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Recent advances in the ecient reduction of graphene


oxide and its application as energy storage electrode
materials
Tapas Kuila,a Ananta Kumar Mishra,b Partha Khanra,a Nam Hoon Kimc
and Joong Hee Lee*abc
Ecient reduction of graphene oxide (GO) by chemical, thermal, electrochemical, and photo-irradiation
techniques has been reviewed. Particular emphasis has been directed towards the proposed reduction
mechanisms of GO by dierent reducing agents and techniques. The advantages of using dierent
kinds of reducing agents on the basis of their availability, cost-eectiveness, toxicity, and easy product
isolation processes have also been studied extensively. We provide a detailed description of the
improvement in physiochemical properties of reduced GO (RGO) compared to pure GO. For example,
the electrical conductivity and electrochemical performance of electrochemically obtained RGO are

Received 11th September 2012


Accepted 31st October 2012
DOI: 10.1039/c2nr32703a
www.rsc.org/nanoscale

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

WCU Programme, Department of BIN Fusion Technology, Chonbuk National


University, Jeonju, Jeonbuk, 561-756, Republic of Korea. E-mail: tkuila@gmail.com;
parthakhanra@gmail.com; jhl@jbnu.ac.kr; Fax: +82 832702341; Tel: +82 832702342

Department of Polymer and Nano Engineering, Chonbuk National University, Jeonju,


Jeonbuk, 561-756, Republic of Korea. E-mail: spuananta@gmail.com

c
Department of Hydrogen and Fuel Cell Engineering, Chonbuk National University,
Jeonju, Jeonbuk, 561-756, Republic of Korea. E-mail: namhk99@naver.com

Dr Tapas Kuila has been


working as a Research Professor
in the Department of BIN Fusion
Technology, Chonbuk National
University since February, 2012.
He joined the Department as
Postdoctoral
Fellow
in
November, 2010. He received his
PhD in Chemistry from Indian
Institute of Technology, Kharagpur, India. He has completed
MSc and BSc from Vidyasagar
University, West Bengal, India.
Presently, he is working on the surface modication of chemically
derived graphene and its application in supercapacitor devices. He
is also working on the green reduction of graphene oxide and
graphene-based composites.

52 | Nanoscale, 2013, 5, 5271

Introduction

The unique physiochemical and electrical characteristics of


graphene make it an ideal choice for use in electronic devices
such as touch panels, pn junction materials, exible thin-lm
transistors, hydrogen storage materials and supercapacitor
electrode materials.18 To meet demand, large-scale production
of graphene is required. Several methods such as chemical

Dr Ananta Kumar Mishra


completed his MSc and MPhil in
Organic Chemistry from Sambalpur University, India. He
received his PhD degree in Polymer Science from Indian Institute of Technology, Kharagpur,
India, in 2010. He has been
pursuing his Post-Doctoral
Research in Chonbuk National
University, South Korea, since
November 2010. Currently, he is
working
on
the
hybrid
membranes for proton exchange membrane fuel cells and fabrication of graphene-based hydrogen barrier lm through layer-bylayer assembly techniques.

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vapour deposition (CVD), plasma-enhanced CVD, epitaxial


growth on electrically insulating surfaces, electric arc discharge,
and solution-based chemical oxidationreduction have been
developed to produce graphene.918 Among these reported
techniques, the most promising method for the large-scale
production of graphene is the chemical oxidation of graphite,
conversion of the resulting graphite oxide to graphene oxide
(GO), and the subsequent reduction of GO. The surface of GO
bears dierent oxygen-containing functional groups such as
carboxyl, hydroxyl, epoxy, and keto groups, which make GO
hydrophilic and insulating in nature.19,20 For application of GO
in supercapacitor devices, it is essential that the GO be reduced
to ensure electronic conjugation. A supercapacitor is also called
an electrochemical capacitor which can store energy by means
of electrical double-layer capacitors (EDLC) and pseudocapacitors.4 The supercapacitor shows high power density and longterm cyclic stability than those of the conventional capacitors.
The EDLC stores charge non-faradically through reversible
adsorption of ions at the electrodeelectrolyte interface. On the
contrary, pseudocapacitance arises for the faradic reactions
occurring due to the remaining oxygen functionalities of RGO.

Mr Partha Khanra has completed


a MSc in Physics from Devi Ahilya
Vishwavidyalaya, Indore, India.
Currently he is continuing his
PhD at Chonbuk National
University, South Korea. He is
working on the chemical and
electrochemical synthesis of
monolayer functionalized graphene. Both the chemically and
electrochemically derived graphene nds application in
supercapacitor devices.

Mr Nam Hoon Kim is perusing


his PhD on graphene based
composite materials at Chonbuk
National University, South
Korea. He has completed Bachelor and Master degrees in
Polymer Science from Chonbuk
National University. He is
working on the simultaneous
reduction and functionalization
of graphene oxide to increase the
electrical conductivity of graphene for composite application.

This journal is The Royal Society of Chemistry 2013

The presence of oxygen functionalities also facilitates better


interaction with the electrolyte.4 Therefore, controlled reduction of GO using strong or mild reducing agents is always
preferred. Dierent kinds of chemical reducing agents have
been used to reduce GO to graphene. In most of the cases,
strong reducing agents such as hydrazine monohydrate,
hydroquinone, sodium borohydride, hydroxylamine, phenylenediamine, and hydrohalic acid have been used as reducing
agents.2127 However, these reducing chemicals may damage the
environment or be cost-prohibitive when used for the largescale production of graphene. Moreover, graphene layers tend
to agglomerate and form graphitic structures when strong
reducing agents are used. Recently, reduction of GO using
metals (Fe, Al, Zn) has attracted signicant interest.2830
However, metal particles may remain as impurities aer the
metal/hydrochloric acid reduction of GO. To overcome these
shortcomings, non-toxic reducing agents such as L-ascorbic
acid, vitamin-C, D-glucose, wild carrot root, alcohols, acetic acid,
dextran, and tea solutions have been used for the reduction of
GO.3136 These non-toxic reducing agents can eciently reduce
GO to graphene and the physicochemical properties of the
reduced GO (RGO) are comparable to those of hydrazineRGO.
Thermal and electrochemical techniques have also been
developed to reduce GO.3742 These approaches can successfully
remove oxygen functionalities from the surface of GO. However,
thermal reduction of GO in the presence of hydrogen gas
requires high temperatures and special reactors, while electrochemical reduction is energy-consuming and requires expensive platinum electrodes. Therefore, new strategies for the largescale production of RGO under mild and environmentally
benign conditions are of great interest.
Numerous groups have investigated the reduction of GO by
chemical, thermal, and electrochemical methods for supercapacitor application. In this article, we review recent trends in
the reduction of GO and provide a short review on the preparation of GO by chemical methods. We also highlight the

Professor Joong Hee Lee has


more than 25 years of research
experience in the fabrication of
polymer and polymer composites for electrical and electronic
applications. He has received a
PhD in Polymer Science from the
University of Minnesota, USA.
He has received a Gold Medal in
Korea Patent Award and Best
Project Award. His current
research interests are focused on
the preparation and surface
modication of graphene. He is also working on graphene-based
supercapacitors, biosensors, and composites. Part of his research
group is engaged in the development of highly conducting
composite bipolar plates and hybrid membranes for proton
exchange membrane fuel cells.

Nanoscale, 2013, 5, 5271 | 53

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structureproperty relationships of GO and discuss why it is


essential to reduce GO for supercapacitor application. All these
methods reduce GO successfully and produce graphene with
excellent physicochemical properties. However, these methods
have limitations with respect to toxicity, cost-eectiveness, ease
of availability, and experimental complexity. We conclude by
proposing future cost eective and green methodologies for
the reduction of GO to graphene for application in various
electrochemical devices.

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Preparation of GO

Natural ake graphite and exfoliated (expandable) graphite are


generally used to prepare graphite oxide. Several methods for
the preparation of graphite oxide have been reported.4353
Hummers' original method has been modied in several ways
to increase the degree of oxidation of graphite. Pre-oxidized
graphite has also been used to prepare graphite oxide by a
modied Hummers' method.44 The Staudenmaier method is
also an eective way to produce chemically oxidized graphite. A
few other oxidants such as Jones' reagent (H2CrO4/H2SO4),
Brodie's reagent, and peroxides have been used to oxidize
graphite.43,49,50 In this section, we discuss the preparation of
graphite oxide using dierent chemical methods.
KMnO4 + 3H2SO4 / K+ + MnO3 + H3+ + 3HSO4
MnO3 + MnO4 / Mn2O7

Alternatively, potassium dichromate (K2Cr2O7) can be used


instead of KMnO4 to oxidize graphite. This reagent is known as
Jones' reagent and is regarded as a relatively inexpensive
method for the conversion of graphite to graphite oxide. In this
case, chromic acid (H2CrO4) is the oxidizing agent, and is
generated in situ by the reaction of K2Cr2O7 and H2SO4. The
conversion proceeds through an intermediate, dichromic acid
(H2Cr2O7), as shown in the following reaction diagram:
K2Cr2O7 + H2SO4 / H2Cr2O7 4 H2CrO4

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,

54 | Nanoscale, 2013, 5, 5271

this method is not popular due to the diculty in controlling


the reaction temperature.54 In a typical preparation procedure, a
reaction ask containing a magnetic stir bar is charged with
sulfuric acid (87.5 ml) and nitric acid (45 ml) and cooled by
immersion in an ice bath. The acid mixture is stirred and
allowed to cool for 15 min, and graphite (5 g) is added under
vigorous stirring to avoid agglomeration. Aer the graphite
powder is well dispersed, potassium chlorate (55 g) is added
slowly over 15 min to avoid sudden increases in temperature.
The reaction ask is loosely capped to allow evolution of gas
from the reaction mixture and stirred for 96 h at room
temperature. The only drawback of this method is the use of
explosive potassium chlorate, which makes it very dicult to
control the temperature of the reaction.
Graphite oxide can be prepared directly in a one-step process
where graphite powder and peroxides are mixed and ground to
ne powder using a mortar and pestle.43 This powder is heated
in a small beaker at 110  C. Peroxides are strong oxidizers and
may explode when heated in a closed container. However, this is
not an eective method for the conversion of graphite to
graphite oxide.
All of the above-mentioned methods are used to prepare
multi-layers of graphite oxides. To obtain a single layer of GO,
graphite oxide is mechanically exfoliated by ultra-sonication in
water. Single layers of GO are separated by centrifugation of the
total graphite oxide dispersion in water. Un-exfoliated graphite
oxide is removed as deposited material at the bottom of the
centrifuge tube. The GO is collected as a stable dispersion in
water, and the water is removed by freeze-drying. The conversion
of graphite oxide to GO depends on the degree of oxidation of the
graphite, the dispersion medium, the ultrasonic frequency, and
the sonication time, among other factors. It has been found that
the degree of exfoliation increases as the extent of oxidation,
ultrasonic frequency, and sonication time increase.

Reduction of GO

Graphite oxide consists of layered GO sheets that contain many


oxygen functional groups (e.g. hydroxyl, epoxide, carbonyl, and
carboxyl groups). These functional groups signicantly alter van
der Waals interactions between the layers and endow GO with
strong hydrophilicity.19,20 Based on the dierent models proposed
by Homann, Ruess, NakajimaMatsuo, and LerfKlinowski
(shown in Fig. 1), GO contains oxygen functionalities on the basal
planes and edges of sheets.5557 The presence of these functional
groups destroys the planar sp2 carbons of graphite and converts
them to sp3 carbons.19,20 Therefore, the pp electronic conjugation
of graphite is destroyed in GO, resulting in a signicant decrease
in electrical conductivity. It has been reported that GO is insulating in nature. In contrast, the electrical conductivity of pure
graphite has been reported to be 2500  15 S m1 at room
temperature.58,59 Therefore, GO cannot be used as a conductive
material for electrical and electrochemical devices without further
processing. In addition, the presence of oxygen functional groups
makes GO thermally unstable when it undergoes pyrolysis at
elevated temperatures.6062 Notably, it has been demonstrated that
the electrical conductivity of GO (and presumably its thermal

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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.)

stability as well) can be restored close to the level of graphite by


chemical reduction.6365 The electrical conductivity of RGO has
been reported to be in the range of 20042 000 S m1 depending
on the type of reducing agent, the reduction time, temperature,
annealing time, and annealing temperature, etc.60,6668 The specic
capacitance of RGO has been found to be signicantly higher than
that of GO. The cyclic stability of GO can also be increased aer the
reduction. However, the transparency and dispersibility of RGO
are signicantly poorer than those of pure GO. Oxygen-containing
functional groups are removed during reduction, resulting in a
decrease in the dispersibility of GO in dierent solvents. The
restoration of p-electronic conjugation and the change in color
from brown to black are the main reasons for the observed
decrease in transparency.
Stankovich et al. were the rst authors to report the preparation of electrically conducting graphenepolystyrene (PS)
composites with a percolation threshold of 0.1 vol% graphene.
These authors reduced the GOPS colloidal suspension using
dimethylhydrazine at 80  C for 24 h.67,69 The excellent electrical
conductivity of the resulting composite spurred great interest in
developing methods to obtain electrically conductive graphene
via chemical, electrochemical, or thermal reduction of GO. In
this section, we discuss dierent approaches to sequentially
reduce GO to graphene.

This journal is The Royal Society of Chemistry 2013

3.1

Chemical reduction

3.1.1 TOXIC REDUCING AGENTS. Reduction of GO to graphene


was rst carried out using dimethylhydrazine at 80  C for 24 h.
Similar to dimethylhydrazine, hydrazine monohydrate was
found to be an eective chemical reducing agent for the
reduction of GO to graphene. Chemically obtained RGO (CRGO)
consists of aggregated layers of graphene with a large surface
area (466 m2 g1).60 The high specic surface area is partially an
indication of the degree of GO exfoliation prior to reduction.
However, this value is still much lower than that of the theoretical surface area of graphene (2620 m2 g1).60,69 This may be
due to the aggregation of exfoliated GO sheets upon reduction.
X-ray photoelectron spectroscopy (XPS) analysis was used to
show that the oxygen-containing functional groups were
removed successfully from the surface of GO. However,
combustion and XPS elemental analysis studies have shown
that the complete removal of oxygen functionalities by chemical
reduction is almost impossible. Fig. 2 shows the possible
mechanism for the chemical reduction of GO by hydrazine.70
According to Stankovich et al. and Gao et al., hydrazine opened
the epoxide ring, resulting in the formation of hydrazino alcohols.60,70 The initial derivative produced by the epoxide ring
opening with hydrazine reacted further via the formation of an

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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

56 | Nanoscale, 2013, 5, 5271

reducing GO without using polymeric or surfactant stabilizers.76


However, in most of the cases, processable graphene was
prepared by surface modication of GO using an organic

Fig. 3 Thermogravimetric analysis (TGA) curves of graphite, GO, and RGO.


(Reproduced with permission from ref. 67.)

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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

This journal is The Royal Society of Chemistry 2013

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

Fig. 4 Schematic of the proposed mechanism for the reduction of GO by


hydroxylamine. (Reproduced with permission from ref. 87.)

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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.)

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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.)

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Fig. 7

FT-IR spectra of GO, ODA and GOODA (20 h) (adapted from ref. 93).

33.5 aer reduction, as determined by XPS elemental analysis.


The RGO had a conductivity of 15 000 S m1. The reaction
between metals (Al, Fe, and Zn) and GO in an acidic solution
can be understood in terms of the reduction potentials of two
half cell reactions as follows:
M (Al, Fe, Zn) / Mn+ + ne,
for Fe and Zn, n 2, and for Al, n 3
GO + aH+ + be / RGO + cH2O
The standard reduction potentials of Al3+/Al, Fe2+/Fe, and
Zn /Zn vs. SHE (standard electrode potential) are +1.66, +0.44,
and +0.76 V, respectively. In contrast, the electrode potential of
GO reduction is about 0.40 V vs. SHE in a solution with a
pH  4.96 Therefore, the eciency of GO reduction decreases in
the following order: Al > Zn > Fe. The main drawback associated
2+

Fig. 8 X-ray diraction patterns of GO before and after reduction via Fe for
dierent reduction times. (Reproduced with permission from ref. 29.)

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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

Fig. 9 Possible reaction mechanism of GO reduction by hydrohalic acids: (a)


ring-opening reaction of an epoxy group and (b) halogenation substitution
reaction of a hydroxyl group. The substituted halogen atoms are expected to be
easy to eliminate from the carbon lattice (X iodine or bromine). (Reproduced
with permission from ref. 97.)

60 | Nanoscale, 2013, 5, 5271

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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

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Fig. 10 Possible mechanism of reduction of GO with L-cysteine. (Reproduced


with permission from ref. 103.)

agent.106 The reduction occurred under mild conditions and the


as-prepared graphene sheet showed good crystalline behavior.
The removal of oxygen functionalities from GO was conrmed
by XPS and Raman spectra analysis. The RGO formed stable
dispersion in water when a large amount of glycine was used.
Jiang et al. prepared nitrogen doped RGO by the reaction of
concentrated ammonia and GO under hydrothermal conditions.107 The eects of temperature on the surface chemistry,
morphology and structure of N-doped graphene sheets were
investigated. Elemental mapping images (Fig. 11) indicated the
presence of N, C and O elements in the RGO. It revealed that the
distribution of N atoms in the RGO sheet was highly homogeneous suggesting the successful formation of N-doped graphene.
Li et al. showed that thermal annealing (at 300  C) of GO in the
presence of ammonia (NH3) gas could be used to generate
nitrogen-doped graphene sheets.108 The oxygen functionalities
of GO are thought to be responsible for this kind of reduction.
Electrical conductivity measurements of individual GO sheets

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.)

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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

Fig. 12 Reduction mechanism of GO by lithium metal in liquid ammonia.


(Reproduced with permission from ref. 109.)

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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

62 | Nanoscale, 2013, 5, 5271

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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.

Fig. 13 Proposed reaction pathway for the deoxygenation of exfoliated GO in a


PDDA solution to obtain graphene nanosheets (G), where RN+ was used to
designate PDDA. (Reproduced with permission from ref. 119.)

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3.2

Thermal reduction

Thermal reduction is a well-known method for the removal of


oxygen functionalities from the surface of GO.120123 In this
method, oxygen functionalities are removed in the form of
water, carbon dioxide, and carbon monoxide. The sample is
placed in a pre-heated furnace at 10001100  C for 3045 s in
the absence of air.54 The generated gases expand the layers of
graphite oxide (or GO) and reduce these materials to graphene.
Schniepp et al. reported thermal reduction of GO in a
specially designed furnace.54 In brief, they inserted GO in an
alumina boat into a 25 mm inner diameter, 1.3 m long quartz
tube that was sealed at one end. The other end of the quartz
tube was closed using a rubber stopper. An argon (Ar) inlet and
thermocouple were then inserted through the rubber stopper.
The sample was ushed with Ar for 10 min, and then the quartz
tube was quickly inserted into a Lindberg tube furnace preheated to 1050  C. These authors reported that the carbon
content in the RGO increased with increasing furnace
temperature.
McAllister et al. studied the exfoliation of GO and its
reduction mechanism using TGA-FT-IR.123 According to their
study, thermal decomposition of GO obeyed second order rate
kinetics and loss can be attributed to the decomposition of
oxygen-containing functional groups. The thermal energy
evolved during the decomposition of GO heats the sample
locally, allowing faster reaction rates and higher internal
temperatures, ensuring sucient rapid pressure buildup for
uniform exfoliation. The resultant RGO samples were highly
aggregated and dispersed easily in solvents. The dispersed
materials consisted of at least 80% single graphene sheets.
Mattevi et al. showed that annealing of GO at 450  C or above
is equivalent to chemical reduction via hydrazine monohydrate
at 80  C followed by heating at 200  C.124 XPS elemental analysis
showed that the RGO contains 8% of oxygen.125 Thermal
treatment of a GO paper at 700  C under Ar or hydrogen
atmosphere can eciently remove the oxygen-containing
functional groups and restore the sp2 network structure. The
resulting RGO exhibited electrical conductivities as high as
8100 S m1 which is ve orders of magnitude higher than that
of the original GO paper. The RGO obtained by thermal exfoliation and reduction can be used as active electrodes in the
positive half-cell of a vanadium redox ow battery.126 It has been
found that the RGO obtained at 1000  C exhibited an
outstanding electrochemical performance in terms of peak
current densities and reversibility. This excellent behavior is
attributed to the restoration of sp2 networks aer thermal
treatment, which implies the formation of a graphene with a
high electrical conductivity and large surface area. Moreover,
the remaining oxygen containing functional groups acted as
active sites towards the vanadium redox reactions. Extensive
research was carried out on the thermal reduction of GO, RGO
characterization and its application but the exact mechanism is
still unclear. Therefore, to investigate the thermal reduction
mechanism, Acik et al. took in situ transmission infrared
absorption spectroscopy measurements of GO lms upon
thermal annealing at 60850  C under vacuum (103 to 104

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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

Fig. 14 Schematic of thermal reduction mechanisms for GO reduction indicating


the decomposition of oxygen species through radical reactions starting with (i)
hydrolysis via combustion reactions (formation of hydroxyl, hydronium, and
hydroperoxyl radicals), (ii) propagation via decarboxylation or attack on hydroxyls
as well as ring-opening of epoxides, and (iii) termination into benzyl/phenyl radicals with CO/CO2 production. (Reproduced with permission from ref. 127.)

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functionalized graphene (R-Ph-GO). The schematic for the


preparation of thermochemically reduced graphene is shown in
Fig. 15. The electrical conductivity of the R-Ph-GO increased
with increasing annealing time and the maximum conductivity
was found to be 42 000 at 6 h annealing time. The enhanced
conductivity of R-I-Ph-GO is attributed to the reduction of GO by
the release of HI from I-Ph-GO during thermal annealing.
Thermal reduction is an easy, cost-eective and environmentally friendly fabrication route for exible conducting graphene papers of great application potential as exible
electrodes in elds, such as energy storage/harvest (supercapacitors, batteries) and sensors. However, this method
requires a complicated experimental set-up and consumes a
huge amount of energy.
3.3

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

Fig. 15 Schematic of functionalized GO (F-GO) and reduced F-GO (RFGO).


Phenyl functionalized GO (Ph-GO) and GO can be thermally reduced. 4-Iodophenyl functionalized GO (I-Ph-GO) can be thermochemically reduced at 300  C.
(Reproduced with permission from ref. 68.)

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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.

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3.4

Microwave and photoreduction

In addition to the conventional reduction techniques described


earlier, various other methods were used to deoxygenate GO.
Cote et al. reported a chemical-free ash reduction process in
which a photographic camera ash triggers instantaneous
deoxygenation of GO by photothermal heating.134 This method
decreased the sheet resistance from 2  108 U sq1 (for pure
GO) to 9.5 kU sq1 (for the RGO). The hydrophilicity of the
ashed area was also signicantly decreased than that of pure
GO. In comparison to chemical, thermal, and electrochemical
reduction, ash reduction is rapid, chemical-free, and energy
ecient. This technique holds great promise for patterning GO
lms for device and composite applications. Ng et al. demonstrated the feasibility of using a bismuth vanadate (BiVO4)
visible light photocatalyst to reduce GO photocatalytically.135
Using the BiVO4RGO system, these authors reported the
generation of a higher photocurrent density in response to
visible light irradiation than that generated by the TiO2 system
in response to UV light irradiation. These authors attributed
this nding to the longer electron lifetime of excited BiVO4
compared to TiO2, as the electrons are injected into RGO
instantly at the site of generation, minimizing charge recombination. Chen et al. reported the rapid and mild thermal
reduction of GO by microwaves.136 Reduction was carried out in
a mixed solution of N,N-dimethylacetamide and water (DMAc
H2O). The mixed solution functioned as both a solvent for the
produced graphene and a medium to control the temperature of
the reactive system up to 165  C. GO can be reduced within few
minutes using microwaves, with the eciency of reduction
dependent on the duration of exposure to microwaves. The RGO
obtained by the microwave induced reduction dispersed well in
DMAc and formed a stable dispersion. Furthermore, the electrical conductivity of the RGO was 104 times higher than that of
pure GO. Yao et al. demonstrated that GO can be directly converted to graphene sheets by applying electric current through
the GO lm deposited on a conductive substrate.137 The
reduction occurred through the following mechanism: GO + H+
+ e RGO + H2O. It is well known that GO contains ionizable
carboxyl functionalities on its surfaces. Therefore, the GO paper
itself can supply the necessary H+ ions for the reduction. It has
been found that completely dried GO disfavors the reduction
process. Go'mez-Navarro et al. prepared RGO on copper or gold
grids by dipping the grids into the GO dispersion for 810
minutes and subsequently chemically reduced under hydrogen
plasma.138 They have determined the atomic structure of RGO
by TEM analysis. The largest portion of the RGO layer is
comprised of clean well crystallized graphene areas as shown in
Fig. 16. The TEM images also revealed the presence of a
remarkable amount of topological defects aer reduction. It
was found that almost 60% of the surface of RGO remained
undisturbed. Akhavan and Ghaderi prepared RGO lms
deposited on the TiO2 substrate by the photocatalytic irradiation.139 The concentration of the COH, C]O, and O]COH
bonds decreased to 73%, 85%, and 72%, respectively, on
increasing the irradiation time to 4 h. This is attributed to the
eective reduction of the GO platelets to graphene. Moreover,

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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. 16 Atomic resolution, aberration-corrected TEM image of a single layer


reduced-GO membrane. (a) Original image and (b) with color added to highlight
the dierent features. (Reproduced with permission from ref. 138.)

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.)

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Review

TiO2 + hn / TiO2 (h + e) / TiO2 (e) + C2H4OH + H+


TiO2 (e) + GO / TiO2 + RGO
The RGO dispersed easily in a range of polar solvents. The
main advantage of photocatalytic reduction is that it can be
triggered on demand by tuning the UV-irradiation. Nanosecond
pulse LASER analysis suggests that this method not only
provides an on-demand UV assisted reduction technique but
also opens up new ways to obtain photoactive graphenesemiconductor composites.

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RGO-based supercapacitor

The insulating nature of GO is not useful for supercapacitor


application because of a very low specic capacitance
value.142152 In contrast, the specic capacitance of GO increases
aer reduction and the value has been reported to be 100300 F
g1. In the previous sections we have discussed the reduction of
GO using dierent kinds of reducing agents to nd out the
environmentally friendly reduction route. The current section
describes the usefulness of RGO as energy storage electrode
materials and its application in supercapacitor devices.
The unique features of RGO, including high electrical
conductivity and porous macrostructure, are credited for
improved cyclic stability and capacitance performance. Owing
to its large surface area, RGO can store electrons in its pp
network and discharges stored electrons non-faradically.141 The
pseudocapacitance arises due to the reversible redox reactions
between the residual oxygen functionalities of RGO and H+ ions
of the electrolyte. Lin et al. observed the faradic reaction of RGO
in a 1 M H2SO4 electrolyte but there was no redox reaction in a 1
M Na2SO4 solution.91 The eect of reduction time on the
supercapacitive performance of hydrazineRGO has been
investigated in detail.143 The C and N contents in the RGO
increase with increasing reduction time at the expense of
specic surface area. This is attributed to the removal of
hydrophilic oxygen functionalities from the surface of RGO
during reduction resulting in extensive agglomeration via pp
interactions. The RGO obtained by 30 min reduction shows
highest specic capacitance of 192 F g1 in a 6 M KOH electrolyte. Zhao et al. investigated the eect of thermal reduction
temperature on the specic capacitance of RGO.144 It has been
found that the specic capacitance of RGO annealed at 200  C is
highest and decreases with increasing annealing temperature.
Oxygen containing functional groups played an important role
in the chargedischarge processes, as they served as a passage
for the ions to the internal electrodeelectrolyte interface.
Fig. 18 shows the variation of specic capacitance of dierent
RGOs at dierent current densities. Ye et al. also reported that
the RGO obtained by annealing at 200  C and ambient pressure
showed good electrochemical performance, with a maximum
specic capacitance of 315 F g1.145 The RGO-based
supercapacitors in two-electrode systems were designed in 1butyl-3-methylimidazolium hexauorophosphate (BMIPF6) and
1-butyl-3-methylimidazolium
tetrauoroborate
(BMIBF4),
respectively.146 The retention in specic capacitance is 141% of

66 | Nanoscale, 2013, 5, 5271

the initial value aer 3000 cycles. An environment-friendly


method to produce water-dispersible RGO by using glutathione
as a reducing and stabilization agent has been developed.147
Fig. 19(af) shows CV, chargedischarge, specic capacitance
retention and Nyquist plots of the RGO electrode. The CV curves
maintain their rectangle shape very well at a scan rate of 10
500 mV s1. The specic capacitance of the RGO electrode was
determined from galvanostatic chargedischarge tests and is
noted to be as high as 238 F g1 at a current density of 0.1 A g1.
Mhamane et al. showed the reduction of GO using triethylene
glycol and its usefulness as energy storage electrode materials.148 Lei et al. reported that urea reduced GO shows a gravimetric capacitance of 255 F g1 and a volumetric capacitance of
196 F cm3.149 The superior capacitive performance of RGO
suggested that urea is a good reducing agent for the mass
production of graphene-based materials for energy storage
devices. Zhu et al. used RGO to fabricate super-capacitor
devices.150 The maximum specic capacitance for the activated
graphene was 166 F g1 at a current density of 2.8 A g1. Li et al.
designed supercapacitor electrode materials by mixing fewlayer-graphene, carbon black and poly(tetrauoroethylene) in a
mass ratio of 80 : 15 : 5 and dispersed in ethanol.151 The
conductivity of the RGO is measured to be 3.2  104 S m1,
which is comparable to that of pristine graphite. The CV
performance and galvanostatic chargedischarge measurement
was performed in a 1 M Na2SO4 solution. The chargedischarge
curves are linear in the total range of potential with constant
slopes, showing a nearly perfect capacitive behavior. The
specic capacitance of the designed electrode can reach upto
180 F g1 which suggests that the RGO can be used as nextgeneration electrode materials for green energy storage systems
due to its higher electrochemical performance. Jiang et al.
investigated the capacitive behavior of N-doped graphene
obtained by the reduction of GO with ammonia.107 Nitrogen
doped graphene possesses greater gravimetric capacitances
(144 F g1 at 0.2 A g1) than that of pure graphene. This is
attributed to the pseudocapacitive eect based on the N-doping

Fig. 18 Rate capacitances of the samples in 6 M KOH with dierent current


densities. GNS is used to designate thermally reduced RGO and the numbers
followed by a hyphen (-) suggest the annealing temperature. (Reproduced with
permission from ref. 144.)

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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.)

for graphene. Aer 500 cycles, the capacitance decreases to only


10% of initial capacitance, exhibiting excellent cycle stability.
Yoo et al. reported an in-plane fabrication approach for an
ultrathin capacitor comprised of pristine graphene and RGO.152
A schematic depiction of the stacked geometry used in the
fabrication of these supercapacitor devices is provided in
Fig. 20. The novel, ultrathin design allowed for the formation of
an ecient electrical double layer and most importantly, for the
utilization of the maximum electrochemical surface area. These
solid-state supercapacitors are prototypes for a broad range of
thin-lm based energy storage devices. Stoller et al. studied the
specic capacitance of chemically modied graphene (CMG).153
Three dierent electrolytes commonly used in commercial
EDLCs were used to check the performance of the CMG-based
ultracapacitor cells. Galvanostatic chargedischarge of CMG
was performed at constant currents of 10 and 20 mA. Specic

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Fig. 20 Schematic of the stacked geometry used for the fabrication of supercapacitor devices. (Reproduced with permission from ref. 152.)

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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.

5 Conclusions and future research


directions
We have highlighted recent advances in the reduction of GO by
chemical, thermal, electrochemical, and photo-irradiation
techniques. For each approach, we provided possible mechanisms for the removal of oxygen functionalities from the surface
of GO. Chemical reduction of GO involves two main types of
reducing agents: toxic chemicals, which are very strong
reducing agents, or eco-friendly reducing agents. The use of
strong reducing agents such as hydrazine, sodium borohydride,
hydroxylamine, and para-phenylenediamine should be minimized due to their adverse environmental impacts. In general,
eco-friendly reducing agents are mild agents and these agents
are derived from natural fruits and vegetables. In some cases,
eco-friendly reducing agents have been found to be more
eective than strong reducing agents. Thermal reduction of GO
requires a very high temperature (1000  C), and can eliminate
the oxygen groups from GO surfaces. We also described electrochemical reduction of GO, although the exact mechanism
underlying electrochemical reduction is still unclear. The RGO
obtained by chemical, thermal, or electrochemical methods has
signicantly improved electrical and electrochemical properties
compared to pure GO. The electrical conductivity and electrochemical stability of ERGO are higher than those of chemically
or thermally obtained RGO. Although we have discussed the
reduction of GO by dierent reducing agents and techniques in
detail, exact mechanisms for each and every case are yet to be
determined. RGO holds great promise for use in supercapacitor
devices due to its high specic capacitance value.
The green reduction of GO by biological reducing agents is
another exciting future direction. Dierent kinds of biological

68 | Nanoscale, 2013, 5, 5271

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.

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