Beruflich Dokumente
Kultur Dokumente
REVIEW
much better than those of chemically or thermally RGO materials. We provide examples of how RGO
has been used as supercapacitor electrode materials. Specic capacitance of GO increases after
reduction and the value has been reported to be 100300 F g1. We conclude by proposing new
environmentally friendly types of reducing agents that can eciently remove oxygen functionalities
from the surface of GO.
1
a
c
Department of Hydrogen and Fuel Cell Engineering, Chonbuk National University,
Jeonju, Jeonbuk, 561-756, Republic of Korea. E-mail: namhk99@naver.com
Introduction
Review
Nanoscale
Nanoscale
Review
Preparation of GO
Recently, there has been increased interest in using preoxidized graphite to increase the extent of oxidation. In this
method, pre-oxidation of graphite (2.0 g) is carried out in the
presence of a concentrated H2SO4 (20 ml) solution in which
K2S2O8 (1.0 g) and P2O5 (1.0 g) are completely dissolved at
80 C.44 The mixture, in a beaker, is kept at 80 C for 5 h using an
oil bath, aer which the mixture is cooled down and diluted
with 1 liter of distilled water. The nal product is ltered and
washed with distilled water followed by vacuum drying at 75 C.
The dry pre-oxidized graphite powder obtained is then oxidized
by Hummers' method. The resulting graphite oxide contains
more than 30% of oxygen (atomic%) as compared to graphite
oxide obtained by the oxidation of pure graphite.
The Staudenmaier method is also regarded as an eective
method to oxidize graphite and the extent of oxidation is
comparable to that obtained by Hummers' method. However,
Reduction of GO
Review
Nanoscale
Fig. 1 (a) Hofman, (b) Ruess, (c) NakajimaMatsuo, and (d and e) LerfKlinowski model structures of GO showing the presence of oxygen functionalities above and
below the basal plane. (Reproduced with permission from ref. 5557.)
3.1
Chemical reduction
Nanoscale
Review
Fig. 2 Proposed reaction mechanisms for the reduction of oxygen functionalities (epoxy and keto carbonyl) of GO using hydrazine monohydrate. (Reproduced with
permission from ref. 70.)
aminoaziridine moiety, which then underwent thermal elimination of diimide to form a double bond. The concept of
thermal elimination of diimide was described in detail by Ren
and colleagues.67 The extent of reduction increased with
increasing reaction temperature. Reduction became complete
at 95 C within 3 h and the C/O ratio at this time was found to be
15.1 by combustion elemental analysis.67 The thermal stability
of CRGO increased gradually with increasing reduction
temperature, and CRGO was much more stable than pure GO
(Fig. 3). This is attributed to the removal of oxygen functionalities during reduction. The transformation of GO to graphene
using hydrazine vapor was also reported.7175 The gradual
transformation of GO was conrmed by UV-vis absorbance
spectroscopy. The main absorbance peak attributed to pp*
transitions of C]C in as-synthesized GO was observed at 230
nm; this peak red-shied to 260 nm upon reduction.
The most widely used reducing agent to prepare RGO sheets
is hydrazine monohydrate.6075 However, agglomeration of graphene sheets during reduction remains a major problem. Li
et al. prepared processable aqueous dispersions of graphene by
Review
stabilizer followed by hydrazine reduction. The presence of
hydrophilic or hydrophobic functionalities on the foreign
stabilizer prevents restacking during reduction. Ongoing
research on graphene revealed that primary alkyl amines,
organic isocyanates, polymeric surfactants, and aromatic polyatomic molecules can be used to modify the surface of GO.
These stabilizing molecules (macromolecules) either formed
direct bonds (covalent interactions) with GO or adsorbed on the
surface of GO and helped it to be dispersed in dierent solvents.
Kuila et al. demonstrated the reduction of 6-amino-4-hydroxy-2naphthalenesulfonic acid (ANS)-functionalized GO using
hydrazine monohydrate.51 XPS elemental analysis revealed that
the ANS functionalized graphene contained 4.2% oxygen
(atomic%), conrming successful reduction, and a satisfactory
electrical conductivity value (145 S m1) was obtained at room
temperature.
The reduction of GO or functionalized GO can also be carried
out in the presence of a polymer when preparing graphenebased composite materials. This type of reduction helps to
produce
homogeneously
dispersed
graphenepolymer
composites. Stankovich et al. were the rst to propose this
technique to prepare phenyl isocyanate-modied GOPS
composites in a dimethylformamide (DMF) solvent.69 Reduction was carried out in situ and excess hydrazine was removed by
washing in methanol. Hu et al. prepared graphenePS
composites using an in situ emulsion polymerization method.77
Kuila et al. prepared graphenepolymethyl methacrylate
(PMMA) composites using a similar method.78 In both the cases,
polymerization of monomers (styrene or methyl methacrylate)
was carried out in the presence of a water dispersion of GO. On
completion of polymerization, hydrazine monohydrate was
used to reduce the polymer (PS or PMMA)-wrapped GO. The
reduction of GO in the presence of PS or PMMA was conrmed
by Fourier transform infrared spectroscopy (FT-IR) and Raman
spectra analysis.77,78 Nanocomposites of polyurethane (PU) with
functionalized graphene sheets (FGS) were prepared by
dierent techniques.7982 The FGS were nely dispersed in the
PU matrices as evidenced from the TEM analysis. Thermal
stability and modulus values in the composites were improved
signicantly. Most notably the nanocomposite containing 2
parts of FGS per 100 parts of PU had an electrical conductivity of
104 S cm1, a 107 times increase over that of pristine PU. This
is attributed to the large surface area, high aspect ratio and
good interfacial adhesion between FGS and PU. Lee et al.
prepared the nanocomposite lms of FGSpoly(ethylene oxide)
(PEO) and GOepoxy by solution mixing.83,84 Dierential scanning calorimetry analysis suggested that FGS had a positive
impact on the nucleating eect of PEO crystallization. The
dynamic mechanical properties of the PEOFGS composites
were signicantly higher than that of pure PEO. The FGS also
eciently improved the electrical conductivity of PEO. It is seen
that the electrical conductivity was increased by more than 103fold compared to that of pristine PEO with the addition of 2
parts of FGS per 100 parts of PEO.
Bourlinos et al. described the reduction of GO and the
formation of graphitic structures using hydroquinone and
sodium borohydride (NaBH4) as reducing agents before the
Nanoscale
discovery of graphene in 2004.63 They found that the intensity of
the XRD peak at 2q 24 increased and that of the XRD peak at
2q 11.2 decreased as the reduction time of GO was increased.
Wang et al. showed that hydroquinone is an ecient reducing
agent for the reduction of GO.85 Although the full reduction
mechanism of GO is not yet known, the reduction process must
involve the removal of oxygen functional groups. The protons
generated by the dissociation of hydroquinone in water can
protonate the oxygen functionalities of GO and help to eliminate these groups at elevated temperatures. The appearance of a
002 reection peak at 2q 25 indicated the stacking of graphene sheets upon reduction. The intensity of the D band
increased and that of the G band decreased in hydroquinone
RGO, conrming the reduction of GO. Shin et al. studied the
eect of NaBH4 reduction on the electrical conductivity of
RGO.86 They found that the eciency of reduction increased on
increasing the concentrations of NaBH4. The reduction of GO to
graphene was conrmed by observing the change in the peak
position from 230 to 260 nm in the UV-vis spectra of GO and
RGO. The removal of oxygen functionalities occurred through
the formation of intermediate, boron oxide complexes, which in
turn increased the interlayer spacing of GO. The intermediate
complexes were then removed by the gradual removal of
carbonyl and hydroxyl groups, causing the interlayer distances
to contract. It has been found that the sheet resistance of
NaBH4RGO is much lower than that of hydrazine-reduced
lms. This is likely due to the formation of CN bonds during
hydrazine reduction.
Zhou et al. described a rapid and cost-eective method for
GO reduction using hydroxylamine as a reducing agent.87 The
reduction of GO with hydroxylamine can occur rapidly under
mild conditions, and the as-produced graphene sheets showed
high electrical conductivity, a fair crystalline state, and good
aqueous dispersibility without the need to use stabilizing
reagents. A proposed mechanism for the removal of epoxide
and hydroxyl groups from GO by hydroxylamine is shown in
Fig. 4. However, the exact mechanism of GO reduction using
hydroxylamine is still unclear. According to Zhou et al.,
hydroxylamine molecules attacked the carbon atom of the
epoxide groups, and converted into hydroxyl groups by ring
opening reactions.87 Aer releasing one water molecule, an Nhydroxylaziridine intermediate was formed. The hydroxylamine
molecules can also attack the b carbon of the hydroxyl group in
GO and transfer a proton to the hydroxyl group to release H2O
with the formation of a similar N-hydroxylaziridine
Nanoscale
intermediate. The N-hydroxylaziridine intermediate will quickly
convert into a conjugated vinyl (ethenyl) group and release
unstable nitrogen oxide (NOx) as well as H2O. The removal of
oxygen functionalities was conrmed by XPS analysis of pure
GO and RGO, as shown in Fig. 5. The electrical conductivity
values of hydroxylamine RGO were almost similar to those of
the hydrazineRGO.
Simultaneous reduction and surface modication of GO
using p-phenylene diamine (PPD) as a reducing and surfacemodifying agent was reported.88 The mechanism of GO reduction is presumably quite similar to that of hydrazine- and
hydroxylamine-based GO reduction. The oxidation product of
PPD (OPPD) was adsorbed on the surface of graphene through
pp interactions and played an important role in the dispersion
of graphene in dierent solvents. It was suggested that the
positively charged OPPD could prevent the aggregation of graphene layers by electrostatic repulsive forces.
Zhou et al. and Sun et al. noted that sodium hydrosulte was
an eective reducing agent for GO reduction.58,89 These authors
used XPS, TGA, XRD, Raman spectroscopy, solid-state 13C NMR
spectroscopy and electrical conductivity to conrm the
successful reduction of GO to graphene. However, the exact
mechanism of GO reduction using sodium hydrosulte is still
an open question. GO might be reduced due to the low electrode
potential of Na2S2O4 (E0 SO32/S2O24 1.12 V). The epoxide
and hydroxyl groups of GO were attacked by a nucleophile with
a back-side SN2 nucleophilic reaction, resulting in the formation of an intermediate. Then, a thermal elimination reaction
was used to obtain RGO and the reducing agent (S2O42) was
oxidized to sulte (SO32). The electrical conductivity of the
sodium hydrosulteRGO was 1377 S m1, which is about seven
Review
orders of magnitude higher than that of GO (3 104 S m1)
and comparable to that of pristine graphite (2500 15 S m1).
Sun et al. showed that the absorption capability of GO can be
enhanced through in situ reduction with sodium hydrosulte as
the reducing agent.89 The adsorption capacity of pure GO
towards acridine orange is almost doubled aer reduction with
sodium hydrosulte. This is due to the conversion of carboxyl
groups into hydroxyl groups aer the reduction of GO.
Recently, simultaneous reduction and functionalization of
GO using a single chemical have been reported. Chemicals with
reducing and functionalizing ability can be used to obtain
processable colloidal dispersions of RGO, which can be used in
a wide range of applications. Lin et al. described the reduction
of GO in a DMFwater solvent at temperatures of 100 and
150 C.90,91 The exact mechanism for this type of reduction is yet
to be determined. It has been proposed that upon the collision of oxygen-containing functional groups within the basal
plane of GO, CO2 or CO gas is released. Solvothermally obtained
RGO (STRG) has been shown to exhibit a specic capacitance of
up to 276 F g1 at a discharge current density of 0.1 A g1 in a 1
M H2SO4 electrolyte.91 Pham et al. reported a simple and eective method for reducing and functionalizing GO into chemically converted graphene by solvothermal reduction of GO
suspension in N-methyl-2-pyrrolidone (NMP).66 Reduction of
GO occurred through a free radical mechanism. The free radicals generated from NMP functionalized the GO sheets during
solvothermal reduction in air. It has been found that the dispersibility of STRG was excellent in various organic solvents,
while slightly functionalized STRG showed excellent electrical
conductivity. A freestanding STRG paper reduced for 1 h
exhibited electrical conductivities as high as 21 600 S m1,
Fig. 5 C 1s XPS spectra of GO before (a) and after reduction for 30 min (b), 1 h (c), and 12 h (d). Peaks 1, 2, 3, and 4 correspond to C]C/CC in aromatic rings, CO
(epoxy and alkoxy), C]O, and COOH groups, respectively. (Reproduced with permission from ref. 87.)
Review
while the dispersibility of STRG that had been reduced for 5 h
was as high as 1.4 mg ml1. Ecient synthesis of processable
graphene sheets using pyrrole as a reducing and surface
modifying agent has also been reported.92 Reduction occurred
through the exchange of electrons between pyrrole monomers
and GO dispersed in water. During the reduction process, the
pyrrole monomers reduced GO to RGO sheets and were themselves oxidized to form an oxidized product of pyrroles (OPy).
OPy, which are possibly oligomers of pyrrole, facilitated the
dispersion of graphene in organic solvents (ethanol, isopropanol, DMF, DMSO, NMP, THF, and acetone) through their
adsorption to GO by pp interactions. The formation of crystalline RGO sheets as compared to amorphous GO was
demonstrated by transmission electron microscopy (TEM)
analysis (Fig. 6). Simultaneous surface functionalization and
reduction of GO with octadecylamine (ODA) can also be used to
obtain RGO sheets.93 FT-IR spectra (Fig. 7) shows that the
carboxyl functionality at 1710 cm1 is absent in the ODA functionalized RGO. The appearance of a new band at 1564 cm1
indicates the formation of CNHC bonds due to the reactions between epoxide and amine groups.
Fan et al. were the rst to describe an environmentally
friendly and ecient route for the reduction of GO by
aluminum powder (Al)/hydrochloric acid (HCl) within 30 min.28
The bulk conductivity of the RGO was 2000 S m1 at room
temperature. They also studied the reduction of GO using iron
(Fe)/HCl at room temperature.29 The appearance of a broad peak
(Fig. 8) centered at 24.5 conrmed the stacking of graphene
sheets during reduction. In comparison to Fe and Al, zinc (Zn)
powder has been used extensively for the reduction of GO to
graphene.30,94,95 According to these authors, reduction was
completed within 1 minute aer ultrasonication. The atomic
ratios of carbon to oxygen in GO increased from 2.58 to
Fig. 6 TEM images of (a) GO (inset shows SAED of GO), (b) low-magnication
image of RGO, (c) scrolled graphene sheet and (d) HRTEM image of the RGO edge.
The inset shows the typical SAED pattern of RGO. (Reproduced with permission
from ref. 92.)
Nanoscale
Fig. 7
FT-IR spectra of GO, ODA and GOODA (20 h) (adapted from ref. 93).
Fig. 8 X-ray diraction patterns of GO before and after reduction via Fe for
dierent reduction times. (Reproduced with permission from ref. 29.)
Nanoscale
with metal reduction of GO is the need to separate the metal
particles from the RGO to avoid metal impurities.
Pei et al. developed a simple but highly eective process to
reduce GO using hydrohalic acids.97 The possible reaction
mechanism is presented in Fig. 9. In the rst step, the acidic
reducing agents can catalyze the ring-opening reaction of epoxy
groups and convert them into hydroxyl groups. In the nal
stage, hydroxyl groups were substituted by halogen atoms. The
substituted halogen atoms can be easily eliminated from the
carbon lattice to produce graphene. GO lms reduced for 1 h at
100 C in 55% hydroiodic (HI) acid had an electrical conductivity as high as 29 800 S m1 and a C/O ratio above 12, both of
which are much higher than those of lms reduced by other
chemical methods. The use of an acetic acidHI mixture for the
ecient reduction of GO was also reported.33 The C/O atomic
ratio in the resulting RGO was 6.6 and the electrical conductivity
of the RGO pellet was recorded as 30 400 S m1. This novel
approach can be used to fabricate and process various graphene
papers and thin lms to develop new exible substrates,
particularly for low-temperature processes. Chen et al. demonstrated the ecient reduction of GO using hydrobromic acid
(HBr).27 The RGO could be dispersed in water and 23 graphene
layers were observed in TEM images. The maximum specic
capacitances of the RGO dispersed in water and ionic liquid
were 348 and 158 F g1, respectively, at a current density of 0.2 A
g1. Hydriodic acid (HI) in the presence of triuoroacetic acid
was also found to be an ecient reducing agent.26 Reduction
using HI occurred at temperatures below 0 C, resulting in
highly graphitized RGO sheets. The resulting graphene sheets
were highly deoxygenated and formed a well-crystallized
graphitic material without any nitrogen and sulfur impurities.
RGOpolymer composite materials that require subzero
temperatures are expected to enter commercial production in
the near future.
Hydrazine, hydrazine monohydrate, dimethylhydrazine,
sodium borohydride, hydroquinone, hydroxylamine, p-phenylene diamine, and sodium hydrosulde have been shown to
eciently reduce GO to graphene. Unfortunately, these reducing
agents introduce additional functional groups onto the surface
of RGO during chemical reduction, thereby increasing sheet
Review
resistance due to the scattering of electrons.98 Moreover, all these
chemical reducing agents are highly poisonous and explosive.
Therefore, strict precautions must be taken when using large
quantities of these chemicals and their use must be minimized
to protect the environment. Consequently, new approaches for
eectively converting GO into stable graphene sheets under mild
conditions need to be explored.
3.1.2 ECO-FRIENDLY REDUCING AGENTS. Vitamin C or Lascorbic acid (L-AA) is an ideal substitute for hydrazine in the
reduction of GO.31,99 It is well known that each L-AA molecule
can release two protons to form dehydroascorbic acid. These
protons commonly have a high binding anity for oxygencontaining groups, such as hydroxyl and epoxide groups, and
when bound to these groups, water molecules are formed and
RGO is produced. The electrical conductivity of RGO was
reported to be 7700 S m1 at room temperature.
Similar to the reduction of GO in acidic solutions, alkaline
solutions are also very ecient for the deoxygenation of GO. The
addition of sodium hydroxide (NaOH) or potassium hydroxide
(KOH) to a GO dispersion results in the conversion of the yellowbrown dispersion of GO to a homogeneous black dispersion.100
Although the proposed mechanism is unclear, it has been
shown that dispersed GO undergoes faster reduction as the
concentration of NaOH or KOH increases.
Dreyer et al. showed that a variety of commercially available
alcohols (methyl alcohol, ethyl alcohol, isopropyl alcohol, and
benzyl alcohol) can eciently reduce GO to graphene.101 The
resulting RGO exhibited high C : O ratios (up to 30 : 1, as
determined by elemental combustion analysis), high conductivities (up to 4600 S m1), and good specic capacitances (up to
35 F g1) when tested as electrode materials in ultracapacitors.
Su et al. reported an ecient technique for the removal of
oxygen functionalities from the surface of GO using ethanol
vapors.102 The RGO lms had highly graphitic structures,
excellent electrical conductivity, good transparency (>96%), and
a high eective eld-eect hole mobility (210 cm2 V1).
Chen et al. and Pham et al. published the rst environmentfriendly method to reduce GO using amino acids.103,104 A
possible mechanism for the chemical reduction of GO by Lcysteine is shown in Fig. 10. L-Cysteine is an amino acid that
contains a thiol group. This thiol group is susceptible to oxidization upon which it releases a proton, thereby functioning as
a nucleophile.105 The binding energy of the protons to oxygencontaining groups, such as the hydroxyl and epoxide groups of
GO, is very high, resulting in the formation of H2O molecules.31
Finally, the L-cysteine is oxidized into L-cystine, leading to the
formation of RGO sheets. The electrical conductivity of LcysteineRGO is about 106 times higher than that of pure GO.
The reduction of GO by L-glutathione also proceeds through
similar pathways. L-GlutathioneRGO can be dispersed in
distilled water and several polar aprotic solvents, including
THF, DMF, and DMSO, at a typical concentration of 0.5 mg ml1
aer ultrasonication for 30 min. The stabilization of graphene
suspensions may originate from the oxidized products of Lcysteine. Bose et al. showed a simple, ecient, and environmentally friendly approach towards the reduction of GO using
glycine as both a chemical functionalizer and a reducing
Review
Fig. 11 (a) The BF-STEM images of the N-doped graphene and the corresponding
EDS maps, (b) C, (c) N, and (d) O. (Reproduced with permission from ref. 107.)
Nanoscale
demonstrated that GO annealed in NH3 exhibited higher
conductivity than that annealed in H2. A novel approach for the
bulk production of lithium-intercalated graphene sheets
through the reduction of GO in liquid NH3 and lithium metal was
reported.109 The proposed mechanism for the reduction of GO by
Li/NH3 is shown in Fig. 12. Electrochemical studies of LiRGO
electrodes showed a signicant enhancement in the specic
capacitance of lithium batteries over commercially available
graphite electrodes. Graphene sheets were prepared from GO
using urea as an expansionreduction agent.110 Thermal
decomposition of urea produces ammonia gas, and the use of
NH3 as a reducing gas is not new. According to Wakeland et al.,
the as-produced NH3 has two functions. First, the local shock
created by the rapid expansion of the gas separated the layers of
the solid GO and increased the amount of surface exposed.
Second, the reducing species generated by the thermal decomposition of expansion-reducing solids combined with the oxygen
functionalities of GO, resulting in the formation of stable
gaseous molecules and leaving RGO sheets on the crucible.
RGOnanocrystalline platinum hybrid materials were
synthesized by simultaneous co-reduction of GO and chloroplatinic acid with sodium citrate in water at 80 C (pH 7 and
Nanoscale
10).111 This RGO served as an excellent support for dispersing
and stabilizing Pt nanoparticles. The resultant hybrid materials
exhibited high thermal stability, and are soluble in nonpolar
organic solvents with the assistance of oleylamine.
Salas et al. and Wang et al. reported the reduction of GO by
the respiration of environmental microbes in the genus Shewanella.112,113 Reduction was facilitated by electron transfer
mechanisms at the ShewanellaGO interface, where at least two
distinct extracellular electron transfer pathways have been
proposed to occur, namely, direct charge transfer from the cell
surface, and self-secreted soluble redox electron mediators. The
electrochemical properties of the microbially reduced graphene
(MRG) were comparable to those of hydrazineRGO. The
specic capacitance of MRG was 117 F g1 at a charging current
density of 1 A g1, and decreased slightly to 91 F g1 at a current
density of 5 A g1. Reduction of GO using wild carrot root was
also found to be a fruitful method for obtaining graphene
sheets.34 Endophytic microorganisms in carrots removed the
oxygen functionalities from the surface of GO and restored
electronic conjugation in graphene.
Zhu et al. reported the preparation of graphene sheets by adding
reducing sugars, such as glucose, fructose, and sucrose to a GO
dispersion in water.32 They explained the reduction of GO and its
stabilization in water as follows. First, glucose is oxidized to aldonic
acid by GO in the presence of an ammonia solution. The aldonic
acid is converted into lactone. This oxidized product of glucose
contains a large number of hydroxyl groups and carboxyl groups.
The RGO may also have some remaining oxygen functionalities,
such as hydroxyl and carboxylic groups. Thus, the hydroxyl and
carboxyl groups in the oxidized products of glucose form hydrogen
bonds with the residual oxygen functionalities of the RGO surfaces.
The resulting RGO showed good electrocatalytic activity toward
catecholamines (dopamine, epinephrine, and norepinephrine).
Kim et al. described the reduction of GO using dextran as a multifunctional reducing agent.35 The reduction mechanism of GO by
dextran might be similar to that of glucose, where glucose is oxidized
to aldonic acid by GO in the presence of ammonia, and then further
converted into lactone which interacts with GO via hydrogen
bonding. The RGOs were found to be highly dispersible in water due
to the adsorption of dextran molecules through hydrogen bonding.
Dopamine-induced reduction and functionalization of GO
was reported by Xu and colleagues. At a weak alkaline pH,
dopamine underwent self-polymerization to produce polydopamine (PDA), which was adsorbed onto the substrate materials.114 Fast reduction, self-polymerization, and adhesion
properties of dopamine allow its use as a simultaneous reducing
agent for GO and as a capping agent to stabilize and decorate the
resulting RGO surfaces for further functionalization. PDA-capped RGO formed a homogeneous dispersion in water at a
concentration of 0.05 mg ml1. Kaminska et al. used a dopamine
derivative for the simultaneous reduction and noncovalent
functionalization of GO using azide terminated dopamine.115
The azide functional groups of dopamine readily reacted with
alkynyl terminated molecules via a click chemistry approach
using the copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition.
Wang et al. prepared water-dispersible graphene via GO reduction in green tea solution.36 It is well known that green tea contains
Review
aromatic polyphenolic compounds that act as both reducing agents
and stabilizers; reduction of GO in green tea resulted in RGO with
good dispersibility in both aqueous and organic solvents. This is a
low-cost, non-toxic, easily scalable method that is highly eective at
removing the functional groups of GO.
Lei et al. reported eco-friendly reduction of GO using tannic
acid (TA).116 TA can act as both a reducing and a surface-modifying
agent. The TARGO was demonstrated to disperse in ethanol,
DMF, and DMSO at a concentration of 0.5 mg ml1. The electrical
conductivity of the TARGO was 656.7 S m1, a value comparable
to that achieved using other chemical reducing agents.
Khanra et al. showed that baker's yeast can be used for the
simultaneous bio-functionalization and reduction of GO.117
Baker's yeast containing nicotinamide adenine dinucleotide
phosphate (NADPH) is the main reducing and functionalizing
agent. The amine functional groups of NADPH can easily couple
with the epoxy functionalities of GO and form a stable water
dispersion of RGO obtained by yeast reduction (YR-GO). The
maximum dispersibility of YR-GO in water was recorded as
2.5 mg ml1 at room temperature. The main advantages of this
technique over the traditional chemical reduction are environmentally friendly approach and easy product isolation process.
Simultaneous reduction and functionalization of GO was performed using amino-terminated poly(amidoamine) (PAMAM)
dendrimers.118 The PAMAM modied RGO catalyzed the Knoevenagel condensation of benzaldehyde and dimethyl acrylate
with yields up to 99%, and thus was a very active organocatalyst.
Zhang et al. showed polyelectrolyte induced reduction of GO to
obtain water dispersible graphene sheets.119 Controlled experiment suggested that there was no conversion of GO to graphene
in the absence of the polyelectrolyte, poly(diallyldimethylammonium chloride) (PDDA). It was found that the
PDDA served the roles of both a reducing and a stabilizing agent
for preparing metal nanoparticle decorated graphene. It is
anticipated that the N+ groups of PDDA attacked the oxygen
atom of epoxide groups in GO inducing ring opening reaction as
shown in Fig. 13. The initial derivative produced by the epoxide
ring opening reacted further via the elimination of nitroso
groups to form a C]C bond. On the other hand, the hydroxyl
groups were removed by a thermal dehydroxylation process.
All the methods discussed above are environment friendly
methods for reducing GO. The RGO obtained using these methods
were demonstrated to have good electrical conductivity, specic
capacitance values, and good dispersibility in dierent organic
solvents. However, 100% removal of oxygen functionalities from
the surface of GO is not possible using mild reducing agents.
Therefore, thermal and electrochemical methods for the largescale production of RGO have been proposed.
Review
3.2
Thermal reduction
Nanoscale
Torr).127 The proposed mechanism for thermal reduction of GO
proceeds through radical reactions as shown in Fig. 14. Based
on this mechanism, thermal reduction of GO occurred in three
steps: initiation, propagation, and termination of free radicals.
During thermal degradation, hydroxyl, hydronium, and hydroperoxyl radicals formed at the sheet edges; this determined the
eciency of the radical reactions. In the rst reaction, reactive
hydroxyl radicals attacked the hydroxyl groups undergoing
radical propagation, leading to the formation of carbonyls.
Carboxylates are known to decompose via decarboxylation,
forming CO2 radicals. The unpaired electrons of the CO2 radicals then migrated through the carbon framework, resulting in
the formation of covalent bonds aer nding other unpaired
electrons. The reactive free hydroxyl radicals are also likely to
convert 1,2-diols at the etch holes into carbonyls. These radicals
then propagated by reaction with the oxygen groups of GO or
the carbon dangling bonds at defective sites. The newly formed
species aer these reactions determined the amount of oxygen
that remained in the RGO structure aer annealing.
Recently Park et al. described thermochemical reduction of
GO for the preparation of highly conducting functionalized
graphene.68 The aryl diazonium salt of 4-iodoaniline was graed
on the surface of GO to prepare phenyl functionalized GO (I-PhGO). Thermal annealing of I-Ph-GO at 300 C for 6 h produces
Nanoscale
Electrochemical reduction
In comparison to chemical and thermal reduction, electrochemical reduction of GO is green and fast, and the reduced
material is contaminant-free. Guo et al. reported a simple
approach for the large-scale synthesis of high quality graphene
sheets through electrochemical reduction of an exfoliated GO
precursor material at a cathodic potential of 1.5 V.128 The electrical conductivity of electrochemically obtained RGO (ERGO)
was higher than that of CRGO. This may be due to the residual
defects in CRGO, which could be minimized during electrochemical reduction. Shao et al. performed electrochemical
reduction of GO by extended cyclic voltammetry (CV, 1.0 to
1.0 V vs. reversible hydrogen electrode, 50 mV s1) in a 0.1 M
Na2SO4 solution in a standard three-electrode cell with Hg/
Hg2SO4 and Pt foil as the reference and counter electrodes,
respectively (all electrode potentials are scaled to RHE except
when stated otherwise).129 The specic capacitance of these
ERGO sheets was 164 F g1, which is much higher than that of
CRGO. ERGO had greatly enhanced catalytic activity with regard
Review
to the electrochemical reduction of O2 and H2O2. Harima et al.
demonstrated the electrochemical reduction of GO casted on
the conductive substrates (uorine-doped-tin-oxide) in the
presence of organic solvents (acetonitrile, propylene carbonate,
DMF, DMSO).130 The electricity required for the complete
reduction was 2.0 coulombs. The resulting ERGO had an electrical conductivity of about 300 S m1 and a specic capacitance
of 147.2 F g1 in propylene carbonate. An et al. described an
eective method for the simultaneous electrochemical reduction and electrophoretic deposition (EPD) of RGO on various
substrates including Cu, Ni, Al, stainless steel, and p-type Si.131
GO sheets in an aqueous dispersion migrated towards the
anode, were deposited there and reduced to RGO when DC
voltage was applied. The deposition rate depends on the
concentration of GO dispersion, applied DC voltage and the
conductivity of the substrate (anode plate). It has been found
that a smooth lm of RGO was obtained under the following
experimental conditions: 1.5 mg ml1 GO concentration in
water, 10 V applied DC voltage and less than 30 s reduction
time. However, the eciency of reduction was less than the
RGO obtained by hydrazine reduction as observed from the XPS
elemental analysis. Electrochemical reduction of oriented graphene layers was proposed by Ramesha and Sampath.132 GO can
be assembled on the conducting gold substrate by a layer-bylayer assembly technique through electrostatic interaction.
Reduction of assembled GO could be performed electrochemically using applied DC bias by scanning the potential from 0 to
1 V vs. a saturated calomel electrode in an aqueous electrolyte.
The electrochemical reduction of assembled GO may open up
another way to obtain highly conducting graphene electrodes
for nano-electronic devices.
Fu et al. prepared grapheneAu composites by electrochemical co-reduction of GO and Au(III) in ionic liquids.39 They
studied It performances to conrm the simultaneous reduction
of GO and Au(III). The composite-modied electrodes exhibited
enhanced electrochemical activity and can potentially be used in
biosensors. The electrochemical reduction of GO prepared from
exfoliated graphite in an acetamideureaammonium nitrate
ternary eutectic melt was reported.40 Electrochemical reduction
of an oriented GO lm was carried out at room temperature using
a ternary molten electrolyte. Wang et al. described a method for
the electrochemical reduction of 3-aminopropyltriethoxysilane
functionalized GO.133 The functionalized GO is adsorbed on the
surface of glassy carbon electrode and reduced to functionalized
graphene in a 0.5 M NaCl solution saturated with N2. The functionalized graphene was further immobilized with glucose
oxidase and used to detect glucose.
Electrochemical reduction of GO is very fast and avoids the use
of harmful chemical reducing agents and hence, further purication of RGO is not required. The defect concentration in the ERGO
is almost negligible suggesting a bright possibility of application in
the areas of supercapacitor devices, touch screens and exible
electronics. Moreover, power consumption for reduction is also
negligible as compared to chemical or thermal reduction.
However, large scale production of RGO is the main disadvantage
for commercial application. The degree of reduction is also not
comparable to that of the chemical or thermal reduction method.
Review
3.4
Nanoscale
on increasing the irradiation time, the antibacterial activity of
the RGOTiO2 thin lm increased under solar light irradiation.
The antibacterial activity of the RGOTiO2 thin lm was 7.5
times higher than that of the GOTiO2 thin lms. Williams et al.
and Guardia et al. investigated UV-assisted photocatalytic
reduction of GO.140,141 The change in the absorption spectrum
following the UV-irradiation over a 15 min period is shown in
Fig. 17. The change in color of the sample from dark brown to
black can be seen as the reduction of GO proceeds. However, no
signicant changes in the absorption could be seen when TiO2
was not used. The TiO2 accumulated electrons and interacted
with the GO in order to reduce certain functional groups. The
following mechanism has been proposed for the reduction of
GO to graphene.
Fig. 17 (A) The absorption spectra of GO and TiO2 suspension in ethanol (a)
before UV-irradiation, (b) after 5 min, and (c) after 15 min of UV irradiation. (B) The
change in color of a 10 mM solution of TiO2 nanoparticles with 0.5 mg ml1 GO
before and after UV irradiation for 2 h. A suspension of 10 mM TiO2 nanoparticles is
also shown for comparison. (Reproduced with permission from ref. 140.)
Nanoscale
Review
RGO-based supercapacitor
Nanoscale
Review
Fig. 19 (a and b) CV curves of GG at various scan rates with potential from 0 V to 0.9 V (vs. SCE) in 1 M H2SO4; (c) galvanostatic chargedischarge curves of graphene
sheets (GG) at dierent current densities of 0.1, 0.5 and 1 A g1; (d) the specic capacitances of GG and graphene by hydrazine reduction (HG) at dierent current
densities; (e) capacitance retention ratio of GG from the 1st to 1000th cycle at the current density of 2 A g1; and (f) the Nyquist impedance plots of GG in the frequency
range of 100 kHz to 0.1 Hz (main chart) and high frequency area (inset image) after the 1st cycle and 1000th cycle m2. (Reproduced with permission from ref. 147.)
Fig. 20 Schematic of the stacked geometry used for the fabrication of supercapacitor devices. (Reproduced with permission from ref. 152.)
Nanoscale
capacitance was determined from galvanostatic charge
discharge using C I/(dV/dt) with dV/dt calculated from the
slope of the discharge curves. A specic capacitance of 135 F g1
in a 5.0 M aqueous KOH solution was recorded. In contrast, the
specic capacitance in 1 M tetraethylammonium tetrauoroborate was found to be 99 F g1. The specic capacitance,
energy density and power density of hydrazine reduced GO154
were found to be 205 F g1, 28.5 W h kg1 and 10 kW kg1. The
retention in specic capacitance was 90% aer 1200 charge
discharge cycles. Du et al. investigated the specic capacitance
behavior of graphene sheets derived by the chemical reduction
of GO.155 The electrochemical performance of EDLC was
aected by the specic surface area, pore characteristics, layer
stacking and oxygen-functionalities of electrode materials. The
high level of oxidation of graphite led to a large specic surface
area and more graphene edges, which are favorable for the
enhancement of capacitive performance. The maximum
specic capacitance of 150 F g1 at a current density of 0.1 A g1
was recorded. Zhu et al. studied the capacitive behavior of RGO
obtained by microwave assisted reduction of GO.156 The simple
preparation of RGO could provide a promising route for the
scalable and cost-eective production of processable graphene
materials. The specic capacitance of the RGO materials was
found to be 191 F g1 in a KOH electrolyte.
Review
reducing agents such as sp. AS2.2241,157 plant tissues,158
coconut water (Cocos nucifera L.),159,160 grapes,161,162 red algae
(Cyanidioschyzon merolae 10D and Cyanidium caldarium)163 and
soaked Phaseolus aureus164 were used in the reduction of
aromatic and aliphatic organic ketones and esters. It is expected
that these kinds of reducing agents will be a good choice for the
reduction of GO to graphene. Therefore, by utilizing abundant
and sustainable natural sources, biocatalysts that are selective,
simple to use, non-toxic, and ultra-low cost can be developed
with the ultimate goal of the large-scale production of RGO.
Acknowledgements
This study was supported by the Converging Research Center
Program (2012K001428), the Human Resource Training Project
for Regional Innovation, and the World Class University (WCU)
program (R31-20029) funded by the Ministry of Education,
Science and Technology (MEST) and National Research Foundation (NRF) of Korea. It was also supported by the Research
Professor Program of Chonbuk National University.
References
1 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang,
Y. Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov,
Science, 2004, 306, 666669.
2 A. K. Geim, Science, 2009, 324, 15301534.
3 Y. B. Zhang, Y. W. Tan, H. L. Stormer and P. Kim, Nature,
2005, 438, 201204.
4 J. J. Yoo, K. Balakrishnan, J. Huang, V. Meunier,
B. G. Sumpter, A. Srivastava, M. Conway, A. L. M. Reddy,
J. Yu, R. Vajta and P. M. Ajayan, Nano Lett., 2011, 11,
14231427.
5 G. Eda, G. Fanchini and M. Chhowalla, Nat. Nanotechnol.,
2008, 3, 270274.
6 M. Terrones, A. R. Botello-M
endez, J. Campos-Delgado,
F. L
opez-Uras, Y. I. Vega-Cant
u, F. J. Rodrguez-Macas,
A. L. Elias, E. Mu~
noz-Sandova, A. G. Cano-M
arquez,
J. Charlier and H. Terrones, Nano Today, 2010, 5, 351372.
7 F. Schedin, A. K. Geim, S. V. Morozov, E. W. Hill, P. Blake,
M. I. Katsnelson and K. S. Novoselov, Nat. Mater., 2007, 6,
652655.
8 S. Chae, F. Gunes, K. K. Kim, E. S. Kim, G. H. Han,
S. M. Kim, H. J. Shin, S. M. Yoon, J. Y. Choi, M. H. Park,
C. W. Yang, D. Pribat and Y. H. Lee, Adv. Mater., 2009, 21,
23282333.
9 X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner,
A. Velamakanni, I. Jung, E. Tutuc, S. K. Banerjee,
L. Colombo and R. S. Ruo, Science, 2009, 324, 13121314.
10 K. S. Kim, Y. Zhao, H. Jang, Y. S. Lee, J. M. Kim, K. S. Kim,
J. H. Ahn, P. Kim, J. Y. Choi and B. H. Hong, Nature, 2009,
457, 706710.
11 Z. Wang, N. Li and Z. Gu, Nanotechnology, 2010, 21, 175602.
12 M. Keidar, A. Shashurin, O. Volotskova, Y. Raitses and
I. I. Beilis, Phys. Plasmas, 2010, 17, 057101.
13 Z. Yan, Z. Peng, Z. Sun, J. Yao, Y. Zhu, Z. Liu, P. M. Ajayan
and J. M. Tour, ACS Nano, 2011, 5, 81878192.
This journal is The Royal Society of Chemistry 2013
Review
14 A. Malesevic, R. Vitchev, K. Schouteden, A. Volodin,
L. Zhang, G. V. Teneloo, A. Vanhulsei and
C. V. Haesendonck, Nanotechnology, 2008, 19, 305604.
15 S. Park and R. S. Ruo, Nat. Nanotechnol., 2009, 4, 217
224.
16 I. Vlassiouk, M. Regmi, P. Fulvio, S. Dai, P. Datskos and
G. Eres, ACS Nano, 2011, 5, 60696076.
17 G. Ruan, Z. Sun, Z. Peng and J. M. Tour, ACS Nano, 2011, 5,
76017607.
18 T. Kuila, S. Bose, A. K. Mishra, P. Khanra, N. H. Kim and
J. H. Lee, Prog. Mater. Sci., 2012, 57, 10611105.
19 J. I. Paredes, S. Villar-Rodil, A. Martnez-Alonso and
J. M. D. Tasc
on, Langmuir, 2008, 24, 1056010564.
20 R. D. Dreyer, S. Park, C. W. Bielawski and R. S. Ruo, Chem.
Soc. Rev., 2010, 39, 228240.
21 M. C. Kim, G. S. Hwang and R. S. Ruo, J. Chem. Phys., 2009,
131, 064704.
22 X. Dong, C. Y. Su, W. Zhang, J. Zhao, Q. Ling, W. Huang,
P. Chen and L. Li, Phys. Chem. Chem. Phys., 2010, 12,
21642169.
23 Y. Li, L. Tang and J. Li, Electrochem. Commun., 2009, 11,
846849.
24 L. A. Mashat, K. Shin, K. Kalantar-zadeh, J. D. Plessis,
S. H. Han, R. W. Kojima, R. B. Kaner, D. Li, X. Gou,
S. J. Ippolito and W. Wlodarski, J. Phys. Chem. C, 2010,
114, 1616816173.
25 S. Mao, K. Yu, S. Cui, Z. Bo, G. Lu and J. Chen, Nanoscale,
2011, 3, 28492853.
26 P. Cui, J. Lee, E. Hwang and H. Lee, Chem. Commun., 2011,
47, 1237012372.
27 Y. Chen, X. Zhang, D. Zhang, P. Yu and Y. Ma, Carbon, 2011,
49, 573580.
28 Z. Fan, K. Wang, T. Wei, J. Yan, L. Song and B. Shao, Carbon,
2010, 48, 16861689.
29 Z. J. Fan, W. Kai, J. Yan, T. Wei, L. J. Zhi, J. Feng, Y. Ren,
L. P. Song and F. Wei, ACS Nano, 2011, 5, 191198.
30 X. Mei and J. Ouyang, Carbon, 2011, 49, 53895397.
31 J. Zhang, H. Yang, G. Shen, P. Cheng, J. Zhang and S. Guo,
Chem. Commun., 2010, 46, 11121114.
32 C. Zhu, S. Guo, Y. Fang and S. Dong, ACS Nano, 2010, 4,
24292437.
33 I. K. Moon, J. Lee, R. S. Ruo and H. Lee, Nat. Commun.,
2010, 1, 7376.
34 T. Kuila, S. Bose, P. Khnara, A. K. Mishra, N. H. Kim and
J. H. Lee, Carbon, 2012, 50, 914921.
35 Y. K. Kim, M. H. Kim and D. H. Min, Chem. Commun., 2011,
47, 31953317.
36 Y. Wang, Z. Shi and J. Yin, ACS Appl. Mater. Interfaces, 2011,
3, 11271133.
37 B. Qi, H. Liu, X. Bo, H. Yang and G. Liping, Chem. Eng. J.,
2011, 171, 340344.
38 J. Ping, Y. Wang, K. Fan, J. Wu and Y. Ying, Biosens.
Bioelectron., 2011, 28, 204209.
39 C. Fu, Y. Kuang, Z. Huang, X. Wang, N. Du, J. Chen and
H. Zhou, Chem. Phys. Lett., 2010, 499, 250253.
40 V. S. Dilimon and S. Sampath, Thin Solid Films, 2011, 519,
23232327.
Nanoscale
41 Z. Wei, D. Wang, S. Kim, S. Y. Kim, Y. Hu, M. K. Yakes,
A. R. Laracuente, Z. Dai, S. R. Marder, C. Berger,
W. P. King, W. A. de Heer, P. E. Sheehan and E. Riedo,
Science, 2010, 328, 13731376.
42 X. Wang, L. Zhi and K. Mullen, Nano Lett., 2008, 8, 323327.
43 J. Shen, Y. Hu, M. Shi, X. Lu, C. Qin, C. Li and M. Ye, Chem.
Mater., 2009, 21, 35143520.
44 B. G. Choi, H. Park, T. J. Park, M. H. Yang, J. S. Kim,
S. Y. Jang, N. S. Heo, S. Y. Lee, J. Kong and W. H. Hong,
ACS Nano, 2010, 4, 29102918.
45 W. S. Hummers and R. E. Oeman, J. Am. Chem. Soc., 1958,
80, 1339.
46 L. Staudenmaier, Ber. Dtsch. Chem. Ges., 1899, 31, 1394
1399.
47 T. Nakajima and Y. Matsuo, Carbon, 1994, 32, 469475.
48 J. Li, H. Shi, N. Li, M. Li and J. Li, Cent. Eur. J. Chem., 2010, 8,
783788.
49 Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts and
R. S. Ruo, Adv. Mater., 2010, 22, 39063924.
50 Y. Zhang, L. Ren, S. Wang, A. Marathe, J. Chaudhuri and
G. Li, J. Mater. Chem., 2011, 21, 53865391.
51 T. Kuila, P. Khanra, S. Bose, N. H. Kim, B. C. Ku, B. Moon
and J. H. Lee, Nanotechnology, 2011, 22, 305710.
52 G. Wang, X. Shen, B. Wang, J. Yao and J. Park, Carbon, 2009,
47, 13591364.
53 J. Geng and H. T. Jung, J. Phys. Chem. C, 2010, 114, 8227
8234.
54 H. C. Schniepp, J. L. Li, M. J. McAllister, H. Sai,
M. H. Alonso, D. H. Adamson, R. K. Prud'home, R. Car,
D. A. Savilley and I. A. Aksay, J. Phys. Chem. B, 2006, 110,
85358539.
55 A. Lerf, H. He, M. Forster and J. Klinowski, J. Phys. Chem. B,
1998, 102, 44774482.
56 T. Szabo, O. Berkesi, P. Forgo, K. Josepovits, Y. Sanakis,
D. Petridis and I. Dekany, Chem. Mater., 2006, 18, 2740
2749.
57 H. He, J. Klinowski, M. Forster and A. Lerf, Chem. Phys. Lett.,
1998, 287, 5356.
58 T. Zhou, F. Chen, K. Liu, H. Deng, Q. Zhang, J. Feng and
Q. Fu, Nanotechnology, 2011, 22, 045704.
59 T. Kuila, S. Bhadra, D. Yao, N. H. Kim, S. Bose and J. H. Lee,
Prog. Polym. Sci., 2010, 35, 13501375.
60 S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas,
A. Kleinhammes, Y. Jia, Y. Wu, S. T. Nguyen and
R. S. Ruo, Carbon, 2007, 45, 15581565.
61 H. P. Boehm, A. Clauss, G. Fischer and U. Hofmann,
Surface properties of extremely thin graphite lamellae,
Proceedings of the Fih Conference on Carbon, Pergamon
Press, 1962, pp. 7380.
62 H. P. Boehm, A. Clauss, G. O. Fischer and U. Hofmann, Z.
Anorg Allg Chem., 1962, 316, 119127.
63 A. B. Bourlinos, D. Gournis, D. Petridis, T. Szabo, A. Szeri
and I. Dekany, Langmuir, 2003, 19, 60506055.
64 P. Xiao, M. Xiao, P. Liu and K. Gong, Carbon, 2000, 38, 626
628.
65 N. A. Kotov, I. Dekany and J. H. Fendler, Adv. Mater., 1996, 8,
637641.
Nanoscale
66 V. H. Pham, T. V. Cuong, S. H. Hur, E. Oh, E. J. Kim,
E. W. Shin and J. S. Chung, J. Mater. Chem., 2011, 21,
33713377.
67 P. G. Ren, D. X. Yan, X. Ji, T. Chen and Z. M. Li,
Nanotechnology, 2011, 22, 055705.
68 O. K. Park, M. G. Hahm, S. Lee, H. I. Joh, S. I. Na, R. Vajtai,
J. H. Lee and B. C. Ku, Nano Lett., 2012, 12, 17891793.
69 S. Stankovich, D. A. Dikin, G. H. B. Dommett,
K. M. Kohlhaas, E. J. Zimney, E. A. Stach, R. D. Piner,
S. T. Nguyen and R. S. Ruo, Nature, 2006, 442, 282286.
70 X. Gao, J. Jang and S. Nagase, J. Phys. Chem. C, 2010, 114,
832842.
71 H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao and
Y. Chen, ACS Nano, 2008, 2, 463470.
72 J. T. Robinson, F. K. Perkins, E. S. Snow, Z. Wei and
P. E. Sheehan, Nano Lett., 2008, 8, 31373140.
73 S. Pei and H.-M. Cheng, Carbon, 2012, 50, 32103228.
74 K. P. Loh, Q. Bao, G. Eda and M. Chhowalla, Nat. Chem.,
2010, 2, 10151024.
75 J. T. Robinson, M. Zalalutdinov, J. W. Baldwin, E. S. Snow,
Z. Wei, P. Sheehan and B. H. Houston, Nano Lett., 2008,
8, 34413445.
76 D. Li, M. B. Muller, S. Gijle, R. B. Kaner and G. G. Wallace,
Nat. Nanotechnol., 2008, 3, 101105.
77 H. Hu, X. Wang, J. Wang, L. Wan, F. Liu, H. Zheng, R. Chen
and C. Xu, Chem. Phys. Lett., 2010, 484, 247253.
78 T. Kuila, S. Bose, P. Khanra, N. H. Kim, K. Y. Rhee and
J. H. Lee, Composites, Part A, 2011, 42, 18561861.
79 A. V. Raghu, Y. R. Lee, H. M. Jeong and C. M. Shin,
Macromol. Chem. Phys., 2008, 209, 24872493.
80 D. A. Nguyen, Y. R. Lee, A. V. Raghu, H. M. Jeong, C. M. Shin
and B. K. Kim, Polym. Int., 2009, 58, 412417.
81 Y. R. Lee, A. V. Raghu, H. M. Jeong and B. K. Kim, Macromol.
Chem. Phys., 2009, 210, 12471254.
82 N. D. Anh, A. V. Raghu, H. M. Jeong and C. M. Shin, Polym.
Polym. Compos., 2010, 18, 351358.
83 H. B. Lee, A. V. Raghu, K. S. Yoon and H. M. Jeong, J.
Macromol. Sci., Part B: Phys., 2010, 49, 802809.
84 Y. R. Lee, S. C. Kim, H. Lee, H. M. Jeong, A. V. raghu,
K. R. Reddy and B. K. Kim, Macromol. Res., 2011, 19, 6671.
85 G. Wang, J. Yang, J. Park, X. Gou, B. Wang, H. Liu and
J. Yao, J. Phys. Chem. C, 2008, 112, 81928195.
86 H. J. Shin, K. K. Kim, A. Benayad, S. M. Yoon, H. K. Park,
I. S. Jung, M. H. Jin, H. K. Jeong, J. M. Kim, J. Y. Choi and
Y. H. Lee, Adv. Funct. Mater., 2009, 19, 19871992.
87 X. Zhou, J. Zhang, H. Wu, H. Yang, J. Zhang and S. Guo, J.
Phys. Chem. C, 2011, 115, 1195711961.
88 Y. Chen, X. Zhang, P. Yu and Y. Ma, Chem. Commun., 2009,
45274529.
89 L. Sun, H. Yu and B. Fugetsu, J. Hazard. Mater., 2010, 203,
101110.
90 Z. Lin, Y. Yao, Z. Li, Y. Liu, Z. Li and C. P. Wong, J. Phys.
Chem. C, 2010, 114, 1481914825.
91 Z. Lin, Y. Liu, Y. Yao, O. J. Hildreth, Z. Li, K. Moon and
C. P. Wong, J. Phys. Chem. C, 2011, 115, 71207125.
92 C. A. Amarnath, C. E. Hong, N. H. Kim, B. C. Ku, T. Kuila
and J. H. Lee, Carbon, 2011, 49, 34973502.
70 | Nanoscale, 2013, 5, 5271
Review
93 W. Li, X. Z. Tang, H. B. Zhang, Z. G. Jiang, Z. Z. Yu, X. S. Du
and Y. W. Mai, Carbon, 2011, 49, 47244730.
94 Y. Liu, Y. Li, M. Zhong, Y. Yang, Y. Wen and M. Wang, J.
Mater. Chem., 2011, 21, 1544915455.
95 R. S. Dey, S. Hajra, R. K. Sahu, C. R. Raj and M. K. Panigrahi,
Chem. Commun., 2012, 48, 17871789.
96 M. Zhou, Y. Wang, Y. Zhai, J. Zhai, W. Ren, F. Wang and
S. Dong, Chem.Eur. J., 2009, 15, 61166120.
97 S. Pei, J. Zhao, J. Du, W. Ren and H. M. Cheng, Carbon,
2010, 48, 44664474.
98 J. H. Park, W. C. Mitchel, H. E. Smith, L. Grazulis and
K. G. Eyink, Carbon, 2010, 48, 16701673.
99 M. J. Fernandez-Merino, L. Guardia, J. I. Paredes, S. VillarRodil, P. Solis-fernandez, A. Martinez-alonso and
J. M. D. Tascon, J. Phys. Chem. C, 2010, 114, 64266432.
100 X. Fan, W. Peng, Y. Li, X. Li, S. Wang, G. Zhang and
F. Zhang, Adv. Mater., 2008, 20, 44904493.
101 D. R. Dreyer, S. Murali, Y. Zhu, R. S. Ruo and
C. W. Bielawski, J. Mater. Chem., 2010, 21, 34433447.
102 C. Y. Su, Y. Xu, W. Zhang, J. Zhao, A. Liu, X. Tang,
C. H. Tsai, Y. Huang and L. J. Li, ACS Nano, 2010, 4,
52855292.
103 D. Chen, L. Li and L. Guo, Nanotechnology, 2010, 22,
325601.
104 T. A. Pham, J. S. Kim, J. S. Kim and Y. T. Jeong, Colloids
Surf., A, 2011, 384, 543548.
105 K. Brocrklehurst and G. Little, Biochem. J., 1972, 128, 471
474.
106 S. Bose, T. Kuila, A. K. Mishra, N. H. Kim and J. H. Lee, J.
Mater. Chem., 2012, 22, 96969703.
107 B. Jiang, C. Tia, L. Wang, L. Sun, C. Chen, X. Nong, Y. Qiao
and H. Fu, Appl. Surf. Sci., 2012, 258, 34383443.
108 X. Li, H. Wang, J. T. Robinson, H. Sanchez, G. Diankov and
H. Dai, J. Am. Chem. Soc., 2009, 131, 1593915944.
109 A. Kumar, A. L. M. Reddy, A. Mukherjee, M. Dubey, X. Zhan,
N. Singh, L. Ci, W. E. Billups, J. Nagurny, G. Mital and
P. M. Ajayan, ACS Nano, 2011, 5, 43454349.
110 S. Wakeland, R. Martinez, J. K. Grey and C. C. Luhrs,
Carbon, 2010, 48, 34633470.
111 Y. Wang, J. Liu, L. Liu and D. D. Sun, Nanoscale Res. Lett.,
2011, 6, 241.
112 E. C. Salas, Z. Sun, A. Luttge and J. M. Tour, ACS Nano, 2010,
4, 48524856.
113 G. Wang, F. Qian, C. W. Saltikov, Y. Jiao and Y. Li, Nano
Res., 2011, 4, 563570.
114 L. Q. Xu, W. J. Yang, K. G. Neoh, E. T. Kang and G. D. Fu,
Macromolecules, 2010, 43, 83368339.
115 I. Kaminska, M. R. Das, Y. Conier, J. Niedziolka-Jonsson,
J. Sobczak, P. Woisel, J. Lyskawa, M. Opallo,
R. Boukherroub and S. Szunerits, ACS Appl. Mater.
Interface, 2012, 4, 10161020.
116 Y. Lei, Z. Tang, R. Liao and B. Guo, Green Chem., 2011, 13,
16551658.
117 P. Khanra, T. Kuila, N. H. Kim, S. H. Bae, D. S. Yu and
J. H. Lee, Chem. Eng. J., 2012, 183, 526533.
118 T. Wu, X. Wang, H. Qiu, J. Gao, W. Wang and Y. Liu, J.
Mater. Chem., 2012, 22, 47724779.
This journal is The Royal Society of Chemistry 2013
Review
119 S. Zhang, Y. Shao, H. Liao, M. H. Engelhard, G. Yin and
Y. Lin, ACS Nano, 2011, 5, 17851791.
120 D. Yang, A. Velamakanni, G. Bozoklu, S. Park, M. Stoller,
R. D. Piner, S. Stankovich, I. Jung, D. A. Field,
C. A. Ventrice and R. S. Ruo, Carbon, 2009, 47, 145152.
121 C. Go'mez-Navarro, R. T. Weitz, A. M. Bittner, M. Scolari,
A. Mews, M. Burghard and K. Kern, Nano Lett., 2007, 7,
34993503.
122 Y. Zhu, M. D. Stoller, W. Cai, A. Velamakanni, R. D. Piner,
D. Chen and R. S. Ruo, ACS Nano, 2010, 4, 12271233.
123 M. J. McAllister, J. Li, D. H. Adamson, H. C. Schniepp,
A. A. Abdala, J. Liu, M. Herrera-Alonso, D. L. Milius,
R. Car, R. K. Prud'home and I. A. Aksay, Chem. Mater.,
2009, 19, 43964404.
124 C. Mattevi, G. Eda, S. Agnoli, S. Miller, K. A. Mkhoyan,
O. Celik, D. Mastrogiovanni, G. Granozzi, E. Garfunkel
and M. Chhowalla, Adv. Funct. Mater., 2009, 19, 25772583.
125 C. Valles, J. D. Nunez, A. M. Benito and W. K. Maser,
Carbon, 2012, 50, 835844.
126 Z. Gonz
alez, C. Botas, P. Alvarez,
S. Rold
an, C. Blanco and
R. Santamara, Carbon, 2012, 50, 828834.
127 M. Acik, G. Lee, C. Mattevi, A. Pirkle, R. M. Wallace,
M. Chhowalla, K. Cho and Y. Chabal, J. Phys. Chem. C,
2011, 115, 1976119781.
128 H. L. Guo, X. F. Wang, Q. Y. Qian, F. B. Wang and X. H. Xia,
ACS Nano, 2009, 3, 26532659.
129 Y. Shao, J. Wang, M. Engelhard, C. Wang and Y. Lin, J.
Mater. Chem., 2010, 20, 743748.
130 Y. Harima, S. Setodoi, I. Imae, K. Komaguchi, Y. Ooyama,
J. Ohshita, H. Mizota and J. Yano, Electrochim. Acta, 2011,
56, 53635368.
131 S. J. An, Y. Zhu, S. H. Lee, M. D. Stoller, T. Emilsson, S. Park,
A. Velamakanni, J. An and R. S. Ruo, J. Phys. Chem. Lett.,
2010, 1, 12591263.
132 G. K. Ramesha and S. Sampath, J. Phys. Chem. C, 2009, 113,
79857989.
133 Z. Wang, X. Zhou, J. Zhang, F. Boey and H. Zhang, J. Phys.
Chem. C, 2009, 113, 1407114075.
134 L. J. Cote, R. Cruz-Silva and J. Huang, J. Am. Chem. Soc.,
2000, 131, 1102711032.
135 Y. H. Ng, A. Iwase, A. Kudo and R. Amal, J. Phys. Chem. Lett.,
2010, 1, 26072612.
136 W. Chen, L. Yan and P. R. Bangal, Carbon, 2010, 48, 11461152.
137 P. Yao, P. Chen, L. Jiang, H. Zhao, H. Zhu, D. Zhou, W. Hu,
B. H. Han and M. Liu, Adv. Mater., 2010, 22, 50085012.
138 C. G. Navarro, J. C. Meyer, R. S. Sundaram, A. Chuvilin,
S. Kurasch, M. Burghard, K. Kern and U. Kaiser, Nano
Lett., 2010, 10, 11441148.
139 O. Akhavan and E. Ghaderi, J. Phys. Chem. C, 2009, 113,
2021420220.
140 G. Williams, B. Seger and P. V. Kamat, ACS Nano, 2008, 2,
14871491.
141 L. Guardia, S. V. Rodil, J. I. Paredes, R. Rozada, A. MartinezAlonso and J. M. D. Tascon, Carbon, 2012, 50, 10141024.
Nanoscale
142 J. G. Radich and P. V. Kamat, ACS Catal., 2012, 2, 807816.
143 L. Z. Fan, J. L. Liu, R. Ud-din, X. Yan and X. Qu, Carbon,
2012, 50, 37243730.
144 B. Zhao, P. Liu, Y. Jiang, D. Pan, H. Tao, J. Song, T. Fang and
W. Xu, J. Power Sources, 2012, 198, 423427.
145 J. Ye, H. Zhang, Y. Chen, Z. Cheng, L. Hu and Q. Ran, J.
Power Sources, 2012, 212, 105110.
146 Y. Chen, X. Zhang, D. Zhang and Y. Ma, Mater. Lett., 2012,
68, 475477.
147 D. Zhang, X. Zhang, Y. Chen, C. Wang and Y. Ma,
Electrochim. Acta, 2012, 69, 364370.
148 D. Mhamane, S. M. Unni, A. Suryawanshi, O. Game,
C. Rode, B. Hannoyer, S. Kurungot and S. Ogale, J. Mater.
Chem., 2012, 22, 1114011145.
149 Z. Lei, L. Lu and X. S. Zhao, Energy Environ. Sci., 2012, 5,
63916399.
150 Y. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. Cai,
P. J. Ferreira, A. Pirkle, R. M. Wallace, K. A. Cychosz,
M. Thommes, D. Su, E. A. Stach and R. S. Ruo, Science,
2011, 332, 15371541.
151 Z. J. Li, B. C. Yang, S. R. Zhang and C. M. Zhao, Appl. Surf.
Sci., 2012, 258, 37263731.
152 J. J. Yoo, K. Balakrishnan, J. Huang, V. Meunier,
B. G. Sumpter, A. Srivastava, M. Conway, A. Leela,
M. Reddy, J. Yu, R. Vajtai and P. M. Ajayan, Nano Lett.,
2011, 11, 14231427.
153 M. D. Stoller, S. Park, Y. Zhu, J. An and R. S. Ruo, Nano
Lett., 2008, 8, 34983502.
154 Y. Wang, Z. Shi, Y. Huang, Y. Ma, C. Wang, M. Chen and
Y. Chen, J. Phys. Chem. C, 2009, 113, 1310313107.
155 X. Du, P. Guo, H. Song and X. Chen, Electrochim. Acta, 2010,
55, 48124819.
156 Y. Zhu, S. Murali, M. D. Stoller, A. Velamakanni, R. D. Piner
and R. S. Ruo, Carbon, 2010, 48, 21182121.
157 W. Yang, J. H. Xu, Y. Xie, Y. Xu, G. Zhao and G. Q. Lin,
Tetrahedron: Asymmetry, 2006, 17, 17691774.
158 Z. H. Yang, R. Zeng, G. Yang, Y. Wang, L. Z. Li, Z. S. Lv,
M. Yao and B. Lai, J. Ind. Microbiol. Biotechnol., 2008, 35,
10471051.
159 A. M. Fonseca, F. J. Q. Monte, M. C. de Oliveira,
M. C. Mattos, G. A. Cordell and R. B. Filho, J. Mol. Catal.
B: Enzym., 2009, 57, 7882.
160 M. Bohn, K. Leppchen, M. Katzberg, A. Lang,
J. Steingroewer, J. Weber, T. Bley and M. Bertau, Org.
Biomol. Chem., 2007, 5, 34563463.
161 B. Xie, J. Yang, Q. Yang and W. Yuan, J. Mol. Catal. B:
Enzym., 2009, 61, 284288.
162 F. Li, J. Cui, X. Qian, R. Zhang and Y. Xiao, Chem. Commun.,
2005, 19011903.
163 T. Utsukihara, O. Misumi, N. Katao, T. Kuroiwa and
C. A. Horiuchi, Tetrahedron: Asymmetry, 2006, 17, 1179
1185.
164 G. Kumaraswamy and S. Ramesh, Green Chem., 2003, 5,
306308.