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Applied Catalysis B: Environmental 93 (2010) 233240

Contents lists available at ScienceDirect

Applied Catalysis B: Environmental


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

A highly stable catalyst for PEM fuel cell based on durable titanium diboride
support and polymer stabilization
Shibin Yin a, Shichun Mu a,b,*, Haifeng Lv a, Niancai Cheng a, Mu Pan a, Zhengyi Fu a
a
b

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR, UK

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 24 June 2009
Received in revised form 3 September 2009
Accepted 26 September 2009
Available online 11 November 2009

Titanium diboride (TiB2) is an electrically conducting ceramic with good conductivity, excellent thermal
stability and corrosion resistance in acid medium. Here we report for the rst time its application as a
new catalyst support in proton exchange membrane (PEM) fuel cells. This novel catalyst (Pt/TiB2) was
formed by a colloid route, in which the highly dispersed Pt nanoparticles were stabilized by Naon
functional polymers. This signicantly facilitates the dispersion of Pt nanoparticles on TiB2. The
electrochemical stability of TiB2 was investigated and showed almost no changes in redox region after
oxidation during 48 h at 1.20 V. Further, it was found that the electrochemical stability of Pt/TiB2 catalyst
is about four times higher than that of the commercial Pt/C under electrochemical oxidation cycles in the
potential range of 0.61.2 V. The excellent stability of Pt/TiB2 could be attributed to the stability of TiB2
support as well as the introduction of Naon as stabilizer, which enhance both the metalsupport
interaction and the steric hindrance effect of the surface of Pt nanoparticles.
2009 Elsevier B.V. All rights reserved.

Keywords:
Catalyst
Conducting ceramic
Titanium diboride
Stability
Proton exchange membrane fuel cells

1. Introduction
Proton exchange membrane (PEM) fuel cells have drawn a great
deal of attention from the aspects of both fundamental studies and
applications as powerful energy converting devices. However, the
commercialization of PEM fuel cells has been seriously obstructed by
their poor durability [1]. The catalyst degradation is one of the most
important reasons for fuel cell performance deterioration. Commonly, the catalysts used in PEM fuel cells are carbon supported Pt or
Pt-based catalysts. The catalyst degradation is mainly caused by
carbon corrosion, which leads to the agglomeration of Pt nanoparticles under extremely harsh working environments [25].
Carbon can be oxidized in the event of fuel starvation [4] or partial
hydrogen coverage [6], and this process will be even promoted by
the catalysis of Pt [7]. Therefore, highly stable catalyst supports are
urgently desired to enhance catalyst lifetime.
Carbon nanotubes (CNTs) have been employed to improve
catalyst durability. It has been reported that Pt/CNTs catalysts have
a lower electrochemical surface area loss, and a higher oxygen
reduction reaction activity and corrosion resistance in comparison
with Pt/C [810]. Usually, a pre-oxidation of the CNTs surface is
necessary to facilitate the Pt precursor distribution throughout the

* Corresponding author at: State Key Laboratory of Advanced Technology for


Materials Synthesis and Processing, Wuhan University of Technology, Wuhan
430070, China. Tel.: +86 27 87651837; fax: +86 27 87879468.
E-mail addresses: msc@whut.edu.cn, mushichun@gmail.com (S. Mu).
0926-3373/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2009.09.034

inert CNTs surface. However, this pre-oxidation treatment


decreases the surface stability of CNTs [11,12]. In addition, CNTs
readily tend to tangle together, resulting in a non-uniformly
dispersion of CNTs in solutions.
Graphite intercalation compounds (GICs) are also used as PEM
fuel cells catalyst supports due to their unusual properties [13].
According to Shioyama et al. [14], an improved oxygen reduction
activity (ORR) has been obtained in the application of GICs as
catalyst supports, but the relatively large particle size of GICs could
limit the catalyst activity. Meanwhile, the inert surface of GICs
needs to be pre-treated to obtain uniformly dispersed Pt catalysts.
Carbon aerogel can increase the contact area between Pt and
electrolyte because of the high pore size distributions [15], and
accordingly, the catalytic surface area of Pt on carbon aerogel
increased with respect to that on Vulcan XC-72. However, the
chemical stability of the catalyst is considered due to the
amorphous property of carbon aerogel.
Tungsten carbide (WC) has also attracted attention for this
purpose. Meng and Shen [16] have studied the synergistic effect of
WC/C and Pt catalysts on the ORR in alkaline media. Chhina et al. [17]
have investigated the thermal and electrochemical stability of WC
catalyst supports, and found WC was more thermally and
electrochemically stable than carbon supports. However, its stability
in acid electrolyte is not ideal because WC can be corroded in sulfuric
acid, which decreases the catalysts stability [18,19].
Both conducting oxides and semiconductor ceramics have been
investigated as oxidation resistant catalyst supports. Magneli phase
titaniumoxygen (TinO2n1, where n is between 4 and 10) has been

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S. Yin et al. / Applied Catalysis B: Environmental 93 (2010) 233240

attempted for this application. In particular, Ti4O7 exhibits a high


electrical conductivity of 1000 S cm1 at room temperature, which
is considerably higher than the graphitized carbon (conductivity of
727 S cm1) [20]. Chhina et al. [21] have found that indium tin oxide
(ITO) shows better electrochemical and thermodynamic stabilities
than carbon black for Pt/C catalysts. However, most of transition
metal oxides are unstable in acidic environments of PEM fuel cells.
Reeve et al. [22] indeed observed that the oxygen reduction activity
of the oxides declines substantially in acidic solutions. The slow
dissolution of metal components in oxides and their re-deposition
would cause severe cumulative poisoning problems.
Recently, it was also reported that titanium nitride (TiN)
supported Pt for PEM fuel cells showed higher catalytic performance than conventional Pt/C catalysts [23], but the durability of
TiN as the support material is not clear yet. Further studies are
necessary to understand TiN as a catalyst support and especially
evaluate its durability properties.
Compared with all these candidates discussed above for PEM
fuel cells catalyst supports, titanium diboride (TiB2) ceramic
obtains many superior properties, including high melting point,
great hardness, good electrical, high thermal conductivity,
excellent thermal stability and corrosion resistance in acidic
medium [24,25], which makes it a promising solution as a support
material in PEM fuel cells. Surprisingly, it is very hard to nd any
published results on its application in fuel cells. Here, we report our
study of Pt/TiB2 as PEM fuel cells catalysts, and demonstrate that
this novel catalyst has an excellent electrochemical stability.
2. Experimental
2.1. Preparation of stable Pt colloids and Pt/TiB2 catalysts
The preparation mechanism of Pt/TiB2 catalysts is shown in
Fig. 1A, where the highly dispersed Pt nanoparticles can be

supported on TiB2 using a colloidal route indicative of a strong


metalpolymersupport interaction. The mixture of 300.0 ml
ethanol, 300.0 ml deionized water, 360.0 mg H2PtCl66H2O and
5.0 ml 5.0 wt.% peruorosulfonic acid (PSFA) Naon1 (Du Pont Co.)
were used as received, and then vigorously stirred for 10 min at
80 8C in a water bath. The Pt colloid was obtained after the pH value
of the mixture was adjusted to 9.0 by using 2.0 M NaOH solution,
and reuxed for 12 h until the solution turned from light yellow
to dark. TEM image (shown in Fig. 1B) shows a very narrow size
distribution of Pt colloid with the average size of about 1.5 nm.
TiB2 powders were prepared by self-propagating high-temperature synthesis (SHS) [24]. TiB2 particles are uniform, and have
a narrow size distribution within about 1.8 mm (see Fig. 1C). Then
490.0 mg TiB2 was added into 20.0 ml ethanol and ultrasonic
stirring for 10 min. The above prepared Pt colloid was then added
drop-wise. Subsequently, the 18.6 wt.% Pt loaded TiB2 catalysts
were obtained after ltering, washing and drying.
2.2. Physicochemical characterization of Pt/TiB2
Lattice phases of Pt crystals and supports were characterized
using powder X-ray diffraction (XRD) with Cu Ka source
(l = 0.15406 nm, 35 mA). The (1 1 1) peak of the Pt diffraction
patterns was tted to Gaussian line shapes on a linear background.
The average size of Pt nano-particles (D) was calculated according
to the DebyeScherrer formula [26]. Infrared spectra of the
prepared Pt/TiB2 catalyst was carried out to detect the presence of
Naon (as protecting agent of Pt) in Pt/TiB2 catalysts by Fourier
transform infrared spectroscopy (Nicolet MAGNA-IR 560, FTIR,
USA). The reference Naon was prepared by evaporating 5.0 wt.%
Naon liquid. The structure of the as-prepared TiB2 support, Pt
colloid, and Pt/TiB2 was characterized by a scanning electron
microscopy (SEM, JSM-5610LV) and a high-resolution transmission electron microscopy (HRTEM, JEM-2010FEF). The presence of

Fig. 1. Schematic of the Pt colloid particles and the Pt/TiB2 catalysts with peruorosulfonic acid Naon as a stabilizer of Pt particles (A); TEM image of the Pt colloid particles (B)
and SEM micrograph of TiB2 powders (C).

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Naon for Pt/TiB2 catalysts was evaluated by the energy dispersive


X-ray spectrometry (EDX) attached to HRTEM combined with FTIR
analysis.
Thermogravimetric analysis (TGA7, PerkinElmer, Norwalk, CT,
USA) was used to characterize the thermal stability of the Pt/TiB2
catalyst in comparison with the commercially available Pt/C
catalyst (20 wt.% Pt on Vulcan XC-72, JM) under air owing at
10 ml min1. The temperature ranged from room temperature to
1000 8C at a heating rate of 5 8C min1.

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measured is referred to the reversible hydrogen electrode (RHE)


without specication. Ultra-pure N2 was passed through H2SO4
solution for 30 min prior to electrochemical experiments. In the
chronoamperometric, a constant potential of 1.20 V in 150 ml
solution was applied for electrochemical oxidation. The ADT was
conducted by cyclic voltammograms (CVs) between 0.6 and 1.20 V.
All the CV curves were recorded from 0 to 1.20 V at a scan rate of
20 mV s1 before and after chronoamperometric and ADT [28]. The
electrochemical surface area (ESA) of catalysts was calculated with
the charge of hydrogen desorption region as follows:

2.3. Electrochemical characterization of Pt/TiB2


The electrochemical accelerated durability test (ADT) was
employed to evaluate the long-term performance of catalyst. The
ADT is an inexpensive and time-effective method for screening
catalysts in terms of stability and performance [27].
A glass carbon (GC) electrode was prepared before ADT. The
supported catalysts (or supports) were added to 500.0 ml
deionized water with 21.0 ml 5.0 wt.% Naon solution, and then
dispersed onto the at surface of a polished GC disk electrode
( = 4.0 mm) using Finnpipette Digital Micropipette (Thermo
electron corp.) with a catalyst loading 0.4 mg cm2. The solvent
on the surface of the electrode was removed by infrared
irradiation.
The prepared GC electrode was tested electrochemically in
0.5 M H2SO4 solution at 25 8C. The scan rate was controlled to
20 mV s1 using a computer-controlled Autolab PGSTAT 30
potentiostat (Eco Chemie B.V., Holand). Platinum electrode was
used as the counter electrode, and Hg/Hg2SO4 electrode as the
reference electrode. It should be noted that all the potential

EAS

QH
Pt  0:21

(1)

where QH is the charge for hydrogen desorption (mC cm2), 0.21 is


the charge required to oxidize a monolayer of H2 on bright Pt, and
[Pt] the Pt loading (mg cm2) on the electrode [29].
In addition, the oxygen reduction reaction (ORR) performance
of the as-prepared catalysts was evaluated by rotating disk
electrode (RDE) technique in 0.5 M H2SO4 electrolyte at a sweep
rate of 10 mV s1 and a speed of 1600 rpm at room temperature.
3. Results and discussion
3.1. Physicochemcial properties of Pt/TiB2
As shown in Fig. 2A, the (1 0 2) peak of TiB2 overlaps with
Pt(2 2 0), and the (1 0 1) peak of TiB2 is very close to Pt(2 0 0).
Therefore, only the peak of Pt(1 1 1) can be used to calculate the
average particle size of Pt nano-crystals using DebyeScherrer

Fig. 2. XRD pattern of (a) as prepared TiB2 powders and (b) the prepared Pt/TiB2 (A); FTIR spectra of the prepared Pt/TiB2 with the peruorosulfonic acid Naon as the
5O asymmetric stretching (SO2OH
protecting agent of Pt nano-particles and the reference peruorosulfonic acid Naon (B), the bands at b1, b2, b3, b4 and b5 are assigned to S5
group), CF2 asymmetric stretching, CF2 symmetric stretching, SO symmetric stretching (SO3 ion) and COC symmetric stretching of Naon respectively; TGA data of Pt/
TiB2 and commercial 20 wt.% Pt/C (C): (a) TG of Pt/C, (b) DSC of Pt/C, (c) TG of Pt/TiB2 and (d) DSC of Pt/TiB2.

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Fig. 3. CV curves of TiB2 (A) and carbon supports (Vulcan XC-72) (B) by held at1.20 V (versus RHE) for different durations (0.5 M H2SO4, scan rate: 20 mV s1, temperature:
25 8C).

formula [26]. The average size of Pt nano-crystals is 3.4 nm, which


is comparable to that of the commercial Pt/C [21].
FTIR spectra of the Naon and Pt/TiB2 catalysts are given in
Fig. 2B. For the Pt/TiB2 catalyst, the strong characteristic band at
1279 cm1 can be assigned to CF2 stretching vibration corresponding to the bands at 1234 cm1 in Naon. The other relatively weak
band at 991 cm1 is associated with the COC symmetric
stretching vibration related to the band at 983 cm-1 in Naon.
These results verify the presence of Naon in the as-prepared
Pt/TiB2 catalysts.
As shown in Fig. 2C, the weight loss of Pt/C catalysts begins at
low temperature (120 8C) due to the evaporation of moisture.

When temperature rises to about 200 8C, the carbon support is


oxidized and a peak at 397.2 8C appears. A minor-peak occurs as
the temperature further ramps to 450 8C, which could be
attributed to the oxidization of the relatively stable carbon. The
loss of Pt/TiB2 is only 2.18% up to 500 8C, in contrast to 80.41% loss
for Pt/C. The low loss can be mainly attributed to the oxidation of
Naon in Pt/TiB2. TiB2 starts to be oxidized as the temperature
increases to 532.2 8C accompanying a weak exothermic peak. A
maximum exothermic peak appears at 685.8 8C, which could be
attributed to the partial evaporation of B2O3. When the temperature further ramps to 1000 8C, Pt/C loses 82.49% of its total weight,
but Pt/TiB2 increases to 62.70% of total weight due to the partial

Fig. 4. CV curves of Pt/TiB2 (A) and the commercial 20 wt.% Pt/C (B) by accelerated durability tests (0.5 M H2SO4, scan rate: 20 mV s1, temperature: 25 8C); oxygen reduction
reaction on the as-prepared Pt/TiB2 and the commercial 20 wt.% Pt/C (C). Changes of electrochemical surface area (ESA) of catalysts related to Pt catalytic surface area with the
increased potential cycles (D).

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oxidation of TiB2. These results clearly indicate that Pt/TiB2 has a


higher thermal stability than the commercial Pt/C because of the
high thermal stability of TiB2.
3.2. Electrochemical performance of TiB2 and Pt/TiB2
As seen from Fig. 3A, TiB2 ceramic has almost no change in
redox region after oxidation treatment for different durations,
which implies that almost no oxide was produced on TiB2 surface
during 48 h hold at 1.20 V. In contrast, a visible current peak occurs
in the redox region for XC-72 carbon black (Fig. 3B), which results
from the surface oxide formation due to the hydroquinone-

237

quinone (HQ-Q) redox couple on the carbon black surface [28]. The
current peak at about 0.60 V in XC-72 electrode indicates a higher
oxidation degree of carbon with potential-holding time. These
results suggest that TiB2 is more resistant to electrochemical
oxidation than carbon black. Meanwhile, the concentration of Ti
ion in solution was ca. 0.07 mg ml1 at 1.20 V for 48 h identied by
inductively coupled plasma atomic emission spectrometry (ICPAES, PE). And the corrosion rate of Ti in TiB2 is only ca. 0.2 mg h1.
The initial and nal CVs of Pt/TiB2 during the ADT are shown in
Fig. 4. The initial ESA of Pt/TiB2 is 34.7 m2 g1, which is lower than
that of Pt/C (61.4 m2 g1) as shown in Fig. 4A and B. This ESA
decrease can be attributed to the large particle size and density of

Fig. 5. TEM images of the as-prepared Pt/TiB2 before accelerated durability tests (ADT) (A) and EDX patterns of the Pt/TiB2 for the selected spot as shown in (A) before ADT (B);
after 6000 potential cycles (C); EDX patterns of the Pt/TiB2 for a selected spot as shown in (C) after ADT (D); particle size distribution of Pt before and after ADT (E).

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TiB2 compared with that of carbon support and also the possibility
of the surface of Pt is partially occupied by Naon. However, an
improvement of ORR activity of Pt/TiB2 is observed in terms of
onset potential. The Pt/TiB2 shows a higher reduced current of
0.29 mA cm2 at 0.9 V as compared to Pt/C (0.11 mA cm2 at
0.9 V) with the same Pt loading (see in Fig. 4C). Similar to TiB2
supports, Avasarala et al. [23] have demonstrated that TiNsupported Pt catalysts have an excellent activity of oxygen
reduction in comparison with carbon-supported catalyst. This
further validates that the improved activity of Pt can be attributed
to the inuence of support materials [30,31]. That is, the
conductive ceramics, as the supports of Pt catalysts, are helpful
to enhance the electrocatalytic activity of Pt catalysts. In addition,
our experimental results indicate a negligible effect of Naon
layers of the outer Pt surfaces on the catalytic activity of the
supported particles. In fact, Tian [32] and our previous studies [33]
have shown that SO3 end groups in the polyelectrolyte chain
structure of Naon can facilitate the reaction species transfer
process for ORR.
Fig. 4D shows the ESA loss of Pt versus the electrochemical
oxidation cycle number. The ESA of Pt/C decreases rapidly with the
cycle numbers increment. However, there is no obvious ESA loss in
the rst 600 cycles for Pt/TiB2, and only a slow decrease in the further
cycles. The ESA loss rate of the Pt/C reaches 1.56  102 m2 g1
cycle1, whereas the Pt/TiB2 has only 4.08  103 m2 g1 cycle1,
which is 3.8 times lower than the Pt/C. This indicates Pt/TiB2 has

approximately four times longer lifetime than Pt/C under the


condition of an electrochemical acceleration.
Fig. 5A shows Pt particles are highly dispersed on the TiB2
before ADT. It is surprising that after 6000 potential cycles there
are still large number of Pt particles remaining on the surface of
TiB2 (see Fig. 5B) with the increase in Pt particle size. The
occurrence of elements F and S shown in Fig. 5C indicates the
existence of Naon polymer as a stabilizer on the Pt particles. The
strong peak of Ti in the substrate (TiB2) compared to that of Pt can
be observed before ADT. After ADT, the relative intensity of Ti is
weakened as compared to that of Pt (Fig. 5D), which indicates that
a rather slow corrosion of TiB2 supports as mentioned previously
occurs during ADT despite the fact that the TiB2 supports show a
higher electrochemical stability than carbon black. In addition, the
average particle size of Pt particles increases from 3.2 to 5.7 nm,
Fig. 5E. Thus, the agglomerated Pt particles may partially prevent
the electron beam from penetrating the Pt metals and possibly
weaken the intensity of Ti.
After 5100 potential cycles, Pt particles agglomerate on carbon
supports into larger ones, leading to a massive decrease of Pt
particles and leaving behind more bare carbon surfaces as shown
in Fig. 6A and B. The average particle size before and after ADT is
about 2.9 and 6.5 nm respectively (see Fig. 6C). The Pt particles
in Pt/C display a faster agglomeration rate compared to the case
of Pt/TiB2. This further demonstrate that Pt/TiB2 has a higher
electrochemical stability than Pt/C catalysts.

Fig. 6. TEM images of the commercial 20 wt.% Pt/C catalyst before ADT (A) and after 5100 potential cycles (B); particle size distribution of Pt before and after ADT (C).

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239

Fig. 7. Schematic of the migration model of Pt particles movement on support surfaces. Pt colloid particles migration driven by an electric eld force (A) and Pt particles
migration companying with Naon polymer oxidization (B).

3.3. Stable mechanism of Pt/TiB2


It has been reported that smaller particle size leads to easier
agglomeration of particles due to higher specic surface energy
[3436]. The Pt particle size in both commercial Pt/C and Pt/TiB2
catalysts is in the range of 25 nm, which endows Pt particles with
a strong tendency to agglomeration, and leads to ESA loss. On the
other hand, it is well known that carbon support can be corroded
during a long-term operation [37,38] and this corrosion can be
promoted especially in the presence of Pt [2,39]. This weakens the
interaction between carbon and Pt particles, and then Pt particles
would collapse into the carbon-decient XC-72 support thus
accelerating the agglomeration of Pt particles. Meanwhile, the
decrease of Pt particle number could be also attributed to the
Ostwald ripening [40]. In contrast, the TiB2 supports have very high
electrochemical and thermal stabilities with respect to carbon
supports, which endow Pt particles on TiB2 supports with a higher
stability and less reduction than that on carbon supports.
The migration of Pt particles on support is regarded to be very
dependant on the Ptsupport interaction as well as the steric
effects of Pt particles. It has been reported that Naon molecules
can be self-assembled onto inorganic nanoparticles through
electrostatic interaction, preventing further growth of inorganic
nanoparticles [41]. In our previous studies, we have reported a
novel approach to signicantly increase lifetime of Pt/C catalysts
through Naon stabilization and given rise to three times higher
durability than conventional Pt/C that commonly used in PEM fuel
cell [33]. Therefore, the Pt particles stabilized with Naon in Pt/

TiB2 with both electron rich SO3 groups in Naon and highly
electron decient surface of TiB2 can offer a strong adhesion to
Naon modied Pt and support surface, which may increases the
interaction between Pt particles and conductive supports. Therefore, the Pt particles can be anchored tightly on the TiB2 surface. At
the same time, the electrostatic repulsion between self-assembled
Naon layer on different Pt surfaces may supply more strong steric
hindrance than that of pure Pt particles that probably enhances the
resistance to Pt particle migration.
Fig. 7 shows two simple migration models of Pt particles
stabilized with Nation on support surfaces. We propose that Pt
particles are mainly driven by a changeable electric eld force (f1)
during electrochemical acceleration tests, and Pt particles only
moves when the electric eld force (f1) applied to the particles is
greater than the friction resistance (f2) of Pt particles. Pt colloid
particles should have a high resistance to migration because of the
strong Ptsupports interaction. Therefore, the gathering of
particles is relatively difcult. When f1 is sufcient magnitude
as compared to f2, as shown in Fig. 7A, the migration and gathering
of Pt colloid particles take place, but the aggregation is possibly
hindered by Naon polymer layer distributed on Pt surfaces, and
can occur when Naon is decomposed by a long-term electrochemical oxidation. When the electric eld force (f1) is not
sufcient magnitude, as shown in Fig. 7B, the migration of Pt
colloid particles will not take place. However, Naon can be
decomposed with the time, leading to the decrease of resistance to
particle migration. Once the critical force to drive particles is
achieved, the Pt particles may move onto the support surface and

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gather each other. In this case, Pt particles may aggregate due to


the absence of the protection role from the integrated Naon
polymers.
In fact, we have observed no signicant change for the catalytic
surface area in the rst 600 cycles for Pt/TiB2 followed by a slow
electrochemical surface area loss after 600 cycles. This phenomenon may be well explained by the Pt particle migration model
with Naon polymer layer oxidization (see Fig. 7B). In the rst 600
cycles, Pt particles are xed on the support surfaces. With the
electrochemical oxidation cycle increment, the oxidation of Naon
occurs, resulting in the decline of both the metal-support
interaction and the steric effect of the surface of Pt particles. As
a result, after 600 cycles, the critical force to drive particles
migration is obtained, which promotes the migration and
agglomeration of Pt particles.
4. Conclusions
Pt/TiB2 catalysts as a potential stable catalyst for PEM fuel cells
have been obtained and evaluated. The Pt/TiB2 prepared by Naonstabilized Pt particles shows an improved oxygen reduction
reaction activity and remarkably high electrochemical stability.
The stability of Pt/TiB2 is approximately 4 times better than that of
the commercial Pt/C, endowing this novel catalyst with an
excellent stability resulting from the TiB2 supports and also
possibly from polymer stabilization effect. It should be noted that
TiB2 powders used in the present investigation is of relatively big
particle size and heavy density that will reduce the Pt utilization
efciency. In this sense, there is still much room to improve Pt/TiB2
activity. Given its desirable activity and excellent stability Pt/TiB2
exhibits very good potential as a stable catalyst for PEM fuel cells.
Acknowledgments
This work was supported by the New Century Excellent Talent
Program of Ministry of Education of China (No. NCET-07-0652), the
National Natural Science Foundation of China (NSFC) (No.
50632050), and the Ministry of Education of China (No. PCSIRT0644).
We would like to thank Prof. P.P. Edward F.R.S., Prof. S.C.E. Tsang, Dr.
M.O. Jones and Dr. A. Sartbaeva in the Inorganic Chemistry
Laboratory, University of Oxford, for their helpful discussion.
References
[1] J.R. Yu, T. Matsuura, Y. Yoshikawa, M.N. Islam, M. Hori, Electrochem. Solid-State
Lett. 8 (2005) A156A158.

[2] Y.Y. Shao, G.P. Yin, Y.Z. Gao, P.F. Shi, J. Electrochem. Soc. 153 (2006) A1093A1097.
[3] L.M. Roen, C.H. Paik, T.D. Jarvic, Electrochem. Solid-State Lett. 7 (2004) A19A22.
[4] S.D. Knights, K.M. Colbow, J. St-Pierre, D.P. Wilkinson, J. Power Sources 127 (2004)
127134.
[5] H.A. Gasteiger, S.S. Kocha, B. Sompalli, F.T. Wagner, Appl. Catal. B 56 (2005) 935.
[6] C.A. Reiser, L. Bregoli, T.W. Patterson, J.S. Yi, J.D. Yang, M.L. Perry, T.D. Jarvi,
Electrochem. Solid-State Lett. 8 (2005) A273A276.
[7] M.H. Shao, P. Liu, R.R. Adzic, J. Am. Chem. Soc. 128 (2006) 74087409.
[8] C. Kim, Y.J. Kim, Y.A. Kim, T. Yanagisawa, K.C. Park, M. Endo, M.S. Dresselhaus, J.
Appl. Phys. 96 (2004) 59035905.
[9] K.P. Gong, F. Du, Z.H. Xia, M. Durstock, L.M. Dai, Science 323 (2009) 760764.
[10] X. Wang, W.Z. Li, Z.W. Chen, M. Waje, Y.S. Yan, J. Power Sources 158 (2006) 154
159.
[11] V. Georgkilas, K. Kordatos, M. Prato, D.M. Guldi, M. Holzinger, A. Hirsch, J. Am.
Chem. Soc. 124 (2002) 760761.
[12] S.C. Mu, H.L. Tang, S.H. Qian, M. Pan, R.Z. Yuan, Carbon 44 (2006) 762767.
[13] R. Setton, Adv. Mater. 1 (1989) 348349.
[14] H. Shioyama, Y. Yamada, A. Ueda, T. Kobayashi, Carbon 43 (2005) 23742378.
[15] A. Smirnova, X. Dong, H. Hara, A. Vasiliev, N. Sammes, Int. J. Hydrogen Energy 30
(2005) 149158.
[16] H. Meng, K.P. Shen, Chem. Commun. 35 (2005) 44084410.
[17] H. Chhina, S. Campbel, O. Kesler, J. Power Sources 164 (2007) 431440.
[18] H. Scholl, B. Hofman, A. Rauscher, Electrochim. Acta 37 (1992) 447452.
[19] H. Scholl, B. Hofman, J. Kupis, K. Polaski, Electrochim. Acta 39 (1994) 115117.
[20] T. Ioroi, Z. Siroma, N. Fujiwara, S. Yamazaki, K. Yasuda, Electrochem. Commun. 7
(2005) 183188.
[21] H. Chhina, S. Campbell, O. Kesler, J. Power Sources 161 (2006) 893900.
[22] R.W. Reeve, P.A. Christensen, A.J. Dickinson, A. Hamnett, K. Scott, Electrochim.
Acta 45 (2000) 42374250.
[23] B. Avasarala, T. Murray, W.Z. Li, P. Haldar, J. Mater. Chem. 19 (2009) 18031805.
[24] J.Y. Zhang, Z.Y. Fu, W.M. Wang, J. Mater. Sci. Technol. 21 (2005) 841844.
[25] B. Basu, G.B. Raju, A.K. Suri, Int. Mater. Rev. 51 (2006) 352374.
[26] V. Radmilovic, H.A. Gasteiger, P.N. Ross, J. Catal. 154 (1995) 98106.
[27] H.R. Colon-Mercado, H.S. Kim, B.N. Popov, Electrochem. Commun. 6 (2004) 795
799.
[28] J.J. Wang, G.P. Yin, Y.Y. Shao, S. Zhang, Z.B. Wang, Y.Z. Gao, J. Power Sources 171
(2007) 331339.
[29] F. Maillard, M. Martin, F. Gloaguen, J.M. Leger, Electrochim. Acta 47 (2002) 3431
3440.
[30] J. Nicole, D. Tsiplakides, C. Pliangos, X.E. Verykios, C. Comninellis, C.G. Vayenas, J.
Catal. 204 (2001) 2334.
[31] Y.H. Zhang, M.L. Toebes, A. van der Eerden, W.E. OGrady, K.P. de Jong, D.C.
Koningsberger, J. Phys. Chem. B108 (2004) 1850918519.
[32] Z.Q. Tian, S.P. Jiang, Z.C. Liu, L. Li, Electrochem. Commun. 9 (2007) 16131618.
[33] N.C. Cheng, S.C. Mu, M. Pan, P.P. Edwards, Electrochem. Commun. 11 (2009)
16101614.
[34] J. Xie, D.L. Wood, K.L. More, P. Atanassov, R.L. Borup, J. Electrochem. Soc. 152
(2005) A1011A1020.
[35] E. Guilminot, A. Corcella, F. Charlot, F. Maillard, M. Chatenet, J. Electrochem. Soc.
154 (2007) B96B105.
[36] G.X. Wang, L. Yang, J.Z. Wang, H.K. Liu, S.X. Dou, J. Nanosci. Nanotechnol. 5 (2005)
11351140.
[37] R.L. Bourp, J.R. Davey, F.H. Garzon, D.L. Wood, M.A. Inbody, J. Power Sources 163
(2006) 7681.
[38] S.C. Ball, S.L. Hudson, D. Thompsett, B. Theobald, J. Power Sources 171 (2007) 18
25.
[39] L.M. Roen, C.T. Paik, D.H. Jarvi, Electrochem. Solid State Lett. 7 (2004) A19A22.
[40] A.V. Virkar, Y.K. Zhou, J. Electrochem. Soc. 154 (2007) B540B547.
[41] J.J. Pan, H.L. Zhang, M. Pan, J. Colloid Interface SCI 326 (2008) 5560.