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CONCEPT
Introduction
Two-dimensional (2D) nanostructures, which possess a high
degree of anisotropy with nanoscale thickness and infinite
length in other dimensions, have attracted tremendous attention due to their unique morphology associated with
prominent physical properties and potential applications,
such as in electronics, sensing, catalysis, energy storage, and
conversion.[1] Various organic and inorganic 2D nanostructures, such as porphyrin, C60, titanium oxide, and transitionmetal nanosheets, have been reported recently.[2] In general,
there are two strategies to prepare 2D nanosheets. One is
the top-down method, which typically involves the delamination of bulk materials with layered structures;[2a,b] however, the bottleneck of this method is the extremely low yield
of product. The other method is based on the bottom-up
fabrication, in which the nanosheets can be obtained from
the anisotropic assembly of inorganic or organic precursors
in a 2D manner. In the past few years, the latter approach
has shown great promise for the convenient and reproducible fabrication of 2D nanomaterials with a large diversity of
functions.[2ci]
The discovery of graphene has triggered intensive research work in the last few years, since this one-atom-thick
hexagonal carbon sheet possesses unique 2D morphology
and intriguing physical properties.[1] It is undeniable that the
pristine defect-free graphene exhibits unprecedented high
[a] Dr. D. Wu, Dr. F. Zhang, Dr. P. Liu, Dr. X. Feng
College of Chemistry and Chemical Engineering
Shanghai Jiao Tong University, 800 Dongchuan Road
Shanghai, 200240 (P. R. China)
[b] Dr. X. Feng
Max Planck Institute for Polymer Research, Ackermannweg 10
55128, Mainz (Germany)
E-mail: feng@mpip-mainz.mpg.de
charge carrier mobility, mechanical robustness, thermal conductivity, and so on.[1] Nevertheless, the cost-effective synthesis of high-quality graphene on a large scale, both by
physical and chemical means, remains a major challenge.
Graphite oxide, readily accessible by the oxidation of graphite with strong acid and oxidant, has been known for more
than hundred years.[3] The exfoliation of graphite oxide generates single-layer graphene oxide (GO), which can be further subjected to chemical reduction to produce reduced
graphene oxide (RGO) with partial recovery of its electrical
properties.[4] In this regard, GO, RGO, and their functional
derivatives, generally termed as chemically modified graphenes (CMGs),[5] have been attractive to chemists and material
scientists due to their easy accessibility and processability.[6]
Due to the termination of hydroxyl and carboxyl groups
in the plane or at the edge, CMGs are negatively charged
and thus have good dispersibility in aqueous solution, given
that the steric hindrance and electrostatic repulsion caused
by these oxygen-containing substitutions can effectively prevent the re-aggregation of CMGs. In addition, these oxygenbased functional groups can serve as anchor points to
couple with organic and inorganic species through covalent
or non-covalent interactions. Similar to pristine graphene,
CMGs also possess 2D character with a large aspect ratio,
high specific surface area (theoretical value of 2600 m2 g 1
for graphene), and excellent flexibility. Therefore, these
unique characteristics qualify CMGs as a promising template for the anisotropic assembly with organic or inorganic
components in solution. Towards this end, 2D sandwich-like
nanocomposites incorporated with graphene sheets have
been successfully synthesized[7] that have a large aspect
ratio, high surface area, and high monodispersity. The graphene sheet in 2D nanocomposites may thus offer an additional platform for the fast transportation of charge carriers,
which can lead to enhanced performance in various applications, such as catalysis, sensing, supercapacitors, batteries,
and fuel cells. In this Concept article, we will summarize different bottom-up approaches for the fabrication of 2D graphene-based nanosheets. These 2D nanosheets should have
individual dispersibility and can be distinctly visualized by
microscopy technology. Nanocomposites of graphene that
suffer from strong aggregation will not be included. The typical physical properties and potential applications of 2D graphene-based materials will be discussed in context. It is anticipated that this Concept article will arouse more attention
towards graphene-based 2D nanomaterials and encourage
future work to push forward the advancement of this emerging area.
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functional groups. Therefore, the introduction of specific organic species at the edge or on the in-plane surface of
CMGs can be achieved through covalent bonds or noncovalent forces, such as aromatic and ionic interactions. In this
section, 2D nanocomposites of CMGs with organic components will be preferentially discussed according to the different driving forces for their formation.
Noncovalent interactions: Owing to the pp interactions between aromatic units, aromatic molecules such as polycyclic
aromatic hydrocarbons (PAHs) and conjugated polymers
have the capability to directly intercalate with CMGs. To
keep the good dispersibility of resultant materials in aqueous solution, aromatic molecules containing anionic groups
are frequently employed to exert the electrostatic repulsion
and thus prevent the re-aggregation of the graphene sheets.
Recently, we have reported the fabrication of 2D nanocomposites of RGO with the sodium salt of pyrene-1-sulfonic
acid (PyS, electron donor, Figure 1) or the diasodium salt of
3,4,9,10-perylenetetracarboxylic diimide bisbenzenesulfonic
acid (PDI, electron acceptor, Figure 1).[8] Both PyS and PDI
have extended aromatic backbones that can strongly immobilize them onto the graphene surface by means of pp interactions. In addition, the negative charges on both molecules can stabilize the graphene dispersion through electrostatic repulsion forces. After the suspension was deposited
on mica, mainly single or double layer RGO sheets were attained. Atomic force microscopy (AFM) investigations indi-
Figure 1. a) Schematic illustration of aqueous dispersions of 2D nanocomposites of RGO-PyS or RGO-PDI. AFM images and cross-section
graphs of b) RGO-Pys and c) RGO-PDI dispersion dip-coated on mica.
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lecular brushes. The growing process of the brushes was
clearly demonstrated by AFM (Figure 3), showing that the
graphene sheets remain isolated from each other after polymer grafting. It was interesting to note that the molecular
weight, height, stability, and dispersibility of glycidyl methacrylate (GMA)-functionalized GO brushes (GO-g-PGMA)
could be tailored through the reaction time (Figure 3). In
addition, various 2D macromolecular brushes could be obtained, which ranged from polar to apolar, water-soluble to
oil soluble, acidic to basic, and from functional to common
polymers, thus facilitating the design, synthesis, and application in biomimetic coatings and nanocomposites.
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GO to TEOS during the fabrication process. More importantly, the graphene-based mesoporous silica nanosheets
could further serve as template to prepare graphene-based
mesoporous carbon and metal oxide nanosheets by means
of nanocasting technology. We believe that this method will
certainly broaden the accessibility and application of different graphene-based 2D nanocomposites.
Biomacromolecules with multiple functional groups also
show potential in the fabrication of CMG-based 2D nanocomposites. In a recent report, GO and RGO were decorated with thiolated d(GT)29SH DNA oligomers by means of
pp interactions, similar to the case of DNA wrapping on
carbon nanotubes.[25] The thiol groups tagged on DNA
strands could then act as the anchor points for the 2D selfassembly of pre-prepared gold nanoparticles on GO or
RGO.[26] Later, the authors used the Tyr residues of bovine
serum albumin (BSA) as both reductant and stabilizer for
GO.[27] It turned out that the resultant BSA-RGO nanocomposites could be further used as template for the uniform
2D assembly of pre-synthesized Au, Pt, Pd, Ag, and latex
(polystyrene sphere) nanoparticles due to the strong interactions between multiple thiol, amine, and imidazole groups
on BSA potine and the nanoparticles.
Exfoliated graphene as a 2D support: Different from previous approaches that use GO, RGO, or modified GO/RGO
as the template for the synthesis of 2D nanocomposites, Dai
et al. reported a step-wise strategy to cover high-quality graphene sheets with Ni(OH)20.75 H2O nanoparticles with
crystalline structure.[28] In the first step, small nanoparticles
of Ni(OH)20.75 H2O were grown on exfoliated graphene
sheets after the adsorption of corresponding metal salt precursors in N,N-dimethylformamide (DMF)/water (10:1). Afterwards, the nanocomposites were hydrothermally treated
at 180 8C in water. It was interesting to find that the small
particles of Ni(OH)20.75 H2O transformed into hexagonal
nanoplates during the hydrothermal process. The morphology, size, and crystallinity of resulting nanocrystals were dependent on the oxidation degree of graphene. For the graphene with lower oxidation degree, large, single-crystalline
hexagonal Ni(OH)2 nanoplates could be obtained that
showed a typical size of several hundred nanometers and
thickness of less than 10 nm (Figure 8). XRD revealed that
the nanoplates were crystalline b-Ni(OH)2 (Figure 8 d). In
contrast, for highly oxidized GO, small Ni(OH)2 nanoparticles remained at their original positions after the hydrothermal treatment. It was assumed that the large amount of
oxygen functional groups, such as carboxylic, hydroxyl, and
epoxy groups, interacted strongly with the anchored inorganic nanoparticles, which therefore hampered the diffusion
and recrystallization of nanoparticles.[29]
nanomaterials may open up enormous opportunities for applications across the fields of biology, medicine, chemistry,
and physics. Regarding the CMG-based 2D nanocomposites,
the recovered electrical conductivity of graphene may provide additional electron-transport pathways and can thus
promote their applications in optoelectronic and electrochemical devices. In the following section, we will specifically discuss a few examples of CMG-based 2D nanocomposites for the applications in electrochemical energy storage
and conversion, as well as catalysis and sensing.
Supercapacitors: The electric double-layer capacitor
(EDLC), also known as supercapacitor, is an electrochemical capacitor with much higher energy density than the traditional electrolytic capacitors. Dai et al. investigated their
Ni(OH)2/GS nanocomposite as the electrode material for
electrochemical pseudocapacitors. It turned out that the
lightly oxidized, highly conductive graphene sheets with
single-crystalline Ni(OH)2 hexagonal nanoplates exhibited a
high specific capacitance of 1335 F g 1 at a current density
of 2.8 A g 1 and 953 F g 1 at 45.7 A g 1 with excellent cyclability, outperforming that of Ni(OH)2 nanoparticles
grown on highly oxidized GO and the simple mixture of
Ni(OH)2 nanoplates with graphene sheets.[29a] This work suggests that the quality of graphene as well as the morphology
and crystallinity of the 2D nanomaterials are all the critical
issues required to achieve high electrochemical performance
materials for supercapcaitors.
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als have been widely used as the anode materials for lithium-ion batteries. The electrochemical performances of lithium storage including the charge/discharge capacity, columbic efficiency, and cycle stability, depend strongly upon the
microstructure of the carbon. CMG-based 2D nanocomposites are very attractive anode materials for lithium storage
due to their unique flat nanostructures and electronic properties. For instance, a high first reversible capacity of
915 mAh g 1 at a rate of C/5 (one lithium per six formula
units (LiC6) was achieved in the case of graphene-based
mesoporous carbon (GM-C) nanosheets.[24] It was further
found that the reversible capacities of GM-C sheets were
stabilized at about 770 mAh g 1, delivering 84 % capacity retention after 30 cycles (Figure 9). GM-C sheets also exhibited excellent rate performance in stark contrast to the traditional non-graphitic carbon, which typically show continuous
and progressive capacity decay along with cycling processes
at various rates. Such good electrochemical performances of
GM-C nanosheets for lithium storage was attributed to their
high surface area, thin thickness, and numerous mesopores,
which were favorable for the accessibility of the electrolyte,
rapid diffusion of lithium ions, and host uptake. Furthermore, the graphene layer within each nanosheet could act as
mini-current collectors homogeneously dispersed in the electrode, which facilitated the fast transport of electrons during
the chargedischarge processes owing to the high electrical
conductivity of graphene.
In another case, Mn3O4/RGO 2D nanocomposites were
prepared by two-step solution-phase reactions and exhibited
a high specific capacity up to 900 mAh g 1 [29b] (close to the
theoretical capacity of Mn3O4), good rate capability, and
cycle stability. The improved electrochemical performance
of Mn3O4/RGO nanocomposites was ascribed to the intimate interaction between graphene and Mn3O4 nanoparti-
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Acknowledgements
The authors acknowledge the support by the 985 project of Shanghai
Jiao Tong University and BASF.
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