ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. (2012)

Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI: 10.1002/apj.1676

Special theme review

Graphene and its application in fuel cell catalysis: a review
Seung Hyun Hur1* and Jin-Nam Park2
1
School of Chemical Engineering and Bioengineering, University of Ulsan, Daehak-ro 102, Nam-gu, Ulsan 680-749, South Korea
2
Department of New and Renewable Energy, Kyungil University, Gamasigil 20, Hayang, Kyungsan, Kyungsangbuk-Do 712-701, South Korea

Received 19 March 2012; Revised 19 July 2012; Accepted 23 July 2012

ABSTRACT: Graphene is considered a promising material for fuel cell vehicles because of its excellent chemical, mechanical,
and electrical properties. Recent studies have revealed that using graphene or modified graphene as the catalyst support or as a
metal-free catalyst results in significant improvement in the electrocatalytic activity, long term durability, and CO tolerance.
This article summarizes both the recent progress of graphene-based fuel cell research and current developments in
graphene fabrication processes such as mechanical exfoliation, chemical vapor deposition, and chemical exfoliation. The
roles of graphene are also discussed by introducing mechanisms on the basis of theoretical calculations as well as
experimental analysis. © 2012 Curtin University of Technology and John Wiley & Sons, Ltd.

KEYWORDS: graphene; PEM fuel cells; catalysts; doping

INTRODUCTION presented micrometer-sized or nanometer-sized multi-

Since graphene, a flat monolayer of carbon atoms sp2
bonded into a two-dimensional (2D) honeycomb lattice,
was experimentally demonstrated in 2004 by Geim
et al.,[1] there have been numerous studies on the search
for possible applications as well as the development
of fabrication processes due to its excellent electronic,
mechanical, thermal properties, and high surface
area.[2–6] Graphene is a basic building block for
various graphitic materials including 0-dimensional
fullerenes (C60), one-dimensional carbon nanotubes
(CNT), and three-dimensional (3D) graphite,[3] which
show excellent thermal conductivity ((4.84
0.44)  103
to (5.30
0.48)  103 W m1 K1),[6] charge carrier
mobility (up to 2  105 cm2 V1 s1),[7] intrinsic strength
(~130 GPa), Young’s modulus (~1.0 TPa),[8] surface
area (~2600 m2 g1),[9] quantum Hall effects even at room
temperature,[10] and single molecule adsorption
capability.[11] With these unique properties, graphene is
considered a promising candidate for a wide range of
applications including transparent electrodes,[12,13] field
effect transistors,[14,15] polymer composites,[16,17] fuel
cells,[18–29] solar cells,[30,31] super capacitors,[32–35] chemi-
cal and optical sensors,[36–38] and hydrogen storage.[39–41]
Several efforts to obtain monolayer graphene have been
conducted, but only thin layered graphite nanoplatelets
were observed before 2004. In 1999, R. Ruoff et al.
layer graphite nanoplatelets exfoliated with an atomic
force microscope tip, as shown in Fig. 1.[42] These plate-
lets were as thin as 200 nm, which was equivalent to
500 layers; later, P. Kim et al. at Columbia University
produced 10-nm-thick graphite nanoplatelets by further
improvement of this process.[43] In 2004, Novoselov
and Geim at Manchester University reported the first
isolation of single-layer graphene using a simple and
repeatable method using common cellophane tape from
a graphite flake (known as the Scotch tape method).[1]
This route is suitable for obtaining high performance
graphene monolayers, but cannot be applied on a
commercial scale. Since then, many other routes have
been developed for the efficient synthesis of single-layer
graphene sheets in large quantities.
There have been some review reports on the graphene-
based composites for energy conversion,[44–47] but they
have dealt with either the wide range of application areas
together or general topics on fuel cell catalysts. In this
report, we presented the synthesis and application of
graphene-based materials for use in the specific reaction
such as an oxygen reduction reaction (ORR) for fuel
cells. The roles of graphene were also discussed in view
of the reaction mechanisms.
GRAPHENE SYNTHESIS

The synthesis of graphene can be broadly categorized

*Correspondence to: Seung Hyun Hur, School of Chemical
Engineering and Bioengineering, University of Ulsan, Daehak-ro 102, into bottom-up methods (chemical vapor deposition
Nam-gu, Ulsan 680-749, South Korea. E-mail: shhur@ulsan.ac.kr and epitaxial growth on SiC) and top-down methods
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
Curtin University is a trademark of Curtin University of Technology
S. H. HUR AND J.-N. PARK Asia-Pacific Journal of Chemical Engineering

Figure 1. Scanning electron microscope images of graphite plates on a

Si(001) substrate.[42]

(mechanical exfoliation and chemical exfoliation).
Table 1 summarizes and compares the synthetic
methods and properties of graphene and its derivatives.
Chemical vapor deposition (CVD)
Graphene sheets can also be prepared on transition metal
substrates such as Ni,[5] Pd,[48] Ru,[49] Ir[50] or Cu.[51]
The carbon solubility in the metal and the cooling rate
strongly affect the final thicknesses of the graphene
films. In the beginning, Ni was generally used as a
metal catalyst to grow graphene, but multilayers were
dominant because of carbon segregation on the Ni
surface owing to its high carbon solubility. At moderate
cooling rates, C atoms segregate and form a graphene
film, whereas C atoms also segregate out of Ni at higher

Table 1. Comparison of the synthetic methods and properties of graphene and its derivatives.

Category Synthesis Conditions Properties Ref.

Bottom up Chemical vapor Pd(111) with ethylene in STM Monolayer graphene islands 48
deposition 200–2000 Å in size
Thermal cycling of a Ru(0001) single Single crystal domains >200 mm 49
crystal in UHV
Ir(111) with ethylene Large-scale continuity 50
Low defects
Cu foils at 1000  C 4050 cm2 V1 s1 mobility 51
centimeter order size
Cu foils role-to-role process 30-inch graphene films 55
30 Ω/□ with 90% optical
transmittance
Epitaxial growth Thermal decomposition on (0001) 1100 cm2 V1 s1mobility 56
6 H-silicon carbide (SiC)
Vacuum graphitization of single SiC >25,000 cm2 V1 s1 mobility 57
Ex situ graphitization of Si-terminated Large grains 58
SiC(0001) 2000 cm2 V1 s1 mobility
Top down Mechanical Wet ball milling in NMP 0.8–1.8 nm thickness 59
exfoliation ~1.2  103 S m1
Wet ball milling in DMF 0.096 mg mL1 in DMF 60
Yield > 32 wt%
Dry ball milling with melamine Low defects and stable dispersion 61
in DMF
Chemical Alkali metal intercalation and ethanol Scaled up to 70 g quantities of 64
exfoliation exfoliation graphite nanoplatelets
Oxidation of natural graphite followed ~200 S m1 electrical conductivity 71
by reduction with N2H4
Reduction with N2H4 in ~16,000 S m1 72
DMF/water(9/1)mixture
Reduction with phenylhydrazine ~21,000 S m1, high dispersion 74
Solvothermal reduction with NMP 21,600 S m1 75
1.4 g mL1 in NMP
Reduction with Vitamin C 14.1 S m1 , non toxic 78
Reduction with Fe catalyst 2300 S m1, non toxic 79

UHV, ultra-high vacuum; NMP, N-methylpyrrolidone; DMF, dimethylformamide; STM, scanning tunneling microscope.
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2012)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
rates but form a weakly crystalline, less defective
graphitic structure. In contrast to Ni substrates, copper
has the lowest affinity to carbon among the transition
metals and has very low carbon solubility compared with
Ni.[52] As copper has minimal reciprocal repulsions due
to the fully filled 3D-electron shell, it shows very low
reactivity toward carbon, which results in good graphitic
carbon formation. The precise mechanism of graphene
growth on poly-crystalline metals is still not clear, but a
qualitative model for the nucleation and growth of
graphene on copper was proposed by H. Chen et al.[53]
The growth of graphene on Cu can be divided into three
stages, as shown in Fig. 2.[54] First, the native oxide on
the Cu film is reduced by annealing in a hydrogen
atmosphere, which also leads to grain growth and repair
of most of the possible surface defects. Second, uniform
graphene islands nucleate on the pre-treated Cu surface.
These initial graphene domains may have different
lattice orientations based on the crystallographic orienta-
tions of the underlying Cu grains. Finally, the initial
graphene domains grow as time increases, which results
in coalescence into a continuous graphene film on the Cu
surface. Because the wrinkles and grain boundaries
are sparse in graphene grown on Cu, excellent opto-
electronic properties can be achieved. This kind of
chemical vapor deposition (CVD)-grown graphene can
be laterally transferred onto arbitrary substrates by the
flexible polydimethylsiloxane without affecting its prop-
erties. The removal of the Cu substrate can be performed
by immersing the substrate with the graphene film into
an etching bath until the free-standing graphene
membrane floats in the solution.[5] Successful transfer
of large-area graphene has been obtained utilizing the
roll-to-roll transfer method using a thermal release tape
as the support polymer.[55] CVD-grown graphene can
be effectively used in electronics because of its excellent
electrical properties, but is not applicable for fuel cell
applications because it does not have a functionalized
surface structure and has disadvantages associated with
processing and cost.
Epitaxial growth
High quality graphene can be obtained by the thermal
desorption of Si on the Si-terminated (0001) face of
Figure 2. Schematic illustrating the three main stages of graphene growth on copper by chemical
vapor deposition: (a) copper foil with native oxide, (b) nucleation of graphene islands, (c) growth of
graphene flakes with different lattice orientations. [54] This figure is available in colour online at
www.apjChemEng.com.
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
GRAPHENE AND ITS APPLICATION IN FUEL CELL CATALYSIS
single-crystal 6H-SiC wafers.[56,57] Graphene sheets
were formed when the H2-etched surface of 6H-SiC
was heated to 1250–1450  C for 1–20 min. The number
of layers depends on the decomposition temperature,
but generally 2–3 layers of graphene were dominant,
and monolayer graphene was rarely observed. More-
over, because the size of the graphene sheet is
controlled by the SiC wafer size, it is very difficult to
obtain large area graphene films by this approach.
Recently, K. Emtsev et al. showed much larger
domain sizes of monolayer graphene film than
previously attainable by using ex situ graphitization of
Si-terminated SiC(0001) in an argon atmosphere of
about 1 bar. Electronic mobilities were measured as
high as 2000 cm2 V1 s1 at T = 27 K.[58]
Mechanical exfoliation
The ‘Scotch tape’ method has limitations in terms of
scale-up, but it is used to create the best graphene
samples for various fundamental studies. Recently,
direct milling of graphite has been reported to fabricate
graphene in cost effective ways. W. Zhao et al. have
demonstrated a feasible way to produce graphene from
graphite flakes using wet ball milling exfoliation.[59,60]
Using shear-force-dominated grinding, single-layer and
few-layer graphene sheets were readily prepared and
homogeneously and stably suspended in a solvent
medium such as ethanol, formamide, acetone, tetrahydro-
furan, tetramethylurea, N,N-dimethylformamide (DMF),
or N-methylpyrrolidone (NMP) with a concentration up
to 0.08 mg ml1 and a yield greater than 32.0 wt%. Due
to the weak van der Waals forces between graphite layers,
the graphene sheets in graphite can be easily exfoliated by
the application of simple mechanical shear forces,
creating isolated graphene sheets in the solvent media.
V. Leon et al. also reported the production of few-layer
graphene sheets using ball-milling, as shown in Fig. 3.[61]
They used ball-milling with melamine (2,4,6-triamine-
1,3,5-triazine) to exfoliate graphite through mutual
interactions under solid conditions. The strong adsorption
of melamine, an aminotriazine, on graphite creates 2D
molecular assemblies on graphite, which weaken the
van der Waals forces between graphite layers and
results in exfoliation. Charge transfer from graphene to
Asia-Pac. J. Chem. Eng. (2012)
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S. H. HUR AND J.-N. PARK Asia-Pacific Journal of Chemical Engineering

Figure 3. Schematic illustration of the exfoliation of graphite through a ball-

milling approach. [61]

aminotriazines seems to also occur in part through the
presence of hydrogen atoms in the substituents.[62]
Chemical exfoliation
In 2003, R. Kaner et al. reported the synthesis of
‘expanded’ graphite by intercalation of graphite using
a stage-1 potassium intercalation compound (KC8)
with various solvents, followed by thermal expan-
sion.[63,64] Recently, S. Jeon et al. reported high
quality, exfoliated monolayer graphene sheets using
stable alkali metal salt intercalation compounds as
shown at Fig. 4.[65] This approach is fully commercia-
lizable and is regarded as suitable to obtain graphene
sheets with fewer defects. However, it also requires
further development as only submicron size graphene
can currently be obtained. Another approach uses
graphite oxide (GO) as a precursor for graphene synth-
esis. GO can be produced by the oxidative treatment of
graphite using the methods developed by either
Brodie,[66] Hummers,[67] or Staudenmeier.[68] In parti-
cular, Hummers methods are widely used because of
the ease and controllability of the reaction. The basal
plane of GO is decorated mostly with epoxide and

Figure 4. Schematic illustration of formation of monolayer graphene sheets using

alkali metal intercalation compounds. [65]
This figure is available in colour online at
www.apjChemEng.com.
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2012)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
hydroxyl groups, in addition to carbonyl and carboxyl
groups, presumably located at the edges. These oxygen
functional groups make the GO hydrophilic, which
results in the intercalation of water molecules between
layers. GO is electrically insulating, but can be converted
to a conductive material after thermal or chemical
reduction through the restoration of C = C bonds, as
shown in Fig. 5.[69,70] Chemical reduction using hydra-
zine is one of the most common methods for reducing
graphene oxide. Homogeneous dispersions of chemi-
cally converted graphene (CCG) or CCG films were
produced by reducing graphene oxide in hydrazine,[12,71]
in a mixture of dimethylformamide (DMF) and water
(9:1 v/v),[72] or in a basic aqueous environment.[73]
When phenylhydrazine was used instead of hydra-
zine, the dispersibility of CCG in organic solvents
such as N,N0 -dimethylacetamide (DMAc), N,N0 -
dimethylformamide (DMF), propylene carbonate,
and 1-methyl-2-pyrrolidinone (NMP) was highly
improved with a similar conductivity due to the attached
phenyl groups on the CCG surface.[74] Solvothermal
reduction is a simple and useful method to reduce
graphene oxide to CCG.[75] The electrical conductivity
of CCG, solvothermally reduced in an NMP solvent at
180  C for 1 h, was as high as 21,600 S m1, whereas
the dispersibility in NMP was as great as 1.4 mg mL1.
Recently, low defect CCGs were reported by G. Shi
et al. through a modified Hummers method using
Figure 5. Schematic illustration of the structures of graphite oxide, chemically reduced
graphene, and thermally reduced graphene.[70] "This figure is available in colour online
at www.apjChemEng.com."
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
GRAPHENE AND ITS APPLICATION IN FUEL CELL CATALYSIS
mild oxidation of graphite[76] or a combined method
excluding NaNO3, increasing the amount of KMnO4,
and performing the reaction in a 9 : 1 mixture of
H2SO4/H3PO4.[77] Environmentally friendly reduction
approaches using Vitamin-C (L-Ascorbic acid) with
L-tryptophan as a stabilizer[78] or based on Fe reduction
of exfoliated GO through electrochemical redox-reactions
have also been reported.[79]
Chemically exfoliated graphenes have been
effectively used in fuel cell applications because of
the versatility of their surface modifications, unique
defect behaviors, functional groups, and advantages
associated with low cost and easy scale up.
APPLICATION OF GRAPHENE IN FUEL CELLS
Graphene can be used for fuel cell as catalyst support or
metal free catalyst and ionomer after proper chemical
modification as summarized at Table 2.
Catalyst support for the improvement of
electrochemical oxygen reduction activity
and durability
Electrocatalysis of oxygen reduction using Pt nanopar-
ticles supported on functionalized graphene sheets
(FGSs) was conducted by R. Kou et al.[23] Pt
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S. H. HUR AND J.-N. PARK
Table 2. Applications of graphene in fuel cells.
Applications Materials and conditions
Catalyst support Fuctionalized graphene sheet
Poly(diallyldimethylammonium chloride)-
coated GNP
One pot reduction of H2PtCl6 and GO
using NaBH4
Perfluorosulfonic acid fuctionalized graphene
Nitrogen doped graphene using melamine
Microwave-heating of graphene in a
NH3 atmosphere
Metal free catalyst CVD in the presence of NH3
(N-doped graphene)
Direct annealing of graphene oxide and
benzyl disulfide in argon (S-doped graphene)
Thermal annealing GO in the presence
of B2O3 (B-doped graphene)
Others Sulfonic acid-functionalized
GO (ionomer)
Hybrid supports composed of functionalized
GO and MWCNT
Hybrid supports composed of functionalized
GO and carbon black
GNP, graphene nanoplatelet; GO, graphite oxide; ORR, oxygen reduction reaction; CVD, chemical vapor deposition; MWCNT, multi-walled
carbon nanotubes.
nanoparticles with an average diameter of 2 nm were
uniformly loaded by impregnation methods on FGSs
prepared by thermal expansion of GO. Electrochemical
tests showed that the Pt nanoparticles supported on
FGSs had good activity and much better stability in
terms of both electrochemical surface area and oxygen
reduction activity compared with the commercial
E-TEK catalyst or Pt-MWCNT catalyst as shown at
Fig. 6. They speculated that the use of FGSs, which
have more p-sites and functional groups, may lead to
a strong metal-support interaction, which results in
high resistance to Pt sintering and improved durability.
Improved durability of Pt catalysts supported on a poly
(diallyldimethylammonium chloride)-coated graphene
nanoplatelet (GNP) was also reported by Y. Shao
et al.[24] Poly(diallyldimethylammonium chloride)-
wrapping was used to provide a facile approach for
the synthesis of Pt nanoparticles on hydrophobic sub-
strates to avoid environmentally unfriendly chemical
functionalization processes using strongly oxidizing
acids.[80] They found that the activity of Pt/GNP
toward oxygen reduction is comparable to those of
commercial E-TEK Pt/C and Pt/CNT catalysts.
However, the durability of Pt/GNP is 2–3 times greater
than those of Pt/CNT and E-TEK Pt/C. They argued
that this enhanced durability can be attributed to the
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
Properties Ref.
Higher electrochemical surface area 23
and oxygen reduction activity compared
with the commercial E-TEK catalyst
or Pt-MWCNT
Improved durability than Pt/CNT and 24
E-TEK Pt/C in ORR
Higher current density and better 82
electrocatalytic stability over Pt/Vulcan
Improved durability, proton transfer and 83
CO tolerance
Improved electrocatalytic activity toward 93
ORR in alkaline electrolytes
High electrochemical active surface area 96
high methanol catalytic activity,
strong CO tolerance
Better electrocatalytic activity, long-term 103
operation stability, and CO tolerance than
the commercially Pt catalysts
Excellent catalytic activity, long-term 104
stability, and high methanol tolerance in
alkaline media for ORR
Excellent electrocatalytic activity toward 105
ORR and high CO tolerance
Four times higher proton conductivity than 106
that of the unmodified membrane
Less restacking of GO improved fuel cell 108
performance
Larger electrochemical surface area and 109
faster interfacial oxygen kinetics
intrinsic high graphitization degree of GNP and the
enhanced Pt-carbon interaction in Pt/GNP. H. Wu also
used graphene nanosheets as an alternative support
material for Pt nanoparticle catalysts for oxygen reduc-
tion in proton exchange membrane (PEM) fuel cells
and compared them with commercial BASF XC-72
catalyst.[81] Therein, 20 wt% Pt/graphene catalysts
were prepared using a simple chemical reduction
method, and electrochemical characterization showed
that graphene had improved corrosion resistance over
XC-72, which can be attributed to the intrinsic high
graphite component and enhanced Pt-carbon interac-
tions. Y. Li et al. fabricated nano-size Pt-decorated
graphene nanosheets via reduction of both GO and
H2PtCl6 in one pot using NaBH4.[82] The particle size
of the Pt was 5–6 nm, and high-resolution transmission
electron microscopy showed a lattice fringe spacing of
0.23 nm in these nanoparticles, which was in good
agreement with the spacing of the (111) planes of Pt
calculated using the X-ray diffraction data. The
current density of the Pt/graphene was higher than that
of Pt/Vulcan catalyst electrodes during cyclic voltam-
metry tests, which indicates that the electrocatalytic
stability of the Pt/graphene catalyst for methanol oxida-
tion was also higher than that of the Pt/Vulcan catalyst.
B. Seger et al. also reported higher electrocatalytic
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Asia-Pacific Journal of Chemical Engineering GRAPHENE AND ITS APPLICATION IN FUEL CELL CATALYSIS

Figure 6. Electrochemical properties tested in 0.5 M H2SO4 aqueous solution. (a) Cyclic
voltammograms of Pt-FGS under a scan rate of 50 mV s1 before and after 5000 cyclic
voltammetry (CV) degradation, (b) polarization curves of the O2 reduction (10 mV s1,
1600 rpm) on Pt-FGS catalyst before and after 5000 cycles, (c) original values of ESA
and oxygen reduction reaction activity at 0.9 V, (d) the percentage of retained ESA
and oxygen reduction reaction activity after 5000 CV degradation cycles. [23] This figure
is available in colour online at www.apjChemEng.com.

activity toward oxygen reduction of Pt/graphene
catalyst partially reduced by borohydride.[20] First,
graphene oxide was partially reduced with NaBH4
along with Pt nanoparticle deposition. The deposition
of the partially reduced GO-Pt on an electrode surface
is then followed by the reduction of the film
with hydrazine. Pt particles anchored on individual
graphene sheets are believed to help prevent sheet
collapse and maximize the available electrocatalyst
area. They found that a partially reduced GO-Pt based
fuel cell showed a maximum power of 161 mW cm2
compared with 96 mW cm2 for an unsupported
Pt-based fuel cell because of the dispersion of the
electrocatalyst on the graphene surface. This result
shows that graphene-based Pt catalysts can increase
the activity of oxygen reduction as well as that in direct
methanol fuel cells. Y. Xin et al. modified this
approach to prevent aggregation of Pt/graphene
catalyst during the drying process by using lyophiliza-
tion.[18] Graphene-based composite materials can
easily aggregate due to their high surface to volume
ratio and strong p–p interactions. By introducing
lyophilization, they obtained a well dispersed graphene
solution. They also reported that Pt/graphene showed
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
not only higher catalytic activity than that of Pt/C
toward both methanol oxidation and ORRs but also
improved stability after a 300  C heat treatment by the
combined effects of the following: (1) the enhancement
of interaction between Pt and graphene, (2) exposure of
additional Pt active sites by the rolling of graphene
sheets, (3) fewer defects on graphene by the reduction
of surface functional groups, and (4) more active
catalytic sites by inducing a more ordered Pt
surface morphology.
E. Yoo et al. reported fabrication of Pt catalyst
supported on 10–20 layers of graphene nanosheets
(GNSs) and observed an unusually high activity for
methanol oxidation on Pt/GNS compared with that of
a Pt/carbon black catalyst.[25] They claimed that the
presence of extremely small Pt clusters (subnanometer
size) suggests a strong interaction between GNS and
platinum atoms, which resulted in no aggregation of
the platinum clusters upon heating treatment in Ar/H2
(4 : 1 v/v) at 400  C. The strong interaction between Pt
and graphene may also induce some modulation in
the electronic structure of the Pt clusters. Pt/GNS also
revealed a much smaller CO adsorption rate (by about
40 times) than that of Pt/carbon black, which resulted
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S. H. HUR AND J.-N. PARK
in improved CO tolerance of the catalyst during fuel
cell operation. Similar results on improved CO toler-
ance were also reported recently by D. He et al.[83]
who prepared Pt nanoparticles supported on GNSs
using perfluorosulfonic acid (PFSA) as a functionaliza-
tion and anchoring agent. Pt nanoparticles 1 to 4 nm in
diameter were uniformly dispersed on the GNS
surface, and the introduction of PFSA enhanced the
Ptgraphene interaction, which resulted in improved
stability. Also, PFSA can provide more channels for
proton (H+) transfer toward Pt surfaces, which intro-
duces more active catalytic sites by enhancing the
effectiveness of the triple-phase boundary, as described
in Fig. 7. Moreover, PFSA facilitates CO-water
absorption on the catalyst and formation of an active
oxy-compound of PtOH, promoting CO oxidation
to CO2, which resulted in the improved CO tolerance.
Roles of graphene in fuel cells
The most important role of graphene as a supporting
material for metal catalysts is the provision of anchor-
ing sites to obtain a uniform distribution of nano-sized
metal particles, which results in high catalytic activity.
Figure 7. (a) Schematic of facilitated electrocatalytic
reaction with increased triple-phase boundary for perfluoro-
sulfonic acid functionalized Pt/GNS catalyst, (b) mechanism
of perfluorosulfonic acid promoted Pt/GNS for enhancing
CO electro-oxidation. [83] This figure is available in colour
online at www.apjChemEng.com.
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
Asia-Pacific Journal of Chemical Engineering
Early studies by T. Cassagneau et al. showed that the
particle size of metal particles can be controlled by con-
trolling the surface chemistry of graphene films.[84]
They reported that monodisperse, 10-nm-diameter
oblate Ag particles effectively protected by 5-Å-thick
GO sheets were obtained by sodium borohydride
reduction of silver ions in aqueous dispersions of
exfoliated GO. Anchoring of gold nanoparticles on
the graphene surface was also recently reported by
G. Goncalves et al. and R. Muszynski et al.,[85,86]
who showed that the presence of oxygen functionalities
on the graphene surface provides reactive sites for the
nucleation and growth of gold nanoparticles as shown
at Fig. 8. The nucleation and growth mechanism
depends on the degree of oxygen functionalization on
the graphene surface sheets, and no gold nanoparticles
were obtained on totally reduced graphene surfaces.
Fast charge transfer between graphene and the
supported nanoparticles may also be a major role of
graphene because of its highly conductive nature.
Anchoring of semiconductor particles such as TiO2 to
graphene sheets has been studied, and the improvement
of photocatalytic activity was observed by the enhance-
ment of charge transfer.[87–89] First, titanium dioxide/
graphene oxide composites were prepared using a
simple colloidal blending method. TiO2/graphene
composites showed improved adsorption and photoca-
talysis performance under both UV and visible radia-
tion relative to those of pure TiO2. As the content of
graphene oxide increased to 10 wt%, the removal
efficiency and the photodegradation rate of methylene
blue were increased. T. Nguyen-Phan et al. reported
that the improved photocatalytic activities irrespective
of light source could be attributed to synergistic effects
of the increased specific surface area because of the
addition of graphene oxide as well as the enhanced
charge transfer by the formation of both p–p conjuga-
tions between dye molecules and aromatic rings and
the ionic interactions between methylene blue and
oxygen-containing functional groups of the GNSs.[88]
In a follow-up study, that group used triethanolamine
and acetylacetone as chelating agents to fabricate
reduced graphene oxide–TiO2 composites and found
that the presence of chelating ligands remarkably facili-
tated the selective growth and regular spread of TiO2
nanocrystals onto individually exfoliated RGO sheets.
Strong coupling and chemical interactions between
TiO2 nanoparticles and RGO resulted in a surface area
increase, rearrangement of the energy level, and
enhanced concentration of oxygen vacancies, leading
to a much higher adsorbability and photocatalytic
degradation of Rhodamine B under both UV and
visible irradiation, as shown in Fig. 9.[89]
Recently, D. Lim et al. proposed a mechanism for
oxygen reduction on defective graphene-supported Pt
nanoparticles[90] and theoretically demonstrated that
defective graphene used as a support material can
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Asia-Pacific Journal of Chemical Engineering GRAPHENE AND ITS APPLICATION IN FUEL CELL CATALYSIS

Figure 8. Schematic representation of the mechanism of nucleation of gold nanoparticles on the

functionalized graphene surface. [85]

Figure 9. Photodegradation of Rhodamine-B on a sandwich-like reduced graphene oxide–TiO2

hybrid under ultra-violet and visible irradiation.[89] "This figure is available in colour online at
www.apjChemEng.com."

enhance the catalytic activity of Pt13 nanoparticles as
depicted at Fig. 10. First, the defective graphene
support prevents sintering of the catalyst through the
strong anchoring of Pt nanoparticles to the surface.
Secondly, it lowers the dissociation activation energy
of O2 from 0.37 to 0.16 eV by promoting charge trans-
fer from Pt atoms to O2 and limiting the degree of
relaxation of the Pt13 nanoparticle. In addition, it
decreases the energy barrier of the rate-limiting step
by reducing the stability of the intermediate species
(HO*). They showed that, at the equilibrium electrode
potential, all four proton/electron transfer reactions
were endothermic regardless of pathway (i.e. either
direct four-electron or series two-electron pathways).
They found that the direct pathway is preferred during
the initial step of the ORR pathway as the O2 dissocia-
tion activation energy for the direct pathway (0.16 eV)
is lower than the minimum energy barrier for HOO*
formation in the series pathway (0.29 eV). The HOO*
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
intermediate species in the series decomposes to O*
and HO* species. The decreased charge depletion on
the Pt13 and decreased charge accumulation on the
adsorbate can be attributed to the relatively weaker
interaction of the HOO* intermediate species with the
supported Pt13 nanoparticle. Upon adsorption of the
ORR intermediate species on Pt13-defective graphene,
the Pt13 nanoparticle serves as a charge donor to both
defective graphene and the intermediate species. In
summary, defective graphene supports reduce not only
the activation energy for O2 dissociation, but also the
energy barrier of the rate-limiting step. This is accom-
plished by reducing the stability of the HO* species
by tuning the relatively high reactivity of free Pt13
nanoparticles, which too strongly bind the ORR inter-
mediates, subsequently leading to slow kinetics.
Recent study by R. Kou et al. also found that
the supported Pt nanoparticles are more stable at the
Pt-ITO-graphene triple junctions and functional groups
Asia-Pac. J. Chem. Eng. (2012)
DOI: 10.1002/apj
S. H. HUR AND J.-N. PARK Asia-Pacific Journal of Chemical Engineering

Figure 10. Free energy diagram for oxygen reduction through direct four-
electron (markers in blue) and series two-electron (markers in green) pathways
on defective graphene-supported Pt13 nanoparticles. Solid and dashed lines
represent reactions at zero cell potential (i.e. U = 0 V) and the equilibrium
potential (i.e. U = 1.23 V), respectively. The inset shows alternative intermediates
(i.e. less stable) of steps 30 , 300 , and 3000 of the series pathway at the equilibrium
potential. [90] This figure is available in colour online at www.apjChemEng.com.

on graphene also play an important role in stabilizing
the catalysts when calculated by density functional
theory (DFT).[91] They argued that the highly conductive
2D graphene sheets provide the high surface area and
greatly increased the electrical conductivity of the triple
junction catalysts. Moreover, the graphene provide many
anchoring sites of the ITO nanoparticles, which protect
the graphene from corrosion, which results in improved
durability of the prepared catalysts.
Chemical modification of graphene for oxygen
reduction reaction
The application of doped graphene as
catalyst supports
Recently, much work has been performed to improve
the activity and durability of graphene-based Pt cata-
lysts by nitrogen doping of graphene.[92–95] Nitrogen
doping of graphene can be accomplished by a
solvothermal treatment in tetrachloromethane with lithium
nitride,[95] microwave heating in a NH3 atmosphere,[96]
converting from a conducting polymer,[97] low-energy
nitrogen implantation,[98] and by CVD with NH3
gas.[99] During doping, the nitrogen atoms enter into
the lattice of graphene, form covalent bonds with C
atoms, which result in a change in the lattice structure
of graphene. This would largely modify the electrical
structure of graphene and suppress the density of states
of graphene near the Fermi energy (Fm) level; thus, the
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
gap between valence and conduction bands can
be tuned.[100]
Z. Sheng et al. prepared nitrogen (N)-doped gra-
phene (NG)via a catalyst-free thermal annealing
method using melamine as the nitrogen source and
showed improved electrocatalytic activity toward
ORR in alkaline electrolytes, similar to that observed
in nitrogen-doped, vertically aligned CNT.[93] They
found that the atomic percentage of nitrogen in
graphene layers can be adjusted up to 10.1%, and the
nitrogen atoms are mainly in a pyridine-like bonding
configuration; further, at higher annealing tempera-
tures, the content of graphitic nitrogen will increase.
Electrocatalytic activities of prepared Pt/graphene
toward ORR in alkaline electrolytes were similar to that
observed in nitrogen-doped, vertically aligned CNT.
However, the nitrogen content did not considerably
affect the overall performance, which implies that the
pyridine-like nitrogen component in NG determines
the electrocatalytic activity toward ORR because
nitrogen bonding configurations in this work were
composed mainly of pyridinic nitrogen. NG using
microwaves showed similar effects according to a
recent report by Y. Xin et al.,[96] who demonstrated a
simple route to synthesize NG with high nitrogen
content (~5.04%) through microwave-heating of
graphene in an NH3 atmosphere. The thermal stability
of the Pt/NG was significantly enhanced by N-doping.
Moreover, the Pt supported on the NG exhibited higher
Asia-Pac. J. Chem. Eng. (2012)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering GRAPHENE AND ITS APPLICATION IN FUEL CELL CATALYSIS

electrochemical active surface area, higher methanol
catalytic activity, stronger tolerance to CO poisoning,
and better long term operation stability under fuel cell
conditions as shown at Fig. 11. They speculated that
N-doping of graphene can repair defects on the
graphene by removing oxygenated functional groups,
resulting in enhancement of the stability and conductiv-
ity of graphene. Further, N-doping can change the
electronic structures as well as modify the graphene
surface by forming nitrogen functional groups. In addi-
tion, N-doping also contributes to the effective immobi-
lization of metal nanoparticles by strengthening the
metal-support interaction because of the high electron
density generated from the incorporation of nitrogen.[101]
Improved tolerance to CO poisoning of graphene-
supported Pt catalyst was also calculated by G. Kim
et al.[92] They introduced various forms of defects in
graphene that can act as Pt binding centers and investi-
gated the catalytic activity and corresponding adsorbate
interactions of Pt as well as their CO tolerance in the
hydrogen oxidization reaction. It was shown that
defects in graphene significantly increase Pt binding
strength and lower the Pt d-band center (edc). Because
of a mismatch in the bond length between Pt and
carbon, Pt clusters change their morphology on top of
pyridine-like nitrogen defects. The binding energy of
Pt13 on N defects is about three times larger than that
on pristine graphene. The strong binding of Pt to defec-
tive graphene prevents particle migration, which is a
dominant process in the degradation of Pt catalysts.
Using thermodynamic analysis, they also showed that
nitrogen doping in graphene improves CO tolerance
of Pt nanoparticles by the strong binding effect, as
shown at Fig. 12. Another theoretical study on the elec-
trocatalytic mechanism of NG in an acidic environment
was conducted using DFT by L. Zhang et al.[94] They
used B3LYP hybrid DFT of Gaussian 03 with a basis
set of 6-31 G(d,p). Modified polarization setting
was used in the calculation considering the breakage
and formation of chemical bonds. C45NH20 and
C45NH18, which contain pyridine and pyrrole species,
respectively, were prepared as two different nitrogen-
containing graphene sheets. Graphene sheets with the
same configuration but no N-doping (C46H20, and
C46H18) were also constructed for comparison. The
ORR was found to be a four-electron pathway in
the case of the N-graphene, but pure graphene did not
have such catalytic activities when the electron
transformation process was simulated. The effect of
N-doping toward ORR could be explained by the level
Figure 12. Averaged adsorption energy difference ΔEad = Ead
(CO)  Ead(H2) between H2 and CO with respect to Pt d-band
center (dc) for Pt1 (yellow), Pt6 (blue), and Pt13 (red) deposited
on defective graphene. Fits of the data are least-square linear.
Pt(111) surface case is also shown for comparison (black star).
The fitted line for Pt13, when extrapolated, is close to Pt
surface data, indicating that Pt13 has similar catalytic charac-
teristics to a Pt surface. Adsorption energies of individual
molecules, Ead(CO) or Ead(H2), on Pt6 or Pt13 do not show
any correlation with dc, in contrast to the case of Pt atoms or
a clean Pt surface. Small ΔEad implies a greater CO tolerance
for H2 adsorption (upper-left corner).[101] This figure is
available in colour online at www.apjChemEng.com.

Figure 11. (A) Cyclic voltammograms for oxygen reduction reaction obtained on (a) bare
GCE, (b) graphene/GCE, and (c) NG5/GCE (N% = 7.1%) in O2 saturated 0.1 M KOH
aqueous solution. (B) cyclic voltammograms for oxygen reduction reaction at N-doped
graphenes synthesized with different mass ratios of graphite oxide and melamine (1 : 1,
1 : 2, 1 : 5, 1 : 10, 1 : 50) at 800  C, modified GCE in an O2 saturated 0.1 M KOH aqueous
solution. [93] This figure is available in colour online at www.apjChemEng.com.
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2012)
DOI: 10.1002/apj
S. H. HUR AND J.-N. PARK Asia-Pacific Journal of Chemical Engineering

of chemical reactivity. A small band gap between the
highest occupied molecular orbital (HOMO) and
lowest unoccupied molecular orbital (LUMO) implies
low kinetic stability and high chemical reactivity
because it is energetically favorable to add electrons
to a high-lying LUMO, to extract electrons from a
low-lying HOMO, and so to form the activated
complex for any potential reaction.[102] For pure
graphene, C46H20, the gap was 2.7 eV, which was reduced
by two times after a nitrogen atom was substituted into
C46H20 to form C45NH20, indicating that the chemical
reactivity of the NG was significantly improved due to
easy excitation of electrons from the valence band to the
conduction band. Also, the high asymmetry spin density
and atomic charge density induced by the substituted
N atoms in N-graphene led to higher electrocatalytic
activities for the ORR.
The application of doped graphene as
metal-free electrocatalysts
Metal-free electrocatalysts using NG[103] and sulfur-
doped graphene[104] for ORR in fuel cells have been
reported recently. The NG fabricated by CVD in the pre-
sence of NH3 (NH3:CH4:H2:Ar = 10 : 50 : 65 : 200 sccm)
showed a much better electrocatalytic activity, long-
term operation stability, and tolerance to crossover
and poison effects than the commercially available
platinum-based electrodes (C2-20, 20% platinumon
VulcanXC-72R; E-TEK) for oxygen reduction.[103]
The steady-state catalytic current density at the
NG electrode was found to be three times higher
than that of the Pt/C electrode over a large potential
range. The number of transferred electrons per oxygen
molecule at the NG electrode calculated by the
Koutecky–Levich (K–L) equation was 3.6–4 for
potentials ranging from 0.4 to 0.8 V. When
10% (v/v) CO in air was introduced into the electrolyte,
the N-graphene electrode was insensitive to CO, whereas
the Pt/C electrode was rapidly poisoned under the same
conditions. In addition, no obvious decrease in current
was observed after 200,000 continuous potential cycles
between 1.0 and 0 V in air saturated 0.1 M KOH. Z.
Yang et al. reported that sulfur-doped graphene,
formed by direct annealing of graphene oxide and
benzyl disulfide in argon, also showed excellent
catalytic activity, long-term stability, and high metha-
nol tolerance in alkaline media for ORR.[104] They
controlled the content and bonding configuration of
sulfur in the S-doped graphenes by varying the mass
ratios of GO and benzyl disulfide or the annealing
temperature. After doping with S atoms, the peak
potential of the ORR for the S-graphene-600 (annealed
at 600  C) electrode shifted positively to 0.32 V, and
its oxygen-reduction current (123 mA ) was higher than
that of the graphene-600 electrode (82 mA), which
was same for all the S-doped graphenes regardless of
annealing temperature, as shown at Fig. 13. They
speculated that the C-S bond is an important catalytic

Figure 13. Cyclic voltammograms for (a) graphene-600 and S-graphene-600, (b)
graphene-900 and S-graphene-900, and (c) graphene-1050 and S-graphene-1050;
(d) linear sweep voltammetry curves for various graphenes and a Pt/C catalyst
on a glass-carbon rotating disk electrode saturated in O2 at a rotation rate of
1600 rpm.[104] This figure is available in colour online at www.apjChemEng.com.
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. (2012)
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering
active site for promoting ORR, and the spin density is
the dominant factor to regulate the observed ORR
activity in the S-graphene. They also reported that the
crossover resistance and durability of S-graphene were
better than those of Pt/C catalyst. They believe that
hetero-doped structures may provide opportunities for
further development of low-cost, non-precious-metal
catalysts with high activities and long lifetimes for
practical fuel cell applications.
Boron doping is another approach to modify
graphene for metal-free electrocatalysts in fuel cells,
as reported by Z. Sheng et al.[105] Boron-doped
graphene was prepared by thermal annealing GO in
the presence of B2O3. It was found that boron atoms
from B2O3 vapor can be successfully doped into the
graphene framework at high temperature (1200  C).
The electrochemical measurements showed that boron
atoms in graphene can accelerate the adsorption of
oxygen, which results in excellent electrocatalytic
activity toward ORR and high CO tolerance. They
speculated that electron-deficient boron atoms doped in
graphene may act as active sites for oxygen adsorption
and to activate the O–O bond cleavage.
Recently, a sulfonic acid-functionalized graphene
oxide (F-GO) was reported by H. Zarrin et al. as a
potential PEM replacement for low humidity and high
temperature polymer electrolyte membrane fuel cell
(PEMFC) applications.[106] They found that F-GO/
Nafion nanocomposites showed a four times higher
proton conductivity than that of the unmodified
membrane at a low humidity value of 30% and high
temperature of 120  C as shown at Fig. 14. They
explained this result on the basis of the Grotthuss mechan-
ism,[107] where protons diffuse through the hydrogen
bond network of water molecules. The extremely high
surface area with an enormous amount of sulfonated
Figure 14. MEA polarization and power density curves
for 10 wt% f-GO/Nafion and recast Nafion membranes,
with commercial E-TEK 20 wt% Pt/C catalyst in a single-
cell H2/O2 system at a temperature (T) of 120  C and
25% relative humidity. [106] This figure is available in
colour online at www.apjChemEng.com.
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
GRAPHENE AND ITS APPLICATION IN FUEL CELL CATALYSIS
functional groups on F-GO enables the membrane to hold
more water, which results in improved proton transfer.
The increase in F-GO nanofiller loading increases the
number of available ion exchange sites per cluster,
resulting in an increase in proton mobility in the
membrane at high temperatures and low humidity values.
Under similar operating conditions, single-cell MEA
testing also showed a significantly higher performance
for a 10 wt% F-GO/ Nafion membrane than that of the
recast Nafion, displaying peak power densities of 0.15
and 0.042 W cm2, respectively. This new approach
illustrates yet another advantage of graphene for fuel cell
applications compared with other catalyst supports.
Hybridized catalyst supports
Because of its 2D nature and strong van der Waals interac-
tions, graphene sheets tend to form irreversible agglomer-
ates and restack to form graphite, which results in low fuel
cell performance. N. Jha et al. reported hybrid supports
composed of functionalized graphene (f-G) and functiona-
lized multi-walled carbon nanotubes (f-MWNT) which
acted as spacers.[108] They reported that the maximum
direct-methanol fuel cell power density (68 mW cm2)
was achieved by dispersing 3D PtRu/Pt nanoparticles over
an equal-quantity mixture of one-dimensional f-MWNTs
and 2D f-G as a catalyst support. They attributed the
improved fuel cell performance to the superior accessibil-
ity of catalyst particles for methanol oxidation and ORRs
because of the prevention of restacking of exfoliated gra-
phene sheets by the PtRu/Pt nanoparticles and f-MWNTs.
S. Park et al. used carbon black as a spacer instead of
MWNTs[109] and found that a cathode with 25 wt%
carbon black produced a larger electrochemical surface
area and faster interfacial oxygen kinetics in PEM fuel
cells. From transmission electron microscopy and scan-
ning electron microscopy results, they concluded that
enhanced exfoliation of graphene sheets decorated with
Pt nanoparticles and the increased distance between
graphene sheets due to the added carbon black particles
altered the array of graphene sheets in the catalyst
layer, resulting in more Pt nanoparticles covered with
ionomer, a higher electrochemical surface area (ESA),
and an increased gas-phase void volume for oxygen
transport, as show in Fig. 15.
CONCLUSIONS
Among many power sources, PEMFCs are regarded as
the best candidates for future electro-mobile devices
compared with other types of systems because of their
higher efficiency, excellent response characteristics,
low operating temperature, and rapid start-up. Many
efforts have been made toward the commercialization
of fuel cells to solve the environmental pollution pro-
blems caused by auto exhaust and the energy crisis
Asia-Pac. J. Chem. Eng. (2012)
DOI: 10.1002/apj
S. H. HUR AND J.-N. PARK Asia-Pacific Journal of Chemical Engineering

separation of Pt particles from the supports and the

agglomeration of Pt particles due to the weakened
adhesion between metals and supports. Eventually,
these result in the loss of active Pt surface area and a
reduction in cell performance.
As investigated, graphene, which shows strong
corrosion resistance and provides strong adhesion with
metal nanoparticles, is one of the best candidates for
use as a commercial catalyst in PEMFCs. Moreover,
using proper surface modification, it can also be used
as a metal-free fuel cell catalyst, which may have a
major impact on the future vehicle industry owing to
its dramatic cost savings.
Finally, further work is required to develop the most
suitable methods for preparing either pure graphene or
modified graphenes for fuel cell applications. The
development of cost effective and high quality
processes for synthesis, doping, layer number control,
defect optimization, and surface functionality modifica-
tion of graphene will be the key factors in future
research. Also, systematic studies for a fundamental
understanding of the chemical and physical mechan-
isms that govern the electrochemical properties of
graphene-based catalysts are essential. This will require
a diverse contribution from many research fields
including chemistry, physics, electronics, mechanics,
and material science.

Figure 15. (a) AC-impedance spectra of the cathodes
prepared using graphene sheets supported Pt catalyst
with and without carbon black at Ecell = 0.9 V.
(Inset) Charge transfer resistance calculated from
AC-impedance spectra; (b) polarization curves of the
proton exchange membrane fuel cells using graphene
sheet-supported Pt catalyst with and without carbon
black. (Inset) Mass activity calculated from the polari-
zation curve at Ecell = 0.9 V. [109] This figure is available
in colour online at www.apjChemEng.com.
associated with fossil fuel depletion. However, much
work remains to meet the cost target set by the
Department of Energy (DOE) as it requires usage of
expensive noble metals (Pt, Pd) and shows relatively
poor long term durability and CO tolerance. Even
though it is well known that the type of supporting
material is regarded as one of the most important
factors in the deactivation of PEMFCs, activated
carbon, which has poor corrosion resistance, is still
widely used in the industry as well as in research.
Electrochemical carbon corrosion causes the structural
breakdown of carbon supports, which results in the
© 2012 Curtin University of Technology and John Wiley & Sons, Ltd.
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