Functionalization of Graphene
Functionalization of Graphene
pubs.acs.org/CR
© XXXX American Chemical Society A dx.doi.org/10.1021/cr3000412 | Chem. Rev. XXXX, XXX, XXX−XXX
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vapor deposition (CVD) growth,6−12 and chemical, electro- and experimental viewpoints. In section 4, we discuss the
chemical, thermal, or photocatalytic reduction of graphene oxide methods of deposition of various nanostructures on graphene
(GO; in this review, GO represents graphene oxide, whereas including a great variety of nanoparticles like noble metals, metal
graphite oxide is written in full) and fluorographene.15−18 The oxides, quantum dots, polymers, and others. The superior
specific approaches involve, for example, reduction of other properties and applicability of these graphene−nanoparticle
graphene derivatives like graphene fluoride toward single composites are extensively analyzed. The specific methods of
graphene nanoplatelets. graphene doping to control the type and concentration of
The developed methods of graphene preparation allowed charged carriers are summarized in section 5. A recent number of
observation of unique properties including a half-integer reviews have dealt with graphene application in biosensors,
quantum Hall effect for both electrons and holes even at room energy storage and production, and photocatalysis.48−51 As such
temperature,19−22 extraordinarily high carrier mobility, and section 6 addresses selected applications of functionalized
single-molecule detection.23 Graphene also exhibits other graphene, including doped graphene electronic devices,
superior characteristics of electronic, mechanical, optical, and magnetic bilayer intercalates, electronic/spintronic devices and
transport nature. These include ambipolar field effect,22 DNA sequencing devices, green chemistry, and bio-imaging.
superlative mechanical strength,24 large specific surface area,25
high transparency,9,26 and high thermal conductivity.27 2. FUNCTIONALIZATION BY COVALENT BONDING
Thanks to these extraordinary and superior properties,
graphene has already revealed a great number of potential 2.1. Covalent Attachment of Organic Functionalities to
applications with possible uses in touch screens, capacitors, Pristine Graphene
spintronic devices, fuel cells, batteries, sensors, transparent Several chemical procedures have been developed to afford
conductive films, high-frequency circuits, toxic material removal, dispersible graphene; in principle they are based on the
and flexible electronics.9,28−32 Once biofunctionalized with exfoliation of graphite, chemical or thermal reduction of GO,
biomolecules (proteins, peptides, etc.), the graphene-based intercalative expansion of graphite, chemical vapor deposition,
nanostructures may open a gateway to new fields in and epitaxial growth.4,52−61 Pristine graphene has been isolated
biotechnology.33 Recently, graphene has been found to be a by sonication of graphite in organic solvents.5 Similarly, Tour and
promising component in the development of fluorescence co-workers described isolation of graphene monolayers with
resonance energy transfer (FRET) biosensors due to its graphite dispersed in ortho-dichlorobenzene (o-DCB).62 Bourli-
quenching capability toward various organic dyes and quantum nos et al.63 achieved dispersion of graphite in a variety of organic
dots,34−36 as well as fast DNA sequencing.37 solvents, including perfluorinated aromatic molecules, pyridine,
Despite the great application potential, it is worth mentioning and chloroacetate, in noticeable yield using a combination of
that graphene itself possesses zero band gap as well as inertness extended bath sonication and careful centrifugation. The
to reaction, which weakens the competitive strength of graphene dispersible material includes mainly monolayer and few-layer
in the field of semiconductors and sensors. This is one of the graphenes, as well as ultrathin layered graphitic sheets, which
reasons for the huge increase in the number of research projects have limited defects. This means that the extended aromatic
aimed at functionalization of graphene including reactions of system of the graphene monolayer is not disrupted and thus the
graphene (and its derivatives) with organic and inorganic electrical conductivity of graphene is almost unaffected. The
molecules, chemical modification of the large graphene surface, dispersion of graphene in organic solvents helps in functionaliza-
and the general description of various covalent and noncovalent tion of graphene by several functional groups. Pristine graphene
interactions with graphene.38−45 Band gap opening of graphene nanoribbons have also been produced by chemical unzipping of
by doping, intercalation, and striping would be useful for carbon nanotubes.44,64
functional nanoelectronic devices.46,47 The functionalization of pristine graphene sheets with organic
This comprehensive review represents the first complex work functional groups has been developed for several purposes. The
covering all modes and methods of graphene functionalization main purpose is the dispersibility of graphene in common
including their classification. The complementary discussion of organic solvents that is usually obtained after attachment of
both experimental and theoretical aspects of graphene certain organic groups. The dispersion of graphene sheets in
functionalization and interaction is presented. The functionaliza- organic solvents is a crucial move toward the formation of
tion modes related to chemistry of graphene derivatives (GO, nanocomposite materials with graphene. In addition, organic
graphane, fluorographene) represent a significant part of the functional groups such as chromophores offer new properties
review, which thus considerably exceeds the chemistry of pristine that could be combined with the properties of graphene such as
graphene. conductivity. In most cases when organic molecules are
As a result we comprehensively discuss both covalent covalently attached on the graphene surface, its extended
functionalization based on binding of organic functionalities aromatic character is perturbed, enabling the control of its
like free radicals and dienophiles on pristine graphene (section electronic properties. The development of a band gap through
2.1) and attachment through the chemistry of oxygen groups of chemical doping is a powerful method for the use of graphene in
GO, that is, methods starting from GO (section 2.2). The nanoelectronic devices.65
covalent attachment of hydrogen and halogens and, generally, The organic covalent functionalization reactions of graphene
the chemistry of graphane and fluorographene is described in include two general routes: (a) the formation of covalent bonds
section 2.3. Section 3 reports noncovalent functionalization and between free radicals or dienophiles and CC bonds of pristine
interactions, which do not disrupt the extended π-conjugation on graphene and (b) the formation of covalent bonds between
the graphene surface, unlike covalent functionalization. A organic functional groups and the oxygen groups of GO.
significant part of this section is devoted to the theory of Based on the previous experimental and theoretical experience
graphene−ligand noncovalent interactions, while various inter- with fullerene and carbon nanotubes, the most attractive organic
action modes (π interactions) are analyzed from both theoretical species for the reaction with sp2 carbons of graphene are organic
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free radicals and dienophiles. Usually both are intermediate workers65 showed that the covalent attachment of nitrophenyls
reactive components that are produced under certain conditions to graphene sheets results in the introduction of a band gap,
in the presence of graphene. which can be controlled, making the functionalized graphenes
2.1.1. Addition of Free Radicals to sp2 Carbon Atoms of potentially useful as semiconducting nanomaterials.
Graphene. Upon heating of a diazonium salt, a highly reactive The strong covalent binding of the nitrobenzyl group on
free radical is produced, which attacks the sp2 carbon atoms of graphene was detected by X-ray photoelectron spectroscopy
graphene forming a covalent bond. This reaction has been used (XPS) (Figure 2, right). The N1s XPS spectrum of the
by Tour and co-workers to decorate graphene with nitro- functionalized graphenes exhibits two peaks at 406 and 400 eV
phenyls.44,64 The graphene sheets in this work were produced that correspond to the nitrogen of NO2 and the partially reduced
through the chemical unzipping of carbon nanotubes. A nitrogen of the product, respectively. The reactions with
measurement of the conductivity of a graphene sheet through diazonium salts have been applied to the functionalization of
a simple device (Figure 1) during chemical functionalization with chemically or thermally converted graphenes, single graphene
sheets obtained by micromechanical cleavage from bulk graphite,
and epitaxial graphenes.64,66−70
Hydroxylated aryl groups grafted covalently on graphene by
the diazonium addition reaction act as initiators for the
polymerization of styrene via the atomic transfer radical
polymerization (ATRP) method (Figure 3). As a consequence
the polymeric chains are covalently grafted on the graphene
surface.71
The ratio between carbon atoms with sp2 and sp3 hybridization
in the graphitic lattice is an indication of the degree of oxidation
or a covalent functionalization reaction. This ratio is estimated
using Raman spectroscopy as the ID/IG ratio, where ID and IG are
the intensities of the peaks at ∼1350 and 1580 cm−1, which
correspond to the number of sp3 and sp2 C atoms, respectively.
Graphene is defined as a pristine two-dimensional sp2 hybridized
carbon sheet; as such the coexistence of sp3 carbons in the lattice
are inherently classified as defects, where these defects can be on
Figure 1. Chemical doping of graphene with 4-nitrophenyl groups: (a) the basal edges or inside defects in the plane. For the
schematic representation; (b) SEM image of a graphene nanoplatelet modification described in Figure 3, the ID/IG ratio increased
between Pt electrodes; (c) AFM image of a fragment of a monolayer from 1.7 to ∼2 after functionalization by diazonium addition.
graphene. Reprinted with permission from ref 64. Copyright 2010 An alternative free radical addition method includes the
American Chemical Society. reaction of benzoyl peroxide with graphene sheets.72 Graphene
isolated mechanically from Kish graphite was deposited on a
diazonium salts results in a remarkable decrease in conductivity silicon substrate and immersed in a benzoyl peroxide/toluene
due to disruption of the aromatic system by transformation of solution. The reaction was initiated photochemically, by focusing
carbon atoms from sp2 to sp3 hybridization. The conductivity of an Ar-ion laser beam onto the graphene sheets in the solution.
the graphene sheets was shown to decrease in a controlled The attachment of the phenyl groups was directly indicated by
manner, showing that conductivity can be controlled by reaction the appearance of a strong D band at 1343 cm−1. The appearance
time (Figure 2, left). In a similar approach, Niyogi and co- of this D band is due to the formation of sp3 carbon atoms in the
Figure 2. Time dependence of current I: (left) Scheme of the experiment shows the device consisted of two parallel resistances derived from the
graphene and the solution, and (right) N1s and C1s XPS spectra of GNRs before and after the functionalization (f-GNRs). Reprinted with permission
from ref 64. Copyright 2010 American Chemical Society.
Figure 3. The attachment of aryl groups on graphene nanoplatelets and the formation of polystyrene chains grafted on graphene nanoplatelets.
Reprinted with permission from ref 71. Copyright 2009 Royal Society of Chemistry.
basal plane of graphene by covalent attachment of phenyl groups an electron transfer from photoexcited graphene to the
(Figure 4). The above reaction was also carried out on a physisorbed benzoyl peroxide. The short-lived benzoyl peroxide
radical anion is then decomposed to produce the phenyl radicals,
which react with the sp2 graphene carbon atoms.
2.1.2. Addition of Dienophiles to Carbon−Carbon
Bonds. Apart from free radicals, dienophiles also react with
sp2 carbons of graphene. Azomethine ylide, which reacts through
a 1,3 dipolar cycloaddition, is one of the most common
dienophiles that have been successfully applied in the
functionalization of carbon nanostructures: fullerenes, nano-
tubes, onions, and nanohorns. This type of reaction affords a
variety of organic derivatives, which display interesting
applications in several areas; these include polymer composites,
biotechnology, nanoelectronic devices, drug delivery, and solar
cells.73−78 After the successful production of graphene sheets
directly from graphite dispersed in organic solvents, 63
Georgakilas et al.79 showed that these graphene sheets could
be substituted with pyrrolidine rings via a 1,3 dipolar cyclo-
addition of azomethine ylide.
The graphene sheets were decorated with dihydroxyl phenyl
groups by pyrrolidine rings that were formed perpendicular to
Figure 4. Schematic representation of the radical addition reaction: (a)
the graphene surface by addition of azomethine ylide precursors
the appearance of D band in the Raman spectrum of a single layer (Figure 5.)79 The azomethine ylide was formed by the
graphene after the photochemical reaction and (b) optical image of a condensation of 3,4-dihydroxybenzaldeyde and sarcosin. The
functionalized single-layer graphene. The arrows indicate holes resulting hydroxyl groups introduced onto a graphene sheet increase its
from prolonged laser exposure. Reprinted with permission from ref 72. dispersibility in polar solvents such as ethanol and N,N-
Copyright 2009 American Chemical Society. dimethyformamide (DMF). The remarkable increase in the
ID/IG ratio and peak broadening after the reaction indicates that
graphene sheet placed in a field effect transistor (FET) device. In the functionalization brings about an impressive increase in the
this case, apart from the significant decrease in conductivity due sp3 planar carbon atoms.
to the increase of sp3 carbon atoms after the covalent addition of The TEM and AFM images reveal the presence of large
phenyl groups, an increase in the level of hole doping was also graphene sheets and few-layer graphitic nanosheets with sizes
observed. The increase in the hole doping was attributed to the ranging between 500 nm and 1 mm (Figure 6). Figure 6, bottom,
physisorbed benzoyl peroxide. Regarding the mechanism of shows an AFM image of a characteristic graphene sheet with a
radical generation, Liu et al.72 suggest that a hot electron initiates thickness of 1.5 nm, generally the thickness of unmodified
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Figure 5. (left) Schematic representation of the 1,3 dipolar cycloaddition of azomethine ylide on graphene. (top, right) Dispersion of functionalized
graphene nanoplatelets in ethanol. (bottom, right) Raman spectra of (a) pristine graphene and (b) pyrrolidine functionalized graphene. Reprinted with
permission from ref 79. Copyright 2010 Royal Society of Chemistry.
Figure 6. (top) Characteristic TEM and (bottom) AFM images of the graphene-f-OH isolated from an ethanol dispersion. Reprinted with permission
from ref 15. Copyright 2009 Nature Publishing Group.
monolayer graphene is between 0.6 and 0.9 nm.15,80 This organic graphene derivatives. By thermally and photochemically
increase in graphene layer thickness indicates the existence of activating a variety of para-substituted perfluorophenylazides
functional groups across the graphene surface. (PFPA), Liu et al.83 were able to attach various functionalities to
The flexibility of this reaction procedure makes it important the graphene sheet via a three-membered aziridine ring (Figure
because one is able to choose among several aldehydes or 7). These modifications result in varying solubility−dispersibility
substituted α-amino acids as precursors, thus yielding a variety of and surface energy of the modified graphenes.
desirable functional groups. For example, to decorate graphene Nitrene addition has also been used in the functionalization of
sheets with tetraphenylporphyrin (TPP) or palladium-TPP, graphene sheets with phenylalanine. The graphene sheets were
Zhang and co-workers81 used tetraphenylporphyrin aldehyde reacted with Boc-protected azidophenylalanine in o-DCB
(and the Pd analogue) and sarcosin as precursors. (Figure 8). The product was determined to have 1 phenylalanine
Quintana et al.82 utilized 1,3-dipolar cycloaddition to graphene substituent per 13 carbons.84
sheets by employing precursors of paraformaldehyde and a Vadukumpully et al.85 reported that graphene sheets can be
specifically designed NH2-terminated α-amino acid. These covalently functionalized with alkylazides, where the alkyl chains
amino groups were shown to selectively bind gold nanorods. include several groups such as hexyl, dodecyl, hydroxyl-
Phenyl and alkyl azides react with the C−C bonds of graphene undecanyl, and carboxy-undecanyl. The carboxylate groups
by the formation of the reactive intermediate nitrene. The introduced on the surface facilitated the attachment of Au
reaction of organic azides with graphene has been used nanoparticles, which were used as markers to investigate the
successfully by several research groups affording a variety of reactive site distribution. The organically modified graphene
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Figure 9. (a) The reaction of alkyl nitrenes with graphene sheets. (b)
TEM images of the Au decorated graphene nanoplatelets after organic
modification with undecanoic acid groups. (c) Raman spectra of
Figure 7. Functionalization of pristine graphene with PFPA. Reprinted graphene sheet before (1) and after the nitrene addition of
with permission from ref 83. Copyright 2010 American Chemical azidoundecanoic acid in 1:1 (2) and 10:1 (3) ratios. Reprinted with
Society. permission from ref 85. Copyright 2011 Royal Society of Chemistry.
Figure 11. (left) Structure of GO and (right) its FTIR spectrum. Left panel reprinted with permission from ref 101. Copyright 2009 Wiley. Right panel
reprinted with permission from ref 102; Copyright 2011 Indian Academy of Sciences.
Figure 12. (top) Structure of oligothiophene functionalized GO. (bottom, left) Fluorescence spectra of oligothiophene−GO compared with that of
pure oligothiophene. (bottom, right) FTIR spectra of GO, oligothiophene (6Thiop), and the functionalized GO (6Thiop-NH-SPFGraphene).
Reprinted with permission from ref 103. Copyright 2009 Elsevier.
aryl-modified graphene sheets were dispersible in DMF, o-DCB, 2.2. Covalent Attachment of Functionalities to Graphene
Oxides
ethanol, chloroform, and water. Additionally, the aryl rings can be
GO can be characterized as a single graphitic monolayer with
substituted by several organic groups (i.e., methyl and fluoro), randomly distributed aromatic regions (sp2 carbon atoms) and
oxygenated aliphatic regions (sp3 carbon atoms) containing
thereby giving a variety of interesting derivatives. hydroxyl, epoxy, carbonyl, and carboxyl functional groups. The
The ID/IG ratio of the functionalized graphenes increased from epoxy and hydroxyl groups lie above and below each graphene
layer and the carboxylic groups exist usually at the edges of the
0.24 for pristine graphene to 0.55 for the fluorinated aryne, 0.69 layers; however it should be noted that the chemistry and
for the methylated aryne, and 0.97 for the unsubstituted aryne heterogeneity of graphene oxide is still heavily debated. The
presence of oxygen groups on the surface of GO provides a
graphene sheets (Figure 10, bottom). remarkable hydrophilic character and analogous chemical
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Figure 13. The reaction between GO and CH2OH-terminated P3HT chains through an esterification reaction. Reprinted with permission from ref 104.
Copyright 2010 American Chemical Society.
Figure 14. (a) Schematic and (b) energy level diagram of a ITO/PEDOT:PSS/GO−P3HT/C60/Al photovoltaic device. Reprinted with permission
from ref 104. Copyright 2010 American Chemical Society.
reactivity. GO is prepared either by methods based on the graphene show no important differences from those of GO, since
oxidation of graphite with strong acidic media57 or ozone58 or the no further structural perturbation occurred. After the function-
chemical/thermal exfoliation of graphite oxide.52−56 GO forms alization of GO a large number of oxygen groups remain, as
unstable dispersions in water and polar organic solvents such as revealed by FTIR analysis of the functionalized GO products in
ethylene glycol, DMF, NMP, and THF, since the exfoliated GO comparison with the starting GO nanoplatelets (Figure
nanoplatelets tend to aggregate through π−π stacking and form 11).101,102
large particles of graphite oxide. Several protective agents have 2.2.1. Addition of Chromophores. Polythiophenes and
been presented for the stabilization of GO nanoplatelets in the oligothiophenes are well-known conjugated polymeric materials
solution such as octadecylamine,89 1-octyl-3-methyl-imidazo- with potential use in various optoelectronic applications, for
lium,90 large aromatic molecules,91 didodecyldimethyl-ammo- example, solar cells, due to high charge mobility arising from the
nium bromide,92 polystyrene,93 and poly(sodium 4-styrenesul- large number of π electrons delocalized along their molecular
fonate)94 and also elastomeric silicon foams95 and DNA.96 The chains.103 Amine-terminated oligothiophenes can be grafted on
presence of these stabilizing groups is not favorable however in GO nanoplatelets through covalent amide bonds, as described by
terms of use of graphenes in technological applications. Liu et al.103 (Figure 12). The disappearance of the carboxyl
Theoretically, a simple reduction of GO should remove the groups and emergence of the amide bonds were recorded in the
oxygen groups and rehybridize the effected sp3 C atoms to sp2 C, FTIR spectrum of the functionalized GO (Figure 12, bottom,
thereby leaving it aromatic and defect free. However left). An important observation from the FTIR spectrum is that
experimentally, after any reductive treatment of GO a critical GO keeps its “oxide” character after functionalization in terms of
number of oxygen groups and defects remain. The reduction of the presence of hydroxyl groups as confirmed by the absorption
GO has been extensively researched, and the methods ranging band at 3431 cm−1 in spectra recorded before and after
from the traditional hydrazine treatment52 to bacterial treat- functionalization. The strong interaction between GO and
ment97 have shown to be successful, as well as a variety of other oligothiophene is indicated by the almost complete fluorescence
methods.56,98−100 These defects affect the properties of the quenching observed in the functionalized graphene in compar-
reduced GO (RGO), most importantly its electric conductivity. ison with pure oligothiophene (Figure 12). The as-synthesized
For this reason, the type of graphene used is usually specified, donor−acceptor material displayed a superior optical limiting
that is, chemically converted graphene, chemically reduced effect compared with the standard optical limiting material C60
graphene, RGO, or thermally reduced graphene, in order to and a control sample consisting of a physical mixture of GO and
discriminate it from pristine graphene.4 oligothiophene.
Thanks to the rich chemistry of hydroxyl, carboxyl, and epoxy In an analogous approach, Yu et al.104 reported functionaliza-
groups, GO has been selected very often as the starting material tion of GO with −CH2OH terminated regioregular poly(3-
for the formation of graphene derivatives through the covalent hexylthiophene) (P3HT) through the formation of ester bonds
attachment of organic groups on its surface. In this type of with the carboxyl groups of GO nanoplatelets (Figure 13). Due
functionalization where the added groups are linked through the to the presence of an abundant number of hydroxyl groups in the
oxygen atoms of GO, the Raman spectra of the functionalized added polymer, P3HT-GO was soluble in common organic
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Figure 21. Representation of the formation of the C60−GO composite. Reprinted with permission from ref 132. Copyright 2008 Elsevier.
Figure 22. Illustration of the preparation of imidazolium-modified GO. Reprinted with permission from ref 135. Copyright 2009 Royal Society of
Chemistry.
polymers with interesting mechanical, optical, and electrical o-DBC and DMF; additionally the incorporation of these
properties.139−142 The effect of the dispersion of carbon organically modified GO nanoplatelets into polymers and
nanostructures in such matrices is greatest when the dispersion conjugated polymers for photovoltaics was facilitated. This
is fine and interfacial interactions between the nanostructures procedure was initially developed by Stankovich et al.3 as a
and the matrix are present. These two factors, fine dispersion and general approach for preparation of GO−polymer composites.
interfacial interaction, are important for chemical functionaliza- Phenyl isocyanate-treated GO nanoplatelets were dispersed in
tion of carbon nanostructures. As an example, in order to PS and other styrenic copolymers, such as acrylonitrile−
enhance the silica monolith structure, Yang et al.143 presented butadiene−styrene or styrene−butadiene, through solution
the functionalization of GO with 3-aminopropyl triethoxysilane phase mixing. The modified GO was then chemically reduced
(APTS). The ATPS was grafted onto the GO surface through in order to improve the electrical conductivity of composites.
covalent bonds with the epoxy groups as represented in Figure This functionalization procedure has been further used by Liu
25. The silicon-functionalized GO (Si−GO) was incorporated and co-workers144−146 in the fabrication of organic photovoltaic
into a silica matrix by hydrolytic condensation of an excess of cells. The phenyl isocyanate functionalized graphene was easily
APTS in the presence of Si−GO. dispersed into o-DBC, and this was further dispersed in P3HT to
The functionalized GO was easily dispersed in water, ethanol, form a donor/acceptor system. After the insertion of modified
DMF, dimethyl sulfoxide (DMSO), and APTS. The GO GO into P3HT, a remarkable quenching of the photo-
reinforced Si monolith showed better mechanical properties in luminescence was observed, indicating a strong interaction and
comparison with the pure Si monolith (Figure 26); the electron transfer from P3HT to GO nanoplatelets. This function
compressive failure strength and toughness were improved by makes the formed composite suitable as an active layer in bulk
20% and 92%, respectively, compared with the pure Si monolith. heterojunction photovoltaic cells as represented in Figure 27. A
An organic GO derivative obtained from the covalent photovoltaic cell containing the P3HT/GO composite showed a
attachment of phenyl isocyanate to GO through the formation power conversion efficiency of 1.1%.146
of an ester bond with the epoxy group has been used in several Finally, Avinash et al.147 obtained covalently functionalized
diverse applications. After this chemical modification, GO GO with ferrocene via a green chemistry approach at room
nanoplatelets were easily dispersible in organic solvents such as temperature on solid phase alumina. The ferrocene/GO
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Figure 23. Preparation of imidazolium-modified GO hybrid materials and anion-exchange reactions: (i) (COCl)2, 80 °C, 18 h; (ii) 1-(3-
aminopropyl)imidazole, 100 °C, 18 h; (iii) 1-bromobutane, 90 °C, 18 h; (iv) H2O, NaPF6 or protoporphyrin IX disodium salt, 25 °C, 18 h. Reprinted
with permission from ref 136. Copyright 2010 Elsevier.
Figure 24. Preparation of butylamine-functionalized RGO nanoplatelets. Reprinted with permission from ref 138. Copyright 2009 American Chemical
Society.
composite material exhibited interesting magnetic properties, not been achieved yet. There are always epoxy and hydroxyl
with the magnetization of the composite material found to be functional groups on the basal plane of the RGO.148 Density
more than that of both GO and ferrocene. functional theory (DFT) investigations of the structure of
2.2.4. Starting from Partially Reduced Graphene graphene after deoxygenation confirm that it is impossible to
Oxide. As referred in the introduction of this chapter the completely remove the oxygen-containing functional groups
complete reduction of GO to graphene via different routes has from the graphene surface using chemical or thermal reduction
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Figure 27. (a) Graphical representation of the modified graphene and P3HT, (b) schematic representation of the bulk heterojunction photovoltaic cells,
and (c) an AFM image of the modified graphene. Reprinted with permission from ref 146. Copyright 2009 Wiley.
Figure 28. Two different grafting methods from the same organic molecule. Reprinted with permission from ref 152. Copyright 2010 American
Chemical Society.
calculations of the optical properties of graphane, which were semimetal and the other an insulator. It should be noted that
carried out with the Bethe−Salpeter equation (BSE), which opening of the graphene zero band gap still represents a
accounts for electron−electron and electron−hole correlations challenge in the manufacture of field effect transistors.165 In this
as well as excitonic effects,164 show an absorption spectra with the respect, the electronic properties of graphene can be relatively
first exciton peak at 3.8 eV (for x or y polarized light, while the finely tuned by its partial hydrogenation.166 Well structured
transition is dipole forbidden for z polarized light, Figure 33).162 partially hydrogenated graphene derivatives represent very
When one considers the electronic properties of graphene and interesting materials with magnetic, metallic, and semiconduct-
graphane two sharply differing materials are represented, one is a ing properties, which can be designed by the degree of
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Figure 29. (a) Thermogravimetric curves and (b) corresponding derivative curves of the starting materials and the derivatives. Photograph showing the
dispersion of graphene, F-graphene/MA-POA2000 and D-graphene/MA-POA2000 in THF (from right to left). Reprinted with permission from ref
152. Copyright 2010 American Chemical Society.
Figure 30. Schematic representation of covalent attachment of PS/PAM copolymer to RGO. Reprinted with permission from ref 153. Copyright 2009
Wiley.
Figure 31. Graphene layer (in green) that is attacked by cold plasma
hydrogen atoms to produce graphane. Reprinted with permission from
ref 159. Copyright 2009 American Association for the Advancement of
Science.
Figure 33. (a) First Brillouin zone and (b) unit cell and bases of graphane in the chair conformation. Blue and white balls represent carbon and hydrogen
atoms, respectively. (c) Band structure in local-density approximation (LDA, full line) and GW approximation (circles) and projected density of states of
graphane. The zero level indicates the vacuum level position. Reprinted with permission from ref 162. Copyright 2010 American Physical Society.
Figure 36. One side fluorination (one side fluorinated graphene C4F, panel b) changes the optical properties of graphene (panel a). Raman signal of
stoichiometric fluorographene (CF, panel c) disappears. The spectra of graphene and fluorographene are offset for clarity. Reprinted with permission
from ref 169. Copyright 2010 American Chemical Society.
intermolecular interactions involving π-systems are pivotal to the in addition to other factors such as solvophobic effects. For the
stabilization of proteins, enzyme−drug complexes, DNA− benzene dimer the edge-to-face conformer is the most stable but
protein complexes, organic supramolecules, and functional is nearly isoenergetic to the parallel displaced conformation. Due
nanomaterials.189−193 These interactions involving π systems to this the isolated benzene dimer is extremely flexible and could
are most relevant in the context of nanomaterial design and coexist in both forms. On the other hand, when considering the
fabrication of nanodevices, because subtle changes in the facial or axial substitution effect on the edge-to-face aromatic
electronic characteristics of the π systems can lead to dramatic interaction, we observe that for the axially substituted aromatic
effects in the structure and properties of the nanosystem.193−195 systems, the electron density at the para position is an important
In the last two decades, extensive studies have been conducted to stabilizing factor. Thus, the stabilization/destabilization by
understand the nature of π-complexes including the nonpolar substitution of an aromatic ring is significantly affected by the
gas−π interaction, H−π interaction, π−π interaction, cation−π electrostatic energy,213 while the dispersion energy is mostly
interaction, and anion−π interaction.196,197 These π-interactions canceled out by the exchange repulsion. This leads to the
are of importance in device and sensing applications of carbon conclusion that stabilization/destabilization by substitution is
nanotubes and graphene sheets.198 Extensive investigations have governed mainly by electrostatic energies. However, the facially
been made regarding the energetic and geometrical significance substituted aromatic system depends not only on the electron-
of π-interactions. Theoretical interpretations based on high-level donating ability responsible for the electrostatic energy but also
ab initio calculations have been instrumental in understanding on the dispersion interaction and exchange repulsion. The
the nature of π-interactions. The strength of the π-interactions is dispersion energy, together with the exchange repulsion,
determined by the combined effect of attractive forces augments the electrostatic energy in the facially substituted
(electrostatic, dispersive, and inductive interactions) and aromatic systems. Using the flipping/flapping motion due to the
repulsive forces (exchange repulsion). Each of these components changes of edge-to-face and face-to-face aromatic interactions,
shows characteristic differences in physical origin, magnitude, Kim et al.216 designed a molecular flipper. In order to have
and directionality. maximum control of this interconversion, electrochemically and
3.1.1. Nonpolar Gas−π Interaction. In π-interactions, photochemically active π systems can be utilized. The π−π
when the countermolecule is either a rare gas atom or a nonpolar interaction is one of the most important driving forces for
molecule (gas dimers, hydrocarbons), dispersion energies supramolecular self-assembly; thus by controlling the relation-
predominate,199,200 while when the countermolecule is either a ships of several noncovalent interactions, we could design and
polar molecule or Lewis acid, both electrostatic and dispersion synthesize novel organic nanostructures.217 While both T-
energies govern the interaction. shaped and stacked structures of the benzene dimer are almost
3.1.2. H−π Interaction. Complexes exhibiting the H−π isoenergetic, (displaced) π-stacked structures tend to be more
interaction190,201−207 are of interest, because this interaction is favored when they involve N-heterocyclic aromatic rings except
also one of hydrogen bonds. In going from CH4 to NH3 to H2O for the tetraazine dimer.218,219
to HF, the increase in the repulsive exchange energies is more 3.1.4. Cation−π Interaction. When the countermolecule is
pronounced in ethene complexes than in benzene complexes.201 a metal cation in the π-interactions, a combination of electrostatic
However, this increase is almost canceled out by both the and induction energies dominate the cation−π interaction.220,221
electrostatic and dispersion energies in the case of the ethene For the interaction of a positively charged organic cation with the
complexes. Consequently, the induction energies become more negatively charged π electron cloud, an accurate estimate of the
important in the case of the ethene complexes. On the other interaction energies requires the inclusion of the polarizability of
hand, electrostatic, induction, and dispersion energies seem to be the π system.222,223 The characteristics of transition metal
significant in the description of the benzene complexes. The complexes with π complexes are different from the typical
polarizabilities of the π-electron systems play a key role in cation−π interactions involving alkali metal cations. While the
governing the nature and geometry of the H−π interaction. The complexes of Na+, Cu+, and Ag+ favor the conformation of C6v
magnitude of the dispersion energies tends to be proportional to symmetry with the cation above the π centroid, those of Au+,
the number of electrons participating in the interaction. In the Pd2+, Pt2+, and Hg2+ prefer the off-centered π coordination to the
case of extended π-systems, like those found in poly complexes, π centroid because of the TMn+ ← π donation.224−229 Various
involving several hydrogen bonds, the multidentate H−π kinds of receptors with strong binding energies and high
complexes are additionally stabilized by a substantial contribu- selectivities for metal cations utilizing the cation−π interactions
tion from the dispersion energy. have been designed.226−228 When the cation−water interactions
3.1.3. π−π Interaction. The π−π interactions197,198,208−213 are compared with cation−π interactions, it is found that the
are one of the most intriguing noncovalent interactions, in the distinct difference between them is the magnitude of the
sense that the negatively charged and diffuse electron clouds of electrostatic energy, which is in general the dominant contributor
the π systems exhibit an attractive interaction. This interaction is to the total interaction energy in the case of the cation−water
predominated by dispersion interactions when both π systems interactions. In the context of nanomaterial design, these findings
possess very similar electron densities. However, when one of the are significant because a greater electrostatic contribution implies
systems is electron-rich and the other electron-deficient, the that the magnitudes of the interaction energies are more
resulting complexes are bound by induction interactions as is the susceptible to the dielectric of the environment. Very similar
case when the negative charge gets transferred from benzene to interaction energies of benzene with ammonium and potassium
hexafluorobenzene.214−219 The interaction of two benzene rings cations result from a balance of dispersion and induction energies
has been widely investigated both experimentally and theoret- because the electrostatic and exchange energies are very similar
ically. Experimental estimates of the interaction energy give a and hence mostly cancel out. However, the ammonium cation
value of ∼2 kcal/mol,220 which indicates that the attraction is complexes exhibit a larger contribution of dispersion energies.
appreciable and this attraction significantly influences the 3.1.5. πcation−π Interaction. It should be noted foremost
interaction of phenyl rings in solution or other environments, that the magnitudes of the electrostatic and induction energies in
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the case of the organic cation complexes of these π systems are magnitude of interactions between the molecule and gra-
much smaller than those observed in the case of the π−alkali phene.245 Nucleobases receive special attention due to a
metal cation complexes, while the contribution of dispersion biological importance of those molecules. Adsorption of adenine
energies becomes significant. If the counterion is an aromatic on graphite was studied by using DFT taking into account van
cation, the contribution of dispersion energy becomes vital. The der Waals interactions.246 A similar study compared the binding
πcation−π interaction229−231 is different from the normal metal energies of nucleobases by using LDA and MP2.247 Umadevi and
cation−π interaction and normal π−π interaction in terms of Sastry248 employed newly developed density functionals to deal
binding energies. In terms of total binding energy, the πcation−π with similar systems, while Antony and Grimme249 reported
interaction is weaker than the cation−π interaction but much DFT-D/GGA, B2PLYP-D, and SCS-MP2 results for these
stronger than the π−π interaction. On the other hand, for anion systems. Berland et al.250 used the vdW-DF method to accurately
templated π+−π+ interactions,232 the binding energies are much calculate the binding energy curve for an adenine molecule
larger than those of π−π and π+−π. The stabilization is attributed approaching graphene surface. The interaction of several amino
to the attractive electrostatic interaction due to antiparallel acids with the graphene surface has been studied using GGA and
displaced geometry with a significant dispersion contribution. In MP2 methods.251 The planar nature of graphene can be
general, when the π+−π+ stacking is in an energetically favored exploited to tune its electric properties. The benzene−metal
configuration the electrostatic interaction is large, similar in (M = Ni, K, Pd, Al, Ag, Cu, Au, and Pt) and graphene−metal
magnitude to the large exchange repulsion and much larger than interface has been studied.244,252−255 It has been shown that a
the dispersion interaction, unlike the case of stacked-displaced SiC substrate is able to induce a band gap in graphene.256,257
π+−π and π−π complexes. Organic molecules can also be used to achieve electronic tuning
3.1.6. Anion−π Interaction. Compared with π−π, of graphene;258 in this sense the interactions of diverse molecules
cation−π, and H−π interactions, the lone pair−π and anion−π with graphene and carbon nanotubes have been utilized in
interactions233−235 have only recently been investigated, because designing devices and sensors that recognize molecular
aromatic rings are considered as electron sources, which give characteristics.259−263 The interaction of nucleobases with
repulsive interactions with anions. Recently, anion−π inter- graphene has been utilized to design a two-dimensional
actions have been extensively investigated as a strategy toward a conductance device toward fast DNA sequencing.37,264,265
new type of anion recognition, host architecture, and supra- 3.2. Graphene−Ligand Noncovalent Interactions:
molecular self-assembly.192,236,237 The total interaction energies Experiment
of anion−π complexes are comparable to those of the The noncovalent functionalization of graphene (G) exploits van
corresponding cation−π complexes. While the largest contribu- der Waals and ionic interactions between graphene and a
tions to the total interaction energy in the cation−π complexes functionalized molecule. The pyrene moiety has been reported
are the electrostatic and induction energies, the contribution of to have a strong affinity toward the basal plane of graphite via π-
the dispersion energies is substantial in the anion−π complexes. stacking.266 Xu et al.267 prepared stable aqueous dispersions of
Apart from the increase in dispersion energy, the anion−π graphene nanoplatelets using a water-soluble pyrene derivative,
interactions are also characterized by a substantial increase in the 1-pyrenebutyrate (PB−), as a stabilizer. GO was functionalized
magnitude of the exchange-repulsion energy. Anions can interact with pyrenebutyric acid in the presence of a base, and the
with the π rings in two different complexation forms: covalent resulting product was reduced with hydrazine. Figure 38 shows
bonding type and noncovalent anion−π type. The covalent type
complexes generally referred to as “Meisenheimer” complexes
are found to be the key intermediates in nucleophilic aromatic
substitution (SNAr) and usually the global minima structures in
the gas phase. However, in the solution phase, the covalent
bonding type complexes merge into the solvent-mediated
anion−π type or displaced anion−π type complexes. It is this
reason that the displaced anion−π type complexes with some
flexible orientations are most common in many crystal
structures.238
3.1.7. Graphene−Ligand Noncovalent Interaction.
Various studies involving molecules adsorbed on a graphene or
graphite surface have been conducted. Hydrogen physisorption
on the graphene surface has been studied for possible
applications toward hydrogen storage.239 Tkatchenko and von
Lilienfeld240 have studied the adsorption of Ar on graphite by
comparing various density functionals. Umadevi and Sastry241 Figure 38. (left) Tapping mode AFM images of exfoliated GO and
also employed DFT methods to study CO2, H2O, Li, Mg, Li+, (right) PB− functionalized graphene on mica. Reprinted with
permission from ref 267. Copyright 2008 American Chemical Society.
and Mg2+ on polycyclic aromatic hydrocarbons. π−π stacking
interactions are of a special interest due to the extended π orbitals
of graphene. Adsorption of benzene and naphthalene on graphite AFM images of GO and PB− graphene nanoplatelets with
was studied by using the nonlocal vdW-DF method to compute thickness 1.3 and 1.7 nm, respectively. The flexible graphene film
accurate binding energy curves.242,243 The vdW-DF method was showed conductivity 7 orders of magnitude larger than that of the
also shown to provide binding energies for Ag, Au, and Pd atoms GO precursor.
adsorbed on graphene surface in good agreement with the Graphene is much more flexible and less expensive than ITO
reference CCSD(T) method.244 Functional groups attached to since its precursor is hydrocarbon gas/graphite. To improve the
an aromatic molecule are shown to affect the nature and power conversion efficiency of graphene, Wang et al.268
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noncovalently modified a graphene film with pyrene butanoic (HPC-Py).270 The functionalized graphene nanoplatelets with
acid succidymidyl ester (PBSA). The π−π interactions between a 3.3 ± 1.4 nm average thickness were characterized using UV−
graphene and PBSA have a negligible effect on the optical vis spectroscopy, fluorescence spectroscopy, atomic force
adsorption of the graphene film in the visible region. This microscopy, attenuated total reflectance micro-Fourier transform
improved the power conversion efficiency to 1.71% for infrared spectroscopy, and Raman spectroscopy.
functionalized graphene compared with pristine graphene Kodali et al.271 have shown that noncovalently functionalized
(0.21%) (Figure 39). epitaxial graphene with pyrenebutanoic acid-succinimidyl ester
(PYR-NHS) can be prepared without disrupting graphene’s
electronic structure. The grafting of pyrene-substituted TbPc2
single molecule magnets on graphene has been reported by
Lopes et al.272 The enhanced Raman intensity of TbPc2 on
graphene allows the detection of a few molecules per laser spot.
van der Waals interactions were responsible for the coupling
between the substituted pyrene and graphene.
Su et al.91 presented a unique approach to functionalize
graphene sheets with pyrene and perylenediimide as electronic
donor and acceptor molecules, respectively. The resulting
aqueous graphene dispersion yields single and double layer
graphene sheets. A solar cell based on these functionalized
graphene nanoplatelets showed an increase in conductivity
(Figure 40).
An et al.269 presented the functionalization of graphene films Figure 40. Current density vs voltage (I−V) curves of P3HT/PCBM
with 1-pyrenecarboxylic acid (PCA), which were laminated onto heterojunction solar cells with 10 nm thick thermally reduced ReG and
flexible and transparent polydimethylsiloxane (PDMS) mem- ReG−PyS films as the transparent electrodes, respectively. Inset is a
branes. The noncovalent (π-stacked) PCA graphene films schematic illustration of the solar cell; the five layers from top to bottom
display a number of unique optical and molecular sensing are Al, ZnO, a blend of P3HT and PCMB, PEDOT:PSS, graphene, and
properties that are absent in pristine graphene films, while the quartz, respectively. Reprinted with permission from ref 91. Copyright
conducting nature of graphene is maintained. The flexible PCA− 2009 Wiley.
graphene−PDMS hybrid structure blocks 70−95% of ultraviolet
(UV) light, while allowing 65% or higher transmittance in the
visible region, rendering them potentially useful for a number of It has been shown by Cheng et al.273 that graphene can be
flexible UV absorbing/filtering applications. In addition, the functionalized with 1,5-diaminonaphthalene (DAN) and 1-
electrical resistance of these structures is found to be sensitive to nitropyrene (NP) as electron-donating and electron-with-
visible light illumination, atmospheric pressure change, and the drawing molecules, respectively. The chemically modified
presence of different types of molecular analytes. Owing to their samples were systematically characterized by optical microscopy,
multifunctionality, these hybrid structures have immense surface topography and potential measurements, and spatially
potential in the development of versatile, low-cost, flexible, resolved Raman spectroscopic imaging.
portable electronic and optoelectronic devices for diverse Wang et al.274 reported the nonconvalent functionalization of
applications. graphene with carboxylate-terminated perylene molecules.
Stable aqueous suspensions of graphene nanoplatelets with a These functionalized graphene nanoplatelets were used to
high concentration (0.6−2 mg/mL) have been prepared by the grow metal oxide via ALD methods (Figure 41). The ultrathin
chemical reduction of exfoliated graphite oxide (EGO) using high dielectric integrated graphene is very useful to achieve high
sodium lignosulfonate (SLS), sodium carboxymethyl cellulose currents and ideal subthreshold swing without substantial gate
(SCMC), and pyrene-containing hydroxypropyl cellulose leakage.
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Figure 44. Illustration of a procedure to design RGON hybrids and the RGON platform used as an electrochemical biosensor. Reprinted with
permission from ref 283. Copyright 2010 American Chemical Society.
Figure 45. HRTEM micrographs of (a) neat ILFG showing the crumpled sheet like texture (inset on right-hand side shows the thickness of the
nanosheet), (b) neat RGO with the inset showing a blown up view of a fold on the nanoplatelet, (c) the PEDOT−RGO nanocomposite; the ellipses
encircle the streak like structures typical of RGO and are surrounded by the amorphous polymer, (d) PEDOT−ILFG nanocomposite, the elongated
shapes (as in the inset) are characteristic of ILFG, (e) coexisting crystalline and amorphous phases in PEDOT−ILFG (inset is a magnified view of a
quasi-ordered arrangement of lattice fringes), and (f) a relatively defect free crystallite of ILFG in PEDOT−ILFG (the inset shows the fringe separation
of 0.85 nm). Reprinted with permission from ref 287. Copyright 2011 American Chemical Society.
Wu et al.282 employed a one-step method for the preparation Liu et al.286 functionalized graphene with a water-soluble
of polystyrene (PS)-functionalized graphene nanoplatelets. The aromatic electroactive dye, methylene green (MG), during the
graphene is homogeneously dispersed in the PS matrix, thereby chemical reduction of GO with hydrazine. Atomic force
creating electrically conductive graphene/PS nanocomposites. microscopy and UV−vis spectrophotometric results demon-
The synthesis of the composite was achieved via in situ peeling of strate that CRG functionalized with MG (CRG−MG) is well-
graphite nanoplatelets into graphene nanoplatelets in the dispersed in water through coulomb repulsion between MG-
presence of a PS solution. The resulting PS-functionalized adsorbed CRG nanoplatelets. The electrochemical properties of
graphene nanoplatelets displayed a fluffy nanostructure. The the CRG−MG composite were investigated, and the results
backbones of PS were stacked onto the basal plane of graphene demonstrate that CRG−MG confined onto a glassy carbon
nanoplatelets by strong π−π interactions with a graft ratio up to electrode has lower charge-transfer resistance and better
85 wt. %. The PS chains effectively prevent the graphene electrocatalytic activity toward the oxidation of NADH than
nanoplatelets from aggregating and the prepared graphene/PS pristine CRG. This method not only offers a facile approach to
nanocomposites, with homogeneously dispersed single- and few- dispersing graphene in water but also is envisaged to be useful for
layer graphene, exhibited extraordinary electrical properties and a graphene-based electrochemistry investigations.
percolation threshold of about 2.7 wt. %, which outperforms that Nanocomposite assemblies of poly(3,4-ethylenedioxythio-
of the starting graphite or carbon black material. phene) (PEDOT), embedded with (a) fluoro alkyl phosphate
Functionalization of graphene through self-assembly of a based ionic liquid functionalized graphene (ILFG) and (b) RGO
hydrophobic backbone of Nafion has been reported by Choi et
prepared from a modified Hummers’ method, have been
al.283 (Figure 44). The resulting graphene nanoplatelets were
synthesized (Figure 45).287 Defect-free graphene nanoplatelets
readily dispersible and displayed high conductivity and electro-
within the size of a few nanometers were achieved in the
chemical biosensing properties for organophosphates. Ansari et
PEDOT−ILFG nanocomposite. In contrast, structures compris-
al.284 reported that a Nafion/graphene nanocomposite can be
produced by dispersion of Nafion in a GO aqueous solution and ing GO wrinkles interspersed with the amorphous polymer were
subsequent reduction with hydrazine. In their report, they obtained in the PEDOT−RGO nanocomposite. X-ray photo-
showed that the presence of Nafion nanochannels dramatically electron spectroscopy showed that ILFG was considerably less
increases the conductivity of graphene. oxidized compared with the pure RGO, which ratified the
The widely soluble graphene nanoplatelet/congo red (GSCR) superiority of the ionic liquid functionalization strategy over the
composite was synthesized by noncovalent interaction cou- conventional chemical approach for exfoliating graphite.
pling.285 The resulting graphene nanoplatelets were completely Substantially higher electrochemical activity, improved ionic/
dispersed in DMF, methanol, DMSO, ethanol, and water and electronic conductivity, much faster switching rates, and an
partially dispersed in many other organic solvents. The almost ballistic enhancement in the electrochromic coloration
mechanism of GSCR’s good solubility was successfully explained efficiency were attained for the PEDOT−ILFG nanocomposite
by Hansen solubility parameters. These functionalized nano- in comparison to the PEDOT−RGO film. This demonstrated
platelets were used to prepare GSCR/Au hybrid materials the ability of the ionic liquid to not only fortify the structure of
through electrostatic interactions. UV−vis absorption, Fourier graphene but also facilitate charge transport through the bulk of
transform infrared, Raman, and X-ray photoelectron spectra the film, by providing less impeded pathways. Since PEDOT−
revealed that congo red (CR) is successfully coupled to the ILFG/−RGO nanocomposites of good uniformity achieved this,
graphene nanoplatelets. to some extent, the challenges associated with the processing of
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Figure 46. Noncovalent functionalization occurs on the basal plane of Figure 47. (a) Synthetic scheme for the preparation of graphene−
defect-free graphene, as opposed to covalent bonding formed on the coronene composites. (b) Photographs of the aqueous solutions of CS,
edge of the graphene. Doping induces modulation of the Fermi level of EG−CS, and HG−CS and (c) corresponding images under UV/vis
graphene. Reprinted with permission from ref 288. Copyright 2010 illumination. (d) Schematic illustration of the exfoliation of few-layer
American Chemical Society. graphene with CS to yield monolayer graphene−CS composites.
Reprinted with permission from ref 291. Copyright 2010 Wiley.
Figure 48. (A) (left) Photograph of a polymer PmPV/DCE solution with GNRs stably suspended in the solution and (right) schematic drawing of a
graphene nanoribbon with two units of a PmPV polymer chain adsorbed on top of the graphene via π stacking. (B−F) Chemically derived graphene
nanoribbons down to sub-10-nm width. Reprinted with permission from ref 59. Copyright 2008 American Association for the Advancement of Science.
from the supernatant (Figure 48). The obtained graphene A stable, biocompatible, free-standing “paperlike” material
nanoribbons (GNR) have widths below 10 nm, as well as single composed of polyoxyethylene sorbitan laurate (TWEEN) and
ribbons with varying widths along their lengths. The GNRs RGO platelets has been presented.297 The TWEEN paper is
exhibited ultrasmooth edges with well-defined zigzag or armchair highly stable in water (no leakage of TWEEN) and sufficiently
edge structures. Electrical transport experiments showed that, robust to be handled by hand without breaking. Furthermore, the
unlike single-walled carbon nanotubes, all of the sub-10-nm material is noncytotoxic to three mammalian cell lines and
GNRs produced were semiconductors, affording graphene field inhibits nonspecific binding of Gram-positive bacteria.
effect transistors with on−off ratios of about 107 at room Graphene flakes with controlled thicknesses have been
temperature. isolated in solution using density gradient ultracentrifugation.298
A simple wet-chemical strategy for synthesizing hemin− These stable graphene dispersions are produced using the bile
graphene hybrid nanoplatelets (H-GNs) through π−π inter- salt sodium cholate, which promotes graphite exfoliation and
actions has been reported by Guo et al.295 This new nanomaterial results in graphene−surfactant complexes having buoyant
exhibits high solubility and stability in water. Using this densities that vary with graphene thickness. The sorted graphene
composite, the authors were able to differentiate between ss- flakes were characterized using atomic force microscopy and
and double-stranded (ds-) DNA in optimum ion concentrations Raman spectroscopy.
due to the different affinities of ss- and ds-DNA toward graphene. The dual role of Pluronic copolymer in dispersing graphene
and in forming supramolecular hydrogels has been reported.299
With this information, a novel assay for single-nucleotide
The required amount of Pluronic copolymer was dispersed in
polymorphism (SNP) detection was developed. This assay is
aqueous GO solution, and subsequent reduction was performed
simple, rapid, and cost-efficient, and there is no need to label the
with hydrazine hydrate. The aqueous graphene solutions were
DNA substrate. The most important characteristic of the assay is
stable for three months, and the viscosity behavior of the
a sensitive probe for direct visualization of SNPs by the naked eye hydrogels as a function of shear rate diminished.300 Liu et al.301
at room temperature. This makes it more convenient than other successfully prepared an aqueous dispersion of graphene
methods that rely on complex instrumentation. nanoplatelets (GNs) via chemical reduction of GO using
Wang and co-workers296 reported a green and facile strategy hydrazine hydrate in the presence of poly[(2-ethyldimethylam-
for the fabrication of soluble RGO. The method is based on the monioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)]
reduction of exfoliated GO in green tea solution by making use of (PQ11), a cationic polyelectrolyte. The noncovalent function-
the reducing capability and the aromatic rings of tea polyphenols alization of graphene nanoplatelets by PQ11 leads to a stable
(TP). Measurements of the resultant graphene (TPG) confirm dispersion for several months. PQ11 is a positively charged
the efficient removal of the oxygen-containing groups in GO. polymer that exhibits the ability to reduce silver salts to Ag
The strong interactions between the RGO and the aromatic TPs nanoparticles. They found that such Ag/graphene nano-
guarantee a good dispersion of the RGO in both aqueous composites exhibit good catalytic activity toward the reduction
solution and a variety of organic solvents. These features endow of hydrogen peroxide (H2O2), leading to an enzymeless sensor
this green approach with great potential in constructing various with a fast amperometric response time of less than 2 s.
graphene-based materials, especially for high-performance Noncovalent functionalization leading to solubilization of
biorelated materials as demonstrated with the chitosan/TPG graphene and single-walled carbon nanotubes (SWNTs) has
composites. been explored in nonpolar organic solvents using various
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Figure 49. (a) Chemical structure of PEG-OPE. (b) The synthesis of PEG-OPE−RGO in H2O. Step 1, oxidation of graphite yields single-layer GO
nanoplatelets. Step 2, Chemical reduction of GO with hydrazine in the presence of PEG-OPE produces a stable aqueous suspension of PEG-OPE−
RGO. (c) Photograph of (A) GO and (B) RGO in water and (C) PEG-OPE−RGO and (D) PEG-OPE in methanol. Reprinted with permission from ref
305. Copyright 2010 Wiley.
Figure 50. TEM images of chemically converted graphene nanoplatelets (a) in the presence of and (b) in the absence of ILP and (c) tapping mode AFM
image of the ILP-G processed from organic suspension and height profiles across the ILP-G sheets indicating a thickness of ∼1.9 nm. Reprinted with
permission from ref 306. Copyright 2010 American Chemical Society.
electron donor and acceptor molecules.302 The large aromatic sonication. The noncovalent grafting via ionic interaction was
surfaces of electron donor and acceptor molecules direct confirmed by attenuated total reflection Fourier transform
themselves onto the surface of the graphene/SWNTs through infrared and Raman spectroscopy. The dispersibility of RGO in
π−π stacking interactions whereas the alkyl chains or glycol 16 different organic solvents was tested, and photographs were
chains on the aromatic molecules promote solubility and thus taken after one month. UV−vis absorption spectroscopy was
produce stable dispersions of SWNT/graphene composites in employed to confirm the dispersibility of the RGO. The
nonpolar solvents. Composites of graphene and SWNTs with absorption peaks of the graphene were observed at 270 nm for
electron donors and acceptors show significant change in their 1-propanol, EtOH, and EG, confirming the stable dispersibility of
electronic and Raman spectra, and these changes were found to RGO in these solvents.304
be characteristic of charge-transfer interactions. An effective method to prepare amphiphilic RGO nano-
Choi et al.303 reported a novel method for dispersing graphene platelets by using a coil−rod−coil conjugated triblock copolymer
in various organic solvents via noncovalent functionalization with (PEG-OPE) as the π−π binding stabilizer has been shown by Qi
amine-terminated polymers. The carboxylate groups remaining et al.305 (Figure 49). PEG-OPE is composed of one lipophilic π-
after chemical reduction of GO successfully provided non- conjugated oligomer and two hydrophilic PEG coils and is
covalent functionalization sites for the protonated amine synthesized by atom-transfer radical polymerization (ATRP).
terminal group of end-functional polymers. The noncovalent Due to the amphiphilicity and π-conjugation of PEG-OPE, PEG-
functionalization facilitated the phase transfer of graphene OPE functionalized RGO form a sandwich structure, making the
nanoplatelets from a water phase to an organic phase via simple composite soluble in a variety of solvents including toluene and
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Figure 51. (Left) Photograph of several dispersions of gold nanoparticles (1 mM) in THF with different concentrations of GO−ODA (octadecylamine)
and (right) the characteristic UV−vis absorption spectra of the dispersions. Reprinted with permission from ref 318. Copyright 2008 American
Chemical Society.
water. The presence of PEG moieties in graphene allows for its highest purity.310 Excluding conductivity, the other forms of
use in the exploration of biological systems, as well as its potential graphene (GO and partially RGO) also exhibit these advantages
application in the attachment and delivery of aromatic water- for the deposition of nanoparticles.
insoluble drugs into cells. 4.1. Deposition of Precious Metal Nanoparticles
Kim et al.306 demonstrated an effective method for the
preparation of solution-processable graphene nanoplatelets Noble metals such as Pt, Au, Ag, Rh, Pd, and related alloys are
(Figure 50) using ionic liquid polymers (ILP). These graphene often used in the form of nanostructures in a variety of
nanoplatelets were readily transferred between the aqueous and applications ranging from catalytic systems to fuel cells, sensors,
organic phases using ILP as the transferring vehicle. Chemically supercapacitors, and storage batteries.311−316 Considering its
converted graphene nanoplatelets decorated with ILP were reducibility, GO could be used to prepare graphene−metal
found to be stable against chemical reduction and were well particle nanocomposites. As such dispersions of metal nano-
dispersed in an aqueous phase without any agglomeration. The particles on graphene sheets potentially provide a new way to
reversible hydrophilic-to-hydrophobic switching of graphene develop catalytic, magnetic, and optoelectronic materials. Efforts
nanoplatelets was possible by simply exchanging the anions are being made to utilize graphene sheets as supports to disperse
associated with ILP. semiconductor and Pt particles and use them in solar cells and
Zhang et al.307 theoretically investigated the binding of organic fuel cells.
donor, acceptor, and metal atoms on graphene sheets. These Usually, the precursors for NPs are metal salts, which are
calculations revealed the effect of the different noncovalent reduced in a solvent that contains dispersed GO, RGO, or
functionalizations on the electronic structure and transport pristine graphene nanoplatelets. The last two are preferred when
properties of graphene. The adsorption of 2,3-dichloro-5,6- the conductivity of the substrate is of high importance. In some
dicyano-1,4-benzoquinone (DDQ) and tetrathiafulvalene cases, the reducing agents or procedures are strong enough to
(TTF) induce hybridization between the molecular levels and reduce GO simultaneously. The formed NPs are spread onto the
the graphene valence bands. This transforms the zero-gap relatively huge surface area of graphitic nanoplatelets.
semiconducting graphene into metallic graphene. However, the Graphene-stabilized gold nanoparticles (3−30 nm in diame-
current versus voltage (I−V) simulation indicates that non- ter) have been synthesized using chemically modified graphene
covalent modification by organic molecules is not sufficient to nanoplatelets, which support the gold nanoparticles. In this
significantly alter the transport properties of graphene for sensing method, gold atoms were deposited onto few-layer graphene.
applications. These gold atoms are then condensed upon annealing to form
nanoparticles.316 Recently, affinity of gold nanoparticles to
graphene has been compared with that of palladium and silver
4. FUNCTIONALIZATION WITH NANOPARTICLES nanoparticles with the conclusion that palladium has the highest
Composite materials derived from fine dispersions of metallic affinity to graphene. The theoretical calculations (at MP2 and
nanoparticles or oxides on carbon nanotubes have been vdW-DF levels) suggested that the high affinity of palladium to
extensively studied and applied in catalytic or optoelectronic graphene is caused by the partial covalent nature of binding
applications, supercapacitors, fuel cells, batteries, etc.308,309 Due between Pd and graphene.317
to the increased interest in graphene arising from its exceptional The deposition of gold nanoparticles on GO nanoplatelets has
electrical and mechanical properties, the immobilization of also been achieved by the direct reduction of AuCl4 by NaBH4 in
metallic and other nanoparticles on graphene sheets has become a GO THF suspension.318 The GO nanoplatelets used in the
the focus of many researchers. synthesis were first functionalized with octadecyl amine (GO−
A typical pristine graphene sheet can be characterized as an ODA) in order to be dispersible in the organic solvent. The
ideal substrate for the dispersion of nanoparticles due to its large formation of the Au nanoparticles (NP) was confirmed using
active surface area per mass unit, in comparison with carbon UV−vis absorption where the evolution of the characteristic
nanotubes, amorphous carbon, or graphite, which have a lower absorption band around 550 nm was observed (Figure 51). The
active surface area because only the external surface is active. size and the dispersibility of the as formed Au NPs were
Additionally pristine graphene has high conductivity and determined by the concentration of GO−ODA in the solution.
mechanical strength, and it is free of metallic or carbon As presented in Figure 52, in the absence of GO−ODA, the Au
impurities since the preparative methods are not catalytic, such NPs formed large aggregates, and this caused precipitation. As
as in carbon nanotubes, and the graphite starting material is of the the concentration of GO−ODA was increased, the Au NPs were
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Figure 53. Schematic representation of the fabrication process of RGO-based memory devices using Au NPs. Reprinted with permission from ref 320.
Copyright 2010 Wiley.
water system has also been used for the reduction of Au, Pt, and
Pd cations in the presence of GO. The as formed NPs are then
capable of catalytically reducing the GO surface in the presence
of ethylene glycol.326
4.2. Deposition of Metal Oxide Nanoparticles
Metal oxide nanostructures have been used in catalytic systems,
gas sensors, energy storage, transparent conducting electrodes,
flexible electronics, photonics, photovoltaic systems, etc.330−338
As an example, tin oxide (SnO2), manganese oxide (Mn3O4),
cobalt oxide (Co3O4), and titanium oxide (TiO2) nanocrystals
supported on carbon substrates have been used successfully as
anodes in Li-ion batteries. A high degree of nanocrystal
dispersion and conductivity of the substrate are the most
important factors for high charge capacity and cycling perform-
ance. Graphene nanostructures are ideally suited as a carbon
substrate for use as anodes in Li-ion batteries.
SnO2 should be a good material as an anode for Li-ion batteries
Figure 54. (Top) Schematic of formation of RGO/Pt and (bottom) with a theoretical Li storage capacity of 782 mA·h·g−1 compared
TEM images of dispersion of Pt nanoparticles on graphenes. Reprinted with graphite, which has a storage capacity of 372 mA·h·g−1. The
with permission from ref 328. Copyright 2010 Royal Society of disadvantage of SnO2 is that during the charge/discharge cycle its
Chemistry. volume increases 3 times, causing breaks and cracks in the anode
and thus shortening its life. This obstacle could be avoided or
was measured when a RGO support was used compared with a minimized by inserting RGO nanoplatelets between SnO2 NPs.
carbon black support.328 This was achieved by mixing homogeneously with RGO
A general method for the reduction of GO with simultaneous nanoplatelets. The pores and void spaces that formed in this
deposition of metal NPs or nanoalloys has been developed by case protect the anode from cracking, minimizing the expansion
Hassan and co-workers.329 In this method, microwaves are of SnO2 (Figure 58). In an alternate synthesis, SnO2 NPs were
utilized to reduce aqueous dispersions of GO in the presence of deposited on RGO nanoplatelets via an alkaline hydrolysis of
various reducing agents like hydrazine hydrate, ethylenediamine, SnCl4 in the presence of RGO. It was shown that the initial
or ammonium hydroxide. Thermogravimetric analysis of GO reversible capacity (810 mA·h·g−1) of the RGO/SnO2 composite
and the as prepared RGO showed that this method was effective is only moderately reduced after 30 cycles (570 mA·h·g−1),
in removing oxygen functionalities, with the RGO showing no showing remarkable improvement compared with that of pure
significant weight loss up to 750 °C (Figure 55). SnO2 NPs.330
In the case that a metal salt such as palladium nitrate, copper Zhang et al.339 have presented a method to increase
nitrate, or a mixture is present in the aquatic phase together with remarkably the loaded amount of metal oxide on graphene
GO, the analogous metal NPs were formed and deposited on the substrate without affecting the quality of the dispersion. The
RGO nanoplatelets (Figure 56). higher loading of metal oxide NPs could increase the charge
An oleylamine and oleic acid mixture is a powerful reducing capacity of the composite. Starting from graphene oxide, the
agent for the formation of Ag, Au, and Cu NPs in the presence of oxygen groups here were used as anchors attracting Sn4+ cations
GO. This method is superior to others because it exhibits a through electrostatic forces when GO and SnCl2 are dispersed in
narrow size distribution as well as fine dispersion of the produced water. After drying by heating, SnO2 nanocrystals are formed and
NPs on the GO surface. Ag, Au, and Cu NPs display a immobilized on the GO surface. TEM images showed the dense
characteristic absorption band in the UV−vis region due to decoration of SnO2 NPs on the GO nanoplatelets (Figure 59),
surface plasmon resonance (Figure 57). The ethylene glycol/ while AFM images showed that SnO2 NPs are possibly deposited
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Figure 56. TEM images of RGO nanoplatelets decorated with (a) Pd, (b) Cu, and (c) CuPd NPs. Reprinted with permission from ref 329. Copyright
2009 Royal Society of Chemistry.
ion batteries, mainly due to its high abundance and low cost.
Graphene nanostructures, as highly conductive materials, acting
as substrates for the deposition of Mn3O4 could help overcome
the low conductivity of this metal oxide. In a characteristic
example a RGO/Mn3O4 composite afforded a high capacity of
810 mA·h·g−1 with good rate capability and cycling stability.340
The decoration of RGO by well crystallized Mn3O4 NPs was
achieved by the hydrolysis of a Mn salt in a suspension of GO in
DMF/H2O followed by hydrothermal reduction of the GO
(Figure 60).
Improved anode performance in Li-ion batteries has also been
Figure 57. (Left) UV−vis absorption spectra of Ag, Au and Cu NPs noted using composites of graphene or RGO and metal oxides
deposited on RGO and (right) TEM image of the RGO nanoplatelet such as MnO2,341 CuO,342 Co3O4,343−345 CoO,346 Fe3O4,347
with Au NPs deposited on the surface. Reprinted with permission from TiO2,348 and Li4Ti5O12.349 For example, the RGO/Co3O4
ref 329. Copyright 2009 Royal Society of Chemistry. composite is formed by deposition of cobalt on RGO
nanoplatelets in the form of Co(OH)2 followed by calcination
on both sides of graphene oxide nanoplatelets explaining the at 450 °C (Figure 61).
observed high loading in this case. The graphene/TiO2 composite has been widely examined and
Since high conductivity is essential for the use of graphene/ its synthesis and physical properties have been reported by
SnO2 composites in Li-ion batteries, thermal reduction of the several researchers.18,348,350−353 An illustrative example of the
GO/SnO2 composite at 300 °C is needed to afford the RGO− use of the nanostructured RGO/TiO2 hybrid is presented by
SnO2 composite. The content of the SnO2 in the final composite Wang et al.348 where they demonstrated the enhanced Li-ion
was about 60%, compared with other carbon supports where the insertion/extraction kinetics in TiO2. This makes the material a
SnO2 content is usually less than 25%. The RGO/SnO2 showed candidate for use in Li-ion batteries or other energy storage
an initial reversible charge capacity of 786 mA·h·g−1, which after materials. For the preparation of the composite, RGO nano-
50 cycles drops to a capacity of 560 mA·h·g−1, is comparable to platelets were dispersed in water by stabilizing them with sodium
results reported by other groups.339 dodecyl sulfate. To this solution, a TiCl3 solution was added,
Although Mn3O4 exhibits very low conductivity, it could be which resulted in deposition of TiO2 NPs upon hydrolysis
considered an attractive oxide for use as an anode material for Li- (Figure 62).
Figure 58. (left) Schematic representation of the formation of RGO/SnO2 and its use in Li ion batteries and (right) cyclic performances for (a) SnO2
nanoparticles, (b) graphite, (c) RGO nanoplatelets, and (d) RGO/SnO2. Reprinted with permission from ref 330. Copyright 2008 American Chemical
Society.
Figure 61. Schematic representation of the formation of the RGO/Co3O4 composite: (a) dispersion of RGO in isopropyl alcohol/water solution, (b)
formation of RGO/Co(OH)2 composite, and (c) formation of RGO/Co3O4 composite by calcination. Reprinted with permission from ref 343.
Copyright 2010 American Chemical Society.
Figure 62. The growth of TiO2 on surfactant-stabilized GO nanoplatelets. Reprinted with permission from ref 348. Copyright 2009 American Chemical
Society.
Figure 64. (left) The change in color of a suspension of GO/TiO2 before and after UV irradiation. A suspension of TiO2 NPs is also shown for
comparison. (right) Absorption spectra of UV-irradiated TiO2 suspension (a) before and (b−d) after the addition of GO suspensions: (b) 50, (c) 150,
and (d) 300 μg of GO (a0 corresponds to the TiO2 suspension prior to UV irradiation). Reprinted with permission from ref 18. Copyright 2008
American Chemical Society.
nanocrystals located on the graphene layer or on the quartz region from blue to red can be produced by the fluorescence of
substrate could be observed, with strong fluorescence quenching the composite solutions (Figure 74).
observed for particles deposited on the graphene sheets (Figure
72). A similar fluorescence quenching was observed when CdS
and CdSe NPs were dispersed on GO nanoplatelets.370,371
Figure 73. Schematic representation of the formation of RGO/CdSe NP composite. Reprinted with permission from ref 372. Copyright 2011 Royal
Society of Chemistry.
5. SUBSTITUTIONAL DOPING
A particularly distinctive position in this chapter should be given
to the substitutional doping of graphenes, where carbon atoms
from the hexagonal honeycomb lattice of graphene can be
substituted by nitrogen or boron atoms. Depending on the
electrophilic character of the atoms that substitute the carbon
atoms, the doped graphene sheets show n- or p-type behavior. In
addition, by controlling the degree of this doping modification,
the electrical properties of graphene could be potentially tailored,
thereby expanding remarkably the application of graphene in
nanoelectronics.
The incorporation of nitrogen atoms is made using their three
sp3 orbitals; this leads to their lone pair electrons being
conjugated with the graphitic π-system. The N-doped graphene
sheets are electron-rich so that n-type semiconducting behavior
Figure 75. (a) AFM image of GO and (b) related height profile, (c) Si/
is expected. In general, N-doped graphene sheets are formed by
GO composite paper, and (d) Si/RGO composite paper obtained by the substitution of O or C atoms with N during reduction or
reduction of Si/GO. Reprinted with permission from ref 373. Copyright annealing43,376−378 or in situ during graphene growth using
2010 Royal Society of Chemistry. CVD,379 arc discharge,380 or solvothermal methods.381 Oxygen
or sp3 carbon atoms that are situated at the defect sites of GO can
be substituted by nitrogen during the reduction step using a
Cobalt hydroxide (Co(OH)2) materials usually display a nitrogen-rich reductive source like ammonia or hydrazine, at high
layered structure with a high interlayer spacing and a well-defined temperature.
electrochemical redox activity. The combination of cobalt Starting from graphene nanoribbons (GNRs), Wang et al.43
hydroxide NPs with GO nanoplatelets are promising candidates demonstrated N-doping using high-power electrical joule
for use in alkaline batteries, fuel cells, and supercapacitors. Chen heating in ammonia gas. The chemically derived GNRs were
et al.375 showed that the abundance of hydroxyl anions produced dispersed on a SiO2/Si chip and immobilized between a
by the hydrolysis of disodium sulfide (Na2S) in an aqueous palladium metal source/drain (S−D) forming a FET-like device
solution of GO and CoCl2·6H2O is sufficient to reduce GO, as (Figure 77). The GNR was electrically annealed under an NH3/
well as facilitate the formation of Co(OH)2 NPs (Figure 76). Ar atmosphere. The existence of C−N bonds in the derived
The GO/Co(OH)2 composite was applied as a supercapacitor GNR was identified by X-ray photoelectron spectroscopy (XPS)
electrode, which displayed enhanced electrochemical perform- and nanometer-scale secondary ion mass spectroscopy. In this
ance. This performance was examined using cyclic voltammetry, case, the C−N bonds are formed mostly at the edges of graphene
electrical impedance spectroscopy, and galvanostatic charge− sheets where the chemical reactivity is higher.
discharge measurements.375
Figure 78. Schematic structure of GO and N-doped GO produced by hydrothermal reduction. Reprinted with permission from ref 377. Copyright 2010
American Chemical Society.
Figure 79. A possible mechanism for the solvothermal synthesis of N-doped graphene. Reprinted with permission from ref 381. Copyright 2011
American Chemical Society.
Figure 80. (a) Concentration of chemically induced charge carriers in SLG exposed to different concentrations of NO2 and (b) changes in resistivity at
zero B field caused by graphene’s exposure to various gases diluted to 1 ppm. Reprinted with permission from ref 384a. Copyright 2008 American
Chemical Society.
In another approach, the same group has studied the nitrogen Here the efficiency of the N-doping tends to be dependent on the
doping and simultaneous reduction of GO during annealing in amount of oxygen groups at the defect and edge sites of GO.
NH3.376 GO was heated in a 2 Torr NH3/Ar (10%) atmosphere. In a similar manner, partially nitrogen-doped reduced GO
N-doping started at 300 °C and reached a maximum level of 5% nanoplatelets were produced by hydrothermal treatment of GO
doping by heating at 500 °C. Several grams of N-doped GO
in a colloidal dispersion in the presence of hydrazine and
could be produced by the described method. It was further
observed that NH3 reduced GO more effectively than H2 under ammonia (Figure 78).377 The structure and surface chemistry of
the same conditions. The N-doping as well as the reduction was the resulting GO nanoplatelets is strongly dependent on the
characterized by XPS and electrical transport measurements. temperature of hydrothermal treatments.
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Figure 81. (a) A general bottom-gated graphene FET structure with phenyl-SAM interface engineering. (b) Illustration of chemical bonding of the
organosilane SAM to the hydroxyl group-enriched dielectric surface. (c) AFM image of a spin-coated ultrasmooth phenyl-SAM with surface roughness
of 0.1−0.2 nm in rms. (d) Microscopy image of a large-area, uniform CVD graphene as patterned to various shapes on a phenyl-SAM engineered silicon
oxide wafer. Reprinted with permission from ref 390. Copyright 2011 American Chemical Society.
Figure 83. AFM images of pentacene films (50 nm) near the interface between SiO2: (a) untreated graphene electrodes and (b) thermally treated
graphene electrodes. Schematic representations of the possible molecular packing orientations near the interface between SiO2 and (c) untreated
graphene electrodes or (d) thermally treated graphene electrodes. Reprinted with permission from ref 391b. Copyright 2011 Wiley.
Figure 84. Schematic models of the bilayer graphene (BLG), the BLG doped with FeCl3 (aBGL) composite system, the BLG dual-doped with FeCl3 and
K (aBLG+K), and the BLG doped with K (BLG+K) (top), tight binding parameters for the onsite potential difference (Δ) obtained by DFT calculation
(center), and band structures calculated by tight binding method and the Dirac point shifts (δεD) obtained by DFT calculation (bottom). Reprinted with
permission from ref 394. Copyright 2011 American Chemical Society.
levels can be achieved using ionic polymer electrolytes or alkali Another method toward doped graphene is to deposit
atoms.388,389 nanoparticles instead of unstable metallic atoms on the graphene
Most simple molecular doping in the atmosphere makes it surface, as described in section 4.
difficult to control the position and magnitude of doping. For this Self-assembled monolayers (SAMs) are ultrathin molecular
reason, interstitial doping investigated so far is usually done films spontaneously formed at oxide surfaces or interfaces due to
under vacuum conditions to avoid unwanted adsorption of chemical or physical interactions of molecules with a substrate,
dopant molecules. Thus, stable doping methods, using organic frequently without necessity of high-vacuum or high-temper-
molecules or polymeric molecules such as tetrafluoro-tetracya- ature processing.46,390−393 The robust ultrathin layer in a defined
noquinodimethane (F4-TCNQ), tetracyanoethylene (TCNE), area is constructed by spontaneous chemical reaction at the
aniline, anisole, benzene, chlorobenzene, or nitrobenzene, are interface, which makes SAMs technologically attractive for
required for use in applications.385−387 Aromatic molecules,385 surface and interface engineering (Figure 81). In addition,
including 1,5-naphthalenediamine (Na-NH2), 9,10-dimethylan- surface energy, dipole moments, and chemical reactivity of the
thracene (An-CH3), 9,10-dibromoanthracene (An-Br), and surface can be easily tuned by attaching functional groups to the
tetrasodium 1,3,6,8-pyrenetetrasulfonic acid (TPA), can stably SAMs. SAMs have received considerable attention due to their
bind to single-layer graphene (SLG) through strong π−π use in organic electronics as active materials or insulators. SAM−
interactions between their aromatic rings and the graphene. graphene systems are found to be very stable in high vacuum and
Electrical measurements of SLG/aromatic molecule composites ambient environments. The robustness and the large electronic
suggest that the aromatic molecules impose carriers on the SLG. effect suggest that the integration of a SAM with graphene
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Figure 86. (a) Raman spectra of intercalated FLGs. (b) Atomic structural model; carbon atoms are shown as gray spheres, iron atoms as red, and
chlorine atoms as brown. (c) Transport measurements of an intercalated bilayer device; Shubnikov-de Haas (SdH) oscillations seen in Rxx(B) are
recorded at temperatures 2, 10, 20, and 40 K. Reprinted with permission from ref 396. Copyright 2011 American Chemical Society.
Figure 87. (a) First and fourth cyclic voltammograms of the Ni/FLG electrode in polymer electrolyte and (b) in situ Raman spectra of the Ni/FLG
electrode at selected potentials during electrochemical lithiation. Reprinted with permission from ref 398a. Copyright 2010 American Chemical Society.
workers.391 The polymer residues remaining on the graphene The band gap opening of graphene is the most desired
surface were shown to alter the performance of the transistor, property in the device industry because it is vital to the
with a stand-up orientation of pentacene formed on the polymer application of graphene as field effect transistor (FET). Chemical
residue surface, which results in a molecular assembly that is doping of graphene can open the band gap of graphene.
optimal for charge transport (Figure 83). In contrast, epitaxial However, it accompanies significant Dirac point shifts, which
growth of pentacene on a polymer-free graphene surface results give a low on/off current ratio and a poor switching property.
in a lying-down structure of the pentacene; this molecular Recently, both theoretical and experimental studies show how to
assembly facilitated by π−π interactions between pentacene and make a wide band gap and reasonable Dirac point shift in
graphene adversely affects lateral charge transport at the interface graphene system by using dual doping of bilayer graphene. Yang
between electrode and channel. et al.394 have investigated bilayer graphene (BLG) dual-doped
These results ultimately improve the potential applications of with FeCl3 acceptor and K donor by employing the first
graphene transistors toward VLSI circuits390 and graphene principles method taking into account van der Waals interaction.
electrodes for high-performance organic field-effect transistors Due to high electronegativity of the FeCl3 molecular layer, FeCl3
(OFETs).46,391 Chemical doping can decrease sheet resistance of adsorbed BLG is hole-doped. Also the asymmetric composite of
graphene while maintaining its high transparency. Lee et al.392 BLG with the FeCl3 layer adsorption is shown to exhibit an
developed a new method to simultaneously transfer and dope energy gap opening (Figure 84). By utilizing this asymmetric
chemical vapor deposition grown graphene onto a target behavior, which increases the band gap, the bilayer graphene with
substrate using a fluoropolymer as both the supporting and dual FeCl3 acceptor and K donor doping makes a significant
doping layer. This method was used to fabricate a flexible and energy gap opening (0.3 eV) with a proper Dirac point shift
transparent graphene electrode on a plastic substrate. (−0.09 eV) toward practical FET device applications.
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Figure 90. Schematic illustration of the LbL deposition of GO and PW clusters and the photoreduction of GO. Cationic polyelectrolytes
polyethyleneimine (PEI) and PAH are used as electrostatic linkers. Reprinted with permission from ref 402. Copyright 2011 American Chemical
Society.
Figure 91. Optical images of a GO/PW multilayer film on a quartz substrate before (A) and after (B) 6 h of UV photoreduction and on a flexible PET
substrate before (C) and after (D) 6 h of UV photoreduction. Both substrates were coated using a PET/PW precursor film. Reprinted with permission
from ref 402. Copyright 2011 American Chemical Society.
Figure 92. Schematic representation of a hybrid multilayer composite of functionalized MWNTs and RGO. Reprinted with permission from ref 401.
Copyright 2010 American Chemical Society.
Park et al.46,47 developed a new method for band gap opening 6.2. Multilayered Graphene Intercalates and Composites
of bilayer graphene by dual molecular doping. The 2,3,5,6- Few layer graphene (FLG) can be chemically modified
tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) interstitially by intercalating molecules into the structure.
molecules deposited onto bilayer graphene induce p-doping Intercalation between layered crystalline materials and graphene
from the top, while NH2-functionalized self-assembled mono- occurs through van der Waals interactions, providing new
layers (SAMs) constructed on SiO2/Si substrate induce n-doping chemical and physical functionality such as superconductivity
from the bottom side. These dual doping-driven perpendicular and quasi-low-dimensional magnetism.395 An FeCl3 bilayer
electric fields with opposite directions remarkably increase the graphene (BLG) intercalate has been synthesized and electrically
on/off current ratio of bilayer graphene field-effect transistors characterized as a minimal graphite intercalation compound
(FETs), which unambiguously proves that it is possible to open a (GIC, Figure 86).396 Interestingly, the resistance behavior of this
band gap with two molecular dopants (namely, F4-TCNQ and intercalation product is related to a magnetic transition. This
NH2-functionalized SAMs) (Figure 85). Both theoretical and work demonstrates the first step toward the synthesis of various
experimental results indicate that band gap opening of bilayer different functional bilayer intercalates including sandwich-like
graphene can be accomplished by dual molecular doping, which structures.397
does not require a complicated fabrication step for preparing a Besides the fundamental study of 2DESs (two-dimensional
device with a dual-gate structure. electron systems), FLG intercalation materials can be considered
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Figure 93. Schematic illustration of the preparation of a GO/ionic liquid multilayered composite and their LbL assembly on a quartz crystal
microbalance (QCM). Reprinted with permission from ref 403. Copyright 2010 Wiley.
Figure 95. Schematic ZGNR-based spin-valve device (left) with parallel and antiparallel spin configurations and the corresponding spin-magnetization
density isosurfaces. The blue boxes represent ferromagnetic electrodes to control spin polarization of the ZGNR device and the red arrows indicate the
directions of spin configurations. In the isosurfaces, red/blue color denotes up/down spin, and a ZGNR skeleton is drawn in green color. Spin-transfer
paths (right) from the left to right density of states of the ferromagnetic leads for parallel (P) and antiparallel (AP) spin configurations in a ZGNR spin-
valve device are compared with those in a conventional spin-valve device. Reprinted with permission from refs 29 and 409. Copyright 2008 Nature
Publishing group and Copyright 2010 American Chemical Society, repectively.
Figure 100. Photocatalytic activity of SEG−P25 and SRGO−P25 nanocomposites. (A) Pseudofirst-order CH3CHO photo-oxidation rate constants for
SEG−P25 and SRGO−P25 nanocomposites under ultraviolet (365 nm) and visible illumination. (B) CO2 photoreduction for SEG−P25 and SRGO−
P25 nanocomposites under ultraviolet (365 nm) and visible illumination. Reprinted with permission from ref 429. Copyright 2011 American Chemical
Society.
6.3. Electronic/Spintronic Devices Including Ultrafast DNA the occupied bands below the Fermi energy (EF) have “C2”
Sequencing symmetry, while the unoccupied bands have “σ” symmetry. Since
Structural and electronic/magnetic properties of graphene both occupied and unoccupied bands have orbital symmetries
nanoribbons (GNRs) have been intensively studied both orthogonal to each other, spin-transfer to FMA is not allowed
experimentally and theoretically. Depending on their various due to mismatching between the orbital symmetries at both
edge structures, GNRs present different electronic properties sides, which lead to an ideal spin-valve with infinite MR value.
ranging from normal semiconductors to spin-polarized half- Although theoretical works have proposed and predicted
metals (Figure 94). Unlike graphene sheets as a zero gap many interesting properties of GNRs, the experimental
semiconductor, armchair GNRs open an energy band gap, as realizations of GNRs are still not easy. Sub-50 nm nanoribbons
semiconductors with energy gaps, which enables the basic were first fabricated by e-beam patterning and oxygen plasma
electric logic states. The electronic structures of GNRs as electric etching from mechanically exfoliated graphene.410 Although the
devices have been investigated based on theoretical calcula- process yielded Ion/Ioff ratios of up to 104, devices showed high
tions.407 Energy gaps decrease as a function of increasing ribbon variability due to the lack of control over edge termination. On
widths arising from the quantum confinement effect, which can the other hand, the challenge of synthesizing reproducible GNRs
be characterized by Eg ≈ 1/W. Thus, enhancing such Ion/Ioff is an interesting one. Isolation of GNRs directly from bulk
ratios by introducing an appreciable band gap has been a major graphite involved sonication of expanded graphite in the
issue in graphene-based logic devices. No magnetism has been presence of a polymer.59,411 The polymer acted to noncovalently
found in armchair GNRs. In contrast, metallic zigzag GNRs functionalize and consequently stabilize nanoribbons formed by
(ZGNRs) are considered as an element for spintronic mechanical fracture. In the presence of the polymer, the ribbons
application.408 can be suspended in organic solvents and then deposited by spin-
Since ZGNRs favor a ferromagnetic state, the ZGNR can be a coating. For such sub-10-nm GNRs, the band gap was inversely
potential spintronic device by controlling the spin state. Based on proportional to their width, with an energy gap of ∼0.4 eV. This
calculations of the quantum transport property for the led to on−off ratios of up to 106 for the thinnest strips.411 In
ferromagnetic state with both the parallel spin configuration addition, recently, high-resolution temperature distribution was
(ferromagnetic parallel; FMP) and the antiparallel spin measured for a self-heated GNR.412
configuration (ferromagnetic antiparallel; FMA), ZGNR exhibits Even though it is difficult to synthesize the ideal GNR with
an extreme enhancement of magnetoresistance (MR).29 This clear edge structures experimentally, theoretical results suggest
abnormality arises not only from the spin symmetry, which is the that GNRs can be candidates for a sensitive molecular sensor as
major origin of the giant magnetoresistance (GMR) and the well as future electronic FET devices and spintronic devices.
tunneling magnetoresistance (TMR), but also from the unique Recently, Cai et al.413 have reported atomically precise bottom-
orbital symmetry of the ZGNR (Figure 95).29,409 For the ZGNR, up fabrication of GNRs. They used surface-assisted coupling of
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Figure 101. GON-induced cancer cell therapy. Reprinted with permission from ref 443. Copyright 2012 Wiley.
molecular precursors into linear polyphenylenes and their functional groups can give us a variety of properties, for example
subsequent cyclodehydrogenation. Since edge structures, semiconductivity with a wide range of band gaps, that is, metallic,
width, and length of GNRs are difficult to control, finding an ferromagnetic, antiferromagnetic, half-metallic, or half-semi-
effective way to overcome these problems becomes more and conducting.
more important, both for academic research and for industry 6.4. Green Chemistry
applications.
As an interesting application, a new method for ultrafast DNA Graphene-based materials display green chemistry applications
sequencing using a GNR-based nanochannel device has been such as water remediation, CO2 capture, and renewable energy
suggested.37 While a single-strand DNA passes beneath a GNR, production.30,416−432
each nucleobase interacts with the GNR via π−π stacking For water remediation, graphene needs to be functionalized to
interactions. Because the conducting properties of a GNR differ be dispersible in solution. Indeed, graphene has been shown to be
when they interact with different nucleobases due to the Fano effective at absorbing organic pollutants from aqueous solutions
resonance phenomena, real-time DNA sequencing is possible by via π−π and other electrostatic interactions. In several cases,
analyzing the real-time conductance of the GNR. Since the stable small organic molecules or surfactants have been used to disperse
π−π stacking interaction reduces stochastic motion of a graphene in organic media or water. These molecules/
nucleobase during the conductance measurement, the overlap surfactants stack permanently on the graphene sheets, thereby
between the signals from each nucleobase can be minimized. preventing aggregation. This kind of dispersion could be
Thus, more reliable DNA sequencing can be realized after several characterized as a noncovalent type of chemical functionaliza-
statistical analyses including a data-mining approach and a two- tion, because these molecules are immobilized on the graphene
dimensional transient autocorrelation function (Figure 96). surface via π−π stacking, H bonds, electrostatic forces, etc.
Modification of the electronic structure of nanoribbons by Xu et al.416 showed that bisphenol A could be removed from
chemical functionalization is an effective way to make them an aqueous solution with a higher capacity than that with other
efficient for their applications. This can be achieved through edge known carbonaceous absorbents. The high capacity of
modification or adsorption of functional groups.43,414,415 A adsorption is believed to be due to hydrogen bonding as well
simple chemical modification of nanoribbons is to saturate the as π−π interactions. Huang et al.417 have shown that graphene
edges by atomic functional groups, such as −H, −O, −F, −OH, can be used to absorb Pb(II) cations from aqueous solution. The
and −NH2, which change electronic/magnetic states of GNRs. authors noted that the adsorption capacity was strongly
Working on obtaining desirable properties by modifying dependent on solution pH (Figure 97). In a similar way,
nanoribbons with appropriate functional groups will help us Vasudevan and Lakshmi418 have demonstrated that phosphate
find the suitable form of graphene nanoribbons for each anions can be removed from aqueous solutions by graphene at an
application. Modification with various types of elements and optimal pH value of ∼7. The absorption kinetics followed a
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Figure 102. Fluorescent images of human breast cancer cell T47D after incubation with green GQDs for 4 h: (a) phase contrast picture of T47D cells;
(b) individual nucleus stained blue with DAPI; (c) agglomerated green GQDs surrounding each nucleus; (d) the overlay high contrast image of
nucleolus stained with blue DAPI and GQDs (green) staining. Reprinted with permission from ref 445. Copyright 2012 American Chemical Society.
Figure 103. (a) In vitro fluorescence microscopy images of T47D cells treated with GO-F (50 μg mL−1) for 24 h. (i−iii) Low magnification images of
T47D cells: (i) phase contrast picture, (ii) fluorescence images of GO-F, and (iii) overlay of images i and ii. (iv−vi) High magnification images of an
individual T47D cell: (iv) phase contrast picture of an individual T47D cell, (v) fluorescence image of GO-F, and (vi) overlay of images iv and v. (b) T2-
weighted MR image showing strong T2 contrast in agarose phantoms. It shows alginate phantoms doped with different concentrations (as shown) of
GO-F. The T2-weighted image was acquired in a 7 T scanner with multislice multiecho sequence. The T2 relaxivity was 297.06 mM−1 s−1. Reprinted
with permission from ref 447. Copyright 2012 Wiley.
second-order kinetic model, suggesting that the absorption was volumes of water. Yang and co-workers420 further showed that
chemically controlled.418 GO has been shown by Zhao et al.419 to methylene blue can be effectively removed from aqueous
be an effective absorbent of both Cd(II) and Co(II) from large solutions using GO; the authors recorded removal efficiency
AV dx.doi.org/10.1021/cr3000412 | Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review
higher than 99%. Sulfonated graphene nanosheets prepared from et al.,430 the water splitting reaction electrophotochemically
GO were shown by Zhao and colleagues421 to be highly effective occurred with a 10-fold enhancement of H2 evolution in
at the removal of naphthalene and 1-naphthol, with very high comparison with pure BiVO4 under visible illumination. Xiang
absorption capacities. Chandra and Kim422 functionalized and co-workers431 have shown that photocatalytic H2 production
graphene sheets with polypyrole (PPy), with the resulting can be achieved in the presence of a TiO2/MoS2/graphene
composite material showing high and selective absorption nanocomposite. The positive synergetic effect between the MoS2
capacity for Hg(II) cations (Figure 98).422 The presence of and graphene sheets can efficiently suppress charge recombina-
graphene in PPy enhances the charge density of the pyrrolic tion, improve interfacial charge transfer, and provide a greater
nitrogen, thus increasing the electrostatic interaction between number of active adsorption sites and photocatalytic reaction
adsorbate and adsorbent. Sui et al.423 have shown that carbon centers for H2 production. Graphene nanomaterials also have
nanotube−graphene hybrid aerogels fabricated by supercritical been used as effective replacements for Pt-based materials (Pt−
CO2 drying of their hydrogel precursors display extremely high C) in the oxygen reduction reaction (ORR) as has been reported
desalination capacity, high binding capacities to some heavy by Liang and colleagues.432 They showed that a Co3O4/N-doped
metal ions and high adsorption capacities for dye stuffs. This graphene hybrid material exhibits comparable elecrocatalytic
hybrid material shows promise in water purification due to its performance with superior stability compared with Pt-based
high versatility, which can be attributed to its light weight, high materials (Pt−C) in alkaline solutions for the ORR reaction, this
conductivity, large BET surface area, and hierarchically porous result shows that this material can be applied to fuel cells.
structure. Graphene−CNT complexes have also been shown to be
Graphene sheets decorated with magnetite nanoparticles have excellent ORR electrocatalysts. The bis-
been shown by Chandra et al.30 to be extremely effective in (trifluoromethanesulfonyl)amide doped graphene could en-
As(III) and As(V) removal. The benefit of using this magnetic hance the power conversion efficiency of solar cell to 8.6% in
graphene material in water remediation is that it can be separated producing electricity from solar energy.433
easily using an external magnetic field once absorption has taken 6.5. Bio-imaging
place. In a similar manner, Geng et al.424 synthesized RGO/
Fe3O4 composites for dye removal from aqueous solutions.424 Graphene can be made luminescent (i.e., quantum dots) by
They demonstrated that by simple annealing in moderate inducing a band gap. This can be achieved by reducing the
conditions, this hybrid adsorbent can be easily and efficiently connectivity of the π-electron network using chemical or physical
regenerated for reuse with hardly any compromise of the methods.434−436 This makes graphene a strong candidate for
adsorption capacity. Graphene decorated with photocatalytically bioimaging applications because it is biocompatible and displays
active SnO2 and TiO2 has been employed in the degradation of flourescence in the infrared and near-infrared.435−440
dyes under visible light irradiation as illustrated by Zhang et al.425 Sun et al.441 reported that pegylated (poly(ethylene glycol))
The degradation activity of these materials were shown to be nanographene oxide (NGO) displays photoluminescence in the
higher than that of the commercially available P25 benchmark visible and infrared regions. They showed that the anticancer
catalyst. Zhang and co-workers426 have reported that a TiO2 drug doxorubicin could be physisorbed onto the pegylated NGO
RGO hybrid material is capable of efficient Cr(VI) to Cr(III) surface that had been functionalized with antibodies. These
reduction. antibodies allowed for selective killing of cancer cells in vitro,
The greenhouse gas CO2 can be captured using N-doped which could be monitored using fluorescence. In a similar
porous graphene with a large surface area as demonstrated by manner, Peng and co-workers442 demonstrated that fluorescein-
Chandra et al.427 The authors achieved a high selective functionalized pegylated graphene oxide (GO) could be used in
absorption capacity of 4.3 mmol/g CO2 at 298 K, thereby intracellular imaging. The poly(ethylene glycol) spacer was
showing the composite materials potential for industrial introduced to prevent GO-induced quenching of the conjugated
application (Figure 99). In a similar manner Mishra and fluorescein. Moreover, the composite material exhibited
Ramaprabhu428 have shown that by using polyaniline decorated excellent pH tunable properties. Li and colleagues443 have
graphene sheets CO2 could be reversibly captured. The increase shown that pegylated NGO functionalized with transferrin can
in CO2 absorption over RGO sheets is attributed to the chemical be used for two-photon luminescence cell imaging and
interaction of CO2 molecules with the nitrogen containing phototherapy. It was observed that irradiation by a laser source
functional groups of the polyaniline. creates microbubbling in the presence of NGO, which causes
Beside “end-of-pipe“ or remediation issues, renewable energy instant cell damage at an order of magnitude lower irradiation
production is conceptualized as alternative processes for green power (Figure 101). It was noted that the damage caused by the
fuels in the near future. The current trend of sustainable irradiation was extremely site specific, only causing cell death at
technology is the harvesting of solar energy, specifically photo- the point of irradiation, thereby offering localized therapy.
assisted water splitting and photovoltaic conversion. Liang and Graphene quantum dots (GQDs) have been used for cellular
colleagues429 have reported that TiO2 modified nanographene imaging due to their low toxicity and high photoluminescence
enhances the photocatalytic reduction of CO2 7 times compared yield as has been illustrated by Zhu et al.444 The authors showed
with pure TiO2. The importance in this work is the role of less- that the GQDs synthesized by a one-step solvothermal method
defective graphene in the hybrid photocatalyst. This work display biocompatibility as well as low cytotoxicity, making them
illustrates the use of the nanocomposite in solar cells as it excellent bioimaging agents. Peng and co-workers445 reported
facilitates the diffusion of photoexcited electrons to the reactive that GQDs can be synthesized from readily available pitch carbon
sites (Figure 100). fibers via chemical exfoliation. It was shown by the authors that
In water splitting, the performance of semiconductor nano- the photoluminescence of the GQDs can be tailored by changing
materials can be significantly enhanced with the electronic the reaction temperature. The QDs were shown to display
support of graphene. In the system of BiVO4/RGO composite minimal toxicity and were employed as imaging agents in two
connected to a collecting electrode, which was investigated by Ng human breast cancer cell lines (Figure 102).
AW dx.doi.org/10.1021/cr3000412 | Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review
Hu et al.446 have demonstrated that GO functionalized with applications of graphene and graphene composite materials will
CdSe/ZnS quantum dots can be used for visible-light imaging more than likely be in devices.454
and near-infrared phototherapy of cancer cells. The authors The use of graphene nanoparticle materials is another
showed that as the QDs are irradiated in the near-infrared region important issue that needs to find solutions with respect to
they display a reduction in fluorescence, thereby making this repeatable and controllable synthetic procedures if their true
composite material suitable for in situ monitoring of the potential is to be attained. The performance of these graphene
treatment. Narayanan and co-workers447 have shown that nanocomposite materials are highly dependent on the
NGO functionalized with Fe3O4 can be used as a dual imaging
architecture of the nanoscale building blocks, which can often
material, utilizing photoluminescence as well as magnetic
resonance imaging (Figure 103). result in nonrepeatable experiments, which makes this another
Kim et al.448 reported that GO modified with low-molecular important point that needs to be addressed. It is only with an
weight branched polyethylenimine (BPEI−GO) is able to act as a advance in these synthetic areas that the promised uses of
cationic gene carrier. It was shown that the composite had a high graphene nanocomposite material in green chemistry will finally
delivery efficiency and biocompatibility when used in trans- be achieved. It may be that for photocatalytic water splitting the
fection studies. The use of the composite for bioimaging was separation of holes and electrons can be successfully achieved
shown when a labeled DNA strand was attached and the using a graphene nanoparticle composite material.
movement of the composite into the cells was monitored using Whatever the future holds for graphene research, one can be
confocal microscopy. Mao and colleagues449 have reported that assured that there will continuously be interesting topics because
p-sulfonated calyx[6]arene modified graphene can be used as a the material has already found interesting applications in fields as
“turn on” fluorescent probe for L-carnitine both in vitro and in far apart as stem cell differentiation,455 highly selective
living cells. The as formed composite displays good stability in separation,456 graphene−nanowire hybrid structure based
biological systems as well as a low toxicity, making this composite photoconductive devices,457 graphene charge-doping based π
material potentially useful in imaging as well as drug delivery.
plasmon control,458 and high-resolution spectroscopy.459
Looking toward the future use of graphene, it may be that in
7. SUMMARY AND OUTLOOK expanding on the already studied synthetic procedures lies a key
In 2004, the initial measurements of the electrical conductivity of to unlocking a new realm of opportunities for this material.
graphene by Geim and Novoselov sent ripples of excitement
through the scientific community. In the past years, the initial AUTHOR INFORMATION
interest in the so-called “wonder” material has not faded, with a
number of potential applications already proposed ranging from Corresponding Author
water remediation to supercapacitors, DNA-sequencing, photo- *R.Z.: e-mail address [email protected]; telephone +420-58-
catalysts, and oxygen reduction reaction catalysts. This says that 563-4947; fax +420-58-563-4958. K.S.K.: e-mail address kim@
there is clearly much work to still be done to understand the postech.ac.kr; telephone +82-54-279-2110; fax +82-54-279-
properties of graphene and functionalized graphene, thereby 8137.
opening new avenues of research. One just has to consider the
Notes
structure of GO to realize that there are multiple manipulations
that can be chemically achieved, if only we understood the The authors declare no competing financial interest.
structure fully.450 This review provides insight into the various
Biographies
ways to functionalize graphene and graphene derivatives, thereby
expanding the number of potential applications for graphene-
based materials. The functionalization modes can be classified
according to the method and materials used and as such have
been categorized as covalent functionalization, noncovalent
functionalization, substitutional doping of graphene, and hybrid-
ization with nanoparticles, nanowires, and other materials. These
various methods of functionalization offer various ways to expand
on the current uses of graphene, that is, bioimaging or band gap
opening, which can be used in electronics.
Graphene as a 2-D material still suffers from controlled
synthetic growth conditions, especially when graphene deriva-
tives are considered. It is imperative that these synthetic issues
are addressed so that graphene and its derivatives can attain the
highly promised application potential. With improved synthetic
procedures graphene should be able to be employed far more
Vasilios Georgakilas received his B.Sc. and Ph.D. degrees in Chemistry
easily in electronics as well as other applications that require fast
and Organic Chemistry from the University of Ioannina (Greece) in
electron transfer like photocatalytic applications toward renew-
able energy. The 3-D manipulation of the 2-D graphene material 1989 and 1998, respectively. He then worked in the Institute of Material
is another very important issue to be addressed as the Science of N.CSR “Demokritos” and at the University of Trieste as a
manipulation of graphene into higher order nanostructures is Postdoctoral Fellow and Research Associate. In 2010, he was elected
already showing promise in supercapacitators,451 fuel cells,452 Assistant Professor in the Material Science Department of the University
water remediation,422 and drug delivery453 among others. of Patras. His research interest lies in the functionalization of carbon
However, as has been noted in the main text, the main nanostructured materials and their application.
Pavel Hobza received his Ph.D. (with R. Zahradnik) degree in Prague. of the Czech Republic (Grant P208/12/G016), Grant Agency of
After postdoctoral study with Camille Sandorfy at the Universite de the Academy of Sciences of the Czech Republic (Grant
Montreal, he spent several periods as a visiting professor and a visiting KAN115600801), Operational Program Research and Develop-
scientist at Montreal, Erlangen, and Muenchen. In 2001, he moved from ment for Innovations − European Regional Development Fund
Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the (Grant CZ.1.05/2.1.00/03.0058), and Operational Program
Czech Republic, to the Institute of Organic Chemistry and Biochemistry Education for Competitiveness − European Social Fund
where he is currently Head of Department of Molecular Modeling. He is (Grant CZ.1.07/2.3.00/20.0017). This work was also a part of
a professor of Physical Chemistry at the Charles University in Prague. the research project RVO:61388963 of the Institute of Organic
His research interests focus on molecular interactions and their role in Chemistry and Biochemistry, Academy of Sciences of the Czech
physical chemistry and biodisciplines. Republic. The authors deeply thank Dr. J. Tucek (Palacky
University, Olomouc, Czech Republic) for the manuscript
editing.
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