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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
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Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road,
Shenyang 110016, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Graphene has attracted great interest for its excellent mechanical, electrical, thermal and
pyrolytic graphite, epitaxial growth, chemical vapor deposition, and the reduction of graph-
ene oxide (GO). The first three methods can produce graphene with a relatively perfect
structure and excellent properties, while in comparison, GO has two important characteristics: (1) it can be produced using inexpensive graphite as raw material by cost-effective
chemical methods with a high yield, and (2) it is highly hydrophilic and can form stable
aqueous colloids to facilitate the assembly of macroscopic structures by simple and cheap
solution processes, both of which are important to the large-scale uses of graphene. A key
topic in the research and applications of GO is the reduction, which partly restores the
structure and properties of graphene. Different reduction processes result in different
properties of reduced GO (rGO), which in turn affect the final performance of materials
or devices composed of rGO. In this contribution, we review the state-of-art status of the
reduction of GO on both techniques and mechanisms. The development in this field will
speed the applications of graphene.
2011 Elsevier Ltd. All rights reserved.
1.
Introduction
5 0 ( 20 1 2 ) 3 2 1 032 2 8
graphene, chemically modified graphene, chemically converted graphene, or reduced graphene [11]. The most straightforward goal of any reduction protocol is to produce
graphene-like materials similar to the pristine graphene obtained from direct mechanical exfoliation (i.e. the Scotch
tape method) of individual layers of graphite both in structure and properties. Though numerous efforts have been
made, the final target is still a dream. Residual functional
groups and defects dramatically alter the structure of the carbon plane, therefore, it is not appropriate to refer to rGO, even
today, simply as graphene since the properties are substantially different.
Nowadays, in addition to reduction from GO, graphene can
be produced by micro-mechanical exfoliation of highly ordered pyrolytic graphite [1], epitaxial growth [1214], and
chemical vapor deposition (CVD) [13,15,16]. These three
methods can produce graphene with a relatively perfect
structure and excellent properties. While in comparison, GO
has two important characteristics: (1) it can be produced
using inexpensive graphite as raw material by cost-effective
chemical methods with a high yield, and (2) it is highly hydrophilic and can form stable aqueous colloids to facilitate the
assembly of macroscopic structures by simple and cheap
solution processes, both of which are important to the
large-scale uses of graphene. As a result, GO and rGO are still
hot topics in the research and development of graphene,
especially in regard to mass applications.
Therefore, the reduction of GO is definitely a key topic, and
different reduction processes result in different properties
that in turn affect the final performance of materials or devices composed of rGO. Though the final target to achieve perfect graphene is hard to reach, research efforts have
continuously made it closer. Here we review work on the
reduction of GO, and because there are many review papers
on synthesis methods [13,1723], and the physical [2,3,24
26] and chemical [9,2731] characteristics of graphene, details
on them will not be repeated.
2.
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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
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Fig. 2 (a) AFM image of GO sheets. (b) STEM-ADF image of a GO film where mono-, bi- and tri-layers are labeled as a, b, and c.
The round opening in the middle is a hole through the single film. (c) High-magnification ADF image of a monolayer GO film.
(d) Simple drawing of monolayer and possible packing of bi- and tri-layers [47].
3.
Criteria used in determining the effect of
reduction
Since reduction can make a great change in the microstructure and properties of GO, some obvious changes can be directly observed or measured to judge the reducing effect of
different reduction processes.
3.1.
Visual characteristics
5 0 ( 20 1 2 ) 3 2 1 032 2 8
3.2.
Electrical conductivity
1
rt
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3.3.
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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
[73]
[58]
a
b
Reduction method
Form
C/O ratio
r (S/cm)
Hydrazine hydrate
Hydrazine reduction in colloid state
150 mM NaBH4 solution, 2 h
Hydrazine vapor
Thermal annealing at 900 C, UHVa
Thermal annealing at 1100 C, UHV
Thermal annealing at 1100 C in Ar/H2
Multi-step treatment:
(I) NaBH4 solution
(II) Concentrated H2SO4 180 C, 12 h
(III) Thermal annealing at 1100 C in Ar/H2
Vitamin C
Hydrazine monohydrate
Pyrogallol
KOH
55% HI reduction
Powder
Film
TCF
Film
10.3
NAb
8.6
8.8
14.1
NA
NA
(I) 4.78
(II) 8.57
(III) >246
2
72
0.045
NG
NG
103
727
(I) 0.823
(II) 16.6
(III) 202
12.5
12.5
NA
NA
>14.9
77
99.6
4.8
1.9103
298
TCF
TCF
Powder
Film
Film
4.
Reduction strategies
4.1.
Thermal reduction
4.1.1.
Thermal annealing
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Fig. 5 Pseudo-3D representation of a 600 nm 600 nm AFM scan of an individual graphene sheet showing the wrinkled and
rough structure of the surface, and an atomistic model of the graphite oxide to graphene transition [45].
Fig. 6 XPS spectra of GO sheets annealed in 2 Torr of (a) NH3/Ar (10% NH3) and (b) H2 at various temperatures [77].
In addition to annealing temperature, annealing atmosphere is important for the thermal annealing reduction of
GO. Since the etching of oxygen will be dramatically increased
at high temperatures, oxygen gas should be excluded during
annealing. As a result, annealing reduction is usually carried
out in vacuum [55], or an inert [72] or reducing atmosphere
[35,72,75,77]. Becerril et al. [55] have reduced GO films by thermal annealing at 1000 C, and found that a quality vacuum
(<105 Torr) is key for the recovery of GO, otherwise the films
can be quickly lost through reaction with residual oxygen in
the system. The same condition should also be considered
in inert atmospheres. Therefore, a reducing gas such as H2
is added to consume the residual oxygen in the atmosphere.
Furthermore, because of the high reducing ability of hydrogen
at elevated temperatures, the reduction of GO can be realized
at a relatively low temperature in a H2 atmosphere. Wu et al.
reported that GO can be well reduced at 450 C for 2 h in an
Ar/H2 (1:1) mixture with a resulting C/O ratio of 14.9 and conductivity of 1 103 S/cm. Li et al. [77] reported that annealing
GO in low-pressure ammonia (2 Torr NH3/Ar (10% NH3)) can
produce simultaneous nitrogen doping and reduction of GO.
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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
As shown in Fig. 6, the highest doping level of 5% N is obtained at 500 C, and electrical measurements of GO sheets
demonstrate that GO annealed in NH3 exhibits a higher conductivity than that annealed in H2 and clearly shows n-type
electron doping behavior. The latter may be beneficial for
the fabrication of electronic devices. Recently, Lopez et al.
[62] demonstrated that vacancies can be repaired partially
by exposing rGO to a carbon source such as ethylene at a high
temperature (800 C), similar to the conditions used for CVD
growth of SWCNTs. With this post-reduction deposition of
carbon, the sheet resistance of individual rGO sheet can be
decreased to 28.6 kX/sq (or 350 S/cm) [78]. Su et al. reported
a similar defect healing effect for rGO sheets functionalized
with aromatic molecules during pyrolysis that results in a
highly graphitic material with a conductivity as high as
1314 S/cm [63].
Based on the above results, reduction of GO by high temperature annealing is highly effective. But the drawback of
thermal annealing is also obvious. First, high temperature
means large energy consumption and critical treatment conditions. Second, if the reduction is performed to an assembled
GO structure, e.g. a GO film, heating must be slow enough to
prevent the expansion of the structure, otherwise quick heating may explode the structure just like the exfoliation of
graphite oxide. But slow heating makes the thermal reduction
of GO a time-consuming process. Finally and importantly,
some applications need to assemble GO on substrates, e.g.
thin carbon films, but the high temperature means that this
reduction method cannot be used for GO films on substrates
with a low melting-point, such as glass and polymers.
4.1.2.
Thermal annealing is usually carried out by thermal irradiation. As an alternative, some unconventional heating resources have been tried to realize thermal reduction
including microwave irradiation (MWI) [79,80] and photo-irradiation [81,82].
The main advantage of MWI over conventional heating
methods is heating substances uniformly and rapidly. By
treating graphite oxide powders in a commercial microwave
oven, rGO can be readily obtained within 1 min in ambient
conditions [79].
4.2.
Chemical reduction
4.2.1.
Fig. 8 Patterned rGO film obtained by (a) flash reduction [81] (Copyright 2009 ACS) and (be) femtosecond laser reduction [82].
Scale bars, 10 lm (Copyright 2009 Elsevier). The black parts in the films are the reduced GO patterns.
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5 0 ( 20 1 2 ) 3 2 1 032 2 8
an additional dehydration process using concentrated sulfuric acid (98% H2SO4) at 180 C after reduction by NaBH4 to further improve the reduction effect on GO. The C/O ratio of rGO
by the two-step treatment is about 8.6 and the conductivity of
the rGO powder produced is about 16.6 S/cm.
Ascorbic acid (Vitamin C: VC) is a newly reported reducing
reagent for GO, which is considered to be an ideal substitute
for hydrazine [73]. Fernandez-Merino et al. revealed that GO
reduced by VC could achieve a C/O ratio of about 12.5 and a
conductivity of 77 S/cm, which are comparable to those produced by hydrazine in a parallel experiment. In addition, VC
has great advantage of its non-toxicity in contrast to hydrazine and a higher chemical stability with water than NaBH4.
Furthermore, the reduction in colloid state does not result
in the aggregation of rGO sheets as produced by hydrazine,
which is beneficial for further applications.
Recently, Pei et al. [58] and Moon et al. [97] reported another strong reducing reagent, hydroiodic acid (HI), for GO.
The two independent investigations report similar reduction
results in that the C/O ratio of rGO is around 15, and the conductivity of the rGO films is around 300 S/cm, both of which
are much better than obtained by other chemical reduction
methods. The reduction by HI can be realized using GO in
the form of a colloid, powder or film in a gas or solution environment, even at room temperature [97]. The comparison of
the reduction effects on GO films with HI, hydrazine vapor,
85% hydrazine hydrate and NaBH4 solution are shown in
Fig. 9. The GO film reduced by HI has good flexibility and even
improved tensile strength, while the hydrazine vapor-reduced
GO film becomes too rigid to be rolled and the film thickness
expanded more than 10 times. Contrarily, the GO films re-
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Fig. 9 Optical photographs of GO films (a) before and (bd) after chemical reduction by different agents: (b) HI, (c) hydrazine
vapor, (d) 85% N2H4H2O (N2H4), 50 mM NaBH4 solution (NaBH4) and 55% HI after immersion for 16 h at room temperature, (e)
the stressstrain curve of the GO film and HI reduced GO film (r = stress, e = strain), and SEM images of the cross-section views
of GO films (f) before and (g, h) after reduction by (g) HI and (h) hydrazine vapor [58].
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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
4.2.2.
Photocatalyst reduction
4.2.3.
Electrochemical reduction
4.2.4.
Solvothermal reduction
Another emerging chemical reduction method is solvothermal reduction [59,114,115]. A solvothermal process is performed in a sealed container, so that the solvent can be
brought to a temperature well above its boiling point by the
increase of pressure resulting from heating [116]. In a hydrothermal process, overheated supercritical (SC) water can play
the role of reducing agent and offers a green chemistry alternative to organic solvents. In addition, its physiochemical
properties can be widely changed with changes in pressure
and temperature, which allows the catalysis of a variety of
heterolytic (ionic) bond cleavage reactions in water. Hydrothermal routes have been used for remarkable transformation of carbohydrate molecules to form homogeneous
carbon nanospheres [117,118] and nanotubes [119].
Zhou et al. [59] proposed a water-only route by hydrothermal treatment of GO solutions. The results show that
the SC water not only partly removes the functional groups
on GO, but also recovers the aromatic structures in the carbon
lattice. The investigation of the pH dependence of the hydrothermal reaction found that a basic solution (pH = 11) yields a
stable rGO solution while an acidic solution (pH = 3) results in
aggregation of rGO sheets, which cannot be re-dispersed even
in a concentrated ammonia solution. This reduction process
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5 0 ( 20 1 2 ) 3 2 1 032 2 8
4.3.
Multi-step reduction
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5.
Reduction mechanism
5.1.
The conductivity of monolayer graphene mainly relies on carrier transport within the carbon plane, as a result, functional
groups attached to the plane are the main influencing factor
on its conductivity, while functional groups attached to the
edge have less influence. Consequently, the reduction of GO
must be mainly aimed at eliminating epoxy and hydroxyl
groups on the plane, while other groups, e.g. carboxyl, carbonyl and ester groups, present at the edges or defective areas
only have a limited influence on the conductivity of an rGO
sheet. As proof, Li et al. [69] reduced GO using hydrazine in
a solvent, and the carboxyl groups attached to the GO are preserved after reduction. This can be used to disperse rGO
sheets in a basic solution but has little influence on the conductivity of rGO sheets and assembled films.
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5.1.1.
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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
Thermal deoxygenation
Table 2 Status of oxygen-containing functional groups upon treatment with hydrazine and thermal annealing [123].
Copyright 2009 ACS.
Groups in Fig. 11
A
A0
B
B0
C
D
Thermal annealing at
7001200 C
Not removed
Not removed
Removed
Removed
Not removed
Removed
Hydrazine reduction
plus thermal annealing
Removed
Not removed
Removed
Removed
Not removed
Removed
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the formation of an aminoaziridine moiety which then undergoes thermal elimination of di-imide to form a double bond
[128,129], resulting in the re-establishment of the conjugated
graphene network.
Kim et al. [122] considered the epoxide reduction with
hydrazine on a graphene monolayer using DFT calculations.
Their results proved that the reduction reaction is mainly
governed by epoxide ring opening which is initiated by hydrogen transfer from hydrazine, and the formation of derivatives
such as NHNH2 during the reduction can facilitate the deepoxidation by lowering the barrier height of the ring-opening
reaction. Gao et al. [123] further elucidated the effect of hydrazine treatment on different functional groups by DFT simulation. Their results show that the hydrazine reduction can only
result in reducing epoxy groups, while no reaction path was
found for the reduction of the hydroxyl, carbonyl and carboxyl groups of GO. They designed several reduction routes
for de-epoxidation by hydrazine, and all the routes start from
the ring-opening of epoxy groups and form hydroxyl groups
on the original sites. According to their calculations (as
shown in former section), hydroxyl groups attached within
an aromatic domain are not stable even at moderate temperatures, and can be removed or migrate to the edges of aromatic domains and restore the conjugated structure after
dehydroxylation.
As a result, a much simple reduction pathway can be expected, in which the reduction of GO is simply the combination of a ring-opening of epoxy groups to form hydroxyl
groups and dehydroxylation by moderate heat treatment.
After this process, the carbon plane of GO can be as clean
as that of pure graphene. This proposal is supported by the
reduction of GO by hot alkaline solutions [99] and hydrohalic
acids [58,97] since the ring-opening reactions can be catalyzed
by both alkalis and acids [130].
Chemical deoxygenation
5.1.3.
A final target of GO reduction is to achieve as high an electrical conductivity as that of graphene. In ideal graphene, electrons can transport without scattering within a graphene
sheet with a lateral size more than sub-micrometers. This is
called the long-range ballistic transport of graphene, which
relies on its perfect long-range conjugated structure. After
oxidation, this perfect structure is destroyed by functional
groups and defects, so the recovery of conductivity depends
on the restoration of the long-range conjugated structure.
Mattevi et al. [66] proposed a structure evolution of GO during thermal annealing as shown in Fig. 13ad. Initially, the sp2
clusters in GO are isolated by functionalized and defective
areas (indicated by light gray dots). As the material is progressively reduced, interactions (hopping and tunneling) among
the clusters increase (Fig. 13b). Further reduction by the removal of oxygen leads to greater connectivity among the ori-
Fig. 12 Proposed reaction pathway for epoxide reduction with hydrazine [56].
Copyr ight
2007 Elsevier.
5.1.2.
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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
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Fig. 13 (ad) Structural model of GO at different stages of reduction by thermal annealing [66]. (a) Room temperature, (b)
100 C, (c) 220 C, (d) 500 C. The dark grey areas represent sp2 carbon clusters and the light grey areas represent sp3
carbon bonded to oxygen groups (represented by small dots). At 220 C, percolation among the sp2 clusters is initiated
(corresponding to sp2 fraction of 0.6). Copyright 2009 Wiley-VCH. (ej) Simulated morphology of (e, h) GO and (f, g, i, j) rGO
sheets with an initial oxygen concentration of 20% (eg) and 33% (hj) in the form of hydroxyl and epoxy groups in the ratio of
3/2 after annealing at 1500 K in (f, i) vacuum and (g, j) H2 atmosphere [127].
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5.2.
5 0 ( 20 1 2 ) 3 2 1 032 2 8
Healing of defects
Since oxygen-containing functional groups can be well removed by a proper reduction route, what is the main reason
for the low conductivity of rGO compared with that of graphene? As shown in Fig. 14, Gomez-Navarro et al. [50] identified
the atomic scale features of an rGO monolayer that was reduced by hydrogen-plasma [51]. The layers are found to comprise defect-free graphene areas with sizes of a few
nanometers interspersed with defective areas dominated by
clustered pentagons and heptagons. Similar to other lowdimensional carbon nanostructures like carbon nanotubes
[132] and fullerenes [133], disorder and defects in graphene
strongly affect its electronic properties, and thus account
for the low conductivity of as-reduced rGO. Thus, if these lattice defects can be healed during reduction, the GO could possibly behave as perfect graphene. Several studies in this
direction have been tried with the expectation of achieving
much improved conductivity from GO.
Lopez et al. [62] proposed a strategy to repair GO by CVD.
The CVD was carried out using ethylene as a carbon source,
under conditions that are very similar to those in the CVD
synthesis of single-wall carbon nanotubes on SiO2 substrates,
except for the presence of metal catalysts in the latter case.
After the CVD, the CVD-GO has a more than 50-fold increase
in electrical conductivity over the rGO prepared by traditional
reduction methods. Unfortunately, the authors did not give
any direct evidence of the restoration of the graphene structures. Recently, by MD simulation, Wang et al. [134] proposed
a possible way to heal defects as well as doping graphene by
3223
Fig. 14 Atomic resolution, aberration-corrected TEM image of a single layer H-plasma-reduced-GO membrane [50]. (a)
Original image and (b) with color added to highlight the different features, (c) atomic resolution TEM image of a nonperiodic
defect configuration, (d) partial assignment of the configurations in defective areas, the inset shows a structural model
showing clearly the strong local deformations associated with defects. All scale bar 1 nm.
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5 0 ( 2 0 1 2 ) 3 2 1 0 3 2 2 8
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Fig. 15 (a) Evolution of the first-order Raman spectra of a monolayer graphene sample deposited on an SiO2 substrate,
subjected to ion bombardment with different doses (indicated next to the respective spectrum in units of Ar+/cm2), (b) the ID/
IG data points from the evolution as a function of the average distance LD between defects. The solid line is the result of a
modeling calculation. The inset to (b) shows ID/IG vs LD plotted on a log scale for the LD axis for two ion-implanted graphite
samples [138].
5.3.
6.
A brief conclusion can be given to the effects and mechanism
of GO reduction as follows. Both functional groups and defects affect the conductivity of GO. Functional groups are relatively easy to remove, while defects, whether formed during
oxidation or reduction, are difficult to heal by post-treatment.
Furthermore, functional groups attached to edges and defects
are more difficult to remove than those attached to graphitic
areas. Thus, the concentration of lattice defects in the carbon
plane is the key to determine whether a GO sheet can be well
reduced.
Where do defects come from? According to the simulation
results proposed by Bagri et al. [127], if the carbon plane of GO
is only covered by functional groups with no lattice defects,
reduction can be realized by choosing a proper reduction
method. Lattice defects in the carbon plane that remain after
reduction are more likely formed during oxidation. Recently,
Zhao et al. [34] and Xu et al. [139] reported mildly-oxidized
GO (MOGO) produced by a modified Hummers method with
a low oxidation degree of the graphite. Though the MOGO
sheets are also highly functionalized according to their low
C/O ratio, they preserve the structure of the conjugated carbon framework with relatively low defect concentrations.
Thus, the MOGO can be reduced to become highly conductive
rGO by hydrazine or HI reduction, both of which show much
improved reduction effects compared with most of the re-
We have reviewed the reduction of GO to prepare graphenelike rGO. This is an attractive route for the mass-scale production and applications of graphene. Though the full reduction
of GO to graphene is still hard to achieve, partial reduction of
GO is rather easy and tens of reduction methods have been
proposed. The accumulation of experimental phenomena
and theoretical simulation results has provided clearer views
of the structure and chemistry of graphene, GO and rGO, and
this may be helpful in promoting the uses as well as the scientific understanding of the nature of graphene.
Different functional groups in a GO sheet have different
binding energies to the carbon plane according to the type
and location of each group. Epoxy and hydroxyl groups located within a graphitic domain without lattice defects are
relatively easy to remove, while those located on the defective
sites and edges are hard to fully remove. A well-designed
reduction procedure with a combination of chemical reduction and thermal annealing is possible to remove most of
the functionalizations in a GO sheet with low defect concentrations. However, GO sheets with a high concentration of lattice defects are difficult to fully deoxygenate and the defects
themselves are difficult to heal by post-treatment. As a result,
a controllable oxidation during the production of GO is
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5 0 ( 20 1 2 ) 3 2 1 032 2 8
needed to achieve highly reducible GO, which can be converted to graphene with high quality and good properties.
The future research on the reduction of GO should mainly
focus on two topics: (1) a much deeper understanding of the
reduction mechanism and (2) how to control the oxidation
of graphite and the reduction of GO. This is because that a
controllable functionalization that can alter the properties
of graphene to fulfill specific requirements in applications is
equally important to obtain a non-defective graphene, for
example, to change the gapless semi-metallic graphene into
a semiconductor with proper band gap. The previous research
on GO and rGO has inspired a possible way to achieve such
change that GO and rGO show obvious semiconductor-like
properties [11]. Recently, Eda et al. [140] and Pan et al. [76] reported a blue photoluminescence of GO (or rGO), which
proves that a properly functionalized graphene sheet can be
a semiconductor. Then the question is how we can obtain
such functionalization of graphene by a reliable technique,
but not an occasional observation. Research on the oxidation
and reduction combined with a deep understanding of graphene structure may give us the key to realize good control of
the attaching and elimination of functional groups to some
specific locations on the carbon plane. Further research on
the controllable oxidation and reduction of graphene may
facilitate the applications of graphene as semiconductors
used in transistor and photo-electronic devices.
Acknowledgements
This work was supported by the Key Research Program of
Ministry of Science and Technology, China (No.
2011CB932604), the National Natural Science Foundation of
China (Nos. 51102243 and 50921004), and by the Chinese
Academy of Sciences (KGCX2-YW-231).
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