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PAPER

www.rsc.org/materials

Synthesis of boron doped graphene for oxygen reduction reaction in fuel cells
Zhen-Huan Sheng, Hong-Li Gao, Wen-Jing Bao, Feng-Bin Wang* and Xing-Hua Xia*
Received 21st September 2011, Accepted 26th September 2011
DOI: 10.1039/c1jm14694g
Boron atoms, with strong electron-withdrawing capability, are doped into graphene frameworks
forming boron doped graphene (BG) via a catalyst-free thermal annealing approach in the presence of
boron oxide. Atomic force microscopic (AFM) and transmission electron microscopic (TEM)
characterizations reveal that the as-prepared BG has a flake-like structure with an average thickness of
ca. 2 nm. X-ray photoelectron spectroscopy (XPS) analysis demonstrates that boron atoms can be
successfully doped into graphene structures with the atomic percentage of 3.2%. Due to its particular
structure and unique electronic properties, the resultant BG exhibits excellent electrocatalytic activity
towards oxygen reduction reaction (ORR) in alkaline electrolytes, similar to the performance of Pt
catalysts. In addition, the non-metallic BG catalyst shows long-term stability and good CO tolerance
superior to that of Pt-based catalysts. These results demonstrate that the BG, as a promising candidate
in advanced electrode materials, may substitute Pt-based nanomaterials as a cathode catalyst for ORR
in fuel cells as well as other electrochemical applications similar to the reported nitrogen doped
graphene.

1. Introduction
The discovery of graphene has opened up a new era of carbon
materials research. As a 2-dimensional (2D) material, graphene is
a one-atom-thick sheet of sp2-bonded carbon atoms that are
densely packed into a honeycomb crystal lattice. The 2D planar
geometry endows graphene with a high aspect ratio (the ratio of
lateral size to layer thickness), large specific surface area, and
unique electronic properties.15 Hence, graphene as nanoscaled
building block is a promising candidate for potential applications
such as nanoelectronics,68 biosensors,9,10 and energy storage.1113
Research in these fields make graphene a superstar material
since its first preparation by peeling-off highly oriented pyrolytic graphite (HOPG) in 2004.14 It is obvious that, with the
development of synthetic methods and research approaches,
graphene will show more broad prospects in various application
areas.
Graphene, carbon nanotubes (CNTs), and other graphitic
carbon nanomaterials have been extensively researched for
various potential applications. Of particular importance is to
understand how to modulate the electronic structure of graphene
based materials through introduction of chemical impurities and/

State Key Laboratory of Analytical Chemistry for Life Science, School of

Chemistry and Chemical Engineering, Nanjing University, Nanjing,
210093, China. E-mail: fbwang@nju.edu.cn; xhxia@nju.edu.cn; Fax:
+86-25-83597436; Tel: +86-25-83597436
Electronic supplementary information (ESI) available: TEM image of
the pristine graphene and BG, PXRD pattern of BG, XPS results of
BG and linear sweep voltammetric curves of ORR on graphene/GCE.
See DOI: 10.1039/c1jm14694g

390 | J. Mater. Chem., 2012, 22, 390395

or creation of defects, and consequently to synthesize these

nanomaterials with desired physical and chemical properties for
any targeted applications. Experimental and theoretical studies
on graphene and/or CNTs doping show the possibility of making
p- and n-type semiconductors by substituting C atoms with B
and N atoms, respectively. The doped atoms can modify the
electronic band structure of graphene, and consequently tune the
mechanical properties and electrocatalytic activity as well.1521
To date, various kinds of methods have been employed to
synthesize heteroatom (such as N and B atom) doped CNTs or
graphene, and these methods can be categorized into two types,
direct synthesis and post treatment. In the first case, CNTs/graphene formation and boron doping occur at the same time, and
heteroatoms containing carbon precursors and metal catalysts
are essential to the doping and formation of the final products.
Of them chemical vapor deposition (CVD), as the most common
method, has been extensively used to synthesize doped carbon
materials.2224 However, the metal catalysts used in the growth
process are difficult to remove completely, hence uncertainty will
remain in understanding the intrinsic electrocatalytic properties.25 In an alternative approach, carbon materials such as
CNTs/graphene prepared in advance are treated with heteroatom-containing species (i.e., NH3 or B2H6) at high temperature,2630 which can prevent carbon materials from metal catalyst
contamination and consequently is favorable for investigating
the intrinsic catalytic performance. Using these approaches,
nitrogen doped graphenes have been synthesized and their
properties also have been extensively investigated.3134 We
noticed that there were only a few reports focusing on the
synthesis and application of boron doped graphene (BG) due to
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the difficulties in synthesis. Rao et al. reported the synthesis of

BG using arc discharge of graphite electrode in the presence of
B2H6 vapor.31 Very recently, a solvothermal method was also
used to synthesize BG using tetrachloromethane (CCl4) and
boron tribromide (BBr3) as the raw materials.35 Both the
methods require special instruments and/or rigorous conditions
and the reagents, B2H6 or BBr3, are poisonous. Obviously,
developing facile and green approaches to synthesize BG on
a large scale remains challenging. In addition, as far as we know,
the intrinsic catalytic activity of BG in electrochemistry has not
been reported.
Here, we report a facile and catalyst-free approach to
synthesize BG by thermal-annealing graphite oxide (GO) in the
presence of B2O3. As expected, boron atoms from B2O3 vapor
can be successfully doped into the graphene framework at high
temperature (Scheme 1). In addition, electrochemical measurements show that boron atoms doped in graphene can accelerate
the adsorption of oxygen, and thus the resultant BG shows
excellent electrocatalytic activity towards ORR and high CO
tolerance.

1200  C at an increasing rate of 5  C min
1. After maintaining at

this temperature for 4 h, the sample was cooled to room
temperature slowly under an Ar atmosphere. The obtained
product was then refluxed in 3 M NaOH aqueous solution for 2 h
to remove any of the unreacted boron oxide. After filtration and
water washing, the product was dried in a vacuum at 60  C. For
comparison, pristine graphene was also prepared using a similar
procedure but without adding B2O3.

2.3 Preparation of graphene or boron doped graphene modified

electrodes
Prior to use, a glassy carbon electrode (GCE, f 3 mm) was
polished with 0.05 mm gamma alumina powders, then rinsed
thoroughly with ethanol and water in an ultrasonic bath to
remove any alumina residues, and finally dried with in a N2 gas
flow. 10 mL sonicated pristine graphene or BG DMF suspension
(1 mg mL
1) was dropped on the pretreated bare GCE using
a micropipet tip, and dried in air.

2. Experimental section
2.1 Chemicals
Graphite powder (99.9995% purity,
100 mesh, briquetting
grade, mesh) was purchased from Alfa Aesar. Boron oxide was
bought from Sinopharm Chemical Reagent Co. Ltd (China).
Other chemicals such as H2SO4, NaOH and N,N-dimethyl
formamide (DMF) were from Nanjing Chemical Reagent Co.
Ltd. All the reagents were of analytical grade and used as
received. All solutions used in the electrochemical experiments
were freshly prepared with Millipore water having a resistivity of
18.2 M (Purelab Classic Corp., USA).
2.2 Synthesis of boron doped graphene
Boron doped graphene was synthesized through thermal
annealing graphite oxide (GO, synthesized by the modified
Hummers method3,36) in the presence of boron oxide (B2O3),
where boron atoms coming from B2O3 vapor can replace carbon
atoms within graphene structures at high temperature in a homemade tubular furnace. In a typical procedure, GO powder was
put onto the surface of B2O3 in a corundum crucible, which was
then placed in the center of a corundum tube with a continuous
flow of argon to guarantee an inert atmosphere in the tube
furnace. The center temperature of the furnace was heated to

Scheme 1 Illustration of electron transfer for ORR on BG surface.

This journal is The Royal Society of Chemistry 2012

2.4 Characterization
The morphologies of graphene and BG samples were characterized by transmission electron microscopy (TEM) and
HRTEM using a JEM-2100 TEM facility (JEOL, Japan) with
a 200 kV accelerating voltage. The TEM samples were prepared
by drying a droplet of the graphene or BG suspensions on a Cu
grid. Atomic force microscopy (AFM) images were collected on
an Agilent 5500 AFM/SPM system with Picoscan v5.3.3 software. Imaging was performed in tapping mode under ambient
conditions. Room-temperature Raman spectra were recorded on
a Renishaw InVia micro-Raman system with an excitation
wavelength of 514 nm (Renishaw, UK). X-ray photoelectron
spectroscopy (K-alpha, USA) analyses were carried out on
a Thermo Fisher X-ray photoelectron spectrometer system
equipped with Al radiation as a probe, with a chamber pressure
of 5  10
9 torr. The source power was set at 72 W, and pass
energies of 200 eV for survey scans and 50 eV for high-resolution
scans were used. The analysis spot size was 400 mm in diameter.
All electrochemical measurements were performed on a CHI 900
Electrochemical Workstation (CH Instruments, USA).

2.5 Electrochemical measurements

Cyclic voltammograms were performed in a three-electrode
system (GCE or modified GCE as the working electrode, a Pt
wire as counter electrode, and an Ag/AgCl electrode as the
reference electrode) at room temperature. For RDE measurements, a HP-1A RRDE system from Jiangfen Electroanalytical
Instrument Co. Ltd., China was used as the working electrode.
This RDE consists of a GC disk (4 mm in diameter). For RDE
measurements, the GCE was modified with 5 mL of 1 mg mL
1
graphene or BG suspensions in DMF. Linear sweep voltammetry
was performed at the GCE at a rotation rate of 1200 rpm. In all
the electrochemical measurements, 0.1 M KOH aqueous solution
saturated with oxygen was used as the electrolyte.
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3. Results and discussion

The method for BG synthesis was based on the preparation of
nitrogen doped graphene (NG) in our lab.32 The whole
synthetic procedure was similar, except B2O3 was employed to
replace the melamine molecules in NG synthesis. As a result,
the doping process is also similar. First, B2O3 was melted and
then vaporized with increasing temperature in the tubular
furnace. At the same time oxygen groups linked to graphene
nanosheets in the GO sample were removed at high temperature. We suggest it is this removal process of oxygen species
and defects in the graphene framework that provides active
sites for boron doping into graphene frameworks. The chemical
reaction is illustrated in eqn (1).37,38
xB2O3 + (2 + 3x)C(graphene) / 2BxC(graphene) + 3xCO (1)

The typical atomic force microscopy (AFM) image shows that

the exfoliated BG has a planar structure with an average thickness of ca. 2 nm (Fig. 1a), indicating BG is a few-layered nanostructure. In the low magnification transmission electron
microscopy (TEM) image (Fig. 1b) flattened BG nanosheets are
randomly stacked together, displaying a flake-like structure
similar to pristine graphene (Fig. S1, ESI). The high-resolution
TEM image reveals that the adjacent interlayer distance in the
BG sample is 0.37 nm (Fig. S2a, ESI), which is closer to the dspacing of the (002) crystal plane of graphite (0.335 nm). The
PXRD pattern (Fig. S2b, ESI) of BG shows an intense peak at
around 25.8 with an interlayer space of 0.35 nm, which is
similar to the HRTEM result.
Raman spectroscopy is the most effective and non-destructive
technique to characterize the structure and quality of carbon
materials,39 in particular to determine the defects, disordered
structures, and the layers of graphene. Therefore, Raman spectra
of the as-prepared BG were collected on a micro-Raman spectrometer at an excitation wavelength of 514 nm under ambient
conditions by dropping the DMF dispersions on Si substrates.
For comparison, the spectrum of pristine graphene obtained
from thermally annealing GO under the same conditions is also
displayed. As shown in Fig. 2, the Raman spectrum of BG
exhibits an intense G peak at 1576 cm
1 and a wide 2D peak at
2696 cm
1, which confirms BG is of graphitic structure with few
layers. The presence of a highly intense D band at 1347 cm
1 in

Fig. 1 Typical AFM image (a) and low-resolution TEM image (b)
of BG.

392 | J. Mater. Chem., 2012, 22, 390395

Fig. 2 Raman spectra of pristine graphene and BG, respectively.

BG samples clearly suggests the existence of many defects in the

graphene layers. These defects are commonly attributed to harsh
oxidation of graphite and boron doping in the carbon hexagonal
lattice. Whereas for pristine graphene the G band and 2D band
are located at 1579 cm
1 and 2694 cm
1, respectively. There are
no significant shifts or line broadening, which clearly suggests
that the graphene structure is retained after boron doping. In
addition, it is noticed that the slightly larger ID/IG value (0.87) for
BG compared with pristine graphene (ID/IG 0.8) also indicates
that the BG possesses many more defects than the pristine graphene prepared under similar conditions due to the boron
doping. Compared to the peak position and shape of single-layer
graphene,40 the BG exhibits a broader and up-shifted band at
around 2696 cm
1, demonstrating the present thermal annealing
process produces few-layer BG samples. These results are
consistent with the above TEM and AFM characterizations.
X-ray photoelectron spectroscopy (XPS) characterization was
carried out to explore the content and configuration of doped
boron in the graphene structure. The full range XPS analysis of
the resultant BG sample clearly shows the presence of boron (B),
carbon (C) and oxygen (O) with atomic percentages of 3.2%,
87.7% and 9.1%, and the corresponding B1s, C1s and O1s peaks
centered at 190.4 eV, 283.9 eV and 531.6 eV, respectively. Only
the core levels of C1s (284.2 eV) and O1s (531.6 eV) are observed
from the survey scan for the pristine graphene (Fig. S3a and 3b,
ESI). In addition, the B1s peak appears at a higher binding
energy (B1s peak: 190.4 eV as compared to 187 eV for pure
boron), which suggest that boron atoms coming from B2O3
vapor have been incorporated into the graphene structure. In the
high resolution spectra, the intense C1s peak for BG with an
asymmetric shape shifts to a lower binding energy compared to
the pristine graphene (Fig. 3a). The decreased binding energy of

Fig. 3 (a) High resolution C1s XPS spectra of BG (black) and pristine
graphene (red). (b) High resolution B1s XPS spectrum.

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the C1s peak might be due to the formation of BC bonding,

which reduces the Fermi level via redistribution of the p-electron
within the graphene structure. Moreover, the peak intensity of
BG at 284 eV is lower than that of pristine graphene, indicating
that, due to boron doping, the graphene structure is broken to
some extent and the number of sp2-bonded carbon atoms
decrease.
Based on the Shirley algorithm, the C1s peak for BG can be
fitted into four components. The most intense peak located at
283.9 eV is still assigned to sp2 hybrid carbon atoms, and small
signals at higher binding energies indicate some CO species
remain in the samples after thermal annealing. However, the
small signal at 281.8 eV, corresponding to carbon atoms
neighboring with boron atoms such as in the B4C system, is not
observed due to the low boron content (Fig. S3c, ESI).14 In the
high-resolution B1s spectrum, the observed up-shift of the B1s
signal indicates boron has been incorporated into the sp2 carbon
networks.41 After curve fitting for the B1s spectrum (Fig. 3b), the
peaks centered at 187.7 eV and 189.0 eV may be assigned to B4C
and BC3 structures, respectively. The peak at 190.4 eV corresponds to the structure of boron atoms bonding to carbon and
oxygen atoms (BC2O). The signal at 191.9 eV reveals that boron
atoms are surrounded by carbon and oxygen atoms (BCO2),
indicating the presence of oxidized boron atoms in this sample.23
All these results indicate the formation of BC bonds in the
annealing process.
The electrocatalytic activity of the as-prepared BG towards
oxygen reduction reaction (ORR) in 0.1 M KOH solution was
evaluated using a conventional three-electrode system. First, the
cyclic voltammograms (CVs) at a BG modified glassy carbon
electrode (GCE) in N2 and O2 saturated 0.1 M KOH solution
were recorded, respectively. Obviously, ORR peak for BG is

observed at 0.34 V in the O2 saturated 0.1 M KOH solution as

compared to the curve in the N2 saturated solution (Fig. S4,
ESI). Moreover, Fig. 4a shows the CVs for the electrochemical
reduction of O2 at a bare GCE, graphene/GCE, and BG/GCE
in O2 saturated 0.1 M KOH aqueous solution. The ORR peaks
at the bare GCE and pure graphene/GCE appear at
0.45 V
and
0.36 V, respectively. Moreover, there are two reduction
peaks for these two electrodes, which indicates that the electrochemical reduction of oxygen occurs in two processes with
the production of HO2
intermediate. On the contrary, for BG/
GCE the ORR peak is located at
0.34 V, a little more positive
than that at graphene/GCE, which suggests much faster electron-transfer kinetics for ORR on BG/GCE than on bare GCE
and graphene/GCE. Consequently, we can conclude that BG
possesses much higher electrocatalytic activity than graphene.
To further investigate the ORR process and evaluate the
transferred electron number (n) per oxygen molecule at the BG/
GCE, the rotating disk electrode (RDE) technique was also
used to investigate the electrocatalytic activity of BG towards
ORR by linear sweep voltammetry (LSV). Fig. 4b shows the
corresponding LSVs for BG/GCE, pristine graphene/GCE and
bulk Pt disk electrode in an O2 saturated 0.1 M KOH electrolyte. The onset potentials for ORR at pristine graphene are at

0.15 V and
0.59 V, respectively. It demonstrates that the
ORR process catalyzed by the pristine graphene is a two-step
two-electron pathway with the formation of intermediate
HO2
ions. By contrast, the BG/GCE, as in the case of the Pt
electrode, exhibits a one-step process for ORR with the onset
potential at about
0.05 V, which is about 100 mV more
positive than that on the pristine graphene/GCE. In addition,
the reduction current at BG is larger than on graphene. The
one-step process suggests a four-electron pathway for the ORR
at BG. Both the positive shift of onset potential and the
enhanced reduction current for ORR on BG/GCE demonstrate
that BG possesses much higher electrocatalytic activity towards
ORR than graphene, which could be due to the faster reaction
kinetics with a higher transferred electron number per oxygen
molecule at the BG surface. As a result, doping boron atoms
into graphene structures can tailor the electronic structures of
graphene and consequently improves the electrocatalytic
performance of BG towards ORR.
Fig. 4c shows the LSV curves of RDE loaded with BG at
different rotation rates. It is obvious that the reduction current
increases with increasing rotation rate. The transferred electron
number (n) per oxygen molecule in the ORR process at the BG/
GCE was calculated by the KoutechyLevich (KL) equation
(eqn (2)).34

1

1
i
1 i
1
+ (0.62nFAD2/3C0y
1/6u /2 )
1 (2)
k + iL (nFAkC0)
1

Fig. 4 (a) CVs of ORR on bare GCE (black), graphene/GCE (red) and
BG/GCE (blue) in O2-saturated 0.1 M KOH aqueous solution (scan rate:
100 mV s
1). (b) Linear sweep voltammetric curves (LSVs) of ORR at
graphene/GCE (red), BG/GCE (blue) and bulk Pt disk electrode (black)
in an O2-saturated 0.1 M KOH aqueous solution (scan rate: 10 mV s
1).
The rotation rate of RDE was 1200 rpm. (c) LSVs of ORR on BG/GCE
at different rotation rates in an O2-saturated 0.1 M KOH aqueous
solution (scan rate: 10 mV s
1). (d) KL plots for ORR on BG/GCE at
different electrode potentials.

This journal is The Royal Society of Chemistry 2012

where i is the measured current, ik and iL are the kinetic- and

diffusion-limiting current, respectively. n is the electron transfer
number in the ORR processes, F is the Faraday constant (96 485
C mol
1), A is the geometric area of RDE, D is the diffusion
coefficient of O2 in the KOH electrolyte (1.9  10
5 cm2 s
1), C0 is
the bulk concentration of O2 (1.2  10
3 mol L
1), y is the kinetic
viscosity of the electrolyte (0.01 cm2 s
1), u is the angular velocity
of the disk (u 2pN, N is the linear rotation speed) and k is the
electron transfer rate constant.34
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activity of BG could be attributed to the incorporation of boron

atoms in graphene layers. The electron-deficient boron atoms
doped in graphene may function as active sites for oxygen
adsorption and activating the OO bond cleavage. The excellent
selectivity towards ORR and remarkable tolerance against CO
poisoning of the BG catalyst make it a promising metal-free
catalyst for ORR in fuel cells and other catalytic applications.

4. Conclusions

Fig. 5 (a) The dependence of n on potential for the BG/GCE ( ), pure

graphene/GCE (-). CVs for the ORR on BG/GCE (b) and Pt disk
electrode (c) in O2-saturated 0.1 M KOH aqueous solution, O2-saturated
0.1 M KOH aqueous solution containing 1 M CH3OH,and O2-saturated
0.1 M KOH aqueous solution containing CO. (d) CVs of BG/GCE for
ORR in O2-saturated 0.1 M KOH aqueous solution. The 1st scan (black)
and the 5000th scan (red). Scan rate: 100 mVs
1.

Appearance of paralleled KL linear plots (Fig. 4d) indicates

the same reaction mechanism for ORR, namely, the electron
transfer number for ORR is the same in the studied potential
range. According to eqn (2), the average electron transfer
number n for ORR at BG/GCE is calculated as 3.5 over the
potential range from
0.4 to
0.9 V (Fig. 5a), which reveals that
the electrocatalytic process of BG/GCE is a one-step four-electron pathway for ORR with a much higher peak current. As
a comparison, the LSV curves of RDE loaded with pristine
graphene were also measured (Fig. S5a and 5b, ESI). The
electron transfer number for ORR is found to be 2.12.7 in the
potential range of
0.4
0.9 V, demonstrating the ORR catalyzed by pristine graphene is a two-electron and two-step process
as in the case of CNTs.26 These results suggest that, similar to
nitrogen doped graphene, carbon materials after boron doping
also show much better electrocatalytic activity towards ORR
than when undoped.
Besides the excellent electrocatalytic activity towards ORR,
BG also shows good methanol and CO tolerances. As shown in
Fig. 5b and 5c, addition of 1 M methanol or CO to the O2
saturated electrolyte does not affect the catalytic activity of BG
towards ORR. By contrast, presence of methanol or CO in the
electrolyte significantly inhibits the ORR at the Pt electrode due
to the poisoning effect of adsorbed CO and other poisoning
intermediates.42 The observed anodic current peaks should be
due to the electrocatalytic oxidation of methanol or CO on the Pt
electrode. These results demonstrate that the BG is an excellent
metal-free catalyst towards ORR, free of poisoning effects from
fuel molecules such as methanol and CO, which is much better
than the platinum-based catalysts. In addition, the BG catalyst
shows considerable stability during ORR. Almost no alteration
occurs in the CVs during continuous potential cycling of the BG
catalyst between 0.2 and
1.2 V in O2 saturated 0.1 M KOH
solution for 5000 cycles (Fig. 5d). The excellent electrocatalytic
394 | J. Mater. Chem., 2012, 22, 390395

In summary, we report a facile, effective and catalyst-free

thermal annealing approach to the preparation of boron doped
graphene on a large scale using boron oxide as the boron source.
Compared to pristine graphene, the product BG exhibits excellent electrocatalytic activity and long-term stability towards
ORR in alkaline electrolytes, and good tolerance to poisons.
Although the real functioning mechanism of doped boron in
graphene is not clear, this will not prevent us using it as
a promising metal-free catalyst towards ORR in fuel cells and
other catalytic applications.

Acknowledgements
This work was supported by grants from the National Natural
Science Foundation of China (NSFC, No. 21035002), the
National Science Fund for Creative Research Groups (20821063)
and the Natural Science Foundation of Jiangsu province
(BK2010009).

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