsorption process.194,195 A representative of
this can be the adsorption of tetracycline from GO in which
univalent sodium ions decrease the adsorption of the organic
pollutant. When 100 mmol L−1 NaCl was present in the
solution which contained 166.67 mg L−1, the adsorption
decreased by 50% which shows that the univalent sodium ions
minimized the adsorption of the tetracycline.98
An adsorbent is desired only when it is cost-effective, and
the easiest way to achieve this is by recycling the adsorbent. If
the efficiency of any adsorbate is retained after processing it
with mechanical methods such as magnetic separation,
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
chemical methods such as solvent wash, or even simple
filtration then the use of that material is coveted. Graphene-
based materials have shown exemplary performance in being
recycled with an efficiency of more than 90% even after a
repeated number of cycles. This is evident by the reusability
column mentioned in Tables 2 and 3.
The adsorption isotherms and kinetic models have been
established for a large number of graphene-based materials and
the environmental factors also play a vital role used for organic
pollutant removal. Some of the examples of these have been
discussed in the following section and have proved that the
adsorption capability of graphene-based materials and their
mechanisms have helped us to understand the role graphene
and its composite play in enhancing this process.
Graphene technology has contributed vastly to water
remediation by the adsorption of organic pollutants. Nano-
sheets of graphene, GO, and rGO have been designed for
adsorption and they have been incorporated in three-
dimensional structures such that the structure formed retains
most properties of pure graphene as this is desirable for
implementing it in large scale water treatment plants and
recycling of these sorbents.237,238 Graphene, GO, and rGO
have been used to prepare aerogels and hydrogels, or have
been chemically doped to tune the properties of graphene and
functionalize it by integrating heteroatoms that improve its
physicochemical properties.239 The industrially used sorbents
are generally polymer based,139,240 carbon based,163 or are
oxygen functional group-containing compounds. As graphene
is a carbon-based compound it forms composites with
polymers and oxides to enhance its adsorption capacity.
With this view the following examples of graphene, GO, rGO,
and their polymer-based and oxide-based composites have
been cited because they aid the understanding of the process of
adsorption and the thermodynamic and kinetic prospect of
their interactions with the organic pollutants in wastewater.
Graphene-based materials are tested for their potentialities as
sorbents by the batch assay method which provides
fundamental information on the adsorption process. The
results obtained from these dynamic experiments are crucial
for the design and feasibility of a full-scale treatment unit.241
The obtained optimal conditions were achieved by studying
parameters such as initial concentration of the contaminant,
pH of the sample, dosage of adsorbent, temperature, and
capacity of adsorption.242
4.1.1. Adsorption by Graphene-Based Polymer Nano-
composite. Graphene related nanocomposites have been
widely investigated for dyes adsorption and pharmaceuticals
as is evident from the adsorption capacities. To understand the
batch processes better some of the studies have been compiled
to support graphene-based materials as adsorbents and prove
their efficacy.243 With increasing demand of green chemistry,
biopolymers in a combination with graphene materials have
also been investigated.244,245 Biocompatibility, biodegradabil-
ity, availability, high reactivity, and easy isolation make a
combination with graphene materials desirable for the
adsorption of organic entities.246
The most easily available natural polymers are polysacchar-
ides and they play many roles in nature, thus their use to clean
water is inevitable. They were functionalized with graphene
and GO, etc. to successfully remove organic entitites. Alginates,
polysaccharide obtained from seaweed, were combined with
porous graphene to obtain porous graphene/alginate double
network nanocomposite beads (GAD). These beads exhibited
H DOI: 10.1021/acs.jced.8b01057
Review
a wrinkled surface distributed unevenly that provided them
with a larger surface area and better thermal stability than the
graphene/alginate single network (GAS). The Langmuir
model was a fit to the MB adsorption isotherm, and adsorption
capacity was determined to be 7.2 and 5.6 mmol g−1,
respectively, and the kinetics followed the pseudo-second-
order rate model. The desorption rate was 60.2% and 47% for
GAD and GAS, respectively. While the porosity played a major
role in the adsorption process the presence of a carboxyl group
also enhanced the efficiency by making the material surface
negatively charged.247 In another study the concentration of
both alginate and GO was altered, and it was noticed that an
increase in both of the components, in two separate processes,
resulted in the increase of adsorption of MB. The increase of
adsorption because of GO was attributed to the interactions of
oxygen functional groups, while that of alginate was attributed
to the porous structure. The highest concentration samples of
both components were then dried by ethanol treatment and
lyophilized which helped in determining the maximum
adsorption capacity as 3.2 and 4.2 mmol g−1 by fitting the
data in the Langmuir adsorption model.248
A layered 3D GO-sodium alginate (SA) and rGO-SA were
other alginate nanocomposites that were used to adsorb MB,
and the adsorption capacity was determined to be 833.3 and
192.2 mg g−1, respectively, at 303 K and contact time of 12 h
and rendered it as a spontaneous process. While the GO
nanocomposite displayed electrostatic interactions and the
reaction was exothermic, the rGO composite interacted via
π−π interactions and the reaction was found to be
endothermic. 153 GO-calcium/alginate nanocomposite,
strengthened the composite structure and acted as a good
adsorbing agent for the eradication of MB dye. A decrease in
adsorption capacity was observed when the temperature was
increased from 298 to 328 K, and the adsorption intensity was
recorded as 163.93 and 140.85 mg g−1, respectively. This
proved that the reaction was exothermic222
Other polysaccharide/GO (PS/GO) nanocomposites con-
sisting of inulin, xylan, and κ-carrageenan formed nanocages
and a highly disordered structure to facilitate adsorption of
MB, R6G, orange II, and acid fuchsin. MB had a maximum
adsorption capacity of 769 mg g−1 and the reaction followed a
pseudo-second-order kinetic model and Langmuir isotherm
model. Also, the reaction was strongly affected by pH
conditions, and electrostatic interactions dominated the
adsorption process. Overall the reaction was spontaneous
and exothermic.249
Another widely available natural polymer is chitin which is
obtained from mainly two types of marine crustaceans, shrimp
and crabs.250 Deacetylation of chitin with alkaline substance
yields chitosan which is a natural polymer used extensively for
many applications such as agriculture,251 medicine,252 etc. Its
role in water purification cannot be undermined,188 and hence
graphene and chitosan composites for organic pollutant
eradication have also been reported. Chitosan and GO (CS−
GO) have amphoteric characteristics and have been utilized to
remove MB and MO from wastewater within 10 min217
especially at low pH levels. The GO−chitosan hydrogel
composite was reported to adsorb MB and eosin Y dyes, and
the interactions were mostly electrostatic. The composite
could be used as a column packing and the dyes could be
removed by filtration with it.235 The removal of chitosan was
made effortless by developing magnetic chitosan−GO nano-
composites that were used for MB adsorption, and adsorption
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
 Table 2. Graphene-Based Composites for Removal of Pharmaceuticals and Other Aromatic Pollutantsa
adsorption iso-
composite pollutants adsorption capacity therm kinetics interactions recycling ref
MAP/G-based monolith BPA 324 mg g−1 Langmuir pseudo- hydrogen bonding, π−π interaction up to 88%, 5cycles, methanol 196
second-
order
biochar-supported rGO Atrazine 67.55 mg g−1 Langmuir pseudo- π−π interactions up to 81%, 4 cycles, MW 197
second- irradiation
order
NaHSO3/rGO aerogels TBBPA 128.37 mg g−1 Langmuir pseudo- π−π interaction 93.17%, 5 cycles, methanol 198
second-
order
biochar-G nanosheets phthalic acid esters (DMP, DEP 45.65,31.78, and 25.43 mg g−1 Langmuir, pseudo- π−π EDA (electron donor−acceptor) inter- thermal treatment 199
and DBP) Freundlich second- action, hydrophobicity, H bonding.
order
Few layer-GO 17b-Estradiol (E2) 149.4 mg g−1 Langmuir pseudo- π−π interactions and hydrogen bonds 94.14%, 5 cycles, strong alkali 200
second-
order
Journal of Chemical & Engineering Data

G nanoplatelets aspirin, caffeine, acetaminophen 13.02 mg g−1, 19.72 mg g−1, and 18.06 mg g−1, N.A. pseudo- van der Waals interactions. N.A. 201
second-
order
GO/CSA Dorzolamide 334 mg g−1 Langmuir− pseudo- amide bond formation 90%, 10 cycles 202
Freundlich second-
order
reduced GO/magnetite com- CIP and NOR 18.22 or 22.20 mgg−1 Langmuir and pseudo- π−π interaction and cation-π bonding N.A. 203
posites (RGO-M), Temkin second-
order

I
GO nanoparticles (GO-NP) Tetracyclines 322.43 mg g−1 Langmuir pseudo- π−π interaction and cation-π bonding N.A. 204
second-
order
rGO1, rGO2 and graphene ketoprofen (KEP), carbamaze- KEP- 62.5, 54.1, and 15.3 mg g−1, CBZ- 115, Dubinin Ash- N.A. π−π EDA interaction, H bonding, electrostatic N.A. 205
pine (CBZ), and bisphenol A 105, and 22.8 mg g−1, BPA- 152, 128, 26 takhov interactions
(BPA) mg g−1
G and activated G(G-KOH) ciprofloxacin (CIP) 145.9, 194.6 mg g−1 Langmuir pseudo- hydrogen bonding, π−π electron donor− N.A. 206
second- acceptor interactions, and electrostatic in-
order teractions).
GO Atenolol (ATL) and propranolol 67 and 116 mg g−1 Langmuir− pseudo- electrostatic forces, H-bonding or π−π inter- 72%, 67% methanol 207
(PRO) Freundlich second- actions
order
GO diclofenac (DCF) and sulfame- 43.9 and 1.19 mg g−1 Freundlich N.A. hydrophobic interactions and π−π electron N.A. 208
thoxazole (SMX) donor−acceptor (EDA) interactions
G acrylonitrile, p-toluene sulfonic ∼1.43 g g−1G, ∼1.46 g g−1G and ∼1.52 g g−1G N.A. N.A. π−π interactions constant during first five 209
acid, 1-naphthalene sulfonic cycles
acid
super paramagnetic G/Fe3O4 Pararosaniline 198.23 mg g−1 Langmuir pseudo- π−π interactions ∼92%, 5 cycles, ethanol 210
second-
order
G sand composite(GSC) rhodamine 6G, chlorpyrifos, 75.4 mg g−1 N.A. pseudo- electrostatic interaction complete regeneration by 211
second- acetone
order
G sand composite (GSC) rhodamine 6G (R6G), chloro- 55, 48 mg g−1 N.A. pseudo- π−π interaction. 1.38 mg/g loss for third run of 212
pyrifos (CP) second- eluent in column by acetone
order
GO (chemically reduced naphthalene and 1-naphthol 21.4(CRG), 57.7(ARG) mg g−1 Langmuir N.A. n−π EDA interaction, cation− π interactions, N.A. 213
Review

(CRG), annealed(ARG)) π−π interaction and hydrogen bonding

J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Journal of Chemical & Engineering Data Review

capacity was determined to be 95.31 mg g−1 at a pH of 5.3 and

213

214

214

215

215

216

216
ref
temperature of 303 K; the reaction was found to be
spontaneous and exothermic. Desorption was done using 0.5
M NaOH and 90% was recycled.236
Cyclodextrin, a complex sugar was also complexed with GO
and chitosan to form magnetic β-cyclodextrin chitosan−GO
recycling

composite and was used to enahnce adsorption of MB dye at

regular pH. The monolayer adsorption intensity was
determined to be 84.32 mg g−1 at 293 K for which the
N.A.

N.A.

N.A.

N.A.

N.A.

N.A.

N.A.
hydrophobicity of GO and the amine and hydroxyl groups of
chitosan together cooperated for the removal of dye.147 Even
n−π EDA interaction, cation− π interactions,

without chitosan, magnetic cyclodextrin−GO composite

hydrophobic interactions and π−π bonding

hydrophobic interactions and π−π bonding

π−π interaction and hydrogen bonding

π−electron donor−acceptor interaction removed MB efficiently with an adsorption capacity of

261.78 mg g−1 at a pH 10 and temperature of 303 K, and
π-electron donor−acceptor interaction

the complex formed was efficiently removed by magnetic

separation. The hydrophobicity of cyclodextrin and iron oxide
interactions

was also overcome by forming the composite with GO which

shows high hydrophilic properties.234
Polydopamine coated GO(PD/GO) composite which was
π−π interactions

π−π interactions

based on the structure of mussels was used for effective

removal of MB, and a range of PD/GO were synthesized with
different concentrations of PD by a percentage that varied from
5%, 15%, 35%, and 70% and their adsorption capability were
reported as 1.3, 1.89, 1.7, and 0.6 mg g−1, respectively.193
second-

second-
kinetics

Synthetic polymers were also doped with graphene and its

pseudo-

pseudo-
order

order
N.A.

N.A.

N.A.

N.A.

N.A.

subsidiaries to enhance adsorption of dyes and pharmaceut-

icals. PVA (poly(vinyl alcohol)) and PAA (polyacrylamide),
adsorption iso-

Polanyi−Dubi-

etc. have shown high adsorption capacities. GO/PVA were

binin-Ashta-
Polanyi− Du-

nin−Ashta-

Freundlich

Freundlich

combined to form an aerogel whose structure stability

therm
Langmuir

Langmuir

Langmuir

khov

khov

depended on the incorporation of PVA that exerted a

reinforcement effect. MB and Congo Red was efficiently
removed. The adsorption capacity of GO/PVA composite for
naphthalene-145(CRG), 52.4(ARG) mg g−1 1-

MB removal was 127.5 mg g−1 and for other cationic dyes the
GNS B- 163.6, 104.7 (mg g−1)/(mg L−1)n
GNS A −208.3, 102.6 (mg g−1)/(mg L−1)n,
naphthol- 269(CRG), 282(ARG) mg g−1

efficiency was up to 96%.253 GO and PAA were used to

eradicate MB and R6G and a multitude of interactions such as
hydrogen bonding, electrostatic interaction, van der Waals
adsorption capacity

174.6, 59.0 (mg g−1)/(mg L−1)n

127.7, 136.4, and 170.2 mg g−1

4.842, 1.028, 46.132 mmol g−1

forces, π−π interactions, and hydrophobic interactions with

2.62, 5.90, and 6.12 mg g−1,

the GO sheet. The behavior of the composite changed with the

change in concentration of the GO and PVA and the
maximum adsorption capacity was determined to be ∼293
1.050 mmol g−1

and ∼288 mg g−1 in 20 and 60 min, respectively. Both

Langmuir and Freundlich model fit the data and the reaction
followed second order kinetics.254
Polystyrene/Fe3O4-GO nanocomposites arranged in a core−
shell structure and bound by electrostatic interactions were
pyrene, anthracene, naphthalene
naphthalene, phenanthrene, and

naphthalene, phenanthrene, and

used for the adsorption studies of RhB, and the adsorption

naphthalene and 1-naphthol

capacity at room temperature for 24 h was determined to be

13.8 mg g−1.232 The magnetic character makes the composite
phenanthrene, biphenyl

phenanthrene, biphenyl
pollutants

easier to separate after adsorption. Photodecolorization was

observed for Rose Bengal using a polymer-based nano-
composite. Polyaniline/graphene (PANI−G) nanocomposites
pyrene

pyrene

were also used to degrade RhB and the photocatalytic activity

pyrene

was much higher than that of PANI. PANI is basically a

polymer of aniline monomers and it was prepared while the
reduced G(CRG-chemical re-

photodegradation was taking place. Superoxide anion, hydro-

G nanosheets(GNS A with
duction, ARG-annealed)

higher surface area than

Table 2. continued

N.A. = not available.

peroxyl, and hydroxyl radical were formed, and their

scavenging led to enhanced photocatalytic activity.255
G nanosheets(GNS)
composite

The natural and synthetic polymers were combined in some

cases for enhanced adsorption. Dorzalamide, a biomedical
GNS B)

waste in effluents was eradicated using GO/PAA grafted

chitosan nanocomposite (GO/CSA).57 The adsorption in-
rGO
GO

GO

GO

tensity was found to be 334 mg g−1 at 25 °C, and the

a

J DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
 Table 3. Graphene-Based Composites for Removal of Dyesa
composite pollutants adsorption capacity adsorption isotherm kinetics interactions reusability ref
chitosan/GO MB, MO 1.60,0.80 mmol g−1 Langmuir, Freundlich pseudo-second- electrostatic interaction, >90% after 5 cycles, 217
order and pseu- π−π-stacking acidic/alkaline elu-
do-first-order ent
amide functionalized MB 97% in 15 min N.A. pseudo-first-order π−π interactions, elec- no significant change, 218
MOF/GO trostatic or acid−base 4 cycles, ethanol
interactions, and DMF
G/Fe3O4 MB 43.82 mg g−1. Langmuir pseudo-second- electrostatic attraction, decreases with each 219
order π−π interactions cycle until 5 cycles
cylindrical G−CNT hy- MB 81.97 mg g−1, 97% Freundlich pseudo-second- hydrophobicity, π−π in- acidic ethanol 220
brid order teraction
magnetic Fe3O4@G MB, CR 45.27 and 33.66 mg g−1, Langmuir pseudo-second- external diffusion magnetic separation 141
(FGC) order
G/Fe3O4 MB 43.82 mg g−1 Langmuir pseudo-second- electrostatic attraction, decreases with each 219
order π−π interactions cycle until 5 cycles.
GO MB 1.939 mg mg−1 Langmuir N.A. electrostatic interaction 37%, 30% acetic acid, 221
Journal of Chemical & Engineering Data

ammonia in etha-
nol
GO MB 240.65 mg g−1, Langmuir pseudo-second- π−π EDA interactions N.A. 222
94.8−98.8% order
GO Acridine Orange 2158 mg g−1, 95% Langmuir N.A. hydrogen bond N.A. 223
GO nanosheet BB41, BR18, and BR46 1429, 1250, and 476 Langmuir pseudo-second- electrostatic interaction N.A. 224
mg g−1, 89%, 94%, 76% order
(50 mg L−1)
GO MB N.A. Freundlich to Langmuir as oxidation degree pseudo-first-order π−π interaction and >90.97 2% NaOH, 225

K
increases and pseudo-sec- electrostatic interac- ethanol
ond-order tion
layered GO MB,MG 350 and 248 mg g−1 Langmuir pseudo-second- electrostatic interaction N.A. 226
order
GO caged in cellulose MG 17.862 mg g−1, >96% Langmuir pseudo-second- π−π EDA interactions, >90%, 5 cycles filter- 151
microbeads (GOCB) order electrostatic ation
MgO/MLG Safranin O ∼3.92 × 10−4 mol/g Langmuir pseudo-second- covalent bond (chemi- ∼73.5% ethanol 152
order sorption)
GO Methyl Green 93% pH 4 to 6-Toth > Sips > Dubinin − pseudo-second- N.A. N.A. 227
Radushkevich (D − R) > Scatchard > order
Langmuir > Temkin > Freundlich
rGO Methyl Green 77% pH 4 to 6-Toth > Sips > Dubinin − pseudo-second- electrostatic interaction N.A. 227
Radushkevich (D − R) > Scatchard > order
Langmuir > Temkin > Freundlich
rGO -based hydrogels MB, RhB ∼100%, 97% Freundlich pseudo-second- π−π stacking and ∼100%, >80%, 3 228
order anion−cation interac- cycles ethylene gly-
tions col
rGO supported ferrite MB, RhB 35, 23 mg g−1, ∼100%, N.A. pseudo-second- electrostatic interaction magnetic separation 229
(Mn/Zn/Co/Ni) 92% order
Fe2O4
rGO/Fe3O4 (for 40 mg Rhodamine 6G (R6G), Acid Blue 92 (AB92), 30, >90, 50, 88, 50, ∼46 N.A. pseudo-second- π−π interactions annealing 230
GO) Orange (II) (OII), Malachite Green (MG), and mg g−1 order
new coc-cine (NC)
rGO−TiO2 hybrids MB 83.26, 75.36 mg g−1, 90% N.A. pseudo-second- N.A. N.A. 149
(sheets, nanotubes) order
magnetite/rGO RhB, Malachite Green 91%, 94% Freundlich pseudo-second- π−π interactions magnetic separation 231
(MRGO) order
Review

J. Chem. Eng. Data XXXX, XXX, XXX−XXX

DOI: 10.1021/acs.jced.8b01057
Journal of Chemical & Engineering Data Review

interactions involved were a combination of electrostatic forces

232

233
234

235

236

147

153

153

193
ref and hydrogen-bond formations, etc.202
Many graphene and GO composites resulted in the

60%, 5 cycles ethanol

90%, 4 cycles 0.5 M
magnetic separation

magnetic separation
magnetic separation
formation of hydrogels and aerogels which shows a great
reusability

water filteration
capacity for adsorption of dyes and pharmaceuticals. Nitrogen
and sulfur codoped graphene hydrogels (N/S-GHs) were

NaOH
synthesized by a chemical route in which glutathione acted as a

N.A.

N.A.

N.A.
binder, modifier, source of N and S, and also as a reducing
agent as it reduces hydroxyl radicals. Malachite Green was
π−π interaction, hydro-

Electrostatic interaction
adsorbed the most because of the porous structure of the
electrostatic interaction

π−π stacking interac-

1,4-Michael addition
composite and accessibility of the composite for adsorption
interactions

ionic interactions

ionic interactions
π−π interaction

followed by MB and crystal violet. The highest adsorption was

gen bonding

observed at 313 K, and the adsorption efficiency was

determined to be 806.5 mg g−1. The Langmuir model was a
tions
proper fit to the experimental data while the reaction followed
N.A.

a pseudo-second-order kinetics. The recycling capacity was

100% even after six cycles of adsorption.256
order, intrapar-
ticle diffusion
pseudo-second-

pseudo-second-

pseudo-second-

pseudo-second-

3-D sodium bisulfite reduced-graphene aerogels (S-rGA) for

kinetics

the removal of tetrabromobisphenol A (TBBPA) showed a

order

order

order

maximum adsorption capacity of 128.37 mg/g, and the

N.A.

N.A.

N.A.

N.A.

N.A.

reaction was found to be exothermic and spontaneous.198

Hydrothermally prepared graphitic carbon nitride−titanium
dioxide−graphene aerogel (g-C3N4−TiO2−GA) composites
showed 20.0 mg L−1 adsorptivity for rhodamine B (RhB) in an
hour and were found to be 75.6% efficient even after four
cycles.257 Tetracycline was adsorbed using GO as a result of
adsorption isotherm

π−π interaction and was evaluated using the Langmuir model,

and the adsorption capacity was determined to be 313 mg g−1.
The extent of adsorption was influenced by pH or the
concentration of univalent sodium ions.98 Graphene CNT
hybrid aerogels were used to adsorb RhB, MB, and fuchsine,
and their adsorption capacities were found to be 150.2, 191.2,
Freundlich
Langmuir

Langmuir

Langmuir

Langmuir

Langmuir

Langmuir

and 180.8 mg g−1, respectively. This composite was obtained

N.A.

N.A.

by GO and CNT with Vitamin C without stirring which led to

CO2 drying.258 MB and RhB were adsorbed using rGO-based
hydrogels which were prepared by sodium ascorbate and
167.2 and 171.3 mg g−1
adsorption capacity

showed 100% and 97% removal, respectively, at a pH of 6.4

and a temperature of 298 K and contact time of 2 h. Ethylene
387,326 mg g−1

glycol was used for regeneration of the hydrogels.228 While

228.5 mg g−1

95.16 mg g−1

84.32 mg g−1

833.3 mg g−1

−1
13.8 mg g−1

192.2 mg g

2.18 g g−1

polymers in the form of graphene and its composites have

made their mark in water purification advancement, they also
give a glimpse of the importance of metal oxide composites.
4.1.2. Adsorption by Graphene-Based Materials and Their
Metal Oxide Composites. Adsorption by graphene-based
material and/or combined with oxides has been an essential
part of pollutant eradication and has been widely catalogued
for pharmaceuticals, dyes, and other organic pollutants
management and disposal. A study on the adsorption of
pollutants

MB and Neutral Red (NR)

antibiotics showed that the number of aromatic rings on

antibiotics affected the adsorption rate, that is, the more
aromatic rings the antibiotics have, the faster is the adsorption
MB and Eosin Y

rate on the carbon-based materials. This was studied by the

adsorption of ofloxacin (OFL), sulfadiazine (SD), sulfame-
thoxazole (SMX), sulfamethazine (SMZ), cefalexin (CFX),
and tetracycline (TC) on graphene-based materials.259 The
RhB

MB

MB

MB

MB

MB

MB

following are some examples of graphene-based materials

Table 3. continued

N.A. = not available.

chitosan/GO(MCCG)

adsorbing aromatic-based substances followed by dyes.

GO−chitosan hydrogels
GO/magnetic cyclodex-

magnetic cyclodextrin−
polystyrene/Fe3O4/GO

magnetic chitosan/GO

rGO-sodium alginate

Chemically reduced graphene and annealing reduced

GO-sodium alginate
CS10−10:1 w/w)
(GO−CS)(GO−
GO−Fe3O4 hybrid
composite

graphene showed adsorption capabilities because of the oxygen

functional groups.214 Graphene nanosheets and GO were
(rGO-SA)
(MCGO)

(GO-SA)

PDA/GO

utilized to adsorb phenanthrene and pyrene where phenan-

trin

threne showed more affinity toward the carbon allotropes and

graphene nanosheets due to the wrinkled surface of the
a

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Journal of Chemical & Engineering Data
nanosheets.214 For the adsorption of phenanthrene and
biphenyls by the same composites, phenanthrene showed
greater adsorption due to greater hydrophobicity. The larger
the surface area was, the greater was the adsorption of
phenanthrene, whereas no such observation was made for
biphenyls. Organic matter did influence the adsorption of
phenanthrene and biphenyls, but it still proved to be more
efficient than the currently used materials such as activated
carbon, proving the efficacy of the graphene in wastewater
treatment.216
Phenol, which is responsible for local and systemic toxicity,
was adsorbed by graphene, and the temperature and pH played
an important role in its removal. Between pH 4 and 6 phenols
were readily adsorbed, and the gradual increase of temperature
from 12 to 60 led to an increase in the adsorption of
phenols.260 Bisphenol A (BPA) was also affected by pH as a
value more than 7 caused a sharp decrease in the adsorption of
BPA which was due to the repulsive electrostatic interactions.
The adsorption process for BPA was spontaneous and
exothermic in nature and established graphene as the preferred
adsorbent for BPA.261 p-Toluene sulfonic acid and 1-
naphthalenesulfonic acid were successfully removed, and
their removal was attributed to the large size and presence of
benzene rings in their structure.209
Other complex phenolic substances such as 1,2,4-trichlor-
obenzene (TCB), 2,4,6-trichlorophenol (TCP), naphthalene,
and 2-naphthol were absorbed by graphene and GO and
adsorption kinetics were studied by the Freundlich isotherm.
The adsorption of TCP and 2-naphthol were also found to be
dependent on the pH. TCP adsorbed more when the pH was
low while the adsorption of 2-naphthol for graphene increased
between pH 8 and 9.2. The study also points out that the
adsorption of the four aromatic hydrocarbons also depended
on the properties graphene and GO offered.262
Acetaminophen, aspirin, and caffeine are pharmaceutical
wastes that have been eradicated using graphene nanoplatelets.
The reaction of graphene with the three compounds was found
to be spontaneous as the change in enthalpy was negative,
while a detailed study with respect to the effect of pH and
temperature was also studied, and the adsorption capacity for
the three compounds was found to be 19.72, 13.02, and 18.76
mg g−1, respectively.201 Tylosin was adsorbed by graphene
nanosheets and GO as a result of electron donor−acceptor
interactions, and it was highlighted that a Lewis acid base-type
of interaction could be the contributing factor in the
adsorption of tylosin50
rGO was also used to adsorb anthracene, pyrene, and
naphthalene, and around 95% was absorbed by the rGO
surface which was significantly higher than that adsorbed by
GO which adsorbed only 60% of the naphthalene. This is due
to the surface structure of the rGO. The adsorption of pyrene
depended on temperature. The size of the adsorbate also
influenced the adsorption process.215
Another method of adsorption of tetracycline on the GO
surface was reported. The extent of adsorption was determined
to be 323 mg g−1, and the reaction was determined to be
endothermic and spontaneous.204 Ketoprofen and carbamaze-
pine were adsorbed by rGO and graphene where rGO showed
better performance of adsorption than graphene. This can be
attributed to the hydrogen bonding and π−π interactions
between the molecules and oxygen functional groups of
rGO.205 Few-layered GO nanosheets (FLG-GO) adsorbed
17β-estradiol from water with great efficiency. The Langmuir
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isotherm established an adsorption intensity as 149.4 mg g−1 at
298 K and the process was found to be spontaneous.263
Biochar-graphene (BG) nanosheet composites were used to
adsorb dimethyl phthalate (DMP), diethyl phthalate (DEP),
and dibutyl phthalate (DBP) as model phthalic acid esters
(PAEs) where the adsorption depended mainly on π−π
interactions and DBP was adsorbed because of hydro-
phobicity.199
GO using magnesium ascorbyl phosphate (MAP) was used
for Bisphenol A (BPA) removal in an endothermic process and
the adsorption intensity of MAP-GBM (graphene-based
monolith) was 324 mg g−1 for BPA and an 88% regeneration
capacity was observed.196 Biochar-supported reduced GO
composite (rGO-BC) was used for eradication of atrazine
through π−π interactions and showed capacity of adsorption at
67.55 mg g−1 for atrazine.197
The adsorption of ciprofloxacin (CIP) and norfloxacin
(NOR), by reduced GO (rGO)/magnetite composites has also
been studied to facilitate the removal of graphene composites
after adsorption. The batch equilibrium tests indicated that
rGO/magnetite-based composite is strongly dependent on
initial pH for the removal of CIP and NOR via adsorption.
π−π interactions as well as electrostatic repulsions were
responsible for adsorption.130 Apart from pharmaceutical
wastes, self-assembled GO after combination with PEI acted
as dye adsorbents for wastewater treatment.264 Other organic
compounds such as toxic polyaromatic hydrocarbons expelled
by industry also reacted with graphene-based materials for
efficient eradication from wastewater. rGO−magnetite compo-
site has been utilized for the removal of fluoroquinolone
antibiotics such as ciprofloxacin (CIP) and norfloxacin (NOX)
for which both electrostatic and π−π interactions helped in the
adsorption process. The monolayer adsorption intensity was
determined to be 18.22−22.20 mg g−1, respectively, using the
Langmuir and Temkin models.203
Organic compounds such as bisphenyl, phenol, anthracene,
pyrene, naphthalene, naphthyl amine, naphthol, benzene,
sulfonic acid, and their derivatives have been successfully
adsorbed on graphene, GO, rGO, and graphene-based
composites. GO was used to adsorb naphthalene and 1-
naphthol in which the naphthalene showed more affinity
toward adsorption while the adsorption intensity of 1-naphthol
was influenced by pH and showed higher adsorption in acidic
medium. The presence of bivalent cadmium ions increased the
adsorption efficiency of 1-napthol by 120%.213
Activated graphene acted as an adsorbent and was efficient
in removal of CIP and the adsorption capacity was determined
to be 194.6 mg g−1.206 The Hummers method was used to
prepare GO that adsorbed beta blockers such as atenolol and
propranolol by varying pH, temperature, time of contact
between adsorbate, and adsorbent and the dosage of GO.
Surface charge and the ionizability played a crucial role in
determining the adsorption capability of GO for adsorption of
these beta blockers. Hydrogen bonding and electrostatic
attractions between positively and negatively charged entities
are involved in the adsorption. It was also observed that
atenolol was more readily adsorbed than propranolol as a result
of more favorable structure.207 The removal of diclofenac and
sulfamethoxazole using GO was found to be favorable under
acidic pH due to hydrophobic and π−π interactions. The
extent of adsorption was determined to be 8.8 and 5.9 kcal
mol−1 for diclofenac and sulfamethoxazole, respectively. The
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Freundlich isotherm was used and 35% diclofenac and 12%
sulfamethoxazole was found to be removed.208,265
Ethylbenzene, toluene, and xylene were adsorbed by GO
which was modified by 4-aminodiphenylamine (GO-A).
Several factors such as time, pH, and adsorbate concentration
affected the adsorption process and at pH 4 the adsorption was
found to be at maximum, and an increase in the adsorbate
concentration increased the adsorption capacity. The regener-
ation of GO-A was also studied, for which even after three
cycles the GO-A performed well as an adsorbent, and only
after seven cycles did their adsorption intensity decline.266
Nanoporous graphene was used for the removal of benzene,
toluene, and xylene and 119, 123, 125 g of benzene, toluene,
and xylene were efficiently adsorbed by 1 g of nanoporous
graphene. The time taken for this process was rapid and was
completed in about a minute.267
Phenanthrene was removed using GO, rGO, and sulfonated
graphene that provided additional nonaggregating properties
due to the HSO3 groups present on the surface. An equilibrium
was attained in 120 min, but compared to other adsorbents this
process was faster.117 Sulfonated graphene was also used to
remove 1-naphthol and naphthalene, and the adsorption
capacity was influenced by pH. As the pH increased the
adsorption decreased although at pH more than 7 the 1-
naphthol adsorption did not follow this trend. The adsorption
efficiency of sulfonated graphene was as high as 95%. It was
also reported that 1-naphthol adsorption increased with
increasing temperature.268,269 1-Naphthylamine, 1-naphthol,
and naphthalene were adsorbed by graphene−iron oxide
nanocomposites. The mechanism of adsorption largely
depended on electron donor−acceptor interaction between
the π electrons of aromatic compounds and the GO-FeO·
Fe2O3 nanocomposite as the increase in polarity led to greater
capability of donating electrons. The removal of naphthalene
was dependent on temperature. These magnetic GO nano-
composites were also used to eradicate 1-naphthol and 1-
naphthylamine and showed great efficiency owing to the
removal of complexes formed using the magnetic character of
the nanocomposites.270,271 All the data with a view on
thermodynamics, kinetics and reusability is compiled in Tables
2 and 3.
Graphene-based materials not only adsorb antibiotics and
other phenolic substances but are efficient to remove dyes that
change the color of water and hinder the growth of flora and
fauna under water. Graphene was used to adsorb MB and
showed promising results with an adsorption intensity of
153.85 to 204.08 mg g−1 when the temperature was increased
from 293 to 333 K. The maximum percentage was 99.68% at a
pH of 10, and the whole process was endothermic and
spontaneous as was the adsorption of Cationic Red X-GRL on
graphene with an adsorption capacity of 238.10 mg g−1 at 333
K. Another method of removing MB by graphene involved the
determination of spontaneous and heat absorbing nature of the
interaction through fluorescence spectroscopy studies and a
variation of pH, temperature at 303 K, and a contact time on 1
h. The initial adsorption was 5 mg/L, and adsorption was
found to be dependent on it. Graphene also eradicated p-
toluenesulfonic acid (p-TA), methylene blue (MB), and 1-
naphthalenesulfonic acid (1-NA). The adsorption capacities of
p-TA, MB, and 1-NA are 1.43, 1.52, and 1.46 g g−1,
respectively.209
rGO was synthesized in situ with a concoction of GO, Zn,
and NH4Cl in wastewater. The mixture was stirred for 10 min
N DOI: 10.1021/acs.jced.8b01057
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thus reducing GO to nanoporous rGO which also adsorbs dyes
such as methylene, congo red, and lemon yellow with an
adsorption efficiency of 2.6, 7.6, and 3.2 g g−1 with an
efficiency of 98.46%. The byproducts can be used for
generating energy or in agricultural fields as fertilizers.272
The process of rGO formation and dye adsorption has been
depicted in Figure 5.
Figure 5. (a) Schematic process for the treatment of polluted water,
(b) photos showing adsorption of MB, CR, and LY, (c) graphs
showing adsorption of MB.272 Reprinted with permission from ref
272. Copyright 2018, Elsevier B.V.
The adsorption of Acid Orange 8(AO 8) and Direct Red
23(DR23) (ionic azo dyes) from aqueous solutions were
studied. The adsorption isotherms were represented by
Langmuir and Redlich Peterson models and maximum
adsorption capacities were determined as 29 mg g−1 and
15.3 mg g−1, respectively, while the reaction pathway followed
a pseudo-second-order model. The reaction was spontaneous
for both dyes although the reaction of AO 8 was classified as
exothermic while that of the DR23 was endothermic. The
adsorption occurred mainly because of electrostatic inter-
actions due to a difference in charges of the dye and the GO at
pH less than 7, but there was a possibility of hydrogen bonding
and π−π stacking as well.273
MB was adsorbed by GO at pH 6 and a temperature of 298
K and adsorption intensity was reported to be 714 mg g−1 with
an efficiency of 99%. The adsorption was dependent on pH
and ionic strength and dissolved organic matter, and the data
supported the Freundlich isotherm with preference to low
temperatures and high pH.274 Another study showed MB
absorbed by GO at pH 3 and a temperature of 298 K, and an
absorption capacity of 1.939 mg g−1 by the Langmuir
adsorption model and was found to be exothermic in nature.
An increase in pH increased the adsorption of the dye onto
GO.221 This has been depicted in Figure 6.
Exfoliated GO was further analyzed for the adsorption of
MB, RhB, methyl violet (MV), and orange G, and due to the
oxygen functional groups showed excellent adsorption
intensity of the cationic dyes (MB, RhB,MV). The observed
adsorption capacities were 17.3, 2.47, and 1.24 mg g−1 for MB,
MV (both at pH 6) and RhB (at pH 10). The RhB has both
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Figure 6. Adsorption of methylene blue on GO221 where the EDA interaction between sulfur (yellow) of MB and oxygen (red) of GO and the π−π
interaction between the aromatic rings are highlighted.
negative and positive charges in its structure because the
adsorption was carried out in the basic medium.95 At a
temperature of 298 K and pH 6, GO showed excellent
adsorption properties, and the extent of adsorption was 243.90
mg g−1 with a contact time of 5 h. The adsorption took place in
a monolayer manner as shown by the Langmuir adsorption
isotherm and is caused by the exchange of electrons.222 In situ
reduction of GO by sodium hydrosulfide and the adsorption of
acridine orange was reported, and this showed much better
adsorption capabilities than GO; the adsorption capacities
were reported to be 3333 mg g−1 and 1428 mg g−1,
respectively. MG was removed by GO by varying the pH
from 4 to 9 at 298 K, and the adsorption intensity was
recorded to be 4.821 to 7.613 mmol g−1223.
Basic Blue 41(BB41), Basic Red 18, and 46(BR18, BR 46)
were adsorbed by GO, and the adsorption intensities were
reported to be 1429, 1250, and 476 mg g−1, respectively, at 298
K and an initial concentration of 5 mg L−1 for an hour. The
Langmuir adsorption isotherm helped to classify the reaction
as chemisorption. As the degree of oxidation of GO was varied
it led to different adsorption capacities. At pH 7 and
temperature of 298 K and a contact time of just 15 min the
adsorption capacities of six differently oxidized GO yielded
adsorption capacities ranging from 40.6 to 570.4 mg g−1224. In
another case GO with different oxidation degrees was
synthesized and was found to be pH independent, and all
the GO variations exhibited high affinity toward MB in water.
Adsorption increased as the oxidation of GO increased, and
the binding changed from parallel stacking to vertical stacking
due to electrostatic interactions.225 The extent of adsorption
was determined to be 351 mg g−1 for MB, and 248 mg g−1 for
malachite green (MaG) for GO synthesized by the modified
Hummers−Offeman method.226
MG was adsorbed by rGO and an outstanding adsorption
intensity of 3.163 mmol/g was observed at pH 5 and
temperature of 298 K with contact time of 1 hour. Electrostatic
interactions increased by the increase in pH, and thus more
MG was absorbed. The increase in temperature showed an
O DOI: 10.1021/acs.jced.8b01057
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increase in adsorption intensity, and the Langmuir adsorption
model showed that adsorption was classified as physisorp-
tion.227
While graphene, GO, and rGO can adsorb dyes on their
own, they are combined with other metal oxides to induce
characteristics that make the adsorbed species easier to extract
from water or to degrade the organic pollutant after being
adsorbed. The ease of removal of adsorbent paves the way to
recycle the adsorbents. This can be done by combining
graphene with magnetic metal oxides to enhance their removal
from water by using a magnet. Magnetic ferric oxide−graphene
composite (GO-Fe2O3) was used for eradication of MB and
Congo Red (CR) for which the adsorption capacities were
reported to be 45.27 mg g−1 and 33.66 mg g−1, respectively, at
298 K by the Langmuir adsorption isotherm.141 Graphene
nanosheets/iron oxide nanocomposite synthesized in a single
step removed MB from aqueous solution with an adsorption
intensity of 43.82 mg g−1 at 298 K.219 Graphene/magnetite
composite was used for eradicating Basic Red 9 and
pararosaniline adsorption capacity was found to be 198.23
mg g−1 at a temperature of 298 K and pH of 6.6. An increase in
pH led to the precipitation of the dye, and hence pH was
important for efficient removal of the dye.210
Superparamagnetic GO-Fe3O4 nanocomposites were deco-
rated with amino-functionalized Fe3O4 (NH2−Fe3O4) particles
to remove MB and neutral red (NR). Their adsorption
intensities were reported as 167.2 and 171.3 mg g−1. The
composite kept the NH2−Fe3O4 particles from agglomerating
and thus enhanced their efficiency for wastewater removal.233
Rhodamine 6G (R6G) was removed by a graphene sand
composite where graphene was immobilized with the help of
asphalt on sand. The extent of adsorption was determined to
be 75.4 mg g−1 at 303 K and 6 h contact time. A pesticide,
chlorpyrifos was also studied along with the dye removal.211
Another study shows the same composite with the adsorption
intensity of R6G to be 55.5 mg g−1 for an 8-h contact time.
The graphene sand composite nanocomposites can be easily
regenerated by acetone.212 GO-wrapped magnetite nano-
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Figure 7. (a) Schematic representation of adsorption of RhB and MB using Fe3O4@GO and recycling of catalyst by magnetic separation and
subsequent ethanol/water wash. Photographs of (b) MB and (c) RhB dye solution before and after adsorption process and separation of adsorbent.
Reprinted with permission from ref 275. Copyright 2018, Elsevier B.V.

Figure 8. Binding mechanism of Rhb dye during adsorption of Bi2O3@GO composite. Reprinted with permission from ref 276. Copyright 2018,
Elsevier B.V.

clusters (Fe3O4@GO) were prepared by utilizing the weak adsorbent could easily be separated by magnetic separation
electrostatic attraction of the negatively charged GO to Fe3O4 and showed excellent regeneration and stability.275 The
to form a hybrid core−shell nanostructure. The adsorption structure can be visualized in Figure 7
capabilities were determined by taking MB and RhB as cationic rGO supported ferrite was efficient in 92% RhB and 100%
dyes and MO as the anionic dye that were adsorbed at the rate MB removal. The metal in ferrite could be Mn, Zn, Co, or Ni
of 131.10, 34.50, and 39.95 mg/g, respectively, at 303 K. The and the ferrites were homogeneously distributed over rGO.
P DOI: 10.1021/acs.jced.8b01057
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Their magnetic nature suggests easy separation from the
sample.229 rGO-Fe3O4 nanoparticles were used for removal of
RB, R6G, and acid blue 92(AB 92), MG, etc. The dye showed
the capability of simultaneous adsorption of multiple dyes
without any effect of pH and temperature, and could be easily
regenerated by annealing without any significant loss in
regeneration capacity.230 Magnetic modified rGO was utilized
for the adsorption of RB and MG dyes, and the adsorption
scope was found to be 13.15 and 22 mg g−1 with pH 7 and
temperature of 298 K and showed a 91 and 94% efficiency,
respectively, for the dye removal.231
In another study, a comparison was made between GO and
Bi2O3@GO for adsorption of RhB as shown in Figure 8.276 At
408 K, at pH 4 with 5 mg of adsorbent, the adsorption capacity
increased from 64% to 80.7% for GO and Bi2O3@GO,
respectively, in 65 min. It followed a Langmuir as well as
Temkin isotherm and followed both pseudo-first-order as well
as an intraparticle diffusion model, effectively.
Graphene-carbon nanotube hybrids (G-CNT) that were
cylindrical in shape and formed as a result of self-assembly
efficiently removed MB, and the adsorption capacity was
determined to be 81.97 mg/g after 3 h contact time. The
Freundlich adsorption isotherm was used and an efficiency of
97% was achieved.220 MB and RhB were adsorbed onto
Cu2O−graphene277 and Mg(OH)2−graphene.278 Cu2O−gra-
phene was synthesized by heating graphene and copper ions in
the presence of glucose while the Mg(OH)2−graphene
generated by chemical deposition method had a mesoporous
structure. Sonochemically synthesized GO-[Zn2(oba)2(bpfb)]·
(DMF)5] metal−organic framework nanocomposite (GO-
TMU-23) for MB eradication showed a 90% efficiency of
removal within 2 min.218
A temperature varying study was done of adsorption of
Methyl Green (MG) onto CoFe2O4/graphene nanocomposite,
and the adsorption intensities were found to be 203.51, 258.39,
and 312.80 at 298, 313, and 323 K by Langmuir adsorption
isotherm which revealed the adsorption to be endothermic and
spontaneous and was classified as a physical adsorption
process. MO was adsorbed by CoFe3O4-functionalized
graphene nanosheets and a maximum adsorption capacity of
71.54 mg g−1 was reported for an initial concentration of 10
mg/L.
N,P co-doped reduced GO (PA-rGO) was used for the
removal of Rhodamine B (RhB) and various parameters such
as different pH of initial solution, dosage, temperature, etc.
were studied. The adsorption intensity of 149 mg g−1 was
established, and the adsorption process followed pseudo-
second-order kinetics.279
GO caged in cellulose bead synthesized by the sol−gel
method also proved efficient for the removal of MaG, and the
adsorption extent was calculated to be 30.091 mg g−1 at pH 7
and temperature of 298 K. As the cellulose is pH dependent, a
pH of 6−8 was maintained.151 Fe3O4/SiO2−GO nano-
composites were used as an adsorbent for MB, and adsorption
extent was reported as 97, 102.6, and 111.1 mg g−1 for
temperatures 298, 318, and 333 K, respectively.274 MgO-multi
layered graphene (MDMLG) synthesized by burning magne-
sium in dry ice was used to remove safrainin-O dye from water,
and the adsorption capacity was reported to be 3.92 × 10−4
mol g−1 at pH 12 with a contact time of 2 h. MDMLG could
also be recycled and it also was supported in the dye
regeneration.152
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rGO-Titanate hybrids synthesized by the solvo-thermal
method were used to remove MB with an adsorption capacity
of 83.26 mg g−1, which was higher than that of graphene and
tubular TiO2. The preparation of the composite depended on
the rise in the autoclave temperature that led to the formation
of nanoribbons in the composite.149
The drawback of adsorption process is the agglomeration of
large amount of waste. Most of this waste can be recycled but
the cost is higher. The adsorption process is efficient in
removal of organic pollutants but it will be more desirable if
these organic wastes could be treated without generating any
waste. This is efficiently done by oxidizing these products into
smaller nontoxic components and graphene-based materials
have shown their capability for these processes which are
highlighted in the following sections.
5. ADVANCED OXIDATION PROCESSES
Wastewater treatment processes-based on radicals are known
as advanced oxidation processes. These processes are advanta-
geous as the pollutants are converted into basic components
such as carbon dioxide and water and other simple and
biofriendly compounds.59 Dehydrogenation, redox reaction,
and hydroxylation are some of the reactions that take place
when a highly reactive hydroxyl radical is involved in the
oxidation process that results in the degradation of persistent
organic pollutants.280,281 Some of the oxidation processes have
been described in this section with an aim to prove their
efficacy as an important tool for wastewater treatment.
Graphene is chemically stable and has a large surface area
and high mobility for charge transport and thus is used
extensively for these processes.
5.1. Fenton Process. The Fenton process deals with the
generation of hydroxyl radicals in water with the help of
ferrous ion and hydrogen peroxide. But the ferrous ions
increase sludge production and are not environment friendly.
Graphene with its exceptional properties was able to replace
ferrous ions and proved highly efficient for the Fenton process
and was found to generate hydroxyl radicals.282 Iron oxide
combined with graphene further improved this process.
The zerovalent cerium and iron ions on rGO resulted in a
breakdown of sulfamethazine.283 The cerium and iron ions are
oxidized and generate hydroxyl ions, turning into superoxide
that enhances the degradation process. Graphene not only
forms the hydroxyl radicals but also helps in converting ferric
ions to ferrous ions for reuse which is generally done by
hydrogen peroxide.284 β-FeOOH/rGO prevented the agglom-
eration of β-FeOOH and enhanced the degradation of 2-
chlorophenol.285 Fe3O4/GO resulted in complete dye removal
and provided higher stability than Fe3O4. FeO/Fe3O4/rGO
was also efficient in removing Methylene Blue(MB) within an
hour with the Fenton process although the efficiency decreased
after two cycles of dye degradation.52 Cobalt ferrite, another
composite that degraded methylene blue did so in just 15 min
but was found to have low metal leaching property.286
The hydrogen peroxide used in this reaction can be
generated while the reaction is being carried out by the
electro-Fenton process. Hydrogen production takes place at
the cathode and so the material of cathode is very important.
Graphene proved to be an excellent option, and the production
of hydrogen peroxide happens at neutral pH.287 This removed
the barrier of maintaining the pH at 3 which was a necessary
condition for the conventional electro-Fenton process.280,281
rGO/carbon felt electrode which was produced by electro-
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Figure 9. (a) GC−MS graphs of intermediates while degrading RhB under different irradiation time. (b) Photo-Fenton degradation: schematic
representation of mechanism of RhB without heavy metal ions. Reprinted with permission from ref 290. Copyright 2018, Elsevier B.V.
deposition of rGO on carbon felt proved its efficiency for the
mineralization of Acid Orange 7 from wastewater.288 The
heterogeneous electro-Fenton process resulted in the degra-
dation of Rhodamine B at the anthraquinone/rGO nanohybrid
cathode.289
The Fe3O4/rGO/PAM hydrogel adsorbed heavy metal ions
in its 3D structure, which accelerated the photo-Fenton
reaction for organic effluent degradation. RhB dye degradation
was studied to understand the mechanism of the Fenton
reaction. Gas chromatography−mass spectrometry (GC−MS)
was employed for the same, and m/z 479 (RhB) and 473 (N-
deethylated intermediates) were in the presence of heavy metal
ions (Ce3+, Cu2+, Ag+, Cd2+) and in their absence the
increase in light radiation showed extra peaks depicting further
breakdown of the dye. The whole procedure took 50 min, and
the breakdown of dye can be understood by Figure 9. A mass
to charge ratio of 73 shows that the dye eventually breaks
down to carbon dioxide and water.290
5.2. Ozonation. The use of ozone for degrading pollutants
is known as ozonation. p-Hydroxybenzoic acid was removed
from wastewater using rGO which was responsible for the
activation of ozone and producing superoxide anions from the
carbonyl groups on rGO.291 α-MnO2/rGO292 and Co3O4/N/
graphene293 also activated the ozone efficiently and degraded
bisphenol A and phenol, respectively. The mechanism of
phenol degradation involves the adsorption of pollutants, then
of the ozonation of the surface of the graphene sheet, and then
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the reaction between them results into degradation of phenol.
The doping of nitrogen on the graphene enhances the ability
to graphene to convert ozone into superoxide anion radicals.59
TiO2/UV/O3 and TiO2 rGO/UV/O3 degraded bisphenol A
but the latter was 1.17 times more efficient than the former for
the reaction.294 Graphitic carbon nitride/rGO oxidized oxalic
acid in the presence of triethanolamine and tert-butanol as hole
and hydroxyl radical scavengers, respectively, Yin et al. (2016),
but the decrease in the efficiency from 90% to 27% and 40%
hinted toward the importance of holes and hydroxyl radicals in
the degradation process.295
5.3. Sulfate-Based AOP. Sulfate radicals are more reactive
than hydroxyl radicals due the interaction of persulfates (PS)
and permethoxysulfates (PMS) with water.60 The hydroxyl
ions have a life span of 20 ns, whereas sulfate radicals have a
life span of 30−40 μs and thus the longer lifespan contributes
to greater efficiency.296,297 This provides sulfate radicals more
time to collide with the pollutants and the larger is the number
of collisions, the greater is the probability of reactions, and thus
they have proved to be efficient at every pH condition.
Graphene, GO, and rGO have been proven good catalysts for
generating these sulfate radicals, and metal oxides of metals
such as cobalt, manganese, and iron have shown great
efficiency in generating sulfate radicals from PS and PMS.
Co3O4/GO298 was reported to be 50% more efficient than
Co3O4 for the removal of Orange II dye and complete dye
removal was observed in 4 min. Co3O4/graphene displayed
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Journal of Chemical & Engineering Data
Figure 10. (a) Setup for photocatalysis, (b) degradation of RR195 dye.
Figure 11. Mechanism of photocatalysis.
complete degradation in 10 min of the same dye, but the
recycling of graphene composite was higher than it was for the
GO part.299 MV, MO, MB, Orange II, and RhB were separated
by using MnFe2O4/rGO which showed excellent reusability
and was easily separable by the magnetic separation
technique.140 Fe3O4/rGO showed almost complete removal
of trichloroethylene within 5 min with the help of sulfate
radicals that were generated by PMS.300 Nitrogen doped/
aminated graphene, a metal-free composite was efficient in
generating sulfate radicals from PS and efficiently removed
sulfamethoxazole in the presence of humic acid and carbonates
and the pH of the solution.301
5.4. Light-Based Oxidation. Light-based oxidation or
photocatalysis plays a major role in the removal of organic
content especially dyes from wastewater. Graphene which acts
as an adsorbent and enhances the photocatalytic activity by
forming nanocomposites has been widely researched. Photo-
electrocatalysis (PEC) is another process which is sought for
the removal of organic pollutants. PEC is a combination of
photocatalysis and electro-catalysis. The photons and electrons
both simultaneously degrade the electron hole recombination
efficiency. Graphene−Ti electrode experienced an improved
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electron migration and the adsorption of dyes was significantly
enhanced302 by this method. rGO/Pt/TiO2 nanotube arrays
were used as anode and were tested for methanol removal and
showed a 4-fold improvement303 for methylene blue removal.
Photocatalysis thus has an important role in dye removal and
has been explained in detail in the following section.
6. ERADICATION OF ORGANIC POLLUTANTS BY
PHOTOCATALYSIS
According to IUPAC a catalyst is “a substance that increases
the rate of a reaction without modifying the overall standard
Gibbs energy change in the reaction; the process is called
catalysis”.304 When the reaction these catalysts alter is
dependent on light energy then it is termed as photocatalysis
and is carried out in a special setup as shown in Figure 10.
There are two types of photocatalysts depending upon the
phase of the catalysts. Catalysts in the same phase of the
reactants are homogeneous while that in different phases are
heterogeneous. Steps involved in heterogeneous photocatalysis
form a well-known sequence of reactions and form a major part
of removal of aqueous organic pollutants.306 Graphene having
a zero-band gap and acting as a semimetal can absorb light
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over a large range of wavelengths and is helpful in light
catalysis.307,308 Few-layered graphene can also act as semi-
conductors which are considered to be good photocatalysts. A
simple mechanism of heterogeneous photocatalysis includes
the excitation of electrons with the help of photon energy from
the valence band (VB) to the conduction band (CB) while
holes are formed in the valence bands where the energy of the
incident light is greater than the band gap of semi-
conductors.309 Both electrons and holes participate in redox
reactions and are responsible for photocatalysis. The reactions
thus cause the generation of several types of radicals or
intermediates such as hydroxyl radicals that act as powerful
oxidizers around the surface of the photocatalyst and are
widely studied for organic pollutant eradication from waste-
water that include dyes and other organic entities.310 (Figure
11). It is also necessary to provide enough reactants so that the
charge carriers are utilized and do not interfere with the
aquatic ecosystem as the radicals generated by them are highly
active. Photocatalysis also requires the presence of an
adsorbent where the reaction can take place and thus graphene
is suitable as it acts as a highly efficient adsorbent thus
enhancing the photocatalytic activity.311
Titanium dioxide (TiO2) possesses photocatalytic properties
that were first demonstrated and published by Akira Fujishima
in 1972.312 TiO2/graphene nanocomposites show excellent
photocatalytic property and have been widely researched and
catalogued.30,313−317 Both UV radiation and visible radiation
enhance the photocatalytic activity of TiO2−graphene
composite.116 The increase in the catalytic activity was thus
due to the transfer of electrons from the conduction band of
TiO2 to graphene and enlarging the band gap and decreasing
the chances of electron hole recombination in TiO2.318
Graphene alone proved to be more efficient in the eradication
of RhB as this was thermodynamically favorable.319 Graphene
behaved as an electron mediator in the composite formed with
SnO2 but in the case of TiO2, electrons were free to move into
the graphene sheet or interact with oxygen functionalities.320 A
similar mechanism was realized with a gold−graphene (Au/
graphene) composite.61 2,4-Dicholorophenoxyacetic acid with
TiO2/graphene resulted in the degradation which was four
times more efficient,321 and that of dodecylbenzenesulfonate-
(DBS) increased three times in comparison with Degussa
P25(commercial TiO2) when platinum was doped onto
graphene in graphene/TiO2 nanocomposites.322 The enhance-
ment of degradation of the organic entities can be attributed to
the effective adsorption of graphene, the charge transfer from
TiO2 to graphene and the bridged bond from titanium to
carbon with the help of oxygen which results in the lessening of
the bandgap value.323−326 P25-graphene was efficient in the
removal of Reactive Black 5 using UV light radiation than the
Degussa P25 alone. More than 90% degradation was observed
for 100 min irradiation with UV owing to the high surface area
and narrow bandgap.327 Flower-like G/titania nanosheets (G/
TNS) were synthesized by a hydrothermal process in which Ti
cryastalline phases of both anatase and sodium titanate formed.
Graphene acted as template for Ti growth and inhibited the
growth of TiO2 and degraded 4-chlorophenol with efficiency
more than 99.2% in 120 min.328 The use of graphene enhanced
the titanium photocatalytic activity due to two reasons: first, it
enhances the rate of transfer of photoexcited electrons
therefore not allowing recombination of holes and electrons;
and second, the narrowing the band gap energy leads to
enhancement in visible light absorption. This has been
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depicted in Figure 12. The hydroxyl radicals were found to
be the reactive oxygen species that degraded 4-chlorophenol
Figure 12. Schematic illustration of mechanisms for graphene-
enhanced photocatalytic activity by G/TNS. Reprinted with
permission from ref 328. Copyright 2018, Elsevier B.V.
and were verified by DFT calculations and maintained their
efficiency even after five cycles.328
TiO2 and graphene-based composites have been widely
studied for the removal of MO.329−336 GO/TiO2 composite
showed higher efficiency toward the removal of MO than GO
combined with carbon nanotubes or fullerenes under UV−vis
light radiation. The self-assembly of the components led to the
composite having properties of both electron donor and
acceptor thus decreasing the charge recombination.337 The
rGO-TiO2 hybrid was also utilized for one step photocatalytic
reduction of dyes and other organic pollutants by capturing
dyes and electrons generated during the photoreaction by
rGO.
TiO2 is widely used in environmental remediation338,339 but
has limited optical absorbance.229 This drawback can easily be
solved by doping TiO2 with any metal such as Cu, Cr, Fe, Mn,
and Mo, etc. or nonmetals such as N, S, and C or stabilizing it
on graphene or other carbon-based materials.340,341 Further
enhancement can be achieved by doping it, and further
immobilizing it on graphene. TiO2 nanoparticles doped with
N, Fe, Cu, and Nd were used to degrade MO, and nitrogen-
doped TiO2 showed maximum efficiency among these.342 One
of the examples of these composites are SnS2 quantum dots
and nanodiscs supported on rGO sheets developed hydro-
thermally that degraded Remazol Brilliant Red (RBR) and
Remazol Brilliant Blue (RBB) under visible light radiation.343
The BET surface area after including rGO increased to
∼103.55 m2/g from ∼71.09 m2/g and the photodegradation
escalated to ∼99.7% and ∼97% for RBB and RBR dye. The
comparison data of photocatalytic degradation of RBB and
RBR dye by SnS2 and SnS2/rGO is shown in Figure 13.
Hexagonally arranged mesopores of graphene−TiO2/SiO2
nanocomposite enhanced the degradation capacity up to a
100% in 30 min under sunlight. The reaction between
graphene and titanium/silicon dioxide increased the quantum
efficiency for which graphene as an acceptor decreased the
charge carrier recombination possibility and increased the
degradation of RhB. The mesoporous structure enhanced the
adsorption thus enhancing the photocatalytic activity.33
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Journal of Chemical & Engineering Data
Figure 13. UV−visible spectra for the photocatalytic degradation of (a and b) RBB dye and (c and d) RBR dye by SnS2 and SnS2/rGO under
visible light photodegradation. Reprinted with permission from ref 343. Copyright 2019, Elsevier B.V.
The same mechanism worked for graphene−tourmaline−
TiO2 nanocomposite and it also showed efficient RhB
removal.345 For TiO2−dextran−rGO nanocomposites in
which dextran reduced GO, the self-assembly of TiO2
nanoparticles took place on the reduced GO. The nano-
composite thus formed is ecofriendly and highly efficient for
the removal of RhB.346 Bi2O3/TiO2/graphene,347 ZnO/Ag/
graphene,348 and Ti/Ce−GO,349 also show good photo-
catalytic activity for the removal of RhB. A removal efficiency
of 94% of Acid Orange 7 was obtained after 30 min of UV
irradiation using GO−TiO2 nanorod composites.350
Reactive Red 195 (RR 195) in aqueous media was treated
with CeO2−TiO2−graphene (CT−G) nanocomposite along
with other substitutes for graphene. The highest degree of
photocatalysis was observed in the graphene-based nano-
composite owing to its unique structure and electronic
properties. An important fact reported was that the graphene
concentration was inversely proportional to the degradation of
dye. 305 Pt or Pd−TiO 2 −graphene were successful in
eliminating RR195 dye using both UV visible radiation. Pt
showed better photocatalytic activity than Pd.351
ZnO/graphene nanocomposites showed excellent photo-
catalytic properties and have been studied for the removal of
MB when irradiated with UV light, and it showed 4−5 fold
enhancement as compared to ZnO due to interelectron
transfer at the interface of the pollutants and the nano-
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composite.352 The presence of graphene proved to be
antiphotocorrosive and another study showed that the ZnO−
graphene for which the percentage of graphene was 2% showed
better degradation capability of MB than commercial titanium
oxide and pure ZnO. The composite containing 2.5% graphene
exhibits high activity and shows 80% efficiency after five times
of recycling.353 ZnO−GO nanohybrids were researched for the
degradation of Crystal Violet and 95% of the dye was found to
degrade on UV irradiation in 80 min.354 ZnO/rGO hybrids
under UV light for 3 h degraded 94% of MO dye.355 ZnO
hollow microspheres/reduced graphene oxide nanocomposites
(ZnO−rGO) synthesized at very low temperature by a
sonochemical method displayed a crystalline structure and
were used to degrade 2,4-dichlorophenoxy acetic acid (2,4-D)
under sunlight irradiation. The hollow microspheres act as
antennas for the transfer of photoelectrons and increasing the
electron transport and the addition of rGO decreases the
electron hole recombination.356
La/TiO2−graphene and graphene−Ag/ZnO composites
also showed higher degradation capability and both were
prepared by solvo-thermal methods. The latter showed an
efficiency of 100% after 90 min of irradiation with visible
light.332 ZnFe2O4/ZnO/G was studied by the Langmuir−
Hinshelwood model and was efficient in the degradation of
MB. Furthermore, its magnetic character was helpful in
separating it from aqueous media. Graphene−Fe2O3/ZnO
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composites are also composites for dye degradation and
possess magnetic character and were efficient even beyond five
degradation cycles.357 ZnO−Bi2O3/GO showed an efficiency
of 99.62% after 2 hours of visible light radiation.358 Bi2O3−
rGO composites also gave similar results.359
The redox reactions on graphene that act as cocatalyst have
been established as rate-determining steps in the degradation
of organic pollutants. Gold,360,361 silver,362,363 and platinum364
form hybrids with graphene nanosheets enhancing the redox
reaction due to excess electrons offered by graphene.
Plasmonic Ag/Ag2CO3−rGO was used for oxidation of
pollutants and was determined to be more efficient than the
standalone Ag2CO3 or when it formed a composite with GO.
The collaborative effect of Ag nanoparticles and graphene leads
to an increase in redox activity and in turn enhances the
photocatalytic efficiency.365 Plasmonic Ag-RGO/Bi 2WO6
results in the increase of efficiency of photocatalysis by three
times than just the Bi2WO6 complex. The mechanism in effect
is the same as that for the nonreactive noble elements and
graphene nanosheets.362 GO−Ag3PO4 composites ensured
complete decomposition of Acid Orange 7 dye under visible
radiation. A mixture of silver acetate and disodium phosphate
in the presence of GO resulted in the composite which showed
excellent dye adsorption capability.366 GO−CdS also removed
Acid Orange 7 dye and enhanced the capability of CdS by
80%. This was caused by the formation of hydroxyl radicals
and confirmed by transient photocurrent detection and
measurement of the scavenging of formed radicals.367 A
mixture of oleic acid and oleyamine with zinc acetate and GO
led to the formation of the ZnO−rGO composite that
augmented the eradication of diamino-triphenylmethane and
Malachite Green dyes showing a high degeneration rate
constant for pseudo-first-order kinetics.368
Ag−ZnO/rGO composite degraded 80% of the RhB dye
after 200 min of UV irradiation. Highly charged carrier species
were formed that promoted the degradation of the given
dye.369 Ag3VO4/TiO2/graphene composite showed higher
activity than one or a combination of two of the
components.370 WO3 nanorods@graphene utilized sunlight
to degrade MO owing to the increase in charge separation.371
α-SnWO4/rGO nanocomposites also showed similar proper-
ties.372
The BiOI/rGO-1 (BG-1) obtained through a chemical
mechanical method with microsphere structure and BiOI/
rGO-2 (BG-2) obtained through microwave hydrothermal
method witha nanoplate-like structure made composites with
graphene and rGO respectively; 40 mg/L Methylene Blue
(MB) and 20 mg/L levofloxacin (LEV) was 11 and 3 times
more efficient than that of P25, respectively, under visible light
radiation. The species that reacted with the hole was found to
be responsible for degradation.373
Other metal oxide such as BiVO4−graphene (BiVO4−G)
showed a 99% degradation with 5 h of visible light exposure.374
BiOBr/graphene nanocomposites showed a greater efficiency
than the commercially available titanium oxide.375 GO/BiOI
and rGO/BiOI both showed photocatalytic activity, but the
efficiency of rGO/BiOI was reported to be more than that of
GO/BiOI.376,377 Bi2O3−rGO showed a 93% efficiency for
degradation of dye under visible light in 4 h.359 BiOBr−
graphene and Bi2WO6/graphene were found to show excellent
photocatalytic activity for the removal of RhB dye under UV−
vis radiation.378 Hydrothermally prepared Bi5Nb3O15/gra-
phene nanocomposites showed a 2.8 times increase in the
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photocatalytic activity when compared to pure bismuth
niobate and to commercially available titanium oxide and
was still efficient after five cycles of dye degradation.379
Graphene−Bi2MoO6 nanocomposite showed 90.4% degrada-
tion potential for remediation of Reactive Brilliant Red X-3B
dye as compared to the metal oxide part alone which had a
degradation capacity of 63.8% and followed a first order
kinetics.380 Hydrothermally prepared graphene/BiOBr was
used to decompose sulforhodamine 640 (Srh 640) dye. A
linear regressional analysis determined it follows first order
kinetics with a rate constant of 0.00798 min−1, which is higher
than the pure BiOBr component.381 Eosin was separated from
aqueous media using graphene−Mn2O3 composites.382 ZnO−
Bi2O3/GO was successful in eradicating Acid Blue, Acid
Yellow, Acid Red, Reactive Blue, Reactive Yellow, and Reactive
Red efficiently and proved helpful in managing textile waste.358
Metal sulfides342 such as CdS/graphene showed a 90%
efficiency after 5 h visible light exposure.383 In2S3 prepared by
solvo-thermal method had its efficiency increased 5 times than
the sulfide on its own, and the maximum efficiency was seen at
a temperature of 180 C.384 An efficiency of 90% was reported
for CdS/Al2O3/GO and 99% efficiency for CdS/ZnO/GO for
60 min of visible light irradiation for degradation of MO.385
Calcined layered double hydroxides (CLDH) photocatalysts
are extremely successful for photodecolorization of organic
dyes. rGO sheets act as a base for LDH crystallites and NiFe-
LDH lamellar crystal and decolorization of methylene blue was
observed with 1% rGO and heating at a temperature of 500
°C; the photocatalytic degradation efficiency was 93.0% in 5 h
duration.386
High photo response, increased charge carrier separation,
and high adsorption affinity resulted in the high performance
of Au/rGO/TiO2 nanotube hybrids which showed an
enhanced photocatalytic activity for the degradation of MO
in the presence of sunlight and when irradiated by UV light.387
Ag/AgCl/rGO, Ag/AgBr/rGO, and Ag@Ag3PO4/rGO have
shown excellent dye removal capabilities.388−390
A 95% efficiency was recorded after 11/2 hours of visible
light irradiation of Cu2O/PA/rGO where Cu2O nanoparticles
were decorated on n-propylamine and coordinated with GO
nanosheets. N-propylamine improved the surface area in turn
improving accessibility for adsorption and photocatalysis.391
The liquid phase deposition synthesis of Ag3PO4/graphene-
oxide composite yielded superior catalytic efficiency, and an
increase in graphene content further enhanced the degradation
process. The oxidation mechanism was found to be dependent
on holes for the degradation of dyes.392
Monodisperse cobalt ferrite (CoFe2O4)/reduced graphene
oxide (rGO) displayed sonocatalytic activity solutions under
ultrasonic irradiation. The sonocatalytic removal of AO7, and
the effect of parameters such as pH, dosage of catalyst, H2O2
concentration, power, and reaction time displayed a photo-
catalytic efficiency of 90.5% at pH 3 under 350 W ultrasonic
power in 120 min. The Langmuir−Hinshelwood (L-H) kinetic
model fit the studies and showed that superoxide anion radicals
dominate the reaction process.393
rGO−CoFe2O4 composite showed better photocatalysis
properties for RhB removal than rGO−ZnFe2O4, rGO−
MnFe2O4, and rGO−NiFe2O4 under visible light irradia-
tion.229 rGO/KNbO3 intertwined nanosheets were developed
and showed moderate efficiency of 68.3% after half an hour of
UV radiation394 CoFe2O4−graphene was hydrothermally
synthesized and used for degradation of Active Black BL-G
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Table 4. Graphene-Based Composites and Their Photocatalytic Degradation of Organic Pollutants

reaction
time
composite pollutant percentage removal (mins) source oxidizing species ref
S@GO/TiO2 MB 93% 120 UV lamp O2·−, ·OH 396
AgBr@Ag/N-rGO 2-CP, phenol, BPA and DP 79(2-CP), ∼88% (phenol, 120 Xe lamp O2·− 397
BPA), 70%(DP)
TiO2-G BPA ∼96% 240 UV lamp O2·−, ·OH 398
ZnFe-CLDH/rGO paracetamol ∼95% 420 Xe Arc lamp O2·−, ·OH, H+ 399
G-Q dots/Mn− 4-NP, CIP and DEP 89%, 74%, 48.6% 120 300 W Xe lamp ·OH 400
N−TiO2/g-C3N4
pCN/GO RhB, CIP ∼100%,96% 40,90 500 W Xe lamp O2·−, H+ 401
SnO2/Zn2SnO4/ NO, acetone <60%, 80% 140 visible O2·−, ·OH 402
graphene
RGO−SnO2 RhB <80% 130 350W Xe lamp O2·−, ·OH 320
RGO−TiO2 RhB <70% 200 350W Xe lamp O2·−, ·OH 320
Ag/Ag2CO3-rGO MO N.A. 50 350 W xenon lamp ·OH 365
Ag−G−Bi2WO6 RhB ∼92% 45 350W Xe lamp O2·− 362
G/ZnO MB ∼80% 30 8W UV lamp O2·− 353
ZnFe2O4/ZnO/G MB ∼98% 30 500 W Xe lamp O2·− 357
ZnO−Bi2O3/GO MB, Acid Blue, Acid Yellow, Reactive Red, Acid 99.62,98.31, 88.69, 85.35, 120 500 W Xe lamp O2·−, ·OH, O2−, OH− 358
Red, Reactive Yellow and Reactive Blue 81.93, 80.28 and 44.23%
Bi2O3−rGO MB, MO 93,96% 240 400W metal halogen O2·− 359
lamp
Ag3PO4/GO MO, RhB 86.7,∼100% 50,30 500 W halogen lamp O2·−, ·OH, ·OH2 392
GO/TiO2 MO 96% 80 300 W high-pressure O2·−, ·OH 329
mercury lamp
BiVO4−G MO, MB, RhB, Active Black BL-G 95, 89, 94,92% 180 500W xenon lamp O2·−, ·OH 374
BiOBr/G MO ∼90% 140 300 W Xe arc lamp N.A. 375
BiOI/G MO ∼88% 240 500W Xe lamp O2·− 376
BiOI/rGO MO ∼100% 180 1000 W Xe lamp O2·− 377
WO3/G MO 92.70% 120 150 W xenon lamp N.A. 371
a-SnWO4/rGO MO 41.20% 360 300 W tungsten N.A. 372
halogen lamp
ZnO/rGO MO 94% 180 300 W Xe arc lamp O2·−, ·OH 355
CdS/G MO 90% 300 500 W Xe lamp N.A. 383
In2S3 MO ∼99% 120 500 W xenon lamp O2·− 384
nanosheets/G
Ag3VO4/TiO2/G MO, RhB 81. ∼98% 180,30 500 W Xe-arc lamp O2·−, ·OH 370
CdS/Al2O3/GO MO ∼90% 60 500 W tungsten O2·−, ·OH 385
halogen lamp
CdS/ZnO/GO MO ∼99% 60 500 W tungsten O2·−, ·OH 385
halogen lamp
Au/RGO−TiO2 MO ∼100% 140 500W xenon arc O2·−, ·OH 387
nanotube arrays lamp
Cu2O/PA/rGO MO ∼99% 360 500 W Xe lamp O2·−, ·OH 391
BiOBr−G RhB ∼100% 24 500 W Xe lamp O2·−, ·OH 378
Bi5Nb3O15 RhB, benzoic acid ∼85, ∼65% 80,120 35 W LED lamp N.A. 379
KNbO3/rGO RhB 68.30% 30 300 W merury lamp O2·−, ·OH 394
G−TiO2/SiO2 atrazine, RhB 93.1, ∼100% 180,30 300W Xe lamp O2·−, ·OH 344
Tourmaline/G- RhB, norfloxacin ∼100% 60,120 Xe lamp O2·−, ·OH 345
doped TiO2
rGO/TiO2-dx RhB ∼98% 45 300 W UV lamp ·OH 346
Bi2O3/TiO2/ RhB ∼99% 60 300 W Xe lamp ·OH 347
graphene
ZnO/Ag/graphene ∼99% 120 300 W high-pressure ·OH 348
Hg lamp
Ti/Ce−GO RhB ∼70% 240 150W Xe lamp O2·− 349
G−Bi2MoO6 Brilliant Red X-3B,phenol ∼90.4,∼92.4 90 250W halogen lamp O2·−, ·OH 380
ZnO/G RhB ∼100% 60 15 W UV light-tube, N.A. 381
150 W Xe lamp
CoFe2O4-graphene MB ∼100% 240 500 W xenon lamp ·OH 395
G/Mn2O3 RhB, Eosin,MB 60, 80, 84% 60, 120, UV lamp ·OH 382
140
P25−G reactive Black 5 90% 160 8 W UV lamp N.A. 327
CeO2/TiO2/G RR195, 2,4-D 90,65% 100 125 W high-pressure N.A. 305
nanosheets mercury lamp
Pt/TiO2/G 2,4-D, RR 195 80,65% 120 125 W high-pressure O2·−, ·OH 351
mercurylamp
PANI−G Rose Bengal 56% 180 300W Xe lamp O2·−, ·OH 255

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Table 4. continued
reaction
time
composite pollutant percentage removal (mins) source oxidizing species ref
ZnO/GO Crystal Violet ∼95% 80 300 W Xe arc lamp O2·−, ·OH,HOO· 354
GO−TiO2 AO 7 94% 30 11 W UV lamp N.A. 350
nanorods
GO−Ag3PO4 AO 7, phenol ∼100% 10, 20 300 W Xe arc lamp O2·−, ·OH,HOO· 366
GO/CdS AO 7 ∼100% 120 solar light simulator ·OH 367
ZnO/G Malachite Green ∼78% 90 UV Lamp N.A. 368
ZnO/rGO RhB 80% 200 UV lamp N.A. 369

and Active Red RGB dyes, although the rGO composite was considered as a milestone by implementing it in real-time
more favored than GO as the conductivity offered better wastewater treatment technology.
charge carrier transport and separation.395
The extent of pollutant removal by photocatalysis has been
highly documented and a part of it has been presented here to
■ AUTHOR INFORMATION
Corresponding Author
enlighten the efficiency and practicality of using graphene- *E-mail: meetkbs@gmail.com.
based material for wastewater treatment technology. These ORCID
data have been compiled in the Table 4 and the high efficiency
Balasubramanian Kandasubramanian: 0000-0003-4257-8807
of these composites can be observed. Hence this section
exemplifies the vast use of graphene-based materials in Notes
The authors declare no competing financial interest.

photocatalysis and provides us with a novel method for
efficient degradation of organic pollutants.
7. CONCLUSION
Graphene and graphene-based materials have proven their
efficiency as novel materials for the removal of organic
pollutants of any kind, and being carbonaceous materials they
have a great scope for environmental remediation without
interfering with the processes of nature. The degradation of
pollutants and their extraction from water has been proven to
be extraordinary owing to the physicochemical properties of
graphene such as large surface area, large number of
unsaturated π-bonds, dual nature of being a zero band gap
material and a semiconductor etc. The oxidation of graphene
to forms such as GO and rGO enhance its properties in
multifolds and increase its hydrophilic nature thereby
augmenting its ability to interact with organic pollutants for
either their adsorption on the surface of graphene-based
materials physically or chemically or their breakdown by
oxidation as observed in photocatalysis and other advanced
oxidation processes. The spectrum of graphene-based materials
varies from magnetic graphene composites, the separation of
which is easily done by applying a magnetic field, or inorganic-
based materials such as N-doped graphene where the
extraction of pollutants multiplies because of the lone pair of
electrons present on them. Even composites with biomaterials
such as chitosan have been synthesized and successfully
implemented for effluent removal. These materials have high
regeneration capacity and can be reused and recycled multiple
times thus proving to be cost-effective and desirable for
wastewater treatment technology. The mechanisms involved in
the interaction of graphene while forming composites or with
the formed composite and the aromatic pollutants have been
briefed in this review, and a comprehensive overview has been
provided for the different forms of graphene-based materials
and their proven efficacy in effluent removal. The generation of
defect free, high quality graphene is yet to be mastered, but the
multitude of reports on the degradation of dyes, pharmaceut-
ical waste, and other aromatic entities ensure us that graphene
is an efficient material for organic waste treatment and can be
■
ACKNOWLEDGMENTS
The authors would like to thank Dr. C. P. Ramnarayanan, Vice
Chancellor, Defence Institute of Advanced technology (DU)
and Dr. Santhosh Chidangil, Head, Department of Atomic and
Molecular Physics, MAHE, Manipal for their continuous
support and encouragement. The authors also acknowledge
Prof. Imtiaz S. Mulla (Emeritus Scientist at CMET, Pune) for
his advice and guidance and Mr. Ramdayal Yadav, Mr. Prakash
Gore, Mr. Swaroop Gharde, and Mr. Ankit Malik for their
technical help during the preparation of this Review.
■ REFERENCES
(1) Faust, S. D.; Samuel, D.; Aly, O. M. Adsorption Processes for
Water Treatment; Butterworth Publishers: Stoneham, MA, 1987.
(2) Langmuir, I. The Adsorption of Gases on Plane Surfaces of
Glass, Mica and Platinum. J. Am. Chem. Soc. 1918, 40, 1361−1403.
(3) Freundlich, H. M. Over the Adsorption in Solution. J. Phys.
Chem. 1906, 57, 385−470.
(4) Freundlich, H. Kapillarchemie: Eine Darstellung Der Chemie Der
Kolloide Und Verwandter Gebiete, 4th ed.; Akademische verlagsgesell-
schaft m.b.h: Leipzig, Germany, 1909.
(5) Bhalara, P. D.; Punetha, D.; Balasubramanian, K. A Review of
Potential Remediation Techniques for Uranium(VI) Ion Retrieval
from Contaminated Aqueous Environment. J. Environ. Chem. Eng.
2014, 2, 1621−1634.
(6) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang,
Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric Field Effect
in Atomically Thin Carbon Films. Science 2004, 306, 666−669.
(7) Castro Neto, A. H.; Guinea, F.; Peres, N. M. R.; Novoselov, K.
S.; Geim, A. K. The Electronic Properties of Graphene. Rev. Mod.
Phys. 2009, 81, 109−162.
(8) Lee, J. U.; Yoon, D.; Cheong, H. Estimation of Young’s Modulus
of Graphene by Raman Spectroscopy. Nano Lett. 2012, 12, 4444−
4448.
(9) Shao, Y.; Wang, J.; Wu, H.; Liu, J.; Aksay, I. A.; Lin, Y. Graphene
Based Electrochemical Sensors and Biosensors: A Review. Electro-
analysis 2010, 22, 1027−1036.
(10) Brownson, D. A. C.; Banks, C. E. Graphene Electrochemistry:
Fabricating Amperometric Biosensors. Analyst 2011, 136, 2084.
(11) Choi, H. J.; Jung, S. M.; Seo, J. M.; Chang, D. W.; Dai, L.; Baek,
J. B. Graphene for Energy Conversion and Storage in Fuel Cells and
Supercapacitors. Nano Energy 2012, 1, 534−551.

X DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(12) Geim, A. K.; Novoselov, K. S. The Rise of Graphene. Nat.
Mater. 2007, 6, 183−191.
(13) Joshi, A.; Bajaj, A.; Singh, R.; Alegaonkar, P. S.;
Balasubramanian, K.; Datar, S. Graphene Nanoribbon-PVA Compo-
site as EMI Shielding Material in the X Band. Nanotechnology 2013,
24, 455705.
(14) Kausar, A.; Rafique, I.; Muhammad, B. Aerospace Application
of Polymer Nanocomposite with Carbon Nanotube, Graphite,
Graphene Oxide, and Nanoclay. Polym.-Plast. Technol. Eng. 2017,
56, 1438−1456.
(15) Balasubramanian, K. Reinforcement of Poly Ether Sulphones
(PES) with Exfoliated Graphene Oxide for Aerospace Applications. In
International Conference on Structural Nano Composites (NANO-
STRUC 2012); Cranfield University:Bedfordshire, UK, 2012; Vol. 40.
(16) Raccichini, R.; Varzi, A.; Passerini, S.; Scrosati, B. The Role of
Graphene for Electrochemical Energy Storage. Nat. Mater. 2015, 14,
271−279.
(17) Avouris, P. Graphene: Electronic and Photonic Properties and
Devices. Nano Lett. 2010, 10, 4285−4294.
(18) Liu, M.; Zhang, X. Silicon Photonics: Graphene Benefits. Nat.
Photonics 2013, 7, 851−852.
(19) Llatser, I.; Kremers, C.; Cabellos-Aparicio, A.; Jornet, J. M.;
Alarcón, E.; Chigrin, D. N. Graphene-Based Nano-Patch Antenna for
Terahertz Radiation. Photonics and Nanostructures - Fundamentals and
Applications 2012, 10, 353−358.
(20) Suk, J. W.; Kirk, K.; Hao, Y.; Hall, N. A.; Ruoff, R. S.
Thermoacoustic Sound Generation from Monolayer Graphene for
Transparent and Flexible Sound Sources. Adv. Mater. 2012, 24,
6342−6347.
(21) Tian, H.; Ren, T. L.; Xie, D.; Wang, Y. F.; Zhou, C. J.; Feng, T.
T.; Fu, D.; Yang, Y.; Peng, P. G.; Wang, L. G.; et al. Graphene-on-
Paper Sound Source Devices. ACS Nano 2011, 5, 4878−4885.
(22) Wu, J.; Agrawal, M.; Becerril, H. A.; Bao, Z.; Liu, Z.; Chen, Y.;
Peumans, P. Organic Light-Emitting Diodes on Solution-Processed
Graphene Transparent Electrodes. ACS Nano 2010, 4, 43−48.
(23) Gomez De Arco, L.; Zhang, Y.; Schlenker, C. W.; Ryu, K.;
Thompson, M. E.; Zhou, C. Continuous, Highly Flexible, and
Transparent Graphene Films by Chemical Vapor Deposition for
Organic Photovoltaics. ACS Nano 2010, 4, 2865−2873.
(24) Nine, M. J.; Cole, M. A.; Tran, D. N. H.; Losic, D. Graphene: A
Multipurpose Material for Protective Coatings. J. Mater. Chem. A
2015, 3, 12580−12602.
(25) Mugele, F. Wetting: Unobtrusive Graphene Coatings. Nat.
Mater. 2012, 11, 182−183.
(26) Kim, J. T.; Choi, S.-Y. Graphene-Based Plasmonic Waveguides
for Photonic Integrated Circuits. Opt. Express 2011, 19, 24557.
(27) Sordan, R.; Ferrari, A. C. Gigahertz Multi-Transistor Graphene
Integrated Circuits. In Technical Digest - International Electron Devices
Meeting; IEDM; IEEE: Washington D.C., 2013; p 111−117.
(28) Shen, H.; Zhang, L.; Liu, M.; Zhang, Z. Biomedical
Applications of Graphene. Theranostics 2012, 2, 283−294.
(29) Georgakilas, V.; Tiwari, J. N.; Kemp, K. C.; Perman, J. A.;
Bourlinos, A. B.; Kim, K. S.; Zboril, R. Noncovalent Functionalization
of Graphene and Graphene Oxide for Energy Materials, Biosensing,
Catalytic, and Biomedical Applications. Chem. Rev. 2016, 116, 5464−
5519.
(30) Zhang, K.; Kemp, K. C.; Chandra, V. Homogeneous Anchoring
of TiO2 Nanoparticles on Graphene Sheets for Waste Water
Treatment. Mater. Lett. 2012, 81, 127−130.
(31) Romanchuk, A. Y.; Slesarev, A. S.; Kalmykov, S. N.; Kosynkin,
D. V.; Tour, J. M. Graphene Oxide for Effective Radionuclide
Removal. Phys. Chem. Chem. Phys. 2013, 15, 2321.
(32) Ashrafi, A. R.; Koorepazan-Moftakhar, F. O. O. Symmetry and
Topology of Graphenes. In Graphene Science Handbook : Nanostruc-
ture and Atomic Arrangement; Aliofkhazraei, M., Ali, N., Milne, W.,
Ozkan, C., Mitura, S., Gervasoni, J., Eds.; CRC Press Inc.: Boca
Raton, 2016; pp 159−164.
(33) Landau, L. Zur Theorie Der Phasenumwandlungen II. Phys. Z.
Sowjet 1937, 11, 26−35.
Y DOI: 10.1021/acs.jced.8b01057
Review
(34) Peierls, R. E. Quelques Proprietes Typiques Des Corpses
Solides. Ann. I. H. Poincare 1935, 5, 177−222.
(35) Mermin, N. D. Crystalline Order in Two Dimensions. Phys.
Rev. 1968, 176, 250−254.
(36) Venables, J. A.; Spiller, G. D. T.; Hanbucken, M. Nucleation
and Growth of Thin Films. Rep. Prog. Phys. 1984, 47, 399−459.
(37) Evans, J. W.; Thiel, P. A.; Bartelt, M. C. Morphological
Evolution during Epitaxial Thin Film Growth: Formation of 2D
Islands and 3D Mounds. Surf. Sci. Rep. 2006, 61, 1−128.
(38) Schafhaeutl, C. Ueber Die Verbindungen Des Kohlenstoffes
Mit Silicium, Eisen Und Andern Metallen, Welche Die Verschiedenen
Arten von Gusseisen, Stahl Und Schmiedeeisen Bilden. J. Prakt. Chem.
1840, 19, 159−174.
(39) Brodie, B. C. On the Atomic Weightof Graphite. Philos. Trans.
R. Soc. London 1859, 149, 249−259.
(40) Boehm, H. P.; Clauss, A.; Fischer, G. O.; Hofmann, U. Dünnste
Kohlenstoff-Folien. Z. Naturforsch., B: J. Chem. Sci. 1962, 17, 150−
153.
(41) Boehm, H.-P. Graphen - Wie Eine Laborkuriosität Plötzlich
Ä ußerst Interessant Wurde. Angew. Chem. 2010, 122, 9520−9523.
(42) Boehm, H. P.; Setton, R.; Stumpp, E. Nomenclature and
Terminology of Graphite Intercalation Compounds (IUPAC
Recommendations 1994). Pure Appl. Chem. 1994, 66, 1893−1901.
(43) Dresselhaus, M. S.; Araujo, P. T. Perspectives on the 2010
Nobel Prize in Physics for Graphene. ACS Nano 2010, 4, 6297−6302.
(44) Altmann, J.; Ruhl, A. S.; Zietzschmann, F.; Jekel, M. Direct
Comparison of Ozonation and Adsorption onto Powdered Activated
Carbon for Micropollutant Removal in Advanced Wastewater
Treatment. Water Res. 2014, 55, 185−193.
(45) Wang, D.; Hu, Q.; Yuan Li, M.; Wang, C.; Ji, M. Evaluating the
Removal of Organic Fraction of Commingled Chemical Industrial
Wastewater by Activated Sludge Process Augmented with Powdered
Activated Carbon. Arabian J. Chem. 2016, 9, S1951−S1961.
(46) Alam, S. N.; Sharma, N.; Kumar, L. Synthesis of Graphene
Oxide (GO) by Modified Hummers Method and Its Thermal
Reduction to Obtain Reduced Graphene Oxide (RGO). Graphene
2017, 06, 1−18.
(47) Zhao, X.; Liu, Z. B.; Yan, W. B.; Wu, Y.; Zhang, X. L.; Chen, Y.;
Tian, J. G. Ultrafast Carrier Dynamics and Saturable Absorption of
Solution-Processable Few-Layered Graphene Oxide. Appl. Phys. Lett.
2011, 98, 121905.
(48) Kemp, K. C.; Seema, H.; Saleh, M.; Le, N. H.; Mahesh, K.;
Chandra, V.; Kim, K. S. Environmental Applications Using Graphene
Composites: Water Remediation and Gas Adsorption. Nanoscale
2013, 5, 3149−3171.
(49) Li, D.; Müller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G.
Processable Aqueous Dispersions of Graphene Nanosheets. Nat.
Nanotechnol. 2008, 3, 101−105.
(50) Ji, L.; Chen, W.; Xu, Z.; Zheng, S.; Zhu, D. Graphene
Nanosheets and Graphite Oxide as Promising Adsorbents for
Removal of Organic Contaminants from Aqueous Solution. J. Environ.
Qual. 2013, 42, 191−198.
(51) Gao, H.; Sun, Y.; Zhou, J.; Xu, R.; Duan, H. Mussel-Inspired
Synthesis of Polydopamine-Functionalized Graphene Hydrogel as
Reusable Adsorbents for Water Purification. ACS Appl. Mater.
Interfaces 2013, 5, 425−432.
(52) Yang, B.; Tian, Z.; Zhang, L.; Guo, Y.; Yan, S. Enhanced
Heterogeneous Fenton Degradation of Methylene Blue by Nanoscale
Zero Valent Iron (NZVI) Assembled on Magnetic Fe3O4/Reduced
Graphene Oxide. J. Water Process Eng. 2015, 5, 101−111.
(53) Liu, T.; Li, Y.; Du, Q.; Sun, J.; Jiao, Y.; Yang, G.; Wang, Z.; Xia,
Y.; Zhang, W.; Wang, K.; et al. Adsorption of Methylene Blue from
Aqueous Solution by Graphene. Colloids Surf., B 2012, 90, 197−203.
(54) Gao, W. The Chemistry of Graphene Oxide. In Graphene
Oxide: Reduction Recipes, Spectroscopy, and Applications; Springer
International Publishing: Cham, 2015; pp 61−95.
(55) Chen, D.; Feng, H.; Li, J. Graphene Oxide: Preparation,
Functionalization, and Electrochemical Applications. Chem. Rev.
2012, 112, 6027−6053.
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(56) Krishnan, D.; Kim, F.; Luo, J.; Cruz-Silva, R.; Cote, L. J.; Jang,
H. D.; Huang, J. Energetic Graphene Oxide: Challenges and
Opportunities. Nano Today 2012, 7, 137−152.
(57) Carmalin Sophia, A.; Lima, E. C.; Allaudeen, N.; Rajan, S.
Application of Graphene Based Materials for Adsorption of
Pharmaceutical Traces from Water and Wastewater- a Review.
Desalin. Water Treat. 2016, 57, 27573−27586.
(58) Wang, X.; Huang, S.; Zhu, L.; Tian, X.; Li, S.; Tang, H.
Correlation between the Adsorption Ability and Reduction Degree of
Graphene Oxide and Tuning of Adsorption of Phenolic Compounds.
Carbon 2014, 69, 101−112.
(59) Nidheesh, P. V. Graphene-Based Materials Supported
Advanced Oxidation Processes for Water and Wastewater Treatment :
A Review. Environ. Sci. Pollut. Res. 2017, 24, 1−23.
(60) Nidheesh, P. V.; Rajan, R. Removal of Rhodamine B from a
Water Medium Using Hydroxyl and Sulphate Radicals Generated by
Iron Loaded Activated Carbon. RSC Adv. 2016, 6, 5330−5340.
(61) Nguyen-Phan, T.-D. D.; Pham, V. H.; Shin, E. W.; Pham, H.-D.
D.; Kim, S.; Chung, J. S.; Kim, E. J.; Hur, S. H. The Role of Graphene
Oxide Content on the Adsorption-Enhanced Photocatalysis of
Titanium Dioxide/Graphene Oxide Composites. Chem. Eng. J.
2011, 170, 226−232.
(62) Brillas, E. A Review on the Degradation of Organic Pollutants
in Waters by UV Photoelectro-Fenton and Solar Photoelectro-
Fenton. J. Braz. Chem. Soc. 2013, 25, 393−417.
(63) Han, Y.; Xu, Z.; Gao, C. Ultrathin Graphene Nanofiltration
Membrane for Water Purification. Adv. Funct. Mater. 2013, 23, 3693−
3700.
(64) Gonte, R. R.; Balasubramanian, K.; Mumbrekar, J. D. Porous
and Cross-Linked Cellulose Beads for Toxic Metal Ion Removal:
Hg(II) Ions. J. Polym. 2013, 2013, 1−9.
(65) Gonte, R. R.; Shelar, G.; Balasubramanian, K. Polymer−agro-
Waste Composites for Removal of Congo Red Dye from Wastewater:
Adsorption Isotherms and Kinetics. Desalin. Water Treat. 2014, 52,
7797−7811.
(66) Davis, A.; K, B. Bioactive Hybrid Composite Membrane with
Enhanced Antimicrobial Properties for Biomedical Applications. Def.
Sci. J. 2016, 66, 434.
(67) Ramdayal; Balasubramanian, K. Antibacterial Application of
Polyvinylalcohol-Nanogold Composite Membranes. Colloids Surf., A
2014, 455, 174−178.
(68) Li, F.; Jiang, X.; Zhao, J.; Zhang, S. Graphene Oxide: A
Promising Nanomaterial for Energy and Environmental Applications.
Nano Energy 2015, 16, 488−515.
(69) Sahoo, B. N.; Balasubramanian, K. Facile Synthesis of Nano
Cauliflower and Nano Broccoli like Hierarchical Superhydrophobic
Composite Coating Using PVDF/Carbon Soot Particles via Gelation
Technique. J. Colloid Interface Sci. 2014, 436, 111−121.
(70) Zhang, M. H.; Zhao, Q. L.; Bai, X.; Ye, Z. F. Adsorption of
Organic Pollutants from Coking Wastewater by Activated Coke.
Colloids Surf., A 2010, 362, 140−146.
(71) Jones, K. C. K. C.; de Voogt, P. Persistent Organic Pollutants
(POPs): State of the Science. Environ. Pollut. 1999, 100, 209−221.
(72) Rakshit, S.; Saha, R.; Singha, A.; Seddigi, Z. S. A.; Pal, S. K.
Molecular Interaction, Co-Solubilization of Organic Pollutants and
Ecotoxicity of a Potential Carcinogenic Fuel Additive MTBE in
Water. J. Mol. Liq. 2013, 180, 235−243.
(73) Delval, F.; Crini, G.; Vebrel, J. Removal of Organic Pollutants
from Aqueous Solutions by Adsorbents Prepared from an Agro-
alimentary By-Product. Bioresour. Technol. 2006, 97, 2173−2181.
(74) Ali, I.; Asim, M.; Khan, T. A. Low Cost Adsorbents for the
Removal of Organic Pollutants from Wastewater. J. Environ. Manage.
2012, 113, 170−183.
(75) Lopes Tiburtius, E. R.; Peralta-Zamora, P.; Leal, E. S.
Contaminaçaõ de Á guas Por BTXS e Processos Utilizados Na
́ Contaminados. Quim. Nova 2004, 27, 441−446.
Remediaçaõ de Sitios
(76) Ali, I.; Alharbi, O. M. L.; Tkachev, A.; Galunin, E.; Burakov, A.;
Grachev, V. A. Water Treatment by New-Generation Graphene
Z DOI: 10.1021/acs.jced.8b01057
Review
Materials: Hope for Bright Future. Environ. Sci. Pollut. Res. 2018, 25,
7315−7329.
(77) Achten, C.; Hofmann, T. Native Polycyclic Aromatic
Hydrocarbons (PAH) in Coals - A Hardly Recognized Source of
Environmental Contamination. Sci. Total Environ. 2009, 407, 2461−
2473.
(78) Boström, C.-E.; Gerde, P.; Hanberg, A.; Jernström, B.;
Johansson, C.; Kyrklund, T.; Rannug, A.; Törnqvist, M.; Victorin,
K.; Westerholm, R. Cancer Risk Assessment, Indicators, and
Guidelines for Polycyclic Aromatic Hydrocarbons in the Ambient
Air. Environ. Health Perspect. 2002, 110, 451−489.
(79) Loeb, L. A.; Harris, C. C. Advances in Chemical Carcino-
genesis: A Historical Review and Prospective. Cancer Res. 2008, 68,
6863−6872.
(80) Korashy, H.; El-Kadi, A. The Role of Aryl Hydrocarbon
Receptor in the Pathogenesis of Cardiovascular Diseases. Drug Metab.
Rev. 2006, 38, 411−450.
(81) McKee, R. H.; Lammers, J. H. C. M.; Muijser, H.; Owen, D. E.;
Kulig, B. M. Neurobehavioral Effects of Acute Exposure to Aromatic
Hydrocarbons. Int. J. Toxicol. 2010, 29, 277−290.
(82) Husain, M.; Husain, Q. Applications of Redox Mediators in the
Treatment of Organic Pollutants by Using Oxidoreductive Enzymes:
A Review. Crit. Rev. Environ. Sci. Technol. 2007, 38, 1−42.
(83) Michael, I.; Rizzo, L.; McArdell, C. S.; Manaia, C. M.; Merlin,
C.; Schwartz, T.; Dagot, C.; Fatta-Kassinos, D. Urban Wastewater
Treatment Plants as Hotspots for the Release of Antibiotics in the
Environment: A Review. Water Res. 2013, 47, 957−995.
(84) Jones, O. a.; Voulvoulis, N.; Lester, J. N. Human
Pharmaceuticals in the Aquatic Environment a Review. Environ.
Technol. 2001, 22, 1383−1394.
(85) Marahel, F.; Khan, M. A.; Marahel, E.; Bayesti, I.; Hosseini, S.
Kinetics, Thermodynamics, and Isotherm Studies for the Adsorption
of BR2 Dye onto Avocado Integument. Desalin. Water Treat. 2015,
53, 826−835.
(86) McGuinness, N. B.; Garvey, M.; Whelan, A.; John, H.; Zhao,
C.; Zhang, G.; Dionysiou, D. D.; Byrne, J. A.; Pillai, S. C.
Nanotechnology Solutions for Global Water Challenges. In ACS
Symposium Series; American Chemical Society: 2015.
(87) Ding, G.; Jiao, W.; Wang, R.; Niu, Y.; Chen, L.; Hao, L.
Ultrafast, Reversible Transition of Superwettability of Graphene
Network and Controllable Underwater Oil Adhesion for Oil
Microdroplet Transportation. Adv. Funct. Mater. 2018, 28, 1706686.
(88) Chen, C.; Li, F.; Zhang, Y.; Wang, B.; Fan, Y.; Wang, X.; Sun,
R. Compressive, Ultralight and Fire-Resistant Lignin-Modified
Graphene Aerogels as Recyclable Absorbents for Oil and Organic
Solvents. Chem. Eng. J. 2018, 350, 173−180.
(89) Akbari, M.; Shariaty-Niassar, M.; Matsuura, T.; Ismail, A. F.
Janus Graphene Oxide Nanosheet: A Promising Additive for
Enhancement of Polymeric Membranes Performance Prepared via
Phase Inversion. J. Colloid Interface Sci. 2018, 527, 10−24.
(90) Liu, Q.; Shi, J.; Sun, J.; Wang, T.; Zeng, L.; Jiang, G. Graphene
and Graphene Oxide Sheets Supported on Silica as Versatile and
High-Performance Adsorbents for Solid-Phase Extraction. Angew.
Chem., Int. Ed. 2011, 50, 5913−5917.
(91) Cheng, C.; Liu, Z.; Li, X.; Su, B.; Zhou, T.; Zhao, C. Graphene
Oxide Interpenetrated Polymeric Composite Hydrogels as Highly
Effective Adsorbents for Water Treatment. RSC Adv. 2014, 4, 42346−
42357.
(92) Zhou, X.; Zhang, Y.; Wang, C.; Wu, X.; Yang, Y.; Zheng, B.;
Wu, H.; Guo, S.; Zhang, J. Photo-Fenton Reaction of Graphene
Oxide: A New Strategy to Prepare Graphene Quantum Dots for DNA
Cleavage. ACS Nano 2012, 6, 6592−6599.
(93) Sun, H.; Liu, S.; Zhou, G.; Ang, H. M.; Tadé, M. O.; Wang, S.
Reduced Graphene Oxide for Catalytic Oxidation of Aqueous
Organic Pollutants. ACS Appl. Mater. Interfaces 2012, 4, 5466−5471.
(94) Fan, X.; Zhang, G.; Zhang, F. Multiple Roles of Graphene in
Heterogeneous Catalysis. Chem. Soc. Rev. 2015, 44, 3023−3035.
(95) Ramesha, G. K. K.; Vijaya Kumara, A.; Muralidhara, H. B. B.;
Sampath, S. Graphene and Graphene Oxide as Effective Adsorbents
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
toward Anionic and Cationic Dyes. J. Colloid Interface Sci. 2011, 361,
270−277.
(96) Liu, Y.; Liu, C. Y.; Liu, Y. Investigation on Fluorescence
Quenching of Dyes by Graphite Oxide and Graphene. Appl. Surf. Sci.
2011, 257, 5513−5518.
(97) Wu, Q.; Zhao, G.; Feng, C.; Wang, C.; Wang, Z. Preparation of
a Graphene-Based Magnetic Nanocomposite for the Extraction of
Carbamate Pesticides from Environmental Water Samples. J.
Chromatogr. A 2011, 1218, 7936−7942.
(98) Gao, Y.; Li, Y.; Zhang, L.; Huang, H.; Hu, J.; Shah, S. M.; Su, X.
Adsorption and Removal of Tetracycline Antibiotics from Aqueous
Solution by Graphene Oxide. J. Colloid Interface Sci. 2012, 368, 540−
546.
(99) Hu, K.; Kulkarni, D. D.; Choi, I.; Tsukruk, V. V. Graphene-
Polymer Nanocomposites for Structural and Functional Applications.
Prog. Polym. Sci. 2014, 39, 1934−1972.
(100) Suárez-Iglesias, O.; Collado, S.; Oulego, P.; Díaz, M.
Graphene-Family Nanomaterials in Wastewater Treatment Plants.
Chem. Eng. J. 2017, 313, 121−135.
(101) Nandi, A. K.; Kundu, A.; Layek, R. K. Functionalization and
Chemical Properties of Graphene. In Handbook of Graphene Science;
Aliofkhazraei, A., Milne, Ozkan, M., Eds.; CRC Press Inc.: Boca
Raton, FL, 2015; Vol. 5, pp 187−213.
(102) Kuila, T.; Bose, S.; Mishra, A. K.; Khanra, P.; Kim, N. H.; Lee,
J. H. Chemical Functionalization of Graphene and Its Applications.
Prog. Mater. Sci. 2012, 57, 1061−1105.
(103) Rossi, R. A.; Rossi, R. H. Aromatic Substitution by the
S[Subscript RN]1 Mechanism; American Chemical Society: Wash-
ington D.C., 1983.
(104) Smith, M. B.; March, J. March’s Advanced Organic Chemistry:
Reactions, Mechanisms, and Structure: Sixth ed.; 2006; Vol.
9780471720.
(105) Rana, S.; Jonnalagadda, S. B. Synthesis and Characterization of
Amine Functionalized Graphene Oxide and Scope as Catalyst for
Knoevenagel Condensation Reaction. Catal. Commun. 2017, 92, 31−
34.
(106) Allen, J. M.; Lambert, T. H. Tropylium Ion Mediated α-
Cyanation of Amines. J. Am. Chem. Soc. 2011, 133, 1260−1262.
(107) Yang, H.; Shan, C.; Li, F.; Han, D.; Zhang, Q.; Niu, L.
Covalent Functionalization of Polydisperse Chemically-Converted
Graphene Sheets with Amine-Terminated Ionic Liquid. Chem.
Commun. 2009, No. 26, 3880.
(108) Wang, G.; Wang, B.; Park, J.; Yang, J.; Shen, X.; Yao, J.
Synthesis of Enhanced Hydrophilic and Hydrophobic Graphene
Oxide Nanosheets by a Solvothermal Method. Carbon 2009, 47, 68−
72.
(109) Shan, D.; Deng, S.; Li, J.; Wang, H.; He, C.; Cagnetta, G.;
Wang, B.; Wang, Y.; Huang, J.; Yu, G. Preparation of Porous
Graphene Oxide by Chemically Intercalating a Rigid Molecule for
Enhanced Removal of Typical Pharmaceuticals. Carbon 2017, 119,
101−109.
(110) Yuan, X.; Wu, Z.; Zhong, H.; Wang, H.; Chen, X.; Leng, L.;
Jiang, L.; Xiao, Z.; Zeng, G. Fast Removal of Tetracycline from
Wastewater by Reduced Graphene Oxide Prepared via Microwave-
Assisted Ethylenediamine−N,N’−disuccinic Acid Induction Method.
Environ. Sci. Pollut. Res. 2016, 23, 18657−18671.
(111) Zhang, D.-D.; Zu, S.-Z.; Han, B.-H. Inorganic−organic Hybrid
Porous Materials Based on Graphite Oxide Sheets. Carbon 2009, 47,
2993−3000.
(112) Stankovich, S.; Dikin, D. A.; Dommett, G. H. B.; Kohlhaas, K.
M.; Zimney, E. J.; Stach, E. A.; Piner, R. D.; Nguyen, S. B. T.; Ruoff,
R. S. Graphene-Based Composite Materials. Nature 2006, 442, 282−
286.
(113) Xu, C.; Wang, X.; Wang, J.; Hu, H.; Wan, L. Synthesis and
Photoelectrical Properties of β-Cyclodextrin Functionalized Graphene
Materials with High Bio-Recognition Capability. Chem. Phys. Lett.
2010, 498, 162−167.
(114) Travlou, N. A.; Kyzas, G. Z.; Lazaridis, N. K.; Deliyanni, E. A.
Functionalization of Graphite Oxide with Magnetic Chitosan for the
AA
Review
Preparation of a Nanocomposite Dye Adsorbent. Langmuir 2013, 29,
1657−1668.
(115) Salavagione, H. J.; Gómez, M. A.; Martínez, G. Polymeric
Modification of Graphene through Esterification of Graphite Oxide
and Poly(Vinyl Alcohol). Macromolecules 2009, 42, 6331−6334.
(116) Xu, Y.; Liu, Z.; Zhang, X.; Wang, Y.; Tian, J.; Huang, Y.; Ma,
Y.; Zhang, X.; Chen, Y. A Graphene Hybrid Material Covalently
Functionalized with Porphyrin: Synthesis and Optical Limiting
Property. Adv. Mater. 2009, 21, 1275−1279.
(117) Shen, Y.; Chen, B. Sulfonated Graphene Nanosheets as a
Superb Adsorbent for Various Environmental Pollutants in Water.
Environ. Sci. Technol. 2015, 49, 7364−7372.
(118) Bekyarova, E.; Itkis, M. E.; Ramesh, P.; Berger, C.; Sprinkle,
M.; De Heer, W. A.; Haddon, R. C. Chemical Modification of
Epitaxial Graphene: Spontaneous Grafting of Aryl Groups. J. Am.
Chem. Soc. 2009, 131, 1336−1337.
(119) Zhu, Y.; Higginbotham, A. L.; Tour, J. M. Covalent
Functionalization of Surfactant-Wrapped Graphene Nanoribbons.
Chem. Mater. 2009, 21, 5284−5291.
(120) Lomeda, J. R.; Doyle, C. D.; Kosynkin, D. V.; Hwang, W. F.;
Tour, J. M. Diazonium Functionalization of Surfactant-Wrapped
Chemically Converted Graphene Sheets. J. Am. Chem. Soc. 2008, 130,
16201−16206.
(121) Sun, Z.; Kohama, S.-i.; Zhang, Z.; Lomeda, J. R.; Tour, J. M.
Soluble Graphene through Edge-Selective Functionalization. Nano
Res. 2010, 3, 117−125.
(122) Avinash, M. B.; Subrahmanyam, K. S.; Sundarayya, Y.;
Govindaraju, T. Covalent Modification and Exfoliation of Graphene
Oxide Using Ferrocene. Nanoscale 2010, 2, 1762.
(123) Pham, V. H.; Cuong, T. V.; Hur, S. H.; Oh, E.; Kim, E. J.;
Shin, E. W.; Chung, J. S. Chemical Functionalization of Graphene
Sheets by Solvothermal Reduction of a Graphene Oxide Suspension
in N-Methyl-2-Pyrrolidone. J. Mater. Chem. 2011, 21, 3371.
(124) Fang, M.; Wang, K.; Lu, H.; Yang, Y.; Nutt, S. Covalent
Polymer Functionalization of Graphene Nanosheets and Mechanical
Properties of Composites. J. Mater. Chem. 2009, 19, 7098.
(125) Verma, S.; Mungse, H. P.; Kumar, N.; Choudhary, S.; Jain, S.
L.; Sain, B.; Khatri, O. P. Graphene Oxide: An Efficient and Reusable
Carbocatalyst for Aza-Michael Addition of Amines to Activated
Alkenes. Chem. Commun. 2011, 47, 12673.
(126) Garg, B.; Ling, Y. Versatilities of Graphene Based Catalysts in
Organic Transformations. Green Mater. 2013, 1, 47−61.
(127) Pan, Y.; Wang, S.; Kee, C. W.; Dubuisson, E.; Yang, Y.; Loh,
K. P.; Tan, C.-H. Graphene Oxide and Rose Bengal: Oxidative C−H
Functionalisation of Tertiary Amines Using Visible Light. Green
Chem. 2011, 13, 3341.
(128) Wan, Q.; Liu, M.; Xie, Y.; Tian, J.; Huang, Q.; Deng, F.; Mao,
L.; Zhang, Q.; Zhang, X.; Wei, Y. Facile and Highly Efficient
Fabrication of Graphene Oxide-Based Polymer Nanocomposites
through Mussel-Inspired Chemistry and Their Environmental
Pollutant Removal Application. J. Mater. Sci. 2017, 52, 504−518.
(129) Xu, Y.; Bai, H.; Lu, G.; Li, C.; Shi, G. Flexible Graphene Films
via the Filtration of Water-Soluble Noncovalent Functionalized
Graphene Sheets. J. Am. Chem. Soc. 2008, 130, 5856−5857.
(130) Peng, B.; Chen, L.; Que, C.; Yang, K.; Deng, F.; Deng, X.; Shi,
G.; Xu, G.; Wu, M. Adsorption of Antibiotics on Graphene and
Biochar in Aqueous Solutions Induced by π-π Interactions. Sci. Rep.
2016, 6, 1−10.
(131) Zhang, J.; Lu, X.; Shi, C.; Yan, B.; Gong, L.; Chen, J.; Xiang,
L.; Xu, H.; Liu, Q.; Zeng, H. Unraveling the Molecular Interaction
Mechanism between Graphene Oxide and Aromatic Organic
Compounds with Implications on Wastewater Treatment. Chem.
Eng. J. 2019, 358, 842−849.
(132) Poggendorf, J. C. Annalen Der Physik Und Chemie. Arch.
Pharm. (Weinheim, Ger.) 1829, 28, 188−191.
(133) Ferrari, L.; Kaufmann, J.; Winnefeld, F.; Plank, J. Interaction
of Cement Model Systems with Superplasticizers Investigated by
Atomic Force Microscopy, Zeta Potential, and Adsorption Measure-
ments. J. Colloid Interface Sci. 2010, 347, 15−24.
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(134) Katoh, S.; Yoshida, F. Adsorption and Chromatography. In
Biochemical Engineering; 2009; pp 165−184.
(135) Soto, M. L.; Moure, A.; Domínguez, H.; Parajó, J. C.
Recovery, Concentration and Purification of Phenolic Compounds by
Adsorption: A Review. J. Food Eng. 2011, 105, 1−27.
(136) Ibezim-Ezeani, M. U.; Anusiem, A. C. I. Kinetic Studies of
Adsorption of Palmitate and Laurate Soaps onto Some Metal Ores in
Aqueous Media. Int. J. Phys. Sci. 2010, 5, 62−67.
(137) Yang, S.; Li, Y.; Wang, S.; Wang, M.; Chu, M.; Xia, B.
Advances in the Use of Carbonaceous Materials for the Electro-
chemical Determination of Persistent Organic Pollutants. Microchim.
Acta 2018, 2. DOI: 10.1007/s00604-017-2638-9
(138) Nitesh Singh, N. S.; Balasubramanian, K. An Effective
Technique for Removal and Recovery of Uranium(VI) from Aqueous
Solution Using Cellulose−camphor Soot Nanofibers. RSC Adv. 2014,
4, 27691−27701.
(139) Rule, P.; K, B.; Gonte, R. R. Uranium(VI) Remediation from
Aqueous Environment Using Impregnated Cellulose Beads. J. Environ.
Radioact. 2014, 136, 22−29.
(140) Yao, Y.; Cai, Y.; Lu, F.; Wei, F.; Wang, X.; Wang, S. Magnetic
Recoverable MnFe2O4and MnFe2O4-Graphene Hybrid as Hetero-
geneous Catalysts of Peroxymonosulfate Activation for Efficient
Degradation of Aqueous Organic Pollutants. J. Hazard. Mater. 2014,
270, 61−70.
(141) Yao, Y.; Miao, S.; Liu, S.; Ma, L. P.; Sun, H.; Wang, S.
Synthesis, Characterization, and Adsorption Properties of Magnetic
Fe3O4@graphene Nanocomposite. Chem. Eng. J. 2012, 184, 326−
332.
(142) Rouquerol, F.; Rouquerol, J.; Sing, K. Chapter 12Properties
of Some Novel Adsorbents. In Adsorption by Powders and Porous
Solids; 1999; pp 401−438.
(143) Sah, R. P.; Choudhury, B.; Das, R. K. A Review on Adsorption
Cooling Systems with Silica Gel and Carbon as Adsorbents. Renewable
Sustainable Energy Rev. 2015, 45, 123−134.
(144) Tso, C. Y.; Chao, C. Y. H. Activated Carbon, Silica-Gel and
Calcium Chloride Composite Adsorbents for Energy Efficient Solar
Adsorption Cooling and Dehumidification Systems. Intl J. Refrig.
2012, 35, 1626−1638.
(145) Weintraub, S. Demystifying Silica Gel. Cycle 2002, 9, 24.
(146) Ayalew, A.; Gonte, R. R.; Balasubramanian, K. Development
of Polymer Composite Beads for Dye Adsorption. Int. J. Green
Nanotechnol. 2012, 4, 440−454.
(147) Fan, L.; Luo, C.; Sun, M.; Qiu, H.; Li, X. Synthesis of
Magnetic β-Cyclodextrin−chitosan/Graphene Oxide as Nanoadsorb-
ent and Its Application in Dye Adsorption and Removal. Colloids Surf.,
B 2013, 103, 601−607.
(148) Shi, J.; Chen, G.; Zeng, G.; Chen, A.; He, K.; Huang, Z.; Hu,
L.; Zeng, J.; Wu, J.; Liu, W. Hydrothermal Synthesis of Graphene
Wrapped Fe-Doped TiO 2 Nanospheres with High Photocatalysis
Performance. Ceram. Int. 2018, 44, 7473−7480.
(149) Nguyen-Phan, T. D.; Pham, V. H.; Kim, E. J.; Oh, E. S.; Hur,
S. H.; Chung, J. S.; Lee, B.; Shin, E. W. Reduced Graphene Oxide-
Titanate Hybrids: Morphologic Evolution by Alkali-Solvothermal
Treatment and Applications in Water Purification. Appl. Surf. Sci.
2012, 258, 4551−4557.
(150) Chen, D.; Wang, D.; Ge, Q.; Ping, G.; Fan, M.; Qin, L.; Bai,
L.; Lv, C.; Shu, K. Graphene-Wrapped ZnO Nanospheres as a
Photocatalyst for High Performance Photocatalysis. Thin Solid Films
2015, 574, 1−9.
(151) Zhang, X.; Yu, H.; Yang, H.; Wan, Y.; Hu, H.; Zhai, Z.; Qin, J.
Graphene Oxide Caged in Cellulose Microbeads for Removal of
Malachite Green Dye from Aqueous Solution. J. Colloid Interface Sci.
2015, 437, 277−282.
(152) Rotte, N. K.; Yerramala, S.; Boniface, J.; Srikanth, V. V. S. S.
Equilibrium and Kinetics of Safranin O Dye Adsorption on MgO
Decked Multi-Layered Graphene. Chem. Eng. J. 2014, 258, 412−419.
(153) Ma, T.; Chang, P. R.; Zheng, P.; Zhao, F.; Ma, X. Fabrication
of Ultra-Light Graphene-Based Gels and Their Adsorption of
Methylene Blue. Chem. Eng. J. 2014, 240, 595−600.
AB
Review
(154) Sahetya, T. J.; Dixit, F.; Balasubramanian, K. Waste Citrus
Fruit Peels for Removal of Hg(II) Ions. Desalin. Water Treat. 2015,
53, 1404−1416.
(155) Chowdhury, P. S. Insight Into Adsorption Thermodynamics. J.
Hazard. Mater. 2003, 162, 440.
(156) Ho, Y. S.; Porter, J. F.; McKay, G. Equilibrium Isotherm
Studies for the Sorption of Divalent Metal Ions onto Peat: Copper,
Nickel and Lead Single Component Systems. Water, Air, Soil Pollut.
2002, 141, 1−33.
(157) Srivastava, V. C.; Swamy, M. M.; Mall, I. D.; Prasad, B.;
Mishra, I. M. Adsorptive Removal of Phenol by Bagasse Fly Ash and
Activated Carbon: Equilibrium, Kinetics and Thermodynamics.
Colloids Surf., A 2006, 272, 89−104.
(158) El-Khaiary, M. I. Least-Squares Regression of Adsorption
Equilibrium Data: Comparing the Options. J. Hazard. Mater. 2008,
158, 73−87.
(159) Limousin, G.; Gaudet, J. P.; Charlet, L.; Szenknect, S.;
Barthès, V.; Krimissa, M. Sorption Isotherms: A Review on Physical
Bases, Modeling and Measurement. Appl. Geochem. 2007, 22, 249−
275.
(160) Vasanth Kumar, K.; Sivanesan, S. Sorption Isotherm for
Safranin onto Rice Husk: Comparison of Linear and Non-Linear
Methods. Dyes Pigm. 2007, 72, 130−133.
(161) Ncibi, M. C. Applicability of Some Statistical Tools to Predict
Optimum Adsorption Isotherm after Linear and Non-Linear
Regression Analysis. J. Hazard. Mater. 2008, 153, 207−212.
(162) Da̧browski, A. Adsorption - From Theory to Practice. Adv.
Colloid Interface Sci. 2001, 93, 135−224.
(163) Dubinin, M. M.; Radushkevich, L. V. The Equation of the
Characteristic Curve of Activated Charcoal. Proc. Acad. Sci. Phys.
Chem. Sect. 1947, 55, 331.
(164) Aharoni, C.; Ungarish, M. Kinetics of Activated Chem-
isorption. Part 2.Theoretical Models. J. Chem. Soc., Faraday Trans.
1 1977, 73, 456.
(165) Kundu, S.; Gupta, A. K. Arsenic Adsorption onto Iron Oxide-
Coated Cement (IOCC): Regression Analysis of Equilibrium Data
with Several Isotherm Models and Their Optimization. Chem. Eng. J.
2006, 122, 93−106.
(166) Horsfall, M. H.; Spiff, A. I. Equilibrium Sorption Study of Al
3+, Co 2+ and Ag + in Aqueous Solutions by Fluted Pumpkin
(Telfairia Occidentalis HOOK f) Waste Biomass. Acta Chim. Slov.
2005, 52, 174−181.
(167) Radke, C. J.; Prausnitz, J. M. Thermodynamics of Multi solute
Adsorption from Dilute Liquid Solutions. AIChE J. 1972, 18, 761.
(168) Sips, R. On the Structure of a Catalyst Surface. J. Chem. Phys.
1948, 16, 490.
(169) Tóth, J. State Equations of the Solid-Gas Interface Layers.
Acta Chim. Acad. Sci. Hungaricae 1971, 69, 311−328.
(170) Koble, R. A.; Corrigan, T. E. ADSORPTION ISOTHERMS
FOR PURE HYDROCARBONS. Ind. Eng. Chem. 1952, 44, 383−387.
(171) Khan, A.; Ataullah, R.; Al-Haddad, A. Equilibrium Adsorption
Studies of Some Aromatic Pollutants from Dilute Aqueous Solutions
on Activated Carbon at Different Temperatures. J. Colloid Interface
Sci. 1997, 194, 154−165.
(172) Vijayaraghavan, K.; Padmesh, T. V. N.; Palanivelu, K.; Velan,
M. Biosorption of Nickel(II) Ions onto Sargassum Wightii:
Application of Two-Parameter and Three-Parameter Isotherm
Models. J. Hazard. Mater. 2006, 133, 304−308.
(173) Lagergren, S. About the Theory of so-Called Adsorption of
Soluble Substances. Kungliga Svenska Vetenskapsakademiens Hand-
lingar 1898, 1−39.
(174) Ho, Y. S. S.; McKay, G. A Comparison of Chemisorption
Kinetic Models Applied to Pollutant Removal on Various Sorbents.
Process Saf. Environ. Prot. 1998, 76, 332−340.
(175) Azizian, S. Kinetic Models of Sorption: A Theoretical Analysis.
J. Colloid Interface Sci. 2004, 276, 47−52.
(176) Sharma, S.; Balasubramanian, K.; Arora, R. Adsorption of
Arsenic (V) Ions onto Cellulosic-Ferric Oxide System: Kinetics and
Isotherm Studies. Desalin. Water Treat. 2016, 57, 9420−9436.
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(177) Corbett, J. F. Pseudo First-Order Kinetics. J. Chem. Educ.
1972, 49, 663.
(178) Ho, Y.; McKay, G. Pseudo-Second Order Model for Sorption
Processes. Process Biochem. 1999, 34, 451−465.
(179) Sparks, D. L. Kinetics of Reactions in Pure and in Mixed Systems;
CRC Press: 1986; pp 83−145.
(180) Gao, J.; Pedersen, J. A. Adsorption of Sulfonamide
Antimicrobial Agents to Clay Minerals. Environ. Sci. Technol. 2005,
39, 9509−9516.
(181) Putra, E. K.; Pranowo, R.; Sunarso, J.; Indraswati, N.; Ismadji,
S. Performance of Activated Carbon and Bentonite for Adsorption of
Amoxicillin from Wastewater: Mechanisms, Isotherms and Kinetics.
Water Res. 2009, 43, 2419−2430.
(182) Bekçi, Z.; Seki, Y.; Yurdakoç, M. K. Equilibrium Studies for
Trimethoprim Adsorption on Montmorillonite KSF. J. Hazard. Mater.
2006, 133, 233−242.
(183) Ö nal, Y.; Akmil-Başar, C.; Sarıcı-Ö zdemir, Ç . Elucidation of
the Naproxen Sodium Adsorption onto Activated Carbon Prepared
from Waste Apricot: Kinetic, Equilibrium and Thermodynamic
Characterization. J. Hazard. Mater. 2007, 148, 727−734.
(184) Naeem, A.; Westerhoff, P.; Mustafa, S. Vanadium Removal by
Metal (Hydr)Oxide Adsorbents. Water Res. 2007, 41, 1596−1602.
(185) El-Sheikh, A. H.; Newman, A. P.; Al-Daffaee, H.; Phull, S.;
Cresswell, N.; York, S. Deposition of Anatase on the Surface of
Activated Carbon. Surf. Coat. Technol. 2004, 187, 284−292.
(186) Stoller, M. D.; Park, S.; Yanwu, Z.; An, J.; Ruoff, R. S.
Graphene-Based Ultracapacitors. Nano Lett. 2008, 8, 3498−3502.
(187) Dillon, E. C.; Wilton, J. H.; Barlow, J. C.; Watson, W. A. Large
Surface Area Activated Charcoal and the Inhibition of Aspirin
Absorption. Ann. Emerg. Med. 1989, 18, 547−552.
(188) Gore, P. M.; Khurana, L.; Siddique, S.; Panicker, A.;
Kandasubramanian, B. Ion-Imprinted Electrospun Nanofibers of
Chitosan/1-Butyl-3-Methylimidazolium Tetrafluoroborate for the
Dynamic Expulsion of Thorium (IV) Ions from Mimicked Effluents.
Environ. Sci. Pollut. Res. 2018, 25, 3320−3334.
(189) Yoon, Y.; Westerhoff, P.; Snyder, S. A.; Esparza, M. HPLC-
Fluorescence Detection and Adsorption of Bisphenol A, 17β-
Estradiol, and 17α-Ethynyl Estradiol on Powdered Activated Carbon.
Water Res. 2003, 37, 3530−3537.
(190) Yu, Z.; Peldszus, S.; Huck, P. M. Adsorption of Selected
Pharmaceuticals and an Endocrine Disrupting Compound by
Granular Activated Carbon. 2. Model Prediction. Environ. Sci. Technol.
2009, 43, 1474−1479.
(191) Chen, L.; Li, Y.; Hu, S.; Sun, J.; Du, Q.; Yang, X.; Ji, Q.; Wang,
Z.; Wang, D.; Xia, Y. Removal of Methylene Blue from Water by
Cellulose/Graphene Oxide Fibres. J. Exp. Nanosci. 2016, 11, 1156−
1170.
(192) Chia, C. H.; Razali, N. F.; Sajab, M. S.; Zakaria, S.; Huang, N.
M.; Lim, H. N. Methylene Blue Adsorption on Graphene Oxide. Sains
Malaysiana 2013, 42, 819−826.
(193) Dong, Z.; Wang, D.; Liu, X.; Pei, X.; Chen, L.; Jin, J. Bio-
Inspired Surface-Functionalization of Graphene Oxide for the
Adsorption of Organic Dyes and Heavy Metal Ions with a Superhigh
Capacity. J. Mater. Chem. A 2014, 2, 5034−5040.
(194) Saravia, F.; Frimmel, F. H. Role of NOM in the Performance
of Adsorption-Membrane Hybrid Systems Applied for the Removal of
Pharmaceuticals. Desalination 2008, 224, 168−171.
(195) Snyder, S. A.; Adham, S.; Redding, A. M.; Cannon, F. S.;
DeCarolis, J.; Oppenheimer, J.; Wert, E. C.; Yoon, Y. Role of
Membranes and Activated Carbon in the Removal of Endocrine
Disruptors and Pharmaceuticals. Desalination 2007, 202, 156−181.
(196) Fang, Z.; Hu, Y.; Wu, X.; Qin, Y.; Cheng, J.; Chen, Y.; Tan, P.;
Li, H. A Novel Magnesium Ascorbyl Phosphate Graphene-Based
Monolith and Its Superior Adsorption Capability for Bisphenol A.
Chem. Eng. J. 2018, 334, 948−956.
(197) Zhang, Y.; Cao, B.; Zhao, L.; Sun, L.; Gao, Y.; Li, J.; Yang, F.
Biochar-Supported Reduced Graphene Oxide Composite for
Adsorption and Coadsorption of Atrazine and Lead Ions. Appl. Surf.
Sci. 2018, 427, 147−155.
AC
Review
(198) Zhang, W.; Chen, J.; Hu, Y.; Fang, Z.; Cheng, J.; Chen, Y.
Adsorption Characteristics of Tetrabromobisphenol A onto Sodium
Bisulfite Reduced Graphene Oxide Aerogels. Colloids Surf., A 2018,
538, 781−788.
(199) Abdul, G.; Zhu, X.; Chen, B. Structural Characteristics of
Biochar-Graphene Nanosheet Composites and Their Adsorption
Performance for Phthalic Acid Esters. Chem. Eng. J. 2017, 319, 9−20.
(200) Jiang, L. h.; Liu, Y. g.; Zeng, G. m.; Xiao, F. yu; Hu, X. j.; Hu,
X.; Wang, H.; Li, T. ting; Zhou, L.; Tan, X. fei. Removal of 17β-
Estradiol by Few-Layered Graphene Oxide Nanosheets from Aqueous
Solutions: External Influence and Adsorption Mechanism. Chem. Eng.
J. 2016, 284, 93−102.
(201) Al-Khateeb, L. A.; Almotiry, S.; Salam, M. A. Adsorption of
Pharmaceutical Pollutants onto Graphene Nanoplatelets. Chem. Eng.
J. 2014, 248, 191−199.
(202) Kyzas, G. Z.; Bikiaris, D. N.; Seredych, M.; Bandosz, T. J.;
Deliyanni, E. A. Removal of Dorzolamide from Biomedical Waste-
waters with Adsorption onto Graphite Oxide/Poly(Acrylic Acid)
Grafted Chitosan Nanocomposite. Bioresour. Technol. 2014, 152,
399−406.
(203) Tang, Y.; Guo, H.; Xiao, L.; Yu, S.; Gao, N.; Wang, Y.
Synthesis of Reduced Graphene Oxide/Magnetite Composites and
Investigation of Their Adsorption Performance of Fluoroquinolone
Antibiotics. Colloids Surf., A 2013, 424, 74−80.
(204) Ghadim, E. E.; Manouchehri, F.; Soleimani, G.; Hosseini, H.;
Kimiagar, S.; Nafisi, S. Adsorption Properties of Tetracycline onto
Graphene Oxide: Equilibrium, Kinetic and Thermodynamic Studies.
PLoS One 2013, 8, 79254.
(205) Liu, F. F.; Zhao, J.; Wang, S.; Du, P.; Xing, B. Effects of
Solution Chemistry on Adsorption of Selected Pharmaceuticals and
Personal Care Products (PPCPs) by Graphenes and Carbon
Nanotubes. Environ. Sci. Technol. 2014, 48, 13197−13206.
(206) Yu, F.; Ma, J.; Bi, D. Enhanced Adsorptive Removal of
Selected Pharmaceutical Antibiotics from Aqueous Solution by
Activated Graphene. Environ. Sci. Pollut. Res. 2015, 22, 4715−4724.
(207) Kyzas, G. Z.; Koltsakidou, A.; Nanaki, S. G.; Bikiaris, D. N.;
Lambropoulou, D. A. Removal of Beta-Blockers from Aqueous Media
by Adsorption onto Graphene Oxide. Sci. Total Environ. 2015, 537,
411−420.
(208) Nam, S.-W. W.; Jung, C.; Li, H.; Yu, M.; Flora, J. R. V. V;
Boateng, L. K.; Her, N.; Zoh, K.-D. D.; Yoon, Y. Adsorption
Characteristics of Diclofenac and Sulfamethoxazole to Graphene
Oxide in Aqueous Solution. Chemosphere 2015, 136, 20−26.
(209) Wu, T.; Cai, X.; Tan, S.; Li, H.; Liu, J.; Yang, W. Adsorption
Characteristics of Acrylonitrile, p-Toluenesulfonic Acid, 1-Naphtha-
lenesulfonic Acid and Methyl Blue on Graphene in Aqueous
Solutions. Chem. Eng. J. 2011, 173, 144−149.
(210) Wu, Q.; Feng, C.; Wang, C.; Wang, Z. A Facile One-Pot
Solvothermal Method to Produce Superparamagnetic Graphene-
Fe3O4 Nanocomposite and Its Application in the Removal of Dye
from Aqueous Solution. Colloids Surf., B 2013, 101, 210−214.
(211) Sreeprasad, T. S.; Gupta, S. S.; Maliyekkal, S. M.; Pradeep, T.
Immobilized Graphene-Based Composite from Asphalt: Facile
Synthesis and Application in Water Purification. J. Hazard. Mater.
2013, 246−247, 213−220.
(212) Gupta, S. S.; Sreeprasad, T. S.; Maliyekkal, S. M.; Das, S. K.;
Pradeep, T. Graphene from Sugar and Its Application in Water
Purification. ACS Appl. Mater. Interfaces 2012, 4, 4156−4163.
(213) Wang, J.; Chen, B. Adsorption and Coadsorption of Organic
Pollutants and a Heavy Metal by Graphene Oxide and Reduced
Graphene Materials. Chem. Eng. J. 2015, 281, 379−388.
(214) Wang, J.; Chen, Z.; Chen, B. Adsorption of Polycyclic
Aromatic Hydrocarbons by Graphene and Graphene Oxide Nano-
sheets Adsorption of Polycyclic Aromatic. Environ. Sci. Technol. 2014,
48, 4817−4825.
(215) Sun, Y.; Yang, S.; Zhao, G.; Wang, Q.; Wang, X. Adsorption of
Polycyclic Aromatic Hydrocarbons on Graphene Oxides and Reduced
Graphene Oxides. Chem. - Asian J. 2013, 8, 2755−2761.
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(216) Apul, O. G.; Wang, Q.; Zhou, Y.; Karanfil, T. Adsorption of
Aromatic Organic Contaminants by Graphene Nanosheets: Compar-
ison with Carbon Nanotubes and Activated Carbon. Water Res. 2013,
47, 1648−1654.
(217) Yan, H.; Yang, H.; Li, A.; Cheng, R. PH-Tunable Surface
Charge of Chitosan/Graphene Oxide Composite Adsorbent for
Efficient Removal of Multiple Pollutants from Water. Chem. Eng. J.
2016, 284, 1397−1405.
(218) Tanhaei, M.; Mahjoub, A. R.; Safarifard, V. Sonochemical
Synthesis of Amide-Functionalized Metal-Organic Framework/
Graphene Oxide Nanocomposite for the Adsorption of Methylene
Blue from Aqueous Solution. Ultrason. Sonochem. 2018, 41, 189−195.
(219) Ai, L.; Zhang, C.; Chen, Z. Removal of Methylene Blue from
Aqueous Solution by a Solvothermal-Synthesized Graphene/Magnet-
ite Composite. J. Hazard. Mater. 2011, 192, 1515−1524.
(220) Ai, L.; Jiang, J. Removal of Methylene Blue from Aqueous
Solution with Self-Assembled Cylindrical Graphene−carbon Nano-
tube Hybrid. Chem. Eng. J. 2012, 192, 156−163.
(221) Zhang, W.; Zhou, C.; Zhou, W.; Lei, A.; Zhang, Q.; Wan, Q.;
Zou, B. Fast and Considerable Adsorption of Methylene Blue Dye
onto Graphene Oxide. Bull. Environ. Contam. Toxicol. 2011, 87, 86−
90.
(222) Li, Y.; Du, Q.; Liu, T.; Peng, X.; Wang, J.; Sun, J.; Wang, Y.;
Wu, S.; Wang, Z.; Xia, Y.; et al. Comparative Study of Methylene Blue
Dye Adsorption onto Activated Carbon, Graphene Oxide, and
Carbon Nanotubes. Chem. Eng. Res. Des. 2013, 91, 361−368.
(223) Sun, L.; Yu, H.; Fugetsu, B. Graphene Oxide Adsorption
Enhanced by in Situ Reduction with Sodium Hydrosulfite to Remove
Acridine Orange from Aqueous Solution. J. Hazard. Mater. 2012,
203−204, 101−110.
(224) Hosseinabadi-Farahani, Z.; Hosseini-Monfared, H.;
Mahmoodi, N. M. Graphene Oxide Nanosheet: Preparation and
Dye Removal from Binary System Colored Wastewater. Desalin.
Water Treat. 2015, 56, 2382−2394.
(225) Yan, H.; Tao, X.; Yang, Z.; Li, K.; Yang, H.; Li, A.; Cheng, R.
Effects of the Oxidation Degree of Graphene Oxide on the
Adsorption of Methylene Blue. J. Hazard. Mater. 2014, 268, 191−198.
(226) Bradder, P.; Ling, S. K.; Wang, S.; Liu, S. Dye Adsorption on
Layered Graphite Oxide. J. Chem. Eng. Data 2011, 56, 138−141.
(227) Sharma, P.; Saikia, B. K.; Das, M. R. Removal of Methyl Green
Dye Molecule from Aqueous System Using Reduced Graphene Oxide
as an Efficient Adsorbent: Kinetics, Isotherm and Thermodynamic
Parameters. Colloids Surf., A 2014, 457, 125−133.
(228) Tiwari, J. N.; Mahesh, K.; Le, N. H.; Kemp, K. C.; Timilsina,
R.; Tiwari, R. N.; Kim, K. S. Reduced Graphene Oxide-Based
Hydrogels for the Efficient Capture of Dye Pollutants from Aqueous
Solutions. Carbon 2013, 56, 173−182.
(229) Bai, S.; Shen, X.; Zhong, X.; Liu, Y.; Zhu, G.; Xu, X.; Chen, K.
One-Pot Solvothermal Preparation of Magnetic Reduced Graphene
Oxide-Ferrite Hybrids for Organic Dye Removal. Carbon 2012, 50,
2337−2346.
(230) Geng, Z.; Lin, Y.; Yu, X.; Shen, Q.; Ma, L.; Li, Z.; Pan, N.;
Wang, X. Highly Efficient Dye Adsorption and Removal: A Functional
Hybrid of Reduced Graphene Oxide−Fe3O4 Nanoparticles as an
Easily Regenerative Adsorbent. J. Mater. Chem. 2012, 22, 3527.
(231) Sun, H.; Cao, L.; Lu, L. Magnetite/Reduced Graphene Oxide
Nanocomposites: One Step Solvothermal Synthesis and Use as a
Novel Platform for Removal of Dye Pollutants. Nano Res. 2011, 4,
550−562.
(232) Wang, J.; Tang, B.; Tsuzuki, T.; Liu, Q.; Hou, X.; Sun, L.
Synthesis, Characterization and Adsorption Properties of Super-
paramagnetic Polystyrene/Fe3O4/Graphene Oxide. Chem. Eng. J.
2012, 204−205, 258−263.
(233) Xie, G.; Xi, P.; Liu, H.; Chen, F.; Huang, L.; Shi, Y.; Hou, F.;
Zeng, Z.; Shao, C.; Wang, J. A Facile Chemical Method to Produce
Superparamagnetic Graphene Oxide-Fe3O4 Hybrid Composite and
Its Application in the Removal of Dyes from Aqueous Solution. J.
Mater. Chem. 2012, 22, 1033−1039.
AD
Review
(234) Li, L.; Fan, L.; Duan, H.; Wang, X.; Luo, C. Magnetically
Separable Functionalized Graphene Oxide Decorated with Magnetic
Cyclodextrin as an Excellent Adsorbent for Dye Removal. RSC Adv.
2014, 4, 37114.
(235) Chen, Y.; Chen, L.; Bai, H.; Li, L. Graphene Oxide−chitosan
Composite Hydrogels as Broad-Spectrum Adsorbents for Water
Purification. J. Mater. Chem. A 2013, 1, 1992−2001.
(236) Fan, L.; Luo, C.; Li, X.; Lu, F.; Qiu, H.; Sun, M. Fabrication of
Novel Magnetic Chitosan Grafted with Graphene Oxide to Enhance
Adsorption Properties for Methyl Blue. J. Hazard. Mater. 2012, 215−
216, 272−279.
(237) Niu, Z.; Liu, L.; Zhang, L.; Chen, X. Porous Graphene
Materials for Water Remediation. Small 2014, 10, 3434−3441.
(238) Cukierman, A. L.; Platero, E.; Fernandez, M. E.; Bonelli, P. R.
Potentialities of Graphene-Based Nanomaterials for Wastewater
Treatment. Smart Mater. Waste Water Appl. 2016, 1−3.
(239) Song, X.; Lin, L.; Rong, M.; Wang, Y.; Xie, Z.; Chen, X.
Mussel-Inspired, Ultralight, Multifunctional 3D Nitrogen-Doped
Graphene Aerogel. Carbon 2014, 80, 174−182.
(240) Gonte, R. R.; K, B. Chemically Modified Polymer Beads for
Sorption of Gold from Waste Gold Solution. J. Hazard. Mater. 2012,
217−218, 447−451.
(241) Nabarlatz, D.; de Celis, J.; Bonelli, P.; Cukierman, A. L. Batch
and Dynamic Sorption of Ni(II) Ions by Activated Carbon Based on a
Native Lignocellulosic Precursor. J. Environ. Manage. 2012, 97, 109−
115.
(242) Kyzas, G. Z.; Deliyanni, E. A.; Matis, K. A. Graphene Oxide
and Its Application as an Adsorbent for Wastewater Treatment. J.
Chem. Technol. Biotechnol. 2014, 89, 196−205.
(243) Shi, G.; Araby, S.; Gibson, C. T.; Meng, Q.; Zhu, S.; Ma, J.
Graphene Platelets and Their Polymer Composites: Fabrication,
Structure, Properties, and Applications. Adv. Funct. Mater. 2018, 28,
1706705.
(244) Terzopoulou, Z.; Kyzas, G. Z.; Bikiaris, D. N. Recent
Advances in Nanocomposite Materials of Graphene Derivatives with
Polysaccharides. Materials 2015, 8, 652−683.
(245) Wan, C.; Li, J. Graphene Oxide/Cellulose Aerogels Nano-
composite: Preparation, Pyrolysis, and Application for Electro-
magnetic Interference Shielding. Carbohydr. Polym. 2016, 150, 172−
179.
(246) Shchipunov, Y. Bionanocomposites: Green Sustainable
Materials for the near Future. Pure Appl. Chem. 2012, 84, 1.
(247) Zhuang, Y.; Yu, F.; Chen, J.; Ma, J. Batch and Column
Adsorption of Methylene Blue by Graphene/Alginate Nanocompo-
site: Comparison of Single-Network and Double-Network Hydrogels.
J. Environ. Chem. Eng. 2016, 4, 147−156.
(248) Platero, E.; Fernandez, M. E.; Bonelli, P. R.; Cukierman, A. L.
Graphene Oxide/Alginate Beads as Adsorbents: Influence of the Load
and the Drying Method on Their Physicochemical-Mechanical
Properties and Adsorptive Performance. J. Colloid Interface Sci.
2017, 491, 1−12.
(249) Qi, Y.; Yang, M.; Xu, W.; He, S.; Men, Y. Natural
Polysaccharides-Modified Graphene Oxide for Adsorption of Organic
Dyes from Aqueous Solutions. J. Colloid Interface Sci. 2017, 486, 84−
96.
(250) Rinaudo, M. Chitin and Chitosan: Properties and
Applications. Prog. Polym. Sci. 2006, 31, 603−632.
(251) Hadwiger, L. A. Plant Science Review: Multiple Effects of
Chitosan on Plant Systems: Solid Science or Hype. Plant Sci. 2013,
208, 42−49.
(252) Ducheyne, P.; Healy, K. E.; Grainger, D. W.; Hutmacher, D.
W.; Kirkpatrick, C. J. Comprehensive Biomaterials; Ducheyne, P., Ed.;
Elsevier: Oxford, 2011; Vol. 1.
(253) Dai, J.; Huang, T.; Tian, S.; Xiao, Y.; Yang, J.; Zhang, N.;
Wang, Y.; Zhou, Z. High Structure Stability and Outstanding
Adsorption Performance of Graphene Oxide Aerogel Supported by
Polyvinyl Alcohol for Waste Water Treatment. Mater. Des. 2016, 107,
187−197.
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(254) Yang, Y.; Song, S.; Zhao, Z. Graphene Oxide (GO)/
Polyacrylamide (PAM) Composite Hydrogels as Efficient Cationic
Dye Adsorbents. Colloids Surf., A 2017, 513, 315−324.
(255) Ameen, S.; Seo, H.-K.; Shaheer Akhtar, M.; Shin, H. S. Novel
Graphene/Polyaniline Nanocomposites and Its Photocatalytic
Activity toward the Degradation of Rose Bengal Dye. Chem. Eng. J.
2012, 210, 220−228.
(256) Shi, Y.-C.; Wang, A.-J.; Wu, X.-L.; Chen, J.-R.; Feng, J.-J.
Green-Assembly of Three-Dimensional Porous Graphene Hydrogels
for Efficient Removal of Organic Dyes. J. Colloid Interface Sci. 2016,
484, 254−262.
(257) Zhang, J.-J.; Fang, S.-S.; Mei, J.-Y.; Zheng, G.-P.; Zheng, X.-C.;
Guan, X.-X. High-Efficiency Removal of Rhodamine B Dye in Water
Using g-C3N4 and TiO2 Co-Hybridized 3D Graphene Aerogel
Composites. Sep. Purif. Technol. 2018, 194, 96−103.
(258) Sui, Z.; Meng, Q.; Zhang, X.; Ma, R.; Cao, B. Green Synthesis
of Carbon Nanotube−graphene Hybrid Aerogels and Their Use as
Versatile Agents for Water Purification. J. Mater. Chem. 2012, 22,
8767.
(259) Feng, Z.; Simeone, A.; Odelius, K.; Hakkarainen, M. Biobased
Nanographene Oxide Creates Stronger Chitosan Hydrogels with
Improved Adsorption Capacity for Trace Pharmaceuticals. ACS
Sustainable Chem. Eng. 2017, 5, 11525−11535.
(260) Li, Y.; Du, Q.; Liu, T.; Sun, J.; Jiao, Y.; Xia, Y.; Xia, L.; Wang,
Z.; Zhang, W.; Wang, K.; et al. Equilibrium, Kinetic and
Thermodynamic Studies on the Adsorption of Phenol onto Graphene.
Mater. Res. Bull. 2012, 47, 1898−1904.
(261) Xu, J.; Wang, L.; Zhu, Y. Decontamination of Bisphenol A
from Aqueous Solution by Graphene Adsorption. Langmuir 2012, 28,
8418−8425.
(262) Pei, Z.; Li, L.; Sun, L.; Zhang, S.; Shan, X. Q.; Yang, S.; Wen,
B. Adsorption Characteristics of 1,2,4-Trichlorobenzene, 2,4,6-
Trichlorophenol, 2-Naphthol and Naphthalene on Graphene and
Graphene Oxide. Carbon 2013, 51, 156−163.
(263) Jiang, L. h.; Liu, Y. g.; Zeng, G. m.; Xiao, F. yu; Hu, X. j.; Hu,
X. j.; Wang, H.; Li, T. t.; Zhou, L.; Tan, X. f. Removal of 17β-Estradiol
by Few-Layered Graphene Oxide Nanosheets from Aqueous
Solutions: External Influence and Adsorption Mechanism. Chem.
Eng. J. 2016, 284, 93−102.
(264) Guo, H.; Jiao, T.; Zhang, Q.; Guo, W.; Peng, Q.; Yan, X.
Preparation of Graphene Oxide-Based Hydrogels as Efficient Dye
Adsorbents for Wastewater Treatment. Nanoscale Res. Lett. 2015, 10,
272.
(265) Yadav, R.; Balasubramanian, K. Metallization of Electrospun
PAN Nanofibers via Electroless Gold Plating. RSC Adv. 2015, 5,
24990−24996.
(266) Azizi, A.; Torabian, A.; Moniri, E.; Hassani, A. H.; Ahmad
Panahi, H. Adsorption Performance of Modified Graphene Oxide
Nanoparticles for the Removal of Toluene, Ethylbenzene, and Xylenes
from Aqueous Solution. Desalin. Water Treat. 2016, 57, 28806−
28821.
(267) Pourmand, S.; Abdouss, M.; Rashidi, A. M. Preparation of
Nanoporous Graphene via Nanoporous Zinc Oxide and Its
Application as a Nanoadsorbent for Benzene, Toluene and Xylenes
Removal. Int. J. Environ. Res. 2015, 9, 1269−1276.
(268) Zhao, G.; Jiang, L.; He, Y.; Li, J.; Dong, H.; Wang, X.; Hu, W.
Sulfonated Graphene for Persistent Aromatic Pollutant Management.
Adv. Mater. 2011, 23, 3959−3963.
(269) Zhao, G.; Li, J.; Wang, X. Kinetic and Thermodynamic Study
of 1-Naphthol Adsorption from Aqueous Solution to Sulfonated
Graphene Nanosheets. Chem. Eng. J. 2011, 173, 185−190.
(270) Yang, X.; Li, J.; Wen, T.; Ren, X.; Huang, Y.; Wang, X.
Adsorption of Naphthalene and Its Derivatives on Magnetic
Graphene Composites and the Mechanism Investigation. Colloids
Surf., A 2013, 422, 118−125.
(271) Yang, X.; Chen, C.; Li, J.; Zhao, G.; Ren, X.; Wang, X.
Graphene Oxide-Iron Oxide and Reduced Graphene Oxide-Iron
Oxide Hybrid Materials for the Removal of Organic and Inorganic
Pollutants. RSC Adv. 2012, 2, 8821.
AE
Review
(272) Hao, J.; Ji, L.; Li, C.; Hu, C.; Wu, K. Rapid, Efficient and
Economic Removal of Organic Dyes and Heavy Metals from
Wastewater by Zinc-Induced in-Situ Reduction and Precipitation of
Graphene Oxide. J. Taiwan Inst. Chem. Eng. 2018, 88, 137−145.
(273) Konicki, W.; Aleksandrzak, M.; Moszyński, D.; Mijowska, E.
Adsorption of Anionic Azo-Dyes from Aqueous Solutions onto
Graphene Oxide: Equilibrium, Kinetic and Thermodynamic Studies. J.
Colloid Interface Sci. 2017, 496, 188−200.
(274) Yang, S.-T. T.; Chen, S.; Chang, Y.; Cao, A.; Liu, Y.; Wang, H.
Removal of Methylene Blue from Aqueous Solution by Graphene
Oxide. J. Colloid Interface Sci. 2011, 359, 24−29.
(275) Ganesan, V.; Louis, C.; Damodaran, S. P. Graphene Oxide-
Wrapped Magnetite Nanoclusters: A Recyclable Functional Hybrid
for Fast and Highly Efficient Removal of Organic Dyes from
Wastewater. J. Environ. Chem. Eng. 2018, 6, 2176−2190.
(276) Das, T. R.; Patra, S.; Madhuri, R.; Sharma, P. K. Bismuth
Oxide Decorated Graphene Oxide Nanocomposites Synthesized via
Sonochemical Assisted Hydrothermal Method for Adsorption of
Cationic Organic Dyes. J. Colloid Interface Sci. 2018, 509, 82−93.
(277) Li, B.; Cao, H.; Yin, G.; Lu, Y.; Yin, J. Cu2O@reduced
Graphene Oxide Composite for Removal of Contaminants from
Water and Supercapacitors. J. Mater. Chem. 2011, 21, 10645.
(278) Li, B.; Cao, H.; Yin, G. Mg(OH)2@reduced Graphene Oxide
Composite for Removal of Dyes from Water. J. Mater. Chem. 2011,
21, 13765.
(279) Wu, Y.; Yang, F.; Liu, X.; Tan, G.; Xiao, D. Fabrication of N,
P-Codoped Reduced Graphene Oxide and Its Application for Organic
Dye Removal. Appl. Surf. Sci. 2018, 435, 281−289.
(280) Brillas, E.; Sirés, I.; Oturan, M. A. Electro-Fenton Process and
Related Electrochemical Technologies Based on Fenton’s Reaction
Chemistry. Chem. Rev. 2009, 109, 6570−6631.
(281) Nidheesh, P. V.; Gandhimathi, R. Trends in Electro-Fenton
Process for Water and Wastewater Treatment: An Overview.
Desalination 2012, 299, 1−15.
(282) Nguyen, L. V.; Busquets, R.; Ray, S.; Cundy, A. B. Graphene
Oxide-Based Degradation of Metaldehyde: Effective Oxidation
through a Modified Fenton’s Process. Chem. Eng. J. 2017, 307,
159−167.
(283) Wan, Z.; Wang, J. Ce-Fe-Reduced Graphene Oxide Nano-
composite as an Efficient Catalyst for Sulfamethazine Degradation in
Aqueous Solution. Environ. Sci. Pollut. Res. 2016, 23, 18542−18551.
(284) Zubir, N. A.; Yacou, C.; Motuzas, J.; Zhang, X.; Zhao, X. S.;
Diniz da Costa, J. C. The Sacrificial Role of Graphene Oxide in
Stabilising a Fenton-like Catalyst GO−Fe 3 O 4. Chem. Commun.
2015, 51, 9291−9293.
(285) Xiao, F.; Li, W.; Fang, L.; Wang, D. Synthesis of Akageneite
(Beta-FeOOH)/Reduced Graphene Oxide Nanocomposites for
Oxidative Decomposition of 2-Chlorophenol by Fenton-like Reaction.
J. Hazard. Mater. 2016, 308, 11−20.
(286) Wu, Q.; Zhang, H.; Zhou, L.; Bao, C.; Zhu, H.; Zhang, Y.
Synthesis and Application of RGO/CoFe2O4 Composite for
Catalytic Degradation of Methylene Blue on Heterogeneous
Fenton-like Oxidation. J. Taiwan Inst. Chem. Eng. 2016, 67, 484−494.
(287) Zhao, X.; Liu, S.; Huang, Y. Removing Organic Contaminants
by an Electro-Fenton System Constructed with Graphene Cathode.
Toxicol. Environ. Chem. 2016, 98, 530−539.
(288) Le, T. X. H.; Bechelany, M.; Lacour, S.; Oturan, N.; Oturan,
M. A.; Cretin, M. High Removal Efficiency of Dye Pollutants by
Electron-Fenton Process Using a Graphene Based Cathode. Carbon
2015, 94, 1003−1011.
(289) Zhang, G.; Zhou, Y.; Yang, F. FeOOH-Catalyzed Heteroge-
neous Electro-Fenton System upon Anthraquinone@Graphene
Nanohybrid Cathode in a Divided Electrolytic Cell: Catholyte-
Regulated Catalytic Oxidation Performance and Mechanism. J.
Electrochem. Soc. 2015, 162, H357−H365.
(290) Dong, C.; Lu, J.; Qiu, B.; Shen, B.; Xing, M.; Zhang, J.
Developing Stretchable and Graphene-Oxide-Based Hydrogel for the
Removal of Organic Pollutants and Metal Ions. Appl. Catal., B 2018,
222, 146−156.
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(291) Wang, Y.; Xie, Y.; Sun, H.; Xiao, J.; Cao, H.; Wang, S. Efficient
Catalytic Ozonation over Reduced Graphene Oxide for P-
Hydroxylbenzoic Acid (PHBA) Destruction: Active Site and
Mechanism. ACS Appl. Mater. Interfaces 2016, 8, 9710−9720.
(292) Li, G.; Lu, Y. T.; Lu, C.; Zhu, M. S.; Zhai, C. Y.; Du, Y. K.;
Yang, P. Efficient Catalytic Ozonation of Bisphenol-A over Reduced
Graphene Oxide Modified Sea Urchin-like Alpha-MnO2 Architec-
tures. J. Hazard. Mater. 2015, 294, 201−208.
(293) Bao, Q.; Hui, K. S.; Duh, J. G. Promoting Catalytic Ozonation
of Phenol over Graphene through Nitrogenation and Co3O4compo-
siting. J. Environ. Sci. (Beijing, China) 2016, 50, 38−48.
(294) Liao, G.; Zhu, D.; Zheng, J.; Yin, J.; Lan, B.; Li, L. Efficient
Mineralization of Bisphenol A by Photocatalytic Ozonation with
TiO2-Graphene Hybrid. J. Taiwan Inst. Chem. Eng. 2016, 67, 300−
305.
(295) Yin, J.; Liao, G.; Zhu, D.; Lu, P.; Li, L. Photocatalytic
Ozonation of Oxalic Acid by G-C3N4/Graphene Composites under
Simulated Solar Irradiation. J. Photochem. Photobiol., A 2016, 315,
138−144.
(296) Georgi, A.; Kopinke, F. D. Interaction of Adsorption and
Catalytic Reactions in Water Decontamination Processes: Part I.
Oxidation of Organic Contaminants with Hydrogen Peroxide
Catalyzed by Activated Carbon. Appl. Catal., B 2005, 58, 9−18.
(297) Antoniou, M. G.; de la Cruz, A. A.; Dionysiou, D. D.
Degradation of Microcystin-LR Using Sulfate Radicals Generated
through Photolysis, Thermolysis and e-Transfer Mechanisms. Appl.
Catal., B 2010, 96, 290−298.
(298) Shi, P.; Dai, X.; Zheng, H.; Li, D.; Yao, W.; Hu, C. Synergistic
Catalysis of Co3O4 and Graphene Oxide on Co3O4/GO Catalysts
for Degradation of Orange II in Water by Advanced Oxidation
Technology Based on Sulfate Radicals. Chem. Eng. J. 2014, 240, 264−
270.
(299) Zhou, X. J.; Shi, P. H.; Qin, Y. F.; Fan, J. C.; Min, Y. L.; Yao,
W. F. Synthesis of Co3O4/Graphene Composite Catalysts through
CTAB-Assisted Method for Orange II Degradation by Activation of
Peroxymonosulfate. J. Mater. Sci.: Mater. Electron. 2016, 27, 1020−
1030.
(300) Yan, J.; Gao, W.; Dong, M.; Han, L.; Qian, L.; Nathanail, C.
P.; Chen, M. Degradation of Trichloroethylene by Activated
Persulfate Using a Reduced Graphene Oxide Supported Magnetite
Nanoparticle. Chem. Eng. J. 2016, 295, 309−316.
(301) Chen, H.; Carroll, K. C. Metal-Free Catalysis of Persulfate
Activation and Organic-Pollutant Degradation by Nitrogen-Doped
Graphene and Aminated Graphene. Environ. Pollut. 2016, 215, 96−
102.
(302) Wang, P.; Ao, Y.; Wang, C.; Hou, J.; Qian, J. Enhanced
Photoelectrocatalytic Activity for Dye Degradation by Graphene-
Titania Composite Film Electrodes. J. Hazard. Mater. 2012, 223−224,
79−83.
(303) Zhai, C.; Zhu, M.; Bin, D.; Wang, H.; Du, Y.; Wang, C.; Yang,
P. Visible-Light-Assisted Electrocatalytic Oxidation of Methanol
Using Reduced Graphene Oxide Modified Pt Nanoflowers-TiO2
Nanotube Arrays. ACS Appl. Mater. Interfaces 2014, 6, 17753−17761.
(304) Catalyst. In IUPAC Compendium of Chemical Terminology;
IUPAC: Research Triagle Park, NC, 1997.
(305) Ghasemi, S.; Setayesh, S. R.; Habibi-Yangjeh, A.; Hormozi-
Nezhad, M. R.; Gholami, M. R. Assembly of CeO2−TiO2
Nanoparticles Prepared in Room Temperature Ionic Liquid on
Graphene Nanosheets for Photocatalytic Degradation of Pollutants. J.
Hazard. Mater. 2012, 199−200, 170−178.
(306) Putri, L. K.; Ng, B.-J.; Ong, W.-J.; Lee, H. W.; Chang, W. S.;
Chai, S.-P. Heteroatom Nitrogen- and Boron-Doping as a Facile
Strategy to Improve Photocatalytic Activity of Standalone Reduced
Graphene Oxide in Hydrogen Evolution. ACS Appl. Mater. Interfaces
2017, 9, 4558−4569.
(307) Byrne, C.; Subramanian, G.; Pillai, S. C. Recent Advances in
Photocatalysis for Environmental Applications. J. Environ. Chem. Eng.
2018, 6, 3531−3555.
AF
Review
(308) Wei, G.; Quan, X.; Chen, S.; Yu, H. Superpermeable Atomic-
Thin Graphene Membranes with High Selectivity. ACS Nano 2017,
11, 1920−1926.
(309) Chowdhury, S.; Balasubramanian, R. Graphene/Semiconduc-
tor Nanocomposites (GSNs) for Heterogeneous Photocatalytic
Decolorization of Wastewaters Contaminated with Synthetic Dyes:
A Review. Appl. Catal., B 2014, 160−161, 307−324.
(310) An, X.; Yu, J. C. Graphene-Based Photocatalytic Composites.
RSC Adv. 2011, 1, 1426.
(311) Li, X.; Yu, J.; Wageh, S.; Al-Ghamdi, A. A.; Xie, J. Graphene in
Photocatalysis: A Review. Small 2016, 12, 6640−6696.
(312) Fujishima, A.; Honda, K. Electrochemical Photolysis of Water
at a Semiconductor Electrode. Nature 1972, 238, 37−38.
(313) Zhao, D.; Sheng, G.; Chen, C.; Wang, X. Enhanced
Photocatalytic Degradation of Methylene Blue under Visible
Irradiation on Graphene@TiO2 Dyade Structure. Appl. Catal., B
2012, 111−112, 303−308.
(314) Š tengl, V.; Bakardjieva, S.; Grygar, T. M.; Bludská, J.;
Kormunda, M. TiO2-Graphene Oxide Nanocomposite as Advanced
Photocatalytic Materials. Chem. Cent. J. 2013, 7, 1−12.
(315) Lui, G.; Liao, J.-Y.; Duan, A.; Zhang, Z.; Fowler, M.; Yu, A.
Graphene-Wrapped Hierarchical TiO2 Nanoflower Composites with
Enhanced Photocatalytic Performance. J. Mater. Chem. A 2013, 1,
12255.
(316) Yin, X.; Zhang, H.; Xu, P.; Han, J.; Li, J.; He, M. Simultaneous
N-Doping of Reduced Graphene Oxide and TiO2 in the Composite
for Visible Light Photodegradation of Methylene Blue with Enhanced
Performance. RSC Adv. 2013, 3, 18474.
(317) Liu, S.; Sun, H.; Liu, S.; Wang, S. Graphene Facilitated Visible
Light Photodegradation of Methylene Blue over Titanium Dioxide
Photocatalysts. Chem. Eng. J. 2013, 214, 298−303.
(318) Wang, P.; Zhai, Y.; Wang, D.; Dong, S. Synthesis of Reduced
Graphene Oxide-Anatase TiO2 Nanocomposite and Its Improved
Photo-Induced Charge Transfer Properties. Nanoscale 2011, 3, 1640.
(319) Liu, J.; Wang, Z.; Liu, L.; Chen, W. Reduced Graphene Oxide
as Capturer of Dyes and Electrons during Photocatalysis: Surface
Wrapping and Capture Promoted Efficiency. Phys. Chem. Chem. Phys.
2011, 13, 13216.
(320) Zhang, J.; Xiong, Z.; Zhao, X. S. Graphene−metal−oxide
Composites for the Degradation of Dyes under Visible Light
Irradiation. J. Mater. Chem. 2011, 21, 3634.
(321) Ng, Y. H.; Lightcap, I. V.; Goodwin, K.; Matsumura, M.;
Kamat, P. V. To What Extent Do Graphene Scaffolds Improve the
Photovoltaic and Photocatalytic Response of TiO2 Nanostructured
Films? J. Phys. Chem. Lett. 2010, 1, 2222−2227.
(322) Neppolian, B.; Bruno, A.; Bianchi, C. L.; Ashokkumar, M.
Graphene Oxide Based Pt-TiO2 Photocatalyst: Ultrasound Assisted
Synthesis, Characterization and Catalytic Efficiency. Ultrason.
Sonochem. 2012, 19, 9−15.
(323) Liu, Z.; Robinson, J. T.; Sun, X.; Dai, H. PEGylated
Nanographene Oxide for Delivery of Water-Insoluble Cancer Drugs.
J. Am. Chem. Soc. 2008, 130, 10876−10877.
(324) Sakthivel, S.; Kisch, H. Daylight Photocatalysis by Carbon-
Modified Titanium Dioxide. Angew. Chem., Int. Ed. 2003, 42, 4908−
4911.
(325) Wang, X.; Zhi, L.; Müllen, K. Transparent, Conductive
Graphene Electrodes for Dye-Sensitized Solar Cells. Nano Lett. 2008,
8, 323−327.
(326) Manga, K. K.; Zhou, Y.; Yan, Y.; Loh, K. P. Multilayer Hybrid
Films Consisting of Alternating Graphene and Titania Nanosheets
with Ultrafast Electron Transfer and Photoconversion Properties. Adv.
Funct. Mater. 2009, 19, 3638−3643.
(327) Li, J.; Zhou, S. l.; Hong, G.-B.; Chang, C.-T. Hydrothermal
Preparation of P25−graphene Composite with Enhanced Adsorption
and Photocatalytic Degradation of Dyes. Chem. Eng. J. 2013, 219,
486−491.
(328) Li, F.; Du, P.; Liu, W.; Li, X.; Ji, H.; Duan, J.; Zhao, D.
Hydrothermal Synthesis of Graphene Grafted Titania/Titanate
Nanosheets for Photocatalytic Degradation of 4-Chlorophenol:
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Solar-Light-Driven Photocatalytic Activity and Computational Chem-
istry Analysis. Chem. Eng. J. 2018, 331, 685−694.
(329) Gao, Y.; Pu, X.; Zhang, D.; Ding, G.; Shao, X.; Ma, J.
Combustion Synthesis of Graphene Oxide−TiO2 Hybrid Materials
for Photodegradation of Methyl Orange. Carbon 2012, 50, 4093−
4101.
(330) Zhang, D.; Pu, X.; Ding, G.; Shao, X.; Gao, Y.; Liu, J.; Gao,
M.; Li, Y. Two-Phase Hydrothermal Synthesis of TiO2−graphene
Hybrids with Improved Photocatalytic Activity. J. Alloys Compd. 2013,
572, 199−204.
(331) Anjusree, G. S.; Nair, A. S.; Nair, S. V.; Vadukumpully, S.
One-Pot Hydrothermal Synthesis of TiO2/Graphene Nanocompo-
sites for Enhanced Visible Light Photocatalysis and Photovoltaics.
RSC Adv. 2013, 3, 12933.
(332) Khalid, N. R.; Ahmed, E.; Hong, Z.; Sana, L.; Ahmed, M.
Enhanced Photocatalytic Activity of Graphene−TiO2 Composite
under Visible Light Irradiation. Curr. Appl. Phys. 2013, 13, 659−663.
(333) Jiang, G.; Lin, Z.; Chen, C.; Zhu, L.; Chang, Q.; Wang, N.;
Wei, W.; Tang, H. TiO2 Nanoparticles Assembled on Graphene
Oxide Nanosheets with High Photocatalytic Activity for Removal of
Pollutants. Carbon 2011, 49, 2693−2701.
(334) Pastrana-Martínez, L. M.; Morales-Torres, S.; Kontos, A. G.;
Moustakas, N. G.; Faria, J. L.; Doña-Rodríguez, J. M.; Falaras, P.
TiO2, Surface Modified TiO2 and Graphene Oxide-TiO2 Photo-
catalysts for Degradation of Water Pollutants under near-UV/Vis and
Visible Light. Chem. Eng. J. 2013, 224, 17−23.
(335) Pu, X.; Zhang, D.; Gao, Y.; Shao, X.; Ding, G.; Li, S.; Zhao, S.
One-Pot Microwave-Assisted Combustion Synthesis of Graphene
Oxide−TiO2 Hybrids for Photodegradation of Methyl Orange. J.
Alloys Compd. 2013, 551, 382−388.
(336) Morales-Torres, S.; Pastrana-Martínez, L. M.; Figueiredo, J.
L.; Faria, J. L.; Silva, A. M. T. Graphene Oxide-P25 Photocatalysts for
Degradation of Diphenhydramine Pharmaceutical and Methyl Orange
Dye. Appl. Surf. Sci. 2013, 275, 361−368.
(337) Pastrana-Martínez, L. M.; Morales-Torres, S.; Papageorgiou, S.
K.; Katsaros, F. K.; Romanos, G. E.; Figueiredo, J. L.; Faria, J. L.;
Falaras, P.; Silva, A. M. T. Photocatalytic Behaviour of Nanocarbon−
TiO2 Composites and Immobilization into Hollow Fibres. Appl.
Catal., B 2013, 142−143, 101−111.
(338) Nakata, K.; Fujishima, A. TiO2 Photocatalysis: Design and
Applications. J. Photochem. Photobiol., C 2012, 13, 169−189.
(339) Nakata, K.; Ochiai, T.; Murakami, T.; Fujishima, A.
Photoenergy Conversion with TiO2 Photocatalysis: New Materials
and Recent Applications. Electrochim. Acta 2012, 84, 103−111.
(340) Leary, R.; Westwood, A. Carbonaceous Nanomaterials for the
Enhancement of TiO2 Photocatalysis. Carbon 2011, 49, 741−772.
(341) Khalid, N. R.; Hong, Z.; Ahmed, E.; Zhang, Y.; Chan, H.;
Ahmad, M. Synergistic Effects of Fe and Graphene on Photocatalytic
Activity Enhancement of TiO2 under Visible Light. Appl. Surf. Sci.
2012, 258, 5827−5834.
(342) Di Paola, A.; García-López, E.; Marcì, G.; Palmisano, L. A
Survey of Photocatalytic Materials for Environmental Remediation. J.
Hazard. Mater. 2012, 211−212, 3−29.
(343) Dashairya, L.; Sharma, M.; Basu, S.; Saha, P. SnS2/RGO
Based Nanocomposite for Efficient Photocatalytic Degradation of
Toxic Industrial Dyes under Visible-Light Irradiation. J. Alloys Compd.
2019, 774, 625−636.
(344) Li, K.; Huang, Y.; Yan, L.; Dai, Y.; Xue, K.; Guo, H.; Huang,
Z.; Xiong, J. Simulated Sunlight Photodegradation of Aqueous
Atrazine and Rhodamine B Catalyzed by the Ordered Mesoporous
Graphene−titania/Silica Composite Material. Catal. Commun. 2012,
18, 16−20.
(345) Li, K.; Chen, T.; Yan, L.; Dai, Y.; Huang, Z.; Guo, H.; Jiang,
L.; Gao, X.; Xiong, J.; Song, D. Synthesis of Mesoporous Graphene
and Tourmaline Co-Doped Titania Composites and Their Photo-
catalytic Activity towards Organic Pollutant Degradation and
Eutrophic Water Treatment. Catal. Commun. 2012, 28, 196−201.
(346) Shi, M.; Shen, J.; Ma, H.; Li, Z.; Lu, X.; Li, N.; Ye, M.
Preparation of Graphene−TiO2 Composite by Hydrothermal
AG
Review
Method from Peroxotitanium Acid and Its Photocatalytic Properties.
Colloids Surf., A 2012, 405, 30−37.
(347) Hou, J.; Yang, C.; Wang, Z.; Jiao, S.; Zhu, H. Bi2O3 Quantum
Dots Decorated Anatase TiO2 Nanocrystals with Exposed {0 0 1}
Facets on Graphene Sheets for Enhanced Visible-Light Photocatalytic
Performance. Appl. Catal., B 2013, 129, 333−341.
(348) Xu, F.; Yuan, Y.; Wu, D.; Zhao, M.; Gao, Z.; Jiang, K.
Synthesis of ZnO/Ag/Graphene Composite and Its Enhanced
Photocatalytic Efficiency. Mater. Res. Bull. 2013, 48, 2066−2070.
(349) Huang, W.; Shu, Z.; Shi, J. Assembly of Ti/Ce Metal-to-Metal
Charge-Transfer Moieties on a Graphene Oxide Surface and Their
Catalytic Activity. Catal. Commun. 2013, 33, 24−28.
(350) Liu, J.; Liu, L.; Bai, H.; Wang, Y.; Sun, D. D. Gram-Scale
Production of Graphene Oxide−TiO2 Nanorod Composites:
Towards High-Activity Photocatalytic Materials. Appl. Catal., B
2011, 106, 76−82.
(351) Ghasemi, S.; Esfandiar, A.; Rahman Setayesh, S.; Habibi-
Yangjeh, A.; Iraji zad, A.; Gholami, M. R. Synthesis and Character-
ization of TiO2−graphene Nanocomposites Modified with Noble
Metals as a Photocatalyst for Degradation of Pollutants. Appl. Catal.,
A 2013, 462−463, 82−90.
(352) Pang, Y. L.; Tee, S. F.; Lim, S.; Abdullah, A. Z.; Ong, H. C.;
Wu, C.-H.; Chong, W. C.; Mohammadu, A. W.; Mahmoudi, E.
Enhancement of Photocatalytic Degradation of Organic Dyes Using
ZnO Decorated on Reduced Graphene Oxide (RGO). Desalin.
WATER Treat. 2018, 108, 311−321.
(353) Xu, T.; Zhang, L.; Cheng, H.; Zhu, Y. Significantly Enhanced
Photocatalytic Performance of ZnO via Graphene Hybridization and
the Mechanism Study. Appl. Catal., B 2011, 101, 382−387.
(354) Ameen, S.; Shaheer Akhtar, M.; Seo, H.-K.; Shik Shin, H.
Advanced ZnO−graphene Oxide Nanohybrid and Its Photocatalytic
Applications. Mater. Lett. 2013, 100, 261−265.
(355) Zhang, Y.; Chen, Z.; Liu, S.; Xu, Y.-J. Size Effect Induced
Activity Enhancement and Anti-Photocorrosion of Reduced Gra-
phene Oxide/ZnO Composites for Degradation of Organic Dyes and
Reduction of Cr(VI) in Water. Appl. Catal., B 2013, 140−141, 598−
607.
(356) Mohamed, H. H. Sonochemical Synthesis of ZnO Hollow
Microstructure/Reduced Graphene Oxide for Enhanced Sunlight
Photocatalytic Degradation of Organic Pollutants. J. Photochem.
Photobiol., A 2018, 353, 401−408.
(357) Sun, L.; Shao, R.; Tang, L.; Chen, Z. Synthesis of ZnFe2O4/
ZnO Nanocomposites Immobilized on Graphene with Enhanced
Photocatalytic Activity under Solar Light Irradiation. J. Alloys Compd.
2013, 564, 55−62.
(358) He, G. Y.; Huang, J.; Liu, W. F.; Wang, X.; Chen, H. Q.; Sun,
X. Q. ZnO−Bi 2 O 3 /Graphene Oxide Photocatalyst with High
Photocatalytic Performance under Visible Light. Mater. Technol. 2012,
27, 278−283.
(359) Liu, X.; Pan, L.; Lv, T.; Sun, Z.; Sun, C. Q. Visible Light
Photocatalytic Degradation of Dyes by Bismuth Oxide-Reduced
Graphene Oxide Composites Prepared via Microwave-Assisted
Method. J. Colloid Interface Sci. 2013, 408, 145−150.
(360) Yu, J.; Yue, L.; Liu, S.; Huang, B.; Zhang, X. Hydrothermal
Preparation and Photocatalytic Activity of Mesoporous Au−TiO2
Nanocomposite Microspheres. J. Colloid Interface Sci. 2009, 334, 58−
64.
(361) Yu, C.; Li, G.; Kumar, S.; Kawasaki, H.; Jin, R. Stable Au 25
(SR) 18 /TiO 2 Composite Nanostructure with Enhanced Visible
Light Photocatalytic Activity. J. Phys. Chem. Lett. 2013, 4, 2847−2852.
(362) Low, J.; Yu, J.; Li, Q.; Cheng, B. Enhanced Visible-Light
Photocatalytic Activity of Plasmonic Ag and Graphene Co-Modified
Bi 2 WO 6 Nanosheets. Phys. Chem. Chem. Phys. 2014, 16, 1111−
1120.
(363) Yu, J.; Xiong, J.; Cheng, B.; Liu, S. Fabrication and
Characterization of Ag−TiO2Multiphase Nanocomposite Thin
Films with Enhanced Photocatalytic Activity. Appl. Catal., B 2005,
60, 211−221.
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
(364) Nie, L.; Zhou, P.; Yu, J.; Jaroniec, M. Deactivation and
Regeneration of Pt/TiO2 Nanosheet-Type Catalysts with Exposed (0
0 1) Facets for Room Temperature Oxidation of Formaldehyde. J.
Mol. Catal. A: Chem. 2014, 390, 7−13.
(365) Song, S.; Cheng, B.; Wu, N.; Meng, A.; Cao, S.; Yu, J.
Structure Effect of Graphene on the Photocatalytic Performance of
Plasmonic Ag/Ag2CO3-RGO for Photocatalytic Elimination of
Pollutants. Appl. Catal., B 2016, 181, 71−78.
(366) Liu, L.; Liu, J.; Sun, D. D. Graphene Oxide Enwrapped
Ag3PO4 Composite: Towards a Highly Efficient and Stable Visible-
Light-Induced Photocatalyst for Water Purification. Catal. Sci.
Technol. 2012, 2, 2525.
(367) Gao, P.; Liu, J.; Sun, D. D.; Ng, W. Graphene Oxide−CdS
Composite with High Photocatalytic Degradation and Disinfection
Activities under Visible Light Irradiation. J. Hazard. Mater. 2013,
250−251, 412−420.
(368) Herring, N. P.; Almahoudi, S. H.; Olson, C. R.; El-Shall, M. S.
Enhanced Photocatalytic Activity of ZnO−graphene Nanocomposites
Prepared by Microwave Synthesis. J. Nanopart. Res. 2012, 14, 1277.
(369) Pant, H. R.; Park, C. H.; Pokharel, P.; Tijing, L. D.; Lee, D. S.;
Kim, C. S. ZnO Micro-Flowers Assembled on Reduced Graphene
Sheets with High Photocatalytic Activity for Removal of Pollutants.
Powder Technol. 2013, 235, 853−858.
(370) Wang, J.; Wang, P.; Cao, Y.; Chen, J.; Li, W.; Shao, Y.; Zheng,
Y.; Li, D. A High Efficient Photocatalyst Ag3VO4/TiO2/Graphene
Nanocomposite with Wide Spectral Response. Appl. Catal., B 2013,
136−137, 94−102.
(371) Zhou, M.; Yan, J.; Cui, P. Synthesis and Enhanced
Photocatalytic Performance of WO3 Nanorods @ Graphene Nano-
composites. Mater. Lett. 2012, 89, 258−261.
(372) Huang, R.; Ge, H.; Lin, X.; Guo, Y.; Yuan, R.; Fu, X.; Li, Z.
Facile One-Pot Preparation of α-SnWO 4 /Reduced Graphene Oxide
(RGO) Nanocomposite with Improved Visible Light Photocatalytic
Activity and Anode Performance for Li-Ion Batteries. RSC Adv. 2013,
3, 1235−1242.
(373) Niu, J.; Dai, P.; Zhang, Q.; Yao, B.; Yu, X. Microwave-Assisted
Solvothermal Synthesis of Novel Hierarchical BiOI/RGO Composites
for Efficient Photocatalytic Degardation of Organic Pollutants. Appl.
Surf. Sci. 2018, 430, 165−175.
(374) Fu, Y.; Sun, X.; Wang, X. BiVO4−graphene Catalyst and Its
High Photocatalytic Performance under Visible Light Irradiation.
Mater. Chem. Phys. 2011, 131, 325−330.
(375) Song, S.; Gao, W.; Wang, X.; Li, X.; Liu, D.; Xing, Y.; Zhang,
H. Microwave-Assisted Synthesis of BiOBr/Graphene Nanocompo-
sites and Their Enhanced Photocatalytic Activity. Dalt. Trans. 2012,
41, 10472.
(376) Liu, H.; Cao, W.-R.; Su, Y.; Chen, Z.; Wang, Y. Bismuth
Oxyiodide−graphene Nanocomposites with High Visible Light
Photocatalytic Activity. J. Colloid Interface Sci. 2013, 398, 161−167.
(377) Liu, Z.; Xu, W.; Fang, J.; Xu, X.; Wu, S.; Zhu, X.; Chen, Z.
Decoration of BiOI Quantum Size Nanoparticles with Reduced
Graphene Oxide in Enhanced Visible-Light-Driven Photocatalytic
Studies. Appl. Surf. Sci. 2012, 259, 441−447.
(378) Tu, X.; Luo, S.; Chen, G.; Li, J. One-Pot Synthesis,
Characterization, and Enhanced Photocatalytic Activity of a BiOBr-
Graphene Composite. Chem. - Eur. J. 2012, 18, 14359−14366.
(379) Min, Y.; Zhang, F.-J.; Zhao, W.; Zheng, F.; Chen, Y.; Zhang,
Y. Hydrothermal Synthesis of Nanosized Bismuth Niobate and
Enhanced Photocatalytic Activity by Coupling of Graphene Sheets.
Chem. Eng. J. 2012, 209, 215−222.
(380) Wang, P.; Ao, Y.; Wang, C.; Hou, J.; Qian, J. A One-Pot
Method for the Preparation of Graphene−Bi2MoO6 Hybrid
Photocatalysts That Are Responsive to Visible-Light and Have
Excellent Photocatalytic Activity in the Degradation of Organic
Pollutants. Carbon 2012, 50, 5256−5264.
(381) Zhang, Q.; Tian, C.; Wu, A.; Tan, T.; Sun, L.; Wang, L.; Fu,
H. A Facile One-Pot Route for the Controllable Growth of Small
Sized and Well-Dispersed ZnO Particles on GO-Derived Graphene. J.
Mater. Chem. 2012, 22, 11778.
AH
Review
(382) Chandra, S.; Das, P.; Bag, S.; Bhar, R.; Pramanik, P. Mn2O3
Decorated Graphene Nanosheet: An Advanced Material for the
Photocatalytic Degradation of Organic Dyes. Mater. Sci. Eng., B 2012,
177, 855−861.
(383) Pan, S.; Liu, X. CdS−Graphene Nanocomposite: Synthesis,
Adsorption Kinetics and High Photocatalytic Performance under
Visible Light Irradiation. New J. Chem. 2012, 36, 1781.
(384) An, X.; Yu, J. C.; Wang, F.; Li, C.; Li, Y. One-Pot Synthesis of
In2S3 Nanosheets/Graphene Composites with Enhanced Visible-
Light Photocatalytic Activity. Appl. Catal., B 2013, 129, 80−88.
(385) Khan, Z.; Chetia, T. R.; Vardhaman, A. K.; Barpuzary, D.;
Sastri, C. V.; Qureshi, M. Visible Light Assisted Photocatalytic
Hydrogen Generation and Organic Dye Degradation by CdS−metal
Oxide Hybrids in Presence of Graphene Oxide. RSC Adv. 2012, 2,
12122.
(386) Zhao, G.; Li, C.; Wu, X.; Yu, J.; Jiang, X.; Hu, W.; Jiao, F.
Reduced Graphene Oxide Modified NiFe-Calcinated Layered Double
Hydroxides for Enhanced Photocatalytic Removal of Methylene Blue.
Appl. Surf. Sci. 2018, 434, 251−259.
(387) Chen, Y.; Tang, Y.; Luo, S.; Liu, C.; Li, Y. TiO2 Nanotube
Arrays Co-Loaded with Au Nanoparticles and Reduced Graphene
Oxide: Facile Synthesis and Promising Photocatalytic Application. J.
Alloys Compd. 2013, 578, 242−248.
(388) Luo, G.; Jiang, X.; Li, M.; Shen, Q.; Zhang, L.; Yu, H. Facile
Fabrication and Enhanced Photocatalytic Performance of Ag/AgCl/
RGO Heterostructure Photocatalyst. ACS Appl. Mater. Interfaces
2013, 5, 2161−2168.
(389) Wang, C. B.; Zhou, J. W.; Chu, L. L.; Liu, J. F. Study on
Photocatalytic Performance of Ag - AgBr/RGO. Adv. Mater. Res.
2013, 662, 163−166.
(390) He, G.; Qian, M.; Sun, X.; Chen, Q.; Wang, X.; Chen, H.
Graphene Sheets-Based Ag@Ag3PO4 Heterostructure for Enhanced
Photocatalytic Activity and Stability under Visible Light. Powder
Technol. 2013, 246, 278−283.
(391) Wang, M.; Huang, J.; Tong, Z.; Li, W.; Chen, J. Reduced
Graphene Oxide−cuprous Oxide Composite via Facial Deposition for
Photocatalytic Dye-Degradation. J. Alloys Compd. 2013, 568, 26−35.
(392) Chen, G.; Sun, M.; Wei, Q.; Zhang, Y.; Zhu, B.; Du, B.
Ag3PO4/Graphene-Oxide Composite with Remarkably Enhanced
Visible-Light-Driven Photocatalytic Activity toward Dyes in Water. J.
Hazard. Mater. 2013, 244−245, 86−93.
(393) Hassani, A.; Ç elikdaǧ, G.; Eghbali, P.; Sevim, M.; Karaca, S.;
Metin, Ö . Heterogeneous Sono-Fenton-like Process Using Magnetic
Cobalt Ferrite-Reduced Graphene Oxide (CoFe2O4-RGO) Nano-
composite for the Removal of Organic Dyes from Aqueous Solution.
Ultrason. Sonochem. 2018, 40, 841−852.
(394) Li, X.; Zhang, T.; Gu, S.; Kang, S.-Z.; Li, G.; Mu, J. Reduced
Graphene Oxide/Potassium Niobate Composite Nanoscrolls with
Enhanced Photocatalytic Activity for Dye Degradation. Sep. Purif.
Technol. 2013, 108, 139−142.
(395) Fu, Y.; Chen, H.; Sun, X.; Wang, X. Combination of Cobalt
Ferrite and Graphene: High-Performance and Recyclable Visible-
Light Photocatalysis. Appl. Catal., B 2012, 111−112, 280−287.
(396) Raghavan, N.; Thangavel, S.; Sivalingam, Y.; Venugopal, G.
Investigation of Photocatalytic Performances of Sulfur Based Reduced
Graphene Oxide-TiO 2 Nanohybrids. Appl. Surf. Sci. 2018, 449, 1−7.
(397) Zhang, L.; Shi, Y.; Wang, L.; Hu, C. AgBr-Wrapped Ag
Chelated on Nitrogen-Doped Reduced Graphene Oxide for Water
Purification under Visible Light. Appl. Catal., B 2018, 220, 118−125.
(398) Zhang, Y.; Cui, W.; An, W.; Liu, L.; Liang, Y.; Zhu, Y.
Combination of Photoelectrocatalysis and Adsorption for Removal of
Bisphenol A over TiO2-Graphene Hydrogel with 3D Network
Structure. Appl. Catal., B 2018, 221, 36−46.
(399) Zhu, J.; Zhu, Z.; Zhang, H.; Lu, H.; Zhang, W.; Qiu, Y.; Zhu,
L.; Küppers, S. Calcined Layered Double Hydroxides/Reduced
Graphene Oxide Composites with Improved Photocatalytic Degra-
dation of Paracetamol and Efficient Oxidation-Adsorption of As(III).
Appl. Catal., B 2018, 225, 550−562.
DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Review

(400) Nie, Y.-C.; Yu, F.; Wang, L.-C.; Xing, Q.-J.; Liu, X.; Pei, Y.;
Zou, J.-P.; Dai, W.-L.; Li, Y.; Suib, S. L. Photocatalytic Degradation of
Organic Pollutants Coupled with Simultaneous Photocatalytic H2
Evolution over Graphene Quantum Dots/Mn-N-TiO2/g-C3N4
Composite Catalysts: Performance and Mechanism. Appl. Catal., B
2018, 227, 312−321.
(401) Xie, L.; Ni, J.; Tang, B.; He, G.; Chen, H. A Self-Assembled
2D/2D-Type Protonated Carbon Nitride-Modified Graphene Oxide
Nanocomposite with Improved Photocatalytic Activity. Appl. Surf. Sci.
2018, 434, 456−463.
(402) Li, Y.; Wu, X.; Ho, W.; Lv, K.; Li, Q.; Li, M.; Lee, S. C.
Graphene-Induced Formation of Visible-Light-Responsive SnO2-
Zn2SnO4 Z-Scheme Photocatalyst with Surface Vacancy for the
Enhanced Photoreactivity towards NO and Acetone Oxidation. Chem.
Eng. J. 2018, 336, 200−210.

AI DOI: 10.1021/acs.jced.8b01057
J. Chem. Eng. Data XXXX, XXX, XXX−XXX