CARBON 4 8 ( 2 0 1 0 ) 1 1 2 4 –1 1 3 0

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journal homepage: www.elsevier.com/locate/carbon

Catalytic performance of Pt nanoparticles on reduced

graphene oxide for methanol electro-oxidation
a,b
Yongjie Li , Wei Gao b, Lijie Ci b, Chunming Wang a,*
, Pulickel M. Ajayan b,1

a
Department of Chemistry, Lanzhou University, Lanzhou 730000, PR China
b
Department of Mechanical Engineering and Materials Science, Rice University, Houston 77005, USA

A R T I C L E I N F O A B S T R A C T

Article history:
Received 30 August 2009
Accepted 19 November 2009
Available online 24 November 2009
We have investigated a simple approach for the deposition of platinum (Pt) nanoparticles
onto surfaces of graphite oxide (GO) nanosheets with particle size in the range of 1–5 nm
by ethylene glycol reduction. During Pt deposition, a majority of oxygenated functional
groups on GO was removed, which resulted in a Pt/chemically converted graphene
(Pt/CCG) hybrid. The electrochemically active surface areas of Pt/CCG and a comparative
sample of Pt/multi-walled carbon nanotubes (Pt/MWCNT) are 36.27 and 33.43 m2/g, respec-
tively. The Pt/CCG hybrid shows better tolerance to CO for electro-oxidation of methanol
compared to the Pt/MWCNT catalyst. Our study demonstrates that CCG can be an alterna-
tive two-dimensional support for Pt in direct methanol fuel cells.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction possesses similar stable physical properties but also larger

Graphene, one-atom thick planar sheet of hexagonally ar-
rayed sp2 carbon atoms, has attracted tremendous scientific
attention in recent years [1–4]. This two-dimensional (2D)
material exhibits excellent physical and chemical properties,
which makes it promising for potential applications in many
technological fields, such as nanoelectronics, sensors, nano-
composites, batteries, supercapacitors and hydrogen storage
[1]. Especially, graphene has potential application as a hetero-
geneous catalyst support in direct methanol fuel cells [5–8]. It
is well known that carbon nanotubes (CNTs), having excellent
electrical, mechanical and structural properties [9], and fasci-
nating performances in biomedicine, catalysts, sensors, and
so on [10], have been extensively studied as supports for the
dispersion of precious metal nanoparticles to enhance elec-
trocatalytic activity in fuel cells [11–13]. The most studied
bimetallic PtRu alloy catalysts have been demonstrated to
be much more effective in the electro-oxidation of methanol
[14–17]. In comparison with CNTs, graphene not only
surface areas [4,18,19]. Additionally, production cost of CCG
sheets in large quantities is much lower than that of CNTs
[4,20]. Several investigations have been carried out to produce
graphene nanosheets in bulk quantity by chemical reduction
of graphite oxide (GO) in solution [21–24]. Since abundant
functional groups on the surfaces of GO can be used as
anchoring sites for metal nanoparticles [25], it is possible to
use them as a support to produce graphene-nanoparticle hy-
brids. Combination of graphene and functional nanoparticles
may lead to materials with interesting properties for a variety
of applications, and they are specifically expected to have en-
hanced electrocatalytic activity.
In this work, a mild and environmental friendly reductant,
ethylene glycol, was used as both reductive and dispersing
agent for deposition of Pt nanoparticles on sheets of GO.
The as-prepared Pt/CCG hybrids show higher electrocatalytic
activity than Pt/MWCNT catalyst. Our study opens a novel,
and insightful way to develop electrocatalyst for fuel cells
application.

* Corresponding author: Tel.: +86 931 8911895; fax: +86 931 8912582.
E-mail addresses: wangcm@lzu.edu.cn (C. Wang), ajayan@rice.edu (P.M. Ajayan).
1
Tel.: +1 713 348 5904; fax: +1 713 348 5423.
0008-6223/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2009.11.034
 CARBON 4 8 ( 20 1 0 ) 1 1 2 4–11 3 0
2. Experimental section
2.1. Synthesis of graphite oxide (GO)
GO was synthesized from graphite powder by a modified
Hummers method [26] as originally presented by Kovtyukh-
ova et al. [27,28].
2.2. Functionalization of multi-walled CNTs (MWCNTs)
The MWCNTs (MWCNTs > 95 wt.% purity from CheapTubes)
have outer diameters in the range of 10–20 nm with the
length of 10–30 lm. The surface treatment process of
MWCNTs is according to the method reported by Xing [11].
In a typical experiment, MWCNTs (100 mg) were mixed with
94 mL of HNO3 (69%), 80 mL of H2SO4 (98%), and 6 mL of
deionized water (DI water) in a 250 mL Pyrex glass flask.
The flask was then put in the ultrasonic bath and treated
for 3 h. After that, the mixture was filtered and washed with
DI water several times. The sonochemically treated
MWCNTs were dried in a vacuum desiccator at room
temperature.
2.3. Synthesis of Pt/CCG, Pt/MWCNT and reduction of GO
by ethylene glycol (EG)
Pt nanoparticles were deposited on GO sheets by a chemical
reduction of chloroplatinic acid (H2PtCl6) in ethylene glycol–
water solution. In a typical procedure, 1.16 ml aqueous solu-
tion of 0.0443 M H2PtCl6, 8.84 ml of DI water and 90 mg of
GO were added into 40 ml ethylene glycol in a 100 ml flask.
The mixture was first ultrasonically treated for 4 h to ensure
GO being uniformly dispersed in ethylene glycol–water solu-
tion. The reduction reaction was then performed at 120 °C
for 24 h under constant stirring. The Pt/CCG hybrids were fi-
nally separated by filtration and washed with deionized water
several times. The resulting product was dried in a vacuum
desiccator at room temperature (Fig. 1). For comparison,
deposition of Pt nanoparticles on MWCNTs was also achieved
by the same procedure. In order to understand the chemical
reduction of GO, GO was treated by ethylene glycol–water
solution without metallic salts in the same condition (labeled
as GO/EG).
2.4. Characterization
X-ray powder diffraction (XRD) was carried out using a Rigaku
D/Max Ultima II diffractometer with Cu Ka radiation
(k = 0.15418 nm). The diffraction data was recorded for 2h an-
gles between 3° and 90°. The morphologies of Pt nanoparticles
supported on CCG and MWCNTs were characterized using
JEOL 2100 field emission gun transmission electron micros-
copy (TEM). X-ray photoelectron spectroscopy (XPS) was per-
formed on a PHI Quantera SXM Scanning X-ray Microprobe
with an Al cathode (hm = 1486.6 eV) as the X-ray source set at
100 W and a pass energy of 26.00 eV. The content of Pt in com-
posite was analyzed by a Q-600 simultaneous thermo-gravi-
metric analyzer (TGA) from room temperature to 1000 °C at
a heating rate of 15 °C/min under air flow.
1125
2.5. Electrochemical measurements
The electrochemical properties of the samples were mea-
sured by cyclic voltammetry in a standard three-electrode cell
using PSGSTAT-30 (Autolab) electrochemical workstation at
room temperature. A glassy carbon electrode (3 mm in diam-
eter) was used as the working electrode, on which 20 lL of a
paste of the catalyst was applied. The paste was a dimethyl-
formamide-nafion (49:1 volume ratio) solution with catalyst’s
concentration approximately 2.5 mg ml1. A Pt wire was used
as the counter electrode and an Ag/AgCl electrode was used
as the reference electrode. Electrochemically active surface
area (ECSA) of Pt nanoparticles was calculated from hydrogen
electrosorption curve, which was recorded between 0.2 and
+1.2 V in 0.5 M H2SO4 solution. To measure methanol electro-
oxidation reaction activity, cyclic voltammetry was per-
formed between 0.2 and +1.0 V in a mixing solution contain-
ing 1 M CH3OH and 0.5 M H2SO4. The scan rate was set at
50 mV s1 and the electrolyte solutions were deaerated with
ultrahigh purity argon prior to any measurements.
3. Results and discussion
Pt/CNTs hybrids have shown excellent properties in some
applications [11–13]; however, the high production cost of
CNTs has placed an obstacle in their applications. Meanwhile,
in order to deposit metal nanoparticles on CNTs surface,
functionalization needs to be done using nitric and sulfuric
acids. Although CNTs have large surface areas, nanotube
bundling and incomplete functionalization makes the acces-
sible areas very limited. Compared to CNTs, CCG nanosheets
can be easily obtained by chemical conversion of inexpensive
graphite oxide. Furthermore, using GO as a starting material
for deposition of metal nanoparticles has several advantages.
Primarily, GO nanosheets have large surface areas and both
sides of nanosheets are accessible. Secondly, the abundance
of functional groups (such as carboxyl, carbonyl, hydroxyl,
and epoxide) on the surfaces and edges of GO nanosheets al-
lows for expedient synthesis of hybrids. Finally, GO can be
easily converted by chemical reduction methods to graphene,
which offers better electrical conductivity.
3.1. Morphologies and size distributions
Morphologies of Pt nanoparticles deposited on CCG nano-
sheets and MWCNTs have been characterized by TEM. Fig. 2
shows the typical TEM images of as-synthesized hybrids. It
is clearly seen in Fig. 2a that all the transparent CCG nano-
sheets are uniformly decorated by the nanosized Pt particles
with very few aggregations, indicating a strong interaction be-
tween graphene support and particles. Furthermore, these
monolayer sheets possess large surface areas, and particles
can be deposited on both sides of these sheets [5,6,29–31].
Additionally, by functioning as a ‘‘spacer’’, these Pt nanoparti-
cles attached onto the graphene surface can prevent the re-
duced GO (as discussed later) from aggregation and
restacking, and both the faces of graphene are accessible in
their applications. Highly dispersed metal nanoparticles on
1126 CARBON 4 8 ( 2 0 1 0 ) 1 1 2 4 –1 1 3 0

Fig. 1 – Scheme shows a formation route to anchor platinum (Pt) nanoparticles onto chemically converted graphene (CCG)
nanosheets. (1) Oxidation of pure graphite powder to graphite oxide. (2) Formation of Pt/CCG hybrids.

Fig. 2 – Transmission electron microscopy (TEM) images of (a) Pt/CCG and (b) Pt/MWCNT hybrids. The insert (c) is high
resolution TEM (HRTEM) image of Pt nanoparticles in Pt/CCG hybrids. The highly crystalline Pt nanoparticles showing fcc
crystal structure are very evident in the Pt/CCG hybrids.

supports with larger surface areas have advantages in cata-
lytic activity and sensor sensitivity [11]. Therefore, Pt/CCG hy-
brids should be a potential material for use in future
nanotechnology. The high resolution image of Pt/CCG hybrid
in Fig. 2c shows the oriented and ordered lattice fringes for
Pt nanoparticles. The d-spacing value of 0.227 nm coincides
with that of fcc Pt (1 1 1).
In Fig. 2b, it can be seen that Pt nanoparticles are also
deposited on MWCNTs, however, their dispersion is not as
uniform as that on CCG surfaces and some Pt nanoparticles
are agglomerated. The mean Pt nanoparticles sizes estimated
from TEM images are 2.75 and 3.5 nm on CCG sheets (shown
in Table 1) and MWNTs, respectively.
3.2. X-ray diffraction
Fig. 3 shows XRD patterns of GO, GO/EG, Pt/CCG and Pt/
MWCNT. In Fig. 3a, the characteristic diffraction peak (0 0 2)
of GO [32] at 2h = 10.6° (corresponding to a d-spacing of
0.749 nm) is ascribed to the introduction of oxygenated
functional groups, such as epoxy, hydroxyl (–OH), carboxyl
(–COOH) and carbonyl (–C@O) groups attached on both sides
and edges of carbon sheets. These surface functional groups
will subsequently act as anchoring sites for metal complexes
[25]. The diffraction peak at around 43° is associated with the
(1 0 0) plane of the hexagonal structure of carbon [33]. It can
be seen in Fig. 3b that the typical diffraction peak (0 0 2) of
 CARBON 4 8 ( 20 1 0 ) 1 1 2 4–11 3 0
Table 1 – Comparison of different parameters between Pt/CCG and Pt/MWCNT hybrids.
Samples Average Pt size (nm)
Pt/CCG 2.75
Pt/MWCNT 3.5
*If/Ib represents ratio of the forward and backward anodic peak currents.
Fig. 3 – XRD patterns: (a) graphite oxide (GO); (b) graphite
oxide after reduction by ethylene glycol (GO/EG); (c) Pt/CCG
and (d) Pt/MWCNT hybrids.
GO shifts to higher angle after reduction by ethylene glycol.
This could be attributed to fact that GO nanosheets are par-
tially reduced to graphene and restacked into an ordered crys-
talline structure.
Fig. 3c and d show X-ray diffractions of Pt/CCG and Pt/
MWCNT, respectively. It is obvious that the position of the
(0 0 2) diffraction peak (d-space 0.34 nm at 26.23°) moves
slightly to higher angle after deposition of Pt nanoparticles
on CCG nanosheets, which indicates that GO is further con-
verted to the crystalline graphene, and the conjugated graph-
ene network (sp2 carbon) has been reestablished due to the
reduction process. Pt nanoparticles are suggested to play a
crucial role in the catalytic reduction of GO when using ethyl-
ene glycol as a reducing agent [5]. The strong diffraction peaks
at 2h = 39.6°, 46.2°, 67.5° and 81.4° can be assigned to the char-
acteristic (1 1 1), (2 0 0), (2 2 0) and (3 1 1) crystalline planes of
Pt, respectively, which possesses face-centered-cubic (fcc)
structure. The diffraction peak for Pt (2 2 0) is used to estimate
the Pt particle size by the Scherrer’s equation: D = 0.89k/(B cos
h) [33]. Here, the wavelength k is equal to 0.15418 nm, and B is
the full width at half-maximum (FWHM). The calculated aver-
age particle size of Pt on CCG sheets and MWCNTs are 2.96
and 3.38 nm, respectively, which are consistent with the
TEM results.
3.3. X-ray photoelectron spectra
XPS was performed on samples containing reduced GO with
and without Pt nanoparticles, which were obtained by chemi-
cal reduction reactions carried out in ethylene glycol–water in
order to understand the individual chemical reduction reac-
1127
ECSA (m2/g) If/Ib
36.27 0.83
33.43 0.72
tions involved. The C1s peak for sp2-hybridized carbon usually
appears near 284.5 eV for pure graphite powder. After oxida-
tion, the intensity of sp2-hybridized C1s peak is significantly re-
duced, and additional peak can be identified as hydroxyl,
epoxide and carboxyl groups, which indicates that graphite is
fully oxidized into GO by introducing these oxygenated func-
tional groups (Fig. 4).
Table 2 summarizes the deconvoluted peak positions and
the areas relative to C1s sp2 peak (expressed as a percentage).
It can be seen that after reducing GO by ethylene glycol with-
out chloroplatinic acid, the carbon–carbon skeleton is rees-
tablished and the intensity of additional peak of oxygenated
functional groups is substantially reduced. On the other hand,
by depositing Pt onto the surfaces of GO nanosheets, the XPS
spectra of Pt/CCG hybrids is much more smooth compared to
original GO and reduced GO by ethylene glycol. The intensity
of some oxygenated functional groups on graphene sheets
after Pt deposition further decreases and carbon–carbon skel-
eton is recovered to a higher extent. Specifically, the hydroxyl
group signal underwent considerable decrease in this hybrids
compared with the starting GO, which could be assumed that
hydroxyl groups act as anchoring sites for Pt nanoparticles.
Meanwhile, the intensity of epoxy and carboxylic groups
was also reduced, which may be because of the reduction
by ethylene glycol and anchoring Pt nanoparticles. It is as-
sumed that Pt nanoparticles play a reductive or catalytic role
during the reduction process [5]. It is well known that graph-
ene can be chemically converted from GO by removing the
surface functional groups using physical or chemical reduc-
Fig. 4 – High-resolution C1s XPS spectra of GO, GO after
reduction by ethylene glycol (GO/EG), Pt/CCG hybrids and
pure graphite powder (PG). Each curve was obtained by 25
scans at high sensitivity. XPS characterization indicates
better restoration of the graphene structure after reduction
by ethylene glycol with chloroplatinic acid than without it.
1128 CARBON 4 8 ( 2 0 1 0 ) 1 1 2 4 –1 1 3 0

Table 2 – XPS data of C1s of GO, GO/EG and Pt/CCG hybrids deconvoluted into four peaks, binding energies and relative area
percentages with respect to C–C bonds in parentheses.

Samples C–C C–OH C–O–C HO–C@O

GO 284.49 (100) 286.40 (175) 287.70 (30) 288.88 (11)

GO/EG 284.48 (100) 286.27 (24) 287.8 (8) 288.93 (3)
Pt/CCG 284.49 (100) 286.12 (8) 287.2 (5) 288.27 (2)

tion [4,34,35]. Usually, chemicals used for reduction of GO are

very toxic, such as hydrazine [21,22,24]. Ethylene glycol is
much less harmful and serves as an alternative for GO reduc-
tion (seen from the data above).

3.4. Electrochemically active surface area

Pt/CNTs hybrids have been widely used in direct methanol

fuel cells [12,13]. It is expected that our as-prepared Pt/CCG
hybrids would present even better performance in this appli-
cation because of their structural advantage. Cyclic voltam-
metry (CV) is a convenient and efficient tool used to
estimate the ECSA of Pt catalyst on an electrode. The ECSA
of an electrocatalyst not only provides important information
regarding the number of electrochemically active sites per
gram of the catalyst, but also is a crucial parameter to com-
pare different electrocatalytic supports. Hydrogen adsorp-
tion/desorption peaks are usually used to evaluate ECSA of
the catalyst. The CV curves for different electrocatalysts,
namely Pt/CCG and Pt/MWCNT, in 0.5 M H2SO4 solution at a
scan rate of 50 mV s1 are shown in Fig. 5a.
It shows characteristic peaks for the formation and reduc-
tion of Pt oxide. In the potential region of 0.2 to 0 V (vs. Ag/
AgCl), typical hydrogen adsorption and desorption peaks
from polycrystalline Pt were observed using CCG nanosheets
and MWCNTs as supporting materials. The integrated area
under the adsorption peak in the CV curves represents the to-
tal charge concerning H+ adsorption, QH, and has been used to
determine ECSA by employing the equation [36]
ECSA ½cm2 =g of Pt
charge ½Q H ; lC=cm2 
¼ :
210 ½lC=cm2   electrode loading ½g of Pt=cm2 

Our calculation indicates that Pt/CCG has higher ECSA va-

lue (36.27 m2/g) than Pt/MWCNT (33.43 m2/g) (Table 1). It is
due to the fact that Pt nanoparticles are smaller and more
uniformly dispersed on the surfaces of CCG sheets, when
compared with MWCNTs. It is well known that smaller cata-
lyst particles show higher catalytic activity. Furthermore, Pt
nanoparticles dispersed on CCG surface will allow for uni-
form dispersion of the graphene nanosheets by reducing
aggregation of the sheets, thereby producing much more
accessible Pt sites for efficient catalytic activity in comparison
with MWCNTs used as catalyst support.
3.5. Methanol electro-oxidation
Cyclic voltammograms (CV) for electro-oxidation of methanol
measured at 0.5 M H2SO4 containing 1 M CH3OH solution are
shown in Fig. 5b. Both CV curves show a similar methanol oxi-
dation current peak in the forward scan and an oxidation peak
in the backward scan corresponding to the removal of the
Fig. 5 – Electrochemical catalytic performances of Pt/CCG
and Pt/MWCNT hybrids. Measurements were performed in
(a) 0.5 M H2SO4 and (b) 0.5 M H2SO4 + 1 M CH3OH solutions
with scan rate of 50 mV s1. The electrochemically active
surface areas measured from (a) for Pt/CCG and Pt/MWCNT
are 36.27 and 33.43 m2/g, respectively. The If/Ib ratios
measured from (b) for Pt/CCG and Pt/MWCNT are 0.83 and
0.72, respectively.
residual carbonaceous species formed in the forward scan. It
shows that the current density of Pt/CCG is higher than that
of the Pt/MWCNT. This indicates that the electrocatalytic
activity of Pt/CCG is obviously higher than that of Pt/MWCNT,
which is consistent with the result of the ECSA. The ratio of
the forward anodic peak current (If) to the backward anodic
peak current (Ib) can be used to evaluate the catalyst tolerance
to the intermediate carbonaceous species accumulated on
electrode surface [37]. The higher If/Ib value indicates higher
 CARBON 4 8 ( 20 1 0 ) 1 1 2 4–11 3 0
tolerance to intermediate carbon species, which means meth-
anol can be oxidized to carbon dioxide much more efficiently.
The ratios for Pt/CCG and Pt/MWCNT are calculated to be 0.83,
0.72, respectively (Table 1), which suggests that Pt/CCG has
less carbonaceous accumulation and hence is much more tol-
erant toward CO poisoning. This indicates that Pt/CCG pos-
sesses a higher catalytic efficiency for methanol oxidation
than Pt/MWCNT. A possible bifunctional effect [38] between
Pt nanoparticles and remaining oxygenated groups is similar
with the commonly accepted bifunctional mechanism of
methanol electro-oxidation between Pt and Ru [39]. Recently,
it has been reported that oxygen-containing groups can im-
prove the electrocatalytic activity of Pt to some extent by play-
ing the role of ruthenium in the case of PtRu catalyst [38,40] to
remove those intermediate carbonaceous species and contrib-
ute to the low poisoning. In the forward scan (Fig. 5b) when the
potential arrives at 0.30 V, methanol molecules adsorb on the
surface of Pt and Pt–CO will form after a dehydrogenation pro-
cess. Meanwhile, oxidation of H2O on CCG defects generates
CCG–OH, and then the adsorption and oxidation will be en-
hanced gradually with the increased potential until the poten-
tial reaches the highest value of 0.65 V. The remaining
functional groups like –COOH and –OH groups in GO nano-
sheets (incomplete reduction in presence of Pt, as shown
above) may be responsible for improved tolerance to CO ob-
served in Pt/CCG hybrids. Thus, by choosing ethylene glycol
as both reductive and dispersing agent, we can not only con-
trol the reduction effectiveness of graphite oxide, but also
modify CCG sheets by Pt nanoparticles, and hence offer en-
hanced performance in methanol electro-oxidation. There-
fore, our simple process for preparation of Pt/CCG hybrids
will have promising applications in the future.
4. Conclusions
In conclusion, we present a facile, economic and environmental
benign strategy to deposit Pt nanoparticles on CCG nanosheets
using an ethylene glycol–water system. We have demonstrated
that GO nanosheets were chemically converted to graphene
during Pt deposition and the concomitant reduction by ethyl-
ene glycol. Moreover, because of the higher ECSA and better tol-
erance towards CO, the Pt/CCG hybrids show much more
enhanced catalytic activity when compared with Pt/MWCNT.
The CCG nanosheet–nanoparticles hybrids could be a promis-
ing system for other heterogeneous catalysts as well.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant No. 20775030). The authors Pulic-
kel M. Ajayan, Lijie Ci and Wei Gao acknowledge support from
Rice University faculty startup funds.
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