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Nitrogen-doped reduced-graphene oxide as an efficient

metal-free electrocatalyst for oxygen reduction in fuel
Cite this: RSC Advances, 2013, 3,
3990 cells
Published on 11 January 2013 on http://pubs.rsc.org | doi:10.1039/C3RA22161J

Zhen-Jiang Lu,a Shu-Juan Bao,*a Yu-Ting Gou,a Chang-Jun Cai,a Chen-Chen Ji,a Mao-
Wen Xu,b Jie Songb and Ruiying Wanga
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Received 13th September 2012,
Accepted 11th January 2013
DOI: 10.1039/c3ra22161j
www.rsc.org/advances
The electronic and chemical properties of reduced-graphene oxide (RGO) can be modulated by chemical
doping of foreign atoms and functional moieties. In this work, a low-cost industrial material,
5-aminotetrazole monohydrate (AM) was chosen to modify RGO by a facile, catalyst-free thermal
annealing approach in largescale. The obtained nitrogen-doped reduced-graphene oxide (N-RGO), as a
metal-free catalyst for oxygen reduction, was characterized by XRD, XPS, Raman, SEM, TEM and
electrochemical measurements. It was found that the optimum synthesis conditions were a mass ratio of
graphene oxide (GO) and AM equal to 1 : 25 and an annealing temperature of 700 uC. Detailed X-ray
photoelectron spectrum analysis of the optimum product shows that the atomic percentage of the N-RGO
samples can be adjusted up to 10.6%. Electrochemical characterizations clearly demonstrate excellent
electrocatalytic activity of N-RGO toward the oxygen reduction reaction (ORR) in alkaline electrolytes via a
four-electron pathway. The total content of graphitic and pyridinic nitrogen atoms is the key factor to
enhance the current density in the electrocatalytic activity for ORR. This simple, cost-effective and scalable
approach opens up the possibility for the synthesis of other nitrogen doping materials in gram-scale. It can
be applied to various carbon materials for the development of other metal-free efficient ORR catalysts for
fuel cell applications and even new catalytic materials for applications beyond fuel cells.

1. Introduction vertically aligned nitrogen-containing carbon nanotubes

Developing catalytic materials for ORR is the current techno-
logical bottleneck for the industrial development of fuel cells.1
Up to now, the most efficient catalysts for ORR are still
platinum-based materials. However, their large scale commer-
cial applications have been precluded by high costs, scarcity of
platinum and several serious problems, including the cross-
over and poisoning effects.2–4 Therefore, the search for non-
precious metal as well as metal-free catalysts for ORR is one of
the most active and competitive fields in chemistry.5
Currently, numerous efforts have been devoted to reduce or
substitute Pt-based catalysts by employing Pt-based alloys,
nonprecious metal catalysts, enzymatic electrocatalysts, or
nitrogen-enriched carbonaceous materials.6,7 In 2006, Ozkan
and co-workers reported that nitrogen-containing carbon
materials have promising catalytic activity toward ORR8,9. In
a 2009 publication in Science, Gong et al.10 reported that
a
Key Laboratory of Material and Technology for Clean Energy, Ministry of Education;
Key Laboratory of Advanced Functional Materials, Xinjiang Autonomous Region;
Institute of Applied Chemistry, Xinjiang University, Urumqi 830046, Xinjiang, P. R.
China. E-mail: shjbao@xju.edu.cn; Fax: +86 991-8588883; Tel: +86 991-8581183
b
Texas Materials Institute, University of Texas at Austin, Austin, TX 78712, USA.
E-mail: maowenxu@mail.utexas.edu
(VANCNTs) can act as a metal-free electrode with a much
better electrocatalytic activity, long-term operation stability,
and tolerance to crossover effect than platinum for oxygen
reduction in alkaline fuel cells. Recently, more nitrogen-doped
carbon materials have been proposed as potential metal-free
catalysts for ORR because they not only exhibit excellent
electrocatalytic activity but also possess the advantages of low
costs, long durability, and environmental friendliness.11,12
Graphene, a new 2-dimensional carbon material, has
recently attracted great interests for both fundamental science
and applied research.13,14 It has not only high surface area,
and excellent conductivity, but also unique graphitic basal
plane structure that should guarantee its durability.15–18
Furthermore, theoretical study has shown that nitrogen
doping can create defects on carbon.19 N-RGO leads to a
higher positive charge on a carbon atom adjacent to nitrogen
atoms and a positive shift of Fermi energy at the apex of the
Brillouin zone of RGO. This readily attracts electrons from the
anode for facilitating the O2 adsorption and the ORR
process.20–22 The unique electronic properties derived from
the conjugation between the nitrogen lone-pair electrons and
the p system23 mean that N-RGO could be able to as a noble-

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RSC Advances
Fig. 1 Metal-free electrocatalyst growth of N-RGO for the ORR.
Published on 11 January 2013 on http://pubs.rsc.org | doi:10.1039/C3RA22161J
metal-free catalyst which may enable fabrication of the next
generation of cheap and sustainable fuel cells.
In this work, a low-cost industrial material, AM was used
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for the first time as the nitrogen source to modify RGO by a
facile and catalyst-free thermal annealing approach (Fig. 1). In
the process, heat treatment under nitrogen rendered the
thermal reduction of GO to RGO. AM was subsequently
impregnated into the graphene sheets and further pyrolysized
at high temperature, RGO was simultaneously etched and
doped by nitrogen. Raman and XPS spectrum were employed
to evaluate the degree of nitrogen doping and nitrogen
bonding configurations in RGO nanosheets under different
annealing conditions. It was found that when the mass ratio of
GO/AM was 1 : 25 and the thermal annealing temperature was
700 uC, the catalyst presented a highest electrocatalytic activity
via a four-electron process in alkaline electrolytes for the ORR.
2. Experimental
2.1 Materials
Graphite powder was purchased from Alfa Aesar. AM was
bought from sigma Aldrich Chemical Reagent CO. Ltd. Other
chemicals such as H2SO4, KMnO4, KOH and anhydrous
ethanol were bought from Nanjing Chemical Reagent CO.
Ltd. The GO was prepared according to modified Hummer’s
method.24 All solutions used in the electrochemical experi-
ments were freshly prepared with Millipore water having a
resistivity of 18.2 MV.
2.2 Synthesis of N-RGO nanosheets
Annealing of GO was carried out in a tube furnace. High purity
nitrogen was used to anneal GO or the mixture of GO and AM.
Detailed procedure is as follows: GO and AM with different
mass ratio (1 : 0, 1 : 10, 1 : 25, 1 : 40) were ground together in
a mortar using pestle for about 5 min, and the mixture was
then placed in the center of a corundum tube with a flow of
nitrogen. When the center of the furnace reached the
designated reaction temperature (600 uC, 700 uC, 800 uC), the
mixture was annealed for 2 h at this temperature. After that,
the sample was cooled to room temperature under nitrogen.
Finally, the products were taken out of the corundum tube.
Similarly, the pristine RGO was synthesized from GO using the
same procedure but without AM.
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2.3 Fabrication of modified electrodes
Prior to use, glassy carbon electrodes (GCE), 3 mm in
diameter, was polished with 0.3 and 0.05 mm alumina slurry,
respectively, and then ultrasonicated in ethanol and deionized
water several times to get a mirror-like surface. Then 4 mg as-
prepared N-RGO was dispersed in 400 mL ethanol-water
solution (volume ratio of ethanol to water is 1 : 1), and
ultrasonicated for 30 min to form a homogeneous ink followed
by dropping 5 mL suspension onto a GCE substrate (loading:
0.17 mg cm22). After solvent evaporation, the deposited
catalyst was covered with 5 mL Nafion solutions (0.5% in
ethanol) in order to fix the catalyst on the GCE surface and the
prepared electrodes were allowed to dry in air.
2.4 Characterization
Morphology and microstructure of the synthesized materials
was investigated by X-ray diffraction (XRD, Bruker D8),
scanning electron microscopy (SEM, JEOL JSM-6300, Japan),
TEM (JEM-2100F), X-ray photoelectron spectroscopy (XPS) data
were acquired with a Kratos AXIS 165 Multitechnique Electron
Spectrometer having a monochromatic Al Ka(1486.6 eV)
source (Manchester, U.K.), and Raman spectroscopy (Bruker
Senterra R200-L).
2.5 Electrochemical experiment
All electrochemical experiments were carried out with CHI
660D electrochemical workstation, using a conventional three-
electrode cell composed of platinum foil (geometrical area 1
cm2) as the auxiliary electrode, saturated calomel electrode
(SCE) as the reference, and modified GCEs as the working
electrode. The catalytic activity of N-RGO for ORR was studied
by CV carried out in a solution of 0.1 M KOH at a scan rate of
50 mVs21. Before each test, the solution was saturated with
nitrogen or oxygen.
3. Results and discussion
3.1. XRD, XPS, Raman spectra, TEM and SEM
The XRD patterns of the as-synthesized samples are displayed
in Fig. 2. The pristine GO shows a peak around 8.18u with an
interlayer space of 10.84 Å, which is consistent with work
previously reported.25 The peaks indexed to (002) of RGO
Fig. 2 XRD patterns of the as-prepared samples.
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Fig. 4 XPS spectra of the N-RGO. The inset is the high-resolution N 1s spectrum.
(Peaks of N1, N2, N3 and N4 centered at 398.3, 399.8, 401.2, and 402.8 eV,
Fig. 3 Raman spectra of N-RGO with different raw mass ratio. respectively).
Published on 11 January 2013 on http://pubs.rsc.org | doi:10.1039/C3RA22161J

obtained by annealing GO and N-RGO prepared by annealing content is about 10.6%. The inset of Fig. 4 is the high-
GO/AM with a mass ratio of 1 : 25 at 700 uC for 2 h are resolution N 1s spectrum, which can be fitted into four peaks
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positively shifts to 26.5 and 26.2u, respectively. These results at 398.3, 399.8, 401.2, and 402.8 eV. The peaks with lower
demonstrate that thermal annealing of GO will partially binding energy located at about 398.3 and 399.8 eV,
restores the graphitic crystal structure due to the reduction correspond to pyridine-like and pyrrole-like nitrogen, which
effect of high temperature. For N-RGO, the interlayer spacing can contribute to the p-conjugated system with a pair of
is about 3.39 Å, which is little bigger than that of RGO (3.36 Å), p-electrons in the graphene layers. When carbon atoms within
maybe due to AM corrosion and defects resulted from nitrogen the graphene layers are substituted by nitrogen atoms in the
doping. However, AM treatment process can not affect the form of ‘‘graphitic’’ nitrogen, the corresponding peak in the
layers of RGO. high-resolution N 1s spectrum is located at 401.2–402.8 eV.28
Raman spectroscopy is the most direct and nondestructive Fig. 5 shows the typical TEM and SEM images of RGO and
technique to characterize the structure and quality of carbon N-RGO. It can be seen that the RGO (Fig. 5 a, c) is transparent
materials, particularly to determine the defects, the ordered with the voile-like structure. However, N-RGO (Fig. 5 b, d)
and disordered structures, and the layers of RGO.26 For consist of randomly crumpled sheets closely associated with
comparison, the spectra of N-RGO and pristine RGO obtained each other and forming a disordered solid, which might be
from thermally annealing GO under the same conditions were attributed to the defective structure formed upon exfoliation
also collected. As shown in Fig. 3, N- RGO displays two and the presence of foreign nitrogen atoms. The RGO planar
prominent peaks at y1585 and y1351 cm21 corresponding to sheets are clearly observed in N-RGO, indicating that the
the G and D bands, respectively. The G band of the pristine features of high surface/volume ratio and the two-dimensional
RGO prepared under similar conditions is up-shifted to 1590 structure of RGO morphology are well maintained.
cm21 as compared with N-RGO (y1580 cm21). This phenom-
enon arising from nitrogen doping is similar to the results of
nitrogen-doped melamine and CNTs.27,28 As is known, the G
band related to the E2g vibration mode of sp2 carbon domains
can be used to explain the degree of graphitization, while the
D band is associated with structural defects and partially
disordered structures of the sp2 domains.29 The intensity ratio
of the D peak to the G peak, namely the ID/IG ratio, provides
the indication of the amount of structural defects and a
quantitative measure of edge plane exposure.16 As expected,
the ID/IG increased obviously from RGO to N-RGO (Fig. 3),
suggesting a decrease of sp2 domain induced and a lower
graphitic crystalline structure by the N-RGO.30 When the mass
ratio of GO powder and AM is adjusted up to 1 : 25, the ID/IG
(about 1.2) shows the highest value (Fig. 3a).
X-ray photoelectron spectroscopy (XPS) characterizations
were further performed to analyze the elemental composition
and nitrogen bonding configurations in N-RGO. As shown in
Fig. 4, the XPS spectrum of N-RGO obtained by annealing GO/
AM with a mass ratio of 1 : 25 at 700 uC for 2 h clearly shows
three peaks centered at 285.8 eV, 398.0 eV and 533.4 eV,
corresponding to C 1s, N 1s and O 1s, respectively. The
appearance of an N 1s peak in the spectrum indicates the
successful nitrogen doping into RGO,31 and the nitrogen Fig. 5 TEM and SEM images of RGO (a and c) and N-RGO samples (b and d).

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current increases with the mass increasing of AM in raw from

1 : 10 to 1 : 25, and then reduction current decrease when the
raw AM mass further increase. When the mass ratio of GO/AM
is 1 : 25, the catalyst presents the highest electrocatalytic
activity. It is believed that with the increase of AM content in
raw, the nitrogen content in N-RGO should increase in a
certain range.34,35 However, as reported in literatures, it is not
the nitrogen content but the nitrogen bonding configurations
in N-RGO that could be the key factor for electrocatalytic
performance toward ORR.28 Fig. 6D displays the Nyquist plots
of N-RGO prepared at 700 uC with different mass ratio. In our
work, after a certain amount of N-doping, the diameter of the
semicircle for the Nyquist plots of N-RGO is little smaller than
Published on 11 January 2013 on http://pubs.rsc.org | doi:10.1039/C3RA22161J

that of RGO, but on the whole, the N-doping does not

effectively improve the resistance of electrochemical reactions
Fig. 6 A: CVs for N-RGO ORR obtained at GCE in O2-saturated and N2-saturated on the N-RGO based electrodes. Although the impedance
of 0.1 MKOH aqueous solution ; B: CVs for N-RGO ORR obtained at GCE at
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spectra on high frequency range have similar shapes, the

different temperature (600 uC, 700 uC, 800 uC); C: CVs for ORR at N-RGO slopping line at lower frequencies for different electrodes is
synthesized with different mass ratio of GO and AM (1 : 10, 1 : 25, 1 : 40,
very different, which indicates that N-doping has obviously
1 : 50, 1 : 0) at 700 uC, modified GCE in O2 saturated 0.1 M KOH aqueous
solution. Scan rate: 50 mV s21; D: Nyquist plots of N-RGO prepared with influence on the diffusion resistance of the electrode materials
different mass ratio of GO and AM (1 : 10, 1 : 25, 1 : 40, 1 : 50, 1 : 0) at 700 uC, may due to the microstructure of GO was changed by etching
measured at O2 saturated 0.1 M KOH aqueous solution. and doping of AM at high temperature. When the mass ratio of
GO/AM is 1 : 25, it exhibited the straightest line, which
suggests that it has the lowest diffusion resistance. With the
3.2 Electrochemical characterization mass ratio continue to increase, the diffusion resistance of
N-RGO increases subsequently. The results further confirm
The electrocatalytic properties of the catalysts were evaluated that the electrical conductivity is not the only factor that
for ORR using a three-electrode electrochemical work station determines the electrocatalytic activity of materials.
with the same amounts of active materials. Fig. 6A depicts
To further investigate the ORR performance, we carried out
cyclic voltammograms (CVs) for O2 reduction on N-RGO based
the linear sweep voltammetry (LSV) measurements on a
GCE in N2- or O2-saturated KOH solution. The N-RGO based
rotating disk electrode (RDE) for each of the electrode
GCE does not show any significant peak in the N2-saturated
materials, including the N-RGO-based and commercial Pt/C
solution but does show a quasi-rectangular voltammogram,
electrocatalysts, in O2-saturated 0.1 M KOH at a scan rate of 10
typical of high-surface-area carbons and supercapacitor
mV s21 and a rotation rate of 2500 rpm. As shown in the inset
performance, while in the presence of oxygen, a well-defined
of Fig. 7, a larger capacitance and distinctive catalytic peak
cathodic peak appears at 20.36 V (vs. SCE). This value is
were obtained for the N-RGO based electrode, which indicated
positively shifted by 0.1 mV in comparison with previous
that electrochemical activity of the N-RGO obtained in our
reports,32 and already indicates the excellent catalytic ability of
work is significantly larger than that of commercial Pt/C
our samples for ORR. Moreover, the catalytic activity of the as-
catalyst, and hence has a higher ORR activity. In Fig. 7, it is
prepared N-RGO for ORR can be tailored by controlling the
synthetic conditions (Fig. 6B and C). worth noting that the limiting diffusion current at 20.4 V
The influence of the annealing temperature on the electro- became about 1.5 times stronger than commercial Pt/C
catalytic properties of N-RGO is further explored because the electrodes in LSV with a relatively wide plateau, which is
annealing temperature can largely affect the structural para-
meters such as interlayer spacing, oxygen content, surface area
and disorder degree.33 When the annealing temperature is
increased from 600 to 800 uC, the optimum temperature
appears to be 700 uC, thus the current density of N-RGO
significantly increases to the highest value at 700 uC and then
decreases. This observation indicates that the electrical
conductivity is not the only factor that determines the
electrocatalytic activity. According to recent reports,19 it has
been suggested that the nitrogen content and N species
proportion in the carbon materials play a key role for the
improved activity.
Fig. 6C displays the CVs for the ORR of N-RGO synthesized
with different mass ratio of GO and AM at 700 uC. It is clearly Fig. 7 LSVs of ORR in an O2-saturated 0.1 MKOH solution at a scan rate of 10
that the CVs show similar electrochemical behavior for the mV s21.The rotation rate is 2500 rpm. The inset shows the CVs of N-RGO and
ORR at all the N-RGO modified GCE. However, the reduction commercial Pt/C tested in O2-saturated KOH solution.

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Fig. 8 A: Rotating-disk voltammograms for the N-RGO electrode in an O2-
saturated 0.1 M solute on of KOH, at a scan rate of 50 mV s21, for different
rotation rates. B: Koutecky-Levich plot (J21 versus v21/2) at different electrode
potentials. The experimental data were obtained from Fig. 8 A and the lines are
linear regressions.
Published on 11 January 2013 on http://pubs.rsc.org | doi:10.1039/C3RA22161J
attributable to the highly porous architectures and high
specific surface area of N-RGO, i.e. High electrolyte-accessible
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surface area enhances utilization of nitrogen active sites,
leading to a much higher electrochemical activity.36 The
current density of N-RGO is higher than that of the Pt/C
catalyst, which could reflect that the incorporation of nitrogen
atom significantly enhanced the electrocatalytic activity of
RGO for ORR and sufficiently promising to warrant further
research efforts in developing novel metal-free catalysts
through inter molecular charge transfer. It also should noted
that the onset potential of ORR on N-RGO (20.25 V) is lower
than that of the commercial Pt/C electrode, which may be
because to the oxygen adsorption of N-RGO is not good
enough, and the oxygen adsorption on the catalysts is the key
step to control the ORR onset potential.37
To even obtain quantitatively the number of transferred
electrons (n) of the ORR catalysis, rotating disk electrode (RDE)
experiments was performed in O2-saturated 0.1 M KOH
solution at a scan rate of 50 mVs21. The RDE current potential
curves, at various rotating speeds are shown in Fig. 8, which
always employed to account for the mass transfer effect of
oxygen diffusion so that the pure kinetic current can be
calculated to provide a true measure of catalyst performance at
a given potential, and the number of electrons involved in the
ORR can be calculated from the Koutecky Levich (K–L)
equation
J21 = JL21 + JK21 = (Bv1/2)21 + JK21
B = 0.62nFC0(D0)2/3u21/6
Where J21 is the measured current density, JK and JL are the
kinetic and diffusion-limiting current densities, v is the
angular velocity of the disk (v = 2 pN, N is the linear rotation
speed), n is the overall number of electrons transferred in the
oxygen reduction, F is the Faraday constant (F = 96485 C
mol21), C0 is the bulk concentration of O2 (C0 = 1.21 6 1026
mol cm21), u is the kinematic viscosity of the electrolyte (u =
0.01 cm2 s21), and D0 is the diffusion coefficient of O2 in 0.1 M
KOH (1.9 6 1025 cm2 s21).38,39 According to eqn (1) and (2),
the number of electrons transferred (n) can be calculated to be
3.7, this calculated number is extremely close to the theoretical
4-electron transferred process of the H2O product.7 These
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results are consistent with the previous report about N-RGO
for ORR in alkaline media.40
4. Conclusions
In this work, N-RGO has been prepared by a simple, cost-
effective, and readily reproducible approach. The resulting
N-RGO serves as a true metal-free catalysts that shows
outstanding electrocatalytic activity for ORR, even higher than
that of commercial Pt/C. Furthermore, our study indicates that
the resulting surface defects due to nitrogen doping in N-RGO
play a crucial role for oxygen reduction, which is also expected
to enhance Li+ storage for Li ion battery a and the anchoring of
Pt nanoparticles on N-RGO for fuel cell electrocatalyst.
Acknowledgements
We acknowledge the financial support from National Natural
Science Foundation of China (20963011, 21063014 and
21163021) and Natural Science Foundation of Xinjiang
(2011211A001, 2010211A09).
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