Solid State Ionics 180 (2009) 746–763

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Solid State Ionics

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s s i

Ceramic materials as supports for low-temperature fuel cell catalysts

E. Antolini a,b,⁎, E.R. Gonzalez b
a
Scuola di Scienza dei Materiali, Via 25 aprile 22, 16016 Cogoleto, Genova, Italy
b
Instituto de Química de São Carlos, USP, C. P. 780, São Carlos, SP 13560-970, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The performance and durability of low-temperature fuel cells seriously depend on catalyst support materials.
Received 26 November 2008 Catalysts supported on high surface area carbons are widely used in low temperature fuel cells. However, the
Received in revised form 4 March 2009 corrosion of carbonaceous catalyst-support materials such as carbon black has been recognized as one of the
Accepted 11 March 2009
causes of performance degradation of low-temperature fuel cells, in particular under repeated start-stop
cycles or high-potential conditions. To improve the stability of the carbon support, materials with a higher
Keywords:
Nanocomposites
graphitic character such as carbon nanotubes and carbon nanofibers have been tested in fuel cell conditions.
Transition metal oxides These nanostructured carbons show a several-fold lower intrinsic corrosion rate, however, do not prevent
Electrocatalyst carbon oxidation, but rather simply decrease the rate. Due their high stability in fuel cell environment,
Fuel cells ceramic materials (oxides and carbides) have been investigated as carbon-substitute supports for fuel cell
catalysts. Moreover, the higher specific electrocatalytic activity of some ceramic supported metals than
unsupported and carbon supported ones, suggests the possibility of a synergistic effect by supporting metal
catalyst on ceramic supports. This paper presents an overview of ceramic materials tested as a support for
fuel cell catalysts, with particular attention addressed to the electrochemical activity and stability of the
supported catalysts.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction nanosized electrocatalyst particles in low temperature fuel cells

Fuel cell technology offers an attractive combination of highly
efficient fuel utilisation and environmentally-friendly operations [1].
Fuel flexibility is an important characteristic of the fuel cells: the ideal
fuel for optimum fuel cell operation is hydrogen, although various
materials, such as low molecular weight alcohols, that can undergo an
oxidation reaction, can be used as fuels for a fuel cell system [2]. In
order to obtain sufficient electrical output from a fuel cell, the
electrochemical reaction must occur at a sufficient rate. In low
temperature fuel cells (such as polymer electrolyte membrane fuel
cells (PEMFCs) and phosphoric acid fuel cells (PAFCs), operating at
temperature b200 °C), this is achieved using platinum-based catalysts
[3]. It has to be promptly pointed out, however, that the acid
environment in the PEMFCs is different from that of PAFCs. The
PEMFCs operate at less than 100 °C, as compared with the PAFCs,
which operate at twice this temperature. Furthermore, the anions of
the perfluorinated sulfonic acid polymer are only weakly adsorbed on
Pt, in contrast to the phosphoric anions, which are strongly adsorbed.
The importance of the metal support in fuel cell catalysis is well
recognized. Typically, the support provides a physical surface for
dispersion of small metal particles, which is necessary for achieving
high surface area. Carbon is a common choice for supporting
⁎ Corresponding author. Scuola di Scienza dei Materiali, Via 25 aprile 22, 16016
Cogoleto, Genova, Italy.
E-mail address: ermantol@libero.it (E. Antolini).
because of its large surface area, high electrical conductivity, and
pore structures [4]. However, porous electrically conductive carbon
blacks do not always exhibit adequate resistance to corrosion caused
by electrochemical oxidation in the fuel cell. The problem of the
electrode stability, particularly of cathode stability, is well known.
Universally, oxygen reduction is a slow reaction, and good catalysts
have been very difficult to find. As reported by Couper et al. [5], the
problems of finding a good electrocatalyst (and a stable, inert
substrate) are compounded by the instability of most materials to
corrosion close to the reversible potential for the O2/H2O couple.
Corrosion can be accelerated by the presence of trace hydrogen
peroxide, and the lifetimes of potential candidate catalysts can be
reduced by poisoning and sintering. Substrate corrosion is as difficult
to avoid as dissolution of the catalyst. Catalyst support corrosion has
been predominantly observed in phosphoric acid fuel cells. Indeed,
thermodynamically, carbon as a material is unstable at the cathode
potential in hot phosphoric acid present in PAFCs. Carbon is lost from
the system through oxidation leading to significant losses of carbon
over a short period of time. The stability of carbon support affects the
loss of platinum surface area following both platinum particle
sintering and platinum release from the carbon support [6–8].
Kangasniemi et al. [9] reported that the surface of carbon Vulcan
XC-72 is oxidized under conditions simulating the cathode environ-
ment of a PEMFC (0.8-1.2 V vs. RHE in 1 M H2SO4 at 65 °C). During
single PEMFC durability testing, Borup et al. [10] found that carbon
corrosion of the cathode catalyst layer increases with increasing

0167-2738/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2009.03.007
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
potential and decreasing humidity. Wang et al. [11] investigated the
durability of Pt/C catalysts with different carbon black supports under
simulated PEMFC conditions. They found that carbon support with
high surface area in PEMFC electrode is susceptible to corrosive
conditions. If the support is oxidized to CO2/CO, Pt may be lost from
the support, so the more the carbon support is oxidized, the more Pt is
lost. If the support is partially oxidized to surface oxide, it may
accelerate the increase of Pt particle size, because the presence of
surface oxides may weaken the platinum–support interaction, leading
to a lower resistance to surface migration of Pt particles. Accordingly,
corrosion of the cathode catalyst support may affect the durability of
the PEMFC. On the other hand, the anode catalyst could also be
exposed to much more oxidative conditions than the cathode during
the cell voltage reversal caused by fuel starvation [12]. Summarizing,
high-surface-area carbon supports in PAFC and PEMFC electrodes are
susceptible to corrosive conditions, which include high water content,
low pH, high temperature, high potential, and high oxygen concen-
tration. In addition, Pt catalysts seem to accelerate the rate of carbon
corrosion [13]. Two different reaction pathways for carbon oxidation
have been distinguished, reversible oxidation to oxygenated surface
carbon species and irreversible oxidation to CO2. If the carbon is partly
oxidized to oxygenated surface carbon species, the conductivity at the
contact between the carbon support and the catalyst nanoparticles
may decrease. If the carbon is oxidized to CO2, catalyst nanoparticles
may be lost from the support, resulting in a significant decrease of the
catalyst active surface area, which in turn reduces the performance
and operation lifetime of the PEMFC. Typically, CO2 formation is
generalized as given by the following equation [14]:
C + 2H2 O Y CO2 + 4H
+ −
+ 4e :
The standard potential for the electrochemical oxidation of carbon
to carbon dioxide is 0.207 V vs. RHE at 25 °C [15]. Therefore, under
typical PEMFC cathode operation conditions, carbon corrosion is not
only thermodynamically feasible due to the high potentials (0.6–
1.2 V) and high O2 concentrations, but also kinetically enhanced by the
elevated temperatures (50–90 °C).
Therefore, various alternatives of electrocatalyst supports are
being searched. Due their high surface area and high amount of
mesopores, which allow high metal dispersion and good reactant flux,
ordered mesoporous carbons and carbon gels have been receiving
attention as fuel cell catalyst supports. Catalysts supported on these
carbons showed higher catalytic activity than the same catalysts
supported on carbon black. Their thermal stability, however, is almost
the same to that of carbon blacks [4]. In view of their high thermal
stability, boron-doped diamonds (BDDs) have been tested as catalyst
supports. The results indicated that the anchoring of metal atoms on
BDD surface in a stable way has to be improved. The use of Nafion as
the binder seems to enhance the stability of BDD supported catalysts
[4]. Recently, nanostructured carbon materials with graphitic struc-
ture, such as carbon nanotubes (CNTs) and carbon nanofibers (CNFs)
were investigated as catalyst supports in fuel cells [4]. The higher
catalytic activity of Pt and Pt–M catalysts supported on CNTs and CNFs
than that of the same catalysts supported on carbon blacks was
ascribed to their unique structure and properties such as high surface
area, good electronic conductivity and chemical stability [4]. Tests
carried out in PEM fuel cell conditions indicated that these materials
can be more durable and can outlast the lifetime of conventional
Vulcan XC-72 [16–18]. By comparing carbon nanotubes and mesopor-
ous carbons, taking into account of the cost of the materials, the
complexity of the synthesis methods, and the versatility in pore size
and pore distribution tailoring, the mesoporous carbons seem to have
more changes to substitute carbon blacks as fuel cell catalyst
substrates. The stability in fuel cell conditions of mesoporous carbons
is lower than that of CNTs, but can be increased by graphitization [4].
747
However, these alternative materials do not prevent carbon
oxidation, but rather simply decrease the rate. For this reason non-
carbon materials have been investigated as catalyst support. Con-
ducting oxides are emerging candidates for oxidation resistant
catalyst supports. In addition to their high stability in fuel cell
environment, unlike carbon, which does not help electrocatalytic
activities, but serves only as a mechanical support, many metal oxide
supports can act as co-catalysts. Indeed, it is well known that metal
oxides such as RuO2, SnO2 and WO3 enhance the catalytic activity of
platinum for methanol and ethanol oxidation [19–24].
The main requirements of a suitable fuel cell catalyst support are
the following:
• high surface area, to obtain high metal dispersion;
• suitable porosity, to boost gas flow;
• high electrical conductivity;
• high stability under fuel cell conditions.
It has to be remarked that, frequently, in the literature the
difference between catalyst-metal oxide dispersion and metal oxide
supported catalyst is not adequately taken into account. In the former
case the metal oxide only acts as a cocatalyst, not as a support, and the
size of metal and metal oxide particles are not correlated, while in the
latter metal particle size depends on, and is considerably lower than
the metal oxide particle size.
This paper presents an overview of some metal oxides and
carbides, which could substitute carbon as fuel cell catalyst support.
Particular attention has been addressed to the electrochemical activity
and stability of the supported catalysts.
2. Inorganic metal oxides
ð1Þ
Inorganic metal oxides have been studied to determine whether
they can serve as good corrosion-resistant supports. Unfortunately,
replacing carbon with traditional metal-oxides is difficult, due to their
electrical-insulating properties at temperatures below 200 °C. How-
ever, sub-stoichiometric metal oxides, such as reduced oxidation state
titania (e.g., Ti4O7 and Ebonex), doped metal oxides, such as doped
TiO2 and SnO2, and nanostructured metal oxides, such as TiO2
nanotubes and WO3 nanorods, have been proposed as electrically
conductive support materials with high corrosion-resistant properties.
2.1. Ti-based oxides
Among the inorganic metal oxides, titanium dioxide, TiO2, is used
in many applications that depend on its photoelectrochemical and
catalytic properties and its excellent resistance to corrosion in various
electrolytic media [25,26]. Titania exists in three main crystallographic
forms e.g., anatase, rutile, and brookite. Each structure exhibits
different physical properties, which lead to their different applica-
tions. It is generally accepted that anatase titania is more efficient as
photocatalyst than rutile titania. Regarding the application in fuel
cells, Gustavsson et al [27] investigated thin film of Pt and
stoichiometric TiO2 in a polymer electrolyte electrochemical cell.
Individual thin films of Pt and TiO2 were deposited directly on Nafion
membranes by thermal evaporation. Oxygen reduction reaction
polarization plots showed that the presence of a thin TiO2 layer
between the platinum and the Nafion increases the performance
compared to a Pt film deposited directly on Nafion. They attributed
this improvement to a better dispersion of Pt on TiO2 compared to on
Nafion and in addition, substantial proton conduction through the
thin TiO2 layer.
Stoichiometric rutile is an insulator with a band gap of 3.06 eV at
room temperature. Bulk transport measurements show that for very
slightly nonstoichiometric TiO2, with a carrier concentration in the
range below 2.0 1020 cm − 3, the low-temperature activation energy
for conduction is about 0.028 eV [26]. n-type dopants for TiO2, as
748 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
vanadium, niobium, and tantalum, can be substitutionally incorpo-
rated within the rutile lattice to occupy at least 50% of the cation sites.
Nb doping gives rise to shallow donor states 0.02–0.03 eV below the
conduction-band minimum and therefore at essentially the same
energy as the donor states introduced by oxygen deficiency [28]. On
the basis of their high chemical stability, various electrically
conductive forms of the titanium–oxygen system have been tested
as a fuel cell catalyst support. Their preparation method and physical
characteristics as well as the catalytic activity and stability in fuel cell
conditions of related supported catalysts are reported in the following
sections.
2.1.1. The homologous series TinO2n−1, 4 ≤ n ≤ 10
The titanium–oxygen system contains a sub-stoichiometric com-
position of the general formula TinO2n−1 (Magneli phases), where n is
a number between 4 and 10 [29]. The phases consist of two-
dimensional slabs of the TiO2 rutile structure with a thickness of n-
layers of Ti atoms separated by oxygen deficient layers [29,30]. Among
this series of distinct oxides, Ti4O7 exhibits the highest electrical
conductivity exceeding 103 S cm − 1 at room temperature [31].
Moreover, these oxides show no peaks or waves between 0.0 and
2.0 V vs. RHE in 1 M sulfuric acid at 25 °C [31], indicating highly
oxidation-resistant characteristics. According to these conductive and
oxidation-resistant properties, TinO2n−1 phases have attracted atten-
tion as a possible support for fuel cell catalysts [32]. Commercially
available products known as Ebonex® are supplied by Atraverda Ltd.
(Sheffield, UK). Ebonex® is an electrically conductive ceramic
consisting of several suboxides of titanium dioxide, mainly, Ti4O7
and Ti5O9. Ebonex® may have a surface morphology (microrough and
porous) which give it particularly good properties as a substrate for
metal layers [33–35]. The structure and properties of Ebonex®
ceramic electrodes, together with their electrochemical behaviour
and applications were excellently reviewed by Smith et al. [36].
Farndon et al. [37] demonstrated that metal deposition on Ebonex®
substrate occurred by a mechanism parallel to that observed at metal
or carbon substrates: nucleation of hemispherical Pt centres was
followed by three dimensional growth under electron transfer control.
As an electrocatalyst support, Ebonex® has the potential of interacting
with the deposited metal so as to alter the activity of the catalyst [38].
Indeed, its chemical composition and hypo-d-electron character
suggests an ability to interact with hyper-d-electron metals such as
Pt, Ni and Co. Farndon and Pletcher [39] investigated the stability of
platinized Ebonex® electrodes prepared by Pt electrodeposition. Pt/
Ebonex® electrodes with Pt loadings of 2 mg cm − 2 were tested in a
flow electrolysis cell (1 M NaOH) for N500 h without significant
changes in properties. Dieckmann and Langer [38] studied the electro-
oxidation of simple aliphatic and aromatic alcohols and formaldeyde
on Ebonex® and graphite supported platinum in acid and basic
electrolytes. The Pt/Ebonex® catalyst was prepared by suspending
Ebonex® pellets in a H2PtCl6 solution (Pt loading 2 mg cm − 2), and
then reducing Pt using the electroless ethanol reduction method. Pt
surface area was more than twice higher on graphite than on
Ebonex®. The catalytic activity of Pt/Ebonex® was lower than that
of Pt/C, even when surface areas were considered. Slavcheva et al. [40]
prepared Ebonex® supported Pt and PtCo catalysts for the oxygen
evolution reaction in alkaline media by impregnation of the metal
precursors on the surface of the support, followed by reduction with
sodium borohydride. The specific surface area of the Ebonex® is very
low (2–3 m2 g − 1), and, as a consequence, the unsupported Pt and
PtCo nanoparticles prepared by NaBH4 reduction possess much higher
specific surface area (SSA, 38 and 40 m2 g − 1, respectively), than that
of Ebonex® supported catalysts (from 5 to 25 m2 g − 1, depending on
the metal/support ratio). The PtCo/Ebonex® catalyst, selected for the
electrochemical testing, contained 50 wt.% Ebonex® and presented a
specific surface areas of 10.37 m2 g − 1. The results of galvanostatic
polarisation experiments showed that, notwithstanding its lower SSA,
the Ebonex® supported PtCo has higher catalytic activity compared to
unsupported PtCo samples. They assumed that the observed improved
catalytic activity of PtCo/Ebonex® is due to formation of surface
oxides and electronic interactions between the metallic components
of the catalyst and the supportive material, in which Co plays a
predominant role. It has to be remarked, however, that no comparison
with carbon supported PtCo was made!
Ioroi et al. [41] prepared Ti4O7 supported Pt catalysts (2.5 and 5 wt.%)
and compared their activity for both the hydrogen oxidation reaction and
the oxygen reduction reaction to that of Vulcan XC-72 supported Pt
catalyst under PEMFC operation at 80 °C. Single-phase sub-stoichiometric
titanium oxide powder was prepared by the reduction of TiO2 powder at
high temperature (6 h at 1050 °C under flowing H2). Platinum was loaded
on the Ti4O7 by a conventional impregnation method, by reducing the Pt
precursor at 250 °C in a flowing mixed H2/N2 atmosphere. Some of the
deposited Pt particles were aggregated, especially in 5 wt.% Pt/Ti4O7,
because the surface area of the Ti4O7 prepared in this study was rather
small (0.95 m2 g − 1). Tests on Pt-free Ti4O7 and Vulcan XC-72 supports
showed that the onset potential of the corrosion current during the
positive direction sweep of cyclic voltammetry (CV) was much higher for
Ti4O7 than for Vulcan XC-72, which indicates that Ti4O7 would be quite
oxidation resistant under the actual PEMFC operating conditions. PEMFC
polarization curves using 5 wt.% Pt/Ti4O7 and conventional 20 wt.% Pt/C
cathodes indicated that the mass activity of Pt/Ti4O7 is lower than that of
Pt/C. Compared to the Pt/C cathode, ca. a 100 mV voltage loss was
observed at 500 mA cm − 2 for the 5 wt.% Pt/Ti4O7 cathode. This was
ascribed to the smaller electrochemically active area of Pt/Ti4O7 relative
to Pt/C, because the Pt particle size deposited on Ti4O7 is larger than that
of the Pt/C catalyst. However, the specific activities of both catalysts,
based on the electrochemically active surface area, were very close to
each other, indicating that the activity for the oxygen reduction reaction
of Pt catalyst particles on both Ti4O7 and Vulcan XC-72 is near the same.
Accordingly, the Ti4O7 support would be applicable to PEMFC electro-
catalysts without degrading the intrinsic catalytic activity of Pt, so that Pt/
Ti4O7 would be a potentially durable catalyst material for PEMFCs. The
same authors [42] investigated the stability of 5 wt.% Pt/Ti4O7 and 30 wt.
% Pt/C cathodes in PEMFCs by polarization measurements to evaluate fuel
cell performance loss and CV measurement to evaluate electrochemically
active area loss after potential holdings (N1.0 V). The Pt/C catalyst was
used after heat treatment at 1000 °C under H2 to obtain Pt dispersion
similar to that of 5 wt.% Pt/Ti4O7, and was denoted as 30% Pt/C-HTT.
Fig. 1a [42] shows the obtained Ti4O7: although the starting material
(TiO2) is a fine powder (70 nm diameter, BET area: 20 m2 g− 1), sintering
occurs during a high-temperature reaction, so that the surface area of the
prepared Ti4O7 powder is considerably low (BET area: 2 m2 g− 1).
Subsequently, Pt particles were deposited on Ti4O7 by the impregnation-
reduction method. As can be seen in the scanning electron microscopy
(SEM) image (Fig. 1b), Pt particles are uniformly dispersed on Ti4O7. The
diameter of the Pt particles was about 10–20 nm, which is much larger
than that of the actually used Pt/C catalyst, because the small surface area
of the Ti4O7 prepared in this study. Fig.1c shows the SEM image of 30% Pt/
C-HTT. Pt particles with a diameter of 10–20 nm are dispersed on Vulcan
XC-72 support, which is similar to the Pt particle size of Pt/Ti4O7. To
compare the catalyst stability, Pt particle size is important because the
stability of Pt particles is strongly affected by the particle size. Smaller
particles are more unstable, especially under high potentials or potential
sweep conditions. The high-potential holding test showed significantly
greater stability of Pt/Ti4O7 than the conventional Pt/C-HTT catalyst. The
effects of potential holding on the CV and cell performance for the Pt/
Ti4O7 cathode were much smaller than for the Pt/C-HTT cathode.
2.1.2. Metal-doped TiO2 (M–TiO2, M = Ru, Nb)
It has been shown that mixtures of NbO2 and TiO2 sintered at
1000 °C lead to the formation of an electrically conducting material
[28,43]. This high temperature synthesis method shows promising
results, but it leads to a low surface area material that requires long
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
Fig. 1. SEM images of (a) prepared Ti4O7 support, (b) 5% Pt/Ti4O7, and (c) 30% Pt/XC-72-HTT.
Reprinted from Ref. 42, copyright 2008, with permission from The Electrochemical Society.
synthesis times. Because TiO2 undergoes a phase transition from
anatase to the less catalytically active rutile near 700 °C [44], the high-
temperature synthesis may also reduce some catalytic promotion of
methanol oxidation by the support. On this basis, to increase the
surface area and avoid the phase transition, a low-temperature
synthesis route for Nb0.1Ti0.9O2 via a surfactant templating method
was proposed by Garcia et al. [45]. The synthesis method is based on
using octadecylamine as a template, and niobium(V)ethoxide and
titanium(IV)butoxide as metal precursors. BET surface area of the
resulting Nb0.1Ti0.9O2 was 136 m2 g − 1. This surface area is much
higher than the value of 1.4 m2 g − 1 that was measured for the same
compound synthesized at high temperature using the ceramic
method [46]. An Nb0.1Ti0.9O2 supported PtRu catalyst was prepared
by a colloidal method. Nb0.1Ti0.9O2 was added to an H2PtCl6/RuCl3
mixture in tetrahydrofuran. Then, the metal precursors were reduced
with LiBH4. Tests in direct methanol fuel cells (DMFCs) were
performed at 70 °C for the PtRu/Nb0.1Ti0.9O 2 catalyst and a
commercial PtRu/C catalyst from E-TEK. The PtRu/Nb0.1Ti0.9O2
749
presented higher current per mass of Pt compared to the E-TEK
PtRu/C at 0.40 V. According to the authors, this result suggests that the
anatase titania support enhances the catalytic activity of PtRu in ways
that carbon cannot.
Park and Seol [47] prepared a Nb–TiO2 supported Pt cathode
catalyst for polymer electrolyte membrane fuel cells. Nb-doped TiO2
nanoparticles were obtained by hydrothermal synthesis at 120 °C
using Ti(IV) isopropoxide and Nb(V) ethoxide as metal precursors. To
activate Nb donor dopant in TiO2, the nanoparticles were annealed at
400 °C for 2 h under pure H2. Nb–TiO2 presented a TiO2 rutile-
dominant crystal structure, and its electrical conductivity was about
0.1 S cm − 1. The Nb–TiO2 supported Pt (40 wt.%) catalyst, prepared by
the borohydride reduction method, exhibited a good dispersion of Pt
catalysts (~3 nm) on the Nb-TiO2 nanostructure supports (~10 nm).
The Pt/Nb–TiO2 showed a higher activity for oxygen reduction than
that of a carbon supported Pt prepared by the same route. According
to the authors, the enhanced catalytic activity of Pt/Nb–TiO2 in
electrochemical half cell measurement may be mainly due to the good
dispersion of Pt nanoparticles on Nb–TiO2 nanosized supports. In
addition, from XANES spectra of Pt L edge obtained with the
supported catalysts, the improved catalytic activity of Pt/Nb–TiO2
for oxygen reduction may be caused by an interaction between oxide
support and metal catalyst.
Recently, Ru-doped TiO2 was prepared by a sol–gel method, then Pt
atoms were supported on this material by an impregnation reduction
method, and finally the supported catalysts was electrochemically
tested in fuel cell conditions by Haas et al. [48]. The composition of
RuxTi1−xO2 was in the range from xRu = 0.17 to xRu = 0.73. XRD
analysis carried out on the mixed oxide indicated that the system
exhibits a change from solid solution above 0.5 mole fraction of
ruthenium to a mix of two phases below 0.5 mol fraction of
ruthenium. Ru–TiO2 particle size from SEM images was estimated to
vary between 200 and 300 nm. The conduction of these oxides can be
compared to semi conductors and varied in the range of 0.1 b σ b 100 S
cm − 1. Regarding the Ru–TiO2 supported catalyst the Pt loading varied
from 23 to 40 wt.%. The Pt crystallite size was in the range 3.3–5.4 nm.
The electrochemical characterization of the catalysts was done by
cyclic voltammetry in half cell configurations in 0.5 M phosphoric acid
electrolyte and showed that the catalysts have an active platinum
surface area comparable to commercial carbon supported catalysts. In
particular, the active surface area of the Pt supported on RuTiO with
xRu = 0.71 was 1) nearly twice as large as the other oxide compositions
and 2) larger than pure Pt on Vulcan at the same Pt loading.
Chen et al. [46] compared the activity and stability as supports for
unitized regenerative fuel cell electrocatalysts of Ebonex®, Ti4O7 and
Nb0.1Ti0.9O2, made, respectively, by reducing and doping rutile
titanium dioxide. The synthesis of both Ti4O7 and Nb0.1Ti0.9O2 started
from the same precursor, ultrafine rutile TiO2, having a BET surface
area of 110 m2 g − 1. Ti4O7 was obtained by hydrogen reduction of TiO2
at 1050 °C, while Nb0.1Ti0.9O2 was prepared by heating a mixture of
TiO2 and NbO2. Both ceramic samples had an electrical conductivity
similar to Ebonex®. The XRD pattern for Nb0.1Ti0.9O2 showed a pure
rutile microcrystalline phase. BET surface area measurements gave
relatively low surface areas for all three supports, 2 and 1.4 m2 g − 1 for
the synthesized Ti4O7 and Nb0.1Ti0.9O2, respectively, and 1 m2 g − 1 for
Ebonex®. Supported Pt4Ru4Ir1 catalysts were prepared forms by
reducing the corresponding metal salts onto Ebonex® and synthe-
sized Ti4O7 and Nb0.1Ti0.9O2, using the borohydride method. These
supported catalysts were then tested in the gas diffusion half-cell for
both oxygen reduction and evolution. The Ti4O7-supported catalyst
showed catalytic activity very similar to that of the Ebonex®
supported catalyst for both reactions, while the catalyst supported
on the Nb0.1Ti0.9O2 gave higher currents at all applied voltages.
Because the difference increased as the catalysts were progressively
oxidized, the authors attributed the lower current at a given bias to a
greater internal IR drop in the Ebonex®- and Ti4O7-supported
750 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
catalysts. To further investigate their electrochemical stability, they
examined Ebonex®- and Nb0.1Ti0.9O2-supported catalysts during a
relatively long period of anodic polarization in the gas diffusion half
cell, with continuous 0.5 M H2SO4 electrolyte flow. The Nb0.1Ti0.9O2-
supported catalyst showed no significant difference in current after
the polarization period. Conversely, there was a distinct current drop
for the Ebonex®-supported catalyst, especially for the oxygen
reduction reaction. The likely cause of this effect is partial oxidation
of Ebonex®, which creates a resistive layer through which current
must pass. The loss in current showed that, although they are stable
for short periods of time, Ebonex® and Ti4O7 are still oxidized to
nonconductive TiO2 at the catalyst/support/electrolyte three-phase
interface after extensive polarization at the positive potentials of the
oxygen electrode. On the other hand, Nb0.1Ti0.9O2 showed good
stability under these conditions.
2.1.3. Nanostructured TiO2
Nanostructured TiO2 materials, with a typical dimension less than
100 nm, have recently emerged. Such materials include spheroidal
nanocrystallite and nanoparticles together with (more recently synthe-
sized) elongated nanotubes, nanosheets, and nanofibers [49]. In view of
to their high stability, high surface area and moderate electrical
conductivity, titanium dioxide nanotubes (TONTs) have been investi-
gated as fuel cell catalyst support [50–53]. The nanotube structure has a
variety of advantages as a support of electrocatalysts associated with the
specific geometry. The geometry of the arrays affects the dispersion of
catalysts, the effective catalyst loading, and easy permeation of reactant
species resulting from the highly porous structure, leading to an
enhancement of catalytic activity [49]. In relation to methanol oxidation
and oxygen reduction processes in DMFCs, Pd and PtRu, and PtNi and
PtCo supported on TONTs were investigated for the methanol oxidation
reaction (MOR) [50,51] and the oxygen reduction reaction (ORR)
[52,53], respectively. Wang et al. [50] investigated the electro-oxidation
of methanol in sulfuric acid solution using palladium well-dispersed on
titanium nanotubes. TONTs were prepared by the alkaline hydrothermal
method [54]. Pd/TONT catalysts were synthesized at 120 °C using the
conventional reduction method with glycol. Pd dispersed on titania
nanotubes, which leads to high surface area substrates, showed higher
catalytic activity for the MOR than that of pure Pd and Pd supported on
TiO2 nanoparticles. Macak et al. [51] tested nanotubular TiO2 matrices
(generated from mixed H2SO4/HF electrolytes using the self-organizing
anodization process) as active support for Pt/Ru nanoparticles for
methanol electrooxidation. The nanotubular TiO2 layers consisted of
individual tubes of 100 nm diameter, 500 nm length and 15 nm wall
thickness. This nanotubular TiO2 support provided a high surface area
and it significantly enhanced the electrocatalytic activity of Pt/Ru for
methanol oxidation (relative to the performance of Pt/Ru at the same
loading but immobilized on a conventional compact TiO2 support).
Annealed to anatase, the TiO2 nanotubular support exhibited even a
higher enhancement effect during electrooxidation of methanol than
when used in the “as-formed” amorphous structure. A key effect of
annealing seems to be a strong adhesion of the bimetallic Pt/Ru
nanoparticles to the nanotubular TiO2 matrix. Moreover, they showed
that the electrocatalytic activity is further enhanced by UV-light
illumination.
Kang et al. [52,53] formed elongated TiO2 nanotube arrays on Ti
substrate using an electrochemical anodization process. TONT arrays
with a length of approximately 1 μm and a diameter of 120 nm were
produced easily and reproducibly. A dual-gun sputtering technique
with Pt, Ni and Co targets was used for deposition of nanoparticle PtNi
(PtNi size 5–10 nm) [52] and PtCo (PtCo size 3–4 nm) [53] catalysts on
the TONT. The crystalline and morphological properties of Pt70Co30
catalyst layer on the TONT were investigated by HRTEM, as shown in
Fig. 2 [53]. Fig. 2a shows the representative top surface morphology of
Pt70Co30/TONT, revealing the nanotubular structure as a support for
the deposition of the binary catalyst and the existence of metal
nanophase particles along the inner and outer wall of TONT. Average
crystalline size of Pt and Co mixed nanophases was estimated by the
magnified image of Fig. 2b, indicative of a well dispersed distribution.
The crystalline planes proving the presence of crystalline Pt and Co,
together with anatase TONT support, were clearly observed in Fig. 2c,
confirming the crystallinity of the binary nanophase layer. SAED
patterns in Fig. 2d also demonstrated that the annealed TiO2
nanotubes were a polycrystalline anatase phase, designated “A.” The
specific crystalline planes associated with Pt and Co nanophase
structure were also found. As-deposited PtNi/TONT showed poor ORR
activity, in particular at high potential, related to OH adsorption.
Annealed PtNi/TONT at 400 °C under hydrogen atmosphere displayed
a significant enhancement of the ORR, also in the presence of
methanol. To clarify the effects of the nanotubular TiO2 structure
and pore size, compact TiO2 films on Ti substrate were prepared and
compared to TiO2 nanotube arrays. A remarkable increase of ORR
activity and a positive shift of onset potential were achieved using
Pt70Co30/TONT. This phenomenon was attributable to the favorable
accessibility of the inner wall of TONT for diffusing oxygen and to the
high surface area of PtCo catalyst layers at the upper lip and inner wall
of TONT [53]. However, it has to be promptly pointed out that in all
these works a comparison of the catalytic activity of TONT supported
catalysts with that of a carbon supported catalysts was not made!
2.2. Sn-based oxides
2.2.1. M-doped SnO2 (M = Sb, Ru)
Tin dioxide, SnO2, belongs to the family of transition-metal dioxide
compounds with rutile structures. The mineral form of SnO2 is called
cassiterite, and this is the main ore of tin. SnO2 is usually regarded as
an oxygen-deficient n-type semiconductor. Hydrous forms of SnO2
have been described in the past as stannic acids, although such
materials appear to be hydrated particles of SnO2 Although SnO2 is
insoluble in water, it is an amphoteric oxide, although cassiterite ore
has been described as difficult to dissolve in acids and alkalis.
SnO2 supported Pt and Pd metals are interesting catalyst systems for
various chemical reactions, such as low temperature oxidation of CO and
methane [55–57], selective reduction of NO by hydrocarbons [58], and
crotonaldeyde hydrogenation [59], because of the synergistic effect. In
the same way, SnO2 has been proposed as a support material for fuel cell
electrocatalysts because of its chemical properties: it adsorbs OH species
at low potentials and/or induces the electronic effect with Pt catalysts.
These properties promote the electrooxidation on Pt of CO [60] and low-
molecular-weight alcohols, such as methanol [61] and ethanol [22]. For
its use as a catalyst support in fuel cells, however, the electrical
conductance of SnO2 has to be improved. Indeed, undoped tin dioxide is
a wide bandgap semiconductor (Eg ~ 3.6 eV) with electrical resistivity
varying from 10 to 106 Ω cm, depending on the temperature and the
stoichiometry of the oxide [62]. The electrical resistivity was found to
drastically decrease to 10 − 2–10 – 3 Ω cm by doping SnO2 with Sb5+ [63].
Santos et al. [64] electrodeposited platinum micro particles on
antimony doped SnO2 (ATO) thin films, and tested their activity for
methanol electro-oxidation. The tin oxide films were prepared through
the thermal decomposition of polymeric precursors. Antimony was
introduced in the precursor solution by directly adding Sb2O3 to the tin
solution. The Sb content was 2 mol%. The platinum particles were
electrodeposited at a constant 0.2 V versus reversible hydrogen
electrode (RHE) potential. The crystallite size of Sb–SnO2 supported Pt
was in the range 8.5–12 nm. The electroactivity of Sb–SnO2 supported Pt
was investigated by chronoamperometry (CA) and compared to the
activity of platinized platinum. Pt/ATO electrodes not only presented
higher roughness factors than platinized Pt electrodes, but also had
larger intrinsic electrocatalytical activity for the electrooxidation of
methanol. According to the authors, these results suggest that tin oxide
can be used as a good matrix for Pt (or Pt alloys) catalyst dispersion for
applications in DMFC. The method applied for the preparation of Sb–
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
Fig. 2. HRTEM images of (a) Pt70Co30/TONT of the top surface nanotubular structure, (b) the distribution of binary alloy nanophases along the inner wall, (c) crystallographic analysis
of the nanophase alloy and anatase TiO2, and (d) SAED of Pt70Co30/TONT, indicating the polycrystalline nature of the individual components. Reprinted from Ref. 53, copyright 2008,
with permission from The Electrochemical Society.
SnO2 films can be useful to prepare small oxide particles as a conductive
support for fuel cell catalysts. On this basis, Lee et al. [65] deposited Pt
colloidal particles on ATO nanoparticles with various amounts of Pt
loading (5, 10, 20, and 40 wt.%), and investigated their electrocatalytic
activities and stabilities for methanol (MOR) and ethanol (EOR)
oxidation reactions. The activities for the MOR and EOR were compared
with those of Pt supported on carbon, prepared through the same
procedure using Vulcan XC-72. The ATO nanoparticles were synthesized
by the reflux method using SnCl4·5H2O and SbCl3 as precursors.
Preparation of Pt/ATO and Pt/C nanoparticles was based on the polyol
method. The size of the ATO nanoparticles was 5.2 nm. The electrical
conductivities of undoped and Sb-doped SnO2 were 0.0028 and 0.11 S
cm − 1, respectively. The specific surface areas of the ATO and the Vulcan
XC-72R from a BET analysis were 99.7 and 239.6 m2 g − 1, respectively.
Fig. 3a–f [65] shows the TEM images of ATO nanoparticles and of the
supported electrocatalysts. As shown in Fig. 3a and b, the ATO particles
were uniform and spherical. In addition, the electron diffraction pattern
(inset of Fig. 4a) showed good crystallinity of the ATO particles. The size
of the ATO particles from TEM images was ~5 nm. Fig. 3c shows well-
distributed Pt particles on carbon support. The average particle size from
TEM was ~2.5 nm. It should be noted that all of the prepared
electrocatalysts were synthesized using the same Pt colloid; therefore,
the Pt particles should have the same average size in all of the prepared
electrocatalysts. Fig. 3d, e and f shows TEM images of the Pt/ATO
electrocatalysts for the 40, 10, and 5 wt.% Pt/ATO samples, respectively.
As the Pt loading decreased, the distribution of Pt particles on the ATO
support became remarkable. In the 40 wt.% Pt/ATO sample, Pt particles
covered most of the ATO surface and were stacked on top of one another;
whereas in the 5 wt.% Pt/ATO sample, the Pt particles were evenly
distributed on the ATO surface. The activities of the Pt/ATO for both MOR
and EOR were greater than those of the Pt/C. These enhanced activities
751
can be attributed to the effects of SnO2 adjacent to Pt. As the Pt/Sn
system is more effective for the EOR than for the MOR [66], the EOR
activity of the Pt/ATO was enhanced over that of Pt/C to a much greater
degree than the MOR activity. The Pt/ATO sample exhibited higher
current density than the 5 wt.% Pt/SnO2 sample, again confirming the
Sb-doping effect. Interestingly, the 5 wt.% Pt/SnO2 exhibited a higher
current density than Pt/C, despite a much lower electrical conductivity
of SnO2 than that of carbon, clearly demonstrating the effect of SnO2 as a
promoting support. The Pt/ATO exhibited much higher stability than Pt/
C, which can be attributed to a higher corrosion resistance of the ATO
support and the strong interaction between Pt redeposited after
electrochemical dissolution and the ATO support.
Pang et al. [67] prepared Ru-doped SnO2 nanoparticles by chemical
precipitation and calcination at 550 °C. The structure and crystallite
size (20 nm) of SnO2 particles did not alter after Ru doping. Pt/Ru–
SnO2 was prepared by impregnation of Ru–SnO2 with H2PtCl6,
followed by reduction of the Pt precursor with NaBH4. Pt particle
size was 4 nm. Safonova et al. [68] reported that the addition of Pd, Ru
and Rh induce an increase in the resistivity of tin dioxide films.
Conversely, Pang et al. [67] found that the electrontransfer resistance
(Rct) decreases with the introduction of Ru. The values of Rct on the
Pt/Ru-doped SnO2/graphite and Pt/SnO2/graphite electrodes were
4.92 and 6.28 Ω, respectively. This implies that Ru doping enhances
the conductance of SnO2. Ru-doping enhance not only the electrical
conductivity, but also the activity and the stability of Pt/SnO2.
Compared with pure SnO2 particles, a certain amount of Ru can
improve the electrocatalytic activity of the Pt/SnO2 catalyst. According
to the authors, in the case of the Ru-doped SnO2 system the
interaction between RuOx and SnO2 promotes the formation of
hydroxyl species to catalyze the oxidation of poisonous species
(such as COads) adsorbed on the active sites of platinum nanoparticles,
752 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763

Fig. 3. TEM images of (a) ATO, (b) magnified one of (a), (c) 40 wt.% Pt/C, (d) 40 wt.% Pt/ATO, (e) 10 wt.% Pt/ATO, and (f) 5 wt.% Pt/ATO. Reproduced from Ref. 65, copyright 2008,
with permission from Elsevier.

which results in the increased MOR activity of Ru-SnO2. Moreover, the
long-term cycle stability of the Pt/Ru-doped SnO2/graphite electrode
was higher than that of the Pt/SnO2/graphite electrode. However,
comparison with Pt/C, which is fundamental for the evaluation of the
suitability of a fuel cell catalyst support, was not made!
Generally SnO2 has a surface area (b 100 m2 g − 1) lower than that of
reference Vulcan XC-72. The synthesis of tin oxide with high surface area is
a primary requirement for its use as catalyst support. Hagemeyer et al. [69]
investigated a variety of methods for the preparation of high surface area
tin oxide. BET surface areas N100 m2 g − 1 were achieved by a variety of
methods after calcination in the temperature range 300–500 °C. High
surface area tin oxides with excellent sintering resistance were
synthesized by the hydrazine method. High surface areas N200 m2 g − 1
could also be achieved by a modified Pechini method, using aqueous
glyoxylic acid as dispersant for Sn(IV) acetate.
2.2.2. SnO2 nanowires
Nanowires (NWs) are a class of one-dimensional nanomaterials
with a high aspect ratio [70]. NWs can be made of various materials
and they have solid cores. The broader choice of various crystalline
materials and easier doping methods provide highly tunable proper-
ties (e.g., electrical) of NWs [70]. While previous studies utilized SnO2
in form of film or particles, Saha et al. [71,72] directly grew SnO2
nanowires on fuel cell backings as catalyst support for fuel cells. NWs
were grown on carbon-paper fuel cell backings form a 3D structure
that leads to a higher gas permeability. According to the authors, this
NW-based 3D structure will take full advantage of combined factors
including increased utilization of the noble metal catalyst, improved
metal-support interaction, and enhanced mass transport in the
electrodes for fuel cell applications. SnO2 NWs were grown directly
on the fibers of a carbon paper by a thermal evaporation method.
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
Fig. 4. SEM and TEM micrographs of SnO2 NWs grown on carbon fibers of carbon paper
by thermal evaporation method. (a) SEM image showing full coverage of SnO2 NWs on
fibers of carbon paper. (Inset) Fibers of bare carbon paper. (b) TEM image showing
individual SnO2 NWs. (c) TEM images showing Pt nanoparticles electrochemically
deposited onto SnO2 NWs. (Inset) Pt nanoparticles deposited onto a single SnO2 NW.
Reprinted from Ref. 71, copyright 2007, with permission from The Electrochemical
Society.
Before the process of metal nanoparticle deposition, the SnO2 NWs
grown on carbon paper were pretreated chemically with 5.0 M HNO3
aqueous solution. This surface activation step produces oxide
functional groups such as hydroxyl, carboxyl and carbonyl on the
surface of the SnO2 NWs. Pt nanoparticles were electrochemically
deposited onto the surface of SnO2 nanowires [71]. Fig. 4 [71] shows
the SEM and TEM images of the SnO2 NWs grown on a commercially
available carbon paper backing used in fuel cell applications. The
carbon paper is made of small carbon fibers with a diameter between
5 and 10 μm (inset in Fig. 4a). As shown in Fig. 4a, a thin layer of high-
density SnO2 NWs completely covers the surface of the carbon fibers
in the carbon paper. The length of the SnO2 NWs is in the range of 20–
30 μm. Further TEM examination shows that the NWs have a straight-
line morphology with a diameter of about 20 nm (Fig. 4b). Fig. 4c
presents the TEM image of the Pt nanoparticles electrochemically
deposited on the SnO2 NWs. Pt nanoparticles with a size of 4–6 nm
can be observed clearly on the surface of NWs. The successful
753
deposition of Pt nanoparticles indicates a good electrical contact
between the SnO2 NWs and the carbon fibers. Higher electrocatalytic
activities of the Pt/SnO2 NW/carbon paper composite electrode for
both oxygen reduction reaction and methanol oxidation reaction have
been achieved in comparison with standard Pt/C electrode. In the
same way the electrocatalytic activities of SnO2 NW supported PtRu
composite electrodes for methanol oxidation were investigated and
higher mass and specific activities in methanol oxidation were
exhibited as compared to Pt–Ru catalysts deposited on glassy carbon
electrode [72]. The higher electrocatalytic activities of SnO2 NW
supported catalysts were attributed to the unique 3D structure and
electronic properties of SnO2 NWs, the strong interaction between Pt
catalyst particles and the SnO2 NW surface, the synergies resulting
from the combined properties of Pt nanoparticles and SnO2 NW
supports, and the low impurity level of SnO2 NWs compared to Vulcan
carbon XC-72. Such a hierarchical electrode with the combined
properties has potential applications for fuel cells. This approach also
provides a route to fabricate electrodes based on depositing noble
metal nanoparticles onto metal oxide NWs grown on the fuel cell
backings. One of the major concerns for the application of NWs to
catalyst supports in PEMFCs and DMFCs is whether there is strong
adhesion of these NWs to the carbon paper during actual fuel cell
operation. To address this concern, Saha et al. [71] carried out
preliminary studies by immersing the SnO2 NW/carbon paper
composite electrode in 0.1 M H2SO4 solution over a period of 2 months
at 50 °C. SEM examinations after the test showed that high-density
NWs are maintained on the surface of carbon fibers, suggesting strong
adhesion between SnO2 NWs and the carbon paper.
2.3. WOx
Tungsten oxide is an n-type semiconductor with a reported
bandgap of about 2.6 to 2.8 eV [73]. Tungsten has many oxidation
states, from 2 to 6, and can exist in many forms, making it suitable for
electrochromic, photochromic, photocatalyst, and gas-sensor applica-
tions. The intrinsic electric conductivity in tungsten oxide arises from
its nonstoichiometric composition, giving rise to a donor level formed
by oxygen-vacancy defects in the lattice [73]. It has also been shown
that tungsten oxides exhibit considerable proton transfer because of
the formation of tungsten trioxide hydrates [74], which is an attractive
property for fuel cell catalyst supports. Tungsten oxide support
material has been shown to be more thermally stable under
electrochemical oxidation conditions than Vulcan XC-72R [75].
Firstly, Niedrach et al. [76,77] reported that Pt admixed with
tungsten oxides (e.g., WO2, W2O5, and WO3) is less susceptible to
carbon monoxide poisoning during its catalytic oxidation in fuel cells.
Then, Kulesza and Faulkner [78,79] observed that the electrocatalytic
activity for methanol oxidation is enhanced when platinum is
dispersed on WOx. The improvement in the electrocatalytic activity
of platinum in the presence of WOx is related to the fact that WOx can
form tungsten bronzes, thereby making the dehydrogenation of
methanol more effective and also the oxophilic nature of the oxide
helps in removing the adsorbed intermediates during methanol
oxidation [80]. Indeed, Hads coming from CH3OH dissociation can
spillover to the WOx substrate according to the reactions [80]:
WOx + yPtH Y Hy WOx + yPt ð2Þ
Hy WOx Y WOx + ye − + yH
+
ð3Þ
leaving free Pt sites for further CH3OH adsorption/dissociation and
leading to accelerated kinetics. Moreover, methanol electrooxidation
proceeds via COads species, and the best COads tolerance with Pt–WOx
materials was achieved when the interaction between Pt and WOx
materials is maximized [81].
754 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
To avoid misunderstanding, it has to be promptly pointed out that
in most works dealing on the Pt–WOx system, the catalyst has not
been dispersed on tungsten oxide to the aim to substitute the carbon
support! Pt was dispersed on the WOx matrix mainly to aim to
increase the catalytic activity of Pt [23,24]. When used in fuel cells, to
increase WO3 surface area, before Pt dispersion, tungsten oxide is
supported on carbon [24,81] or, to increase Pt dispersion, WOx is
deposited on preformed Pt/C [82,83].
Mcleod and Birss [84], for the first time, evaluated WOx/Pt films in
terms not only of the suitability of WOx as a co-catalyst for methanol
oxidation, but also of the relevance of WOx as a support material for
fuel cell catalysts. Then, recently, Ganesan and Lee [85] and Cui et al.
[86], in microsphere and mesoporous form, respectively, and Rajeswari
et al. [87] and Maiyalagan and Wiswanathan [88], in nanorod form,
tested WO3 as a carbon substitute support for DMFC catalysts.
Currently, DMFC electrocatalysts are supported on carbon, which is
electronically, but not ionically conductive. This necessitates the
addition of the fuel cell electrolyte, typically a polymer such as
Nafion™, into the PtM/C mixture to create a high surface area triple
phase boundary where the catalyst, fuel, and electrolyte meet. Any Pt
sites that are not in contact with the Nafion™ electrolyte cannot act
catalytically and are therefore wasted. By using a support material such
as WOx, which is both ionically and electronically conductive, a
significantly greater portion of the Pt catalyst should be utilized. A
problem for the use of WOx as a fuel cell catalyst support could be the
dissolution of WO3 in the acidic medium [89]. Raghuveer and
Viswanathan [24] reported that the stability of WO3 in the acid
medium can be improved by transition metal ion substitution such as
Ti4+ into the oxide framework. The improvement in the stability could
be due to the alteration in the rate of hole capturing process of WO3 by
the Ti4+ at the interface, which is responsible for the dissolution of
tungsten in acidic solution. McLeod and Birss [84] synthesized WOx
from W(OC2H5)6 by two different methods using the sol–gel approach,
with ethanol (Type 1) or water (Type 2) as the solvent. Through the use
of sweep rate experiments, they found that Type 1 films had both a
smaller total electroactive area and fewer electroactive surface sites
than Type 2 films. This can be attributed to a higher film density, and
therefore, a lower porosity of Type 1 film. XRD analysis revealed that
the products of both syntheses were either amorphous, or poorly
crystallized. Methanol oxidation CVs for WOx/Pt films made from both
Type 1 and Type 2 syntheses exhibited a low resistance, which is a
necessary property of a fuel cell catalyst support in order to maximize
the cell efficiency. The WOx/Pt films derived from both Type 1 and Type
2 sols clearly exhibited methanol oxidation activity. For Type 1 films,
methanol oxidation currents are observed to increase with time, which
was matched with a decrease in CV charge and a loss of WOx, while the
methanol oxidation currents on the more porous Type 2 films are more
stable. Methanol oxidation currents for the Type 1 film were also
observed to decrease as the WOx:Pt ratio increased. Thus, it can be
concluded that the Type 1 WOx blocked Pt sites and that the increase in
methanol oxidation currents with time is due to a physical loss of WOx
and a corresponding increase in the number of exposed Pt sites.
Regarding Type 2 films, above a WOx:Pt ratio of 3 it exhibited methanol
oxidation currents that decayed only very slowly. In terms of a fuel cell
catalyst support, WOx produced via the Type 2 synthesis seems to be
more promising than Type 1 WOx. The more porous structure of the
Type 2 films allows methanol to reach the Pt sites, even as the amount
of WOx on the electrode is increased. The WOx synthesised in this
manner presented some co-catalytic properties, as evidenced by the
stable methanol oxidation currents of Type 2 films with WOx:Pt molar
ratios of 3:1 or higher. According to the authors, combined with the
overall ease of the synthesis method, these advantages of Type 2 films
suggest that this may be a valid approach to synthesis a DMFC
electrocatalyst, without the need for a carbon support.
Ganesan and Lee [85] prepared tungsten trioxide microspheres of 2–
4 μm diameter by controlled oxidation of tungsten carbide micro-
spheres. Tungsten carbide (W2C) microspheres were synthesized by
heating resorcinol-formaldehyde polymer as a carbon precursor and
ammonium metatungstate salt as a tungsten precursor. The carbon in
the tungsten carbide microspheres was selectively removed by calcining
tungsten carbide at 500 °C in an oxygen atmosphere for 3 h to obtain
WO3 microspheres. Platinum particles were supported on the WO3
microspheres and the carbon microspheres by the conventional
borohydride reduction method. By XRD analysis they found that the
average crystallite size is 6.5, 15 and 12 nm for Pt, WO3 and W2C,
respectively. The pore-size distribution of WO3 showed a large number
of pores of around 45 nm. The large pore-size was attributed to the inter-
particle spaces between WO3 nanoparticles of ~15 nm in diameter. The
BET surface area of the WO3 microspheres was about 18 m2 g − 1. WO3
supported Pt displayed higher activity for the electrochemical oxidation
of methanol than a commercial Pt–Ru/C catalyst by a factor of 1.9 (per
mass of Pt) even without Ru. The onset potential and peak potential of
methanol oxidation on Pt/WO3 was shifted by 100 and 50 mV more
negative than PtRu/C. This is probably due to better CO tolerance of the
catalyst. The stability of the Pt/WO3-microsphere catalyst was tested by
repeating electrochemical reaction cycles in a 1 M H2SO4–1 M CH3OH
solution. The specific activity increased initially, but stabilized after
about 15 cycles. Once a steady-state is established, there was no sign of
deactivation during 100 consecutive reaction cycles.
Cui et al. [86] synthesized mesoporous WO3 with ordered pore
structure by a template replicating route. The mesoporous WO3
support materials were prepared using mesoporous silica with cubic
Ia3d symmetry as hard template and 12-phosphotungstic acid as
tungsten source, followed by the removal of the hard template using
2 M HF solution. Pt/WO3 was obtained by deposition of H2PtCl6 on the
mesoporous WO3, followed by reduction with NaBH4. The average
crystallite size of Pt and WO3 was found to be about 6.5 nm and
6.2 nm, respectively. The BET specific surface area of the prepared
mesoporous WO3 was 86 m2 g − 1, and the wall thickness (diameter of
WO3 nanorods or nanoparticles) is 6.2 nm, close to the pore size of
silica template (6.51 nm). TEM images of 15 and 20 wt.% Pt/WO3, in
Fig. 5 [86], parts a and b, respectively, show that Pt nanoparticles
(darker dots) are dispersed well in the pore structure of mesoporous
WO3. No very large metal particles/aggregates can be found. However,
some metal Pt nanoparticles may exist outside of the mesopores of
WO3 when the Pt loading amount comes up to 20 wt.% as shown in the
selected area in Fig. 5b. Small Pt nanoparticles can be found existing
within the pores of the mesoporous WO3 support in a larger
magnification image of Fig. 5c. The high-resolution TEM in Fig. 5d
shows two kinds of crystal lattice stripes. The smaller one of
d = 0.23 nm belongs to the Pt metal, and another one of
d = 0.27 nm should be WO3, which is an additional evidence to
prove the Pt particles existing in the pores of the support. A more
direct evidence of Pt nanoparticles dispersed in the WO3 matrix is the
clear Pt signals easily detected by EDS in Fig. 6e obtained on these
composites. Pt/WO3 showed high electro-catalytic activity toward
methanol oxidation and good electrochemical stability. The activity
for methanol oxidation of 20 wt.% Pt/WO3 was significantly higher
than that of commercial 20 wt.% Pt/C catalysts, and comparable to or
even higher than that of 20 wt.% PtRu/C catalyst by ETEK in the
potential region 0.5–0.7 V and lower than 20 wt.% PtRu/C in the low
potential region 0.3–0.4 V. The enhanced electro-catalytic activity for
methanol oxidation on Pt/WO3 was ascribed to the enhanced catalytic
effect and the mesoporous structure of WO3 support.
2.3.1. WO3 nanorods
Recently, one-dimensional (1D) nanorods have attracted remark-
able attention owing to their unique properties and potential for
various novel applications [90]. Nanorods have large specific surface
areas, so WO3 in a nanorod form could be an efficient support for FC
catalysts. Rajeswari et al. [87] synthesized WO3 nanorods by pyrolysis
of tetrabutylammonium decatungstate ((C4H9)4N)4W10O32 at 450 °C.
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763 755

Fig. 5. TEM images of mesostructured 15 wt.% Pt/WO3 (a, c), 20 wt.% Pt/WO3 (b); high-resolution TEM image (d) and EDS pattern (e) of 15 wt.% Pt/WO3. Reproduced from Ref. 86,
copyright 2008, with permission from the American Chemical Society.

In the precursor compound, inorganic metal oxide clusters (W10O432−)
are charge balanced with the surfactant group tetrabutylammonium
bromide (TBABr). TBABr restricts the irregular arrangement of the
metal oxide clusters by providing a steric environment around them.
This leads to the formation of 1D array of metal oxide clusters. During
pyrolysis at 450 °C, removal of the surfactant species ((C4H9)4N+) and
decomposition of the W10O32 leads to the formation of pure, single
crystalline WO3 nanorods. The dimensions of the nanorods varied in
the ranges of 130–480 nm and 18–56 nm of length and width,
respectively. Pt nanoparticles were supported on WO3 (20 wt.% Pt) by
the wet impregnation method. The size of the Pt nanoparticles was is
in the range of 4–6 nm. The electrochemical stability of WO3 nanorods
and bulk WO3 was studied in 1 M H2SO4. The stability was evaluated
by performing uninterrupted cycling of the potential between −0.2
and 1.0 V. For the WO3 nanorods almost no activity variation was
observed even after several cycles indicating its stability in sulfuric
acid medium. Whereas for the bulk WO3, the peak current was
observed to decrease, showing a poor stability in acid medium. The
electrochemical activity for methanol oxidation of platinum loaded
WO3 nanorods, and for comparison of a commercial 20 wt.% PtRu/C
and Pt loaded on bulk WO3, was studied by CV in 1 M H2SO4/1 M
CH3OH. The catalyst activities were in the following order: Pt/WO3
nanorods NPtRu/C N Pt/WO3 bulk. The activities of Pt/WO3 nanorods
was approximately six times higher than that of the Pt/WO3 bulk,
clearly indicating that the nanostructure of the catalytic support plays
an essential role. MOR activity of Pt loaded WO3 nanorods was slightly
higher or comparable to that of the commercial PtRu catalyst. This
shows that replacement of the noble metal Ru in the commercial
catalyst is possible with WO3 nanorods. All these facts demonstrate
that WO3 nanorods are better supports for platinum than bulk WO3
and carbon and hence they constitute a better catalytic system for
methanol oxidation.
756 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
Fig. 6. SEM and reflected electron (COMPO) images of the S–ZrO2 and Pt/S–ZrO2 particles. Pt particles were whitened in COMPO image. (a) SEM image of S–ZrO2. (b) SEM image of
Pt/S–ZrO2. (c) COMPO image of Pt/S–ZrO2. Reprinted from Ref. 104, copyright 2007, with permission from The Electrochemical Society.
Maiyalagan and Wiswanathan [88] synthesized tungsten oxide
nanorods infiltrating a phosphotungstic acid (H3PW12O40) solution
into an Anodisc alumina membrane as a template, and platinum
nanoparticles were supported on the nanorods by an impregnation
method. The diameter of the nanorods was found to be around
200 nm. The size of the Pt nanoparticles was in the range of 3–4 nm.
WO3 stability tests, carried out by repeated voltammetric cycles in 1 M
H2SO4, showed that WO3 nanorods have higher stability compared
with bulk WO3. Pt/WO3 nanorods exhibited higher methanol
oxidation activity than the commercial Pt/C catalyst by a factor of
two. Platinum supported on such nanorods was found to be stable
over several cycles in an electrochemical environment.
2.4. RuO2·xH2O
Ruthenium dioxide, RuO2, belongs to the family of transition-metal
dioxide compounds with rutile structures. Pure RuO2 is a metallic
conductor due to a d-band conduction mechanism [91]. Single crystals
of anhydrous RuO2 exhibit conductivity on the order of 104 S cm − 1,
despite an oxygen deficiency which is charge compensated by Ru3+
defects in the lattice. Unlike its anhydrous, crystalline parent rutile,
hydrous ruthenium dioxide, RuO2·xH2O or RuOxHy, exhibits mixed
electron-proton conductivity [92]. RuO2·xH2O has important techno-
logical applications and opportunities in electrocatalysis [93] and
charge storage [94]. The conductivity of a 25–40% dense pellet of
RuO2·yH2O (y ~ 1.3) is ~ 1 S cm − 1 [95]. This indicates that Ru(III)
defects are present and exhibit electronic conductivity due to
semiconduction or electron hopping from Ru(IV) centers to Ru(III)
defects. EXAFS analysis results for partially hydrated RuO 2
(RuO2·0.29H2O) indicated that the structure is a disordered RuO2
rutile-like structure, where the RuO6 octahedra are similar to those
found in the crystal structure, while the three-dimensional network of
octahedral chains does not extend as far as in RuO2 rutile [96].
Amorphous RuO2·2.32H2O had disordered RuO6 octahedra connected
in chains, but the data show no evidence of a three-dimensional
network of octahedra. The orientation of water within this structure is
not discernible from the EXAFS data, but clearly the presence of
structural water disrupts the three-dimensional rutile structure [96].
The structures of RuOxHy materials correlate to their mixed con-
ductivity and pseudocapacitance. The local structures of RuOxHy
materials control their electrical properties through the balance of
electron and proton transport.
Long et al. [19] demonstrated that, for Pt–Ru nanoscale blacks in
which the Pt–Ru chemical state is known and varied from Pt0Ru0 to
Pt–RuOxHy to Pt–RuO2, Pt0Ru0 has orders of magnitude less activity for
the oxidation of methanol than does a mixed-phase electrocatalyst
containing Pt0 and RuOxHy. The importance of the proton-conducting
contribution of RuOxHy in Pt–Ru nanoscale electrocatalysts was
demonstrated by the drastic loss of activity for methanol oxidation
once the structural water is thermally removed from the hydrous
oxide to form RuO2. They also show that bulk, rather than near-
surface, quantities of RuOxHy are required to achieve the highest
activity for methanol oxidation. The presence of RuOxHy in practical
DMFC catalysts has important mechanistic implications for direct
methanol oxidation, because RuOxHy is mixed III/IV valent; conducts
both electrons and protons; and innately expresses Ru–OH speciation,
as denoted by Eq. (4) [19]:
p Y Ru
IV 2− + − III
Ru O + H + e OH: ð4Þ
RuOxHy also efficiently dissociates H2O, as that is one of the
mechanisms by which protons are transported in proton conductors.
RuO2·xH2O was investigated as active support material for fuel cell
catalysts by Lasch et al. [97] and by Chen et al. [98]. In both works,
RuO2·xH2O was prepared by oxidation of ruthenium chloride with
sodium hydroxide. The catalyst was deposited on the oxide support by
a colloidal method. First, Lasch et al. [97] investigated the activity of
anhydrous RuO2 and hydrous RuO2·xH2O in half-cell experiments by
stationary current voltage measurements. Pt–Ru-catalysts deposited
on a Vulcan XC-72 carbon black were used for comparison. High
surface area ruthenium oxides (≥120 m2 g − 1) were used as catalyst
supports for Pt- and PtRu-catalysts. The electric conductivity of these
materials was comparable to that of Vulcan XC-72. X-ray diffraction
showed that hydrous RuO2·xH2O consists of amorphous phases which
are partly reduced to metallic ruthenium in the course of the catalyst
preparation. For that reason, a part of the material was annealed at
370 °C in oxygen. From the XRD spectra, it was found that the calcined
material consists of crystalline anhydrous RuO2. No Ru-metal phases
are observed. However, anhydrous RuO2 is a very bad proton
conductor and therefore did not show any contribution as an ‘‘active
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
support material’’. Deposition of noble metal catalysts on calcined
RuO2 resulted in electrochemical activities comparable to those
obtained for the Vulcan XC-72 support. On the other hand, catalysts
supported on hydrous RuO2 were completely inactive. The formation
of a metallic ruthenium phase either reduces drastically the proton
transfer to the support material or it blocks the catalytic activity of the
deposited Pt-particles. It is well known that the ideal Ru-content for
electrochemical methanol oxidation should not be larger than 50%
[99], which in this case was much exceeded. Conversely, Chen et al.
[98] found that Pt/RuO2·xH2O possess higher electrocatalytic activity
towards methanol oxidation with respect to PtRu black catalysts. It has
to be promptly pointed out, however, that the comparison with PtRu
black is not appropriate, due to its low surface area.
2.5. Sulfated zirconia (S–ZrO2)
Zirconia, when modified with anions such as sulfate, forms a highly
acidic or super-acidic catalyst that exhibits superior catalytic activity in
many reactions. Sulfated zirconia (SO2− 4 /ZrO2, S–ZrO2) is a crystalline
solid acid that has monoclinic and tetragonal phases [100]. Sulfated
zirconia is a strong superacid with a Hammett acid strength H0 of −16.03,
whereas Nafion® has only about −12 [101]. Data on the stability of
sulfated samples vs. temperature in the presence of methanol and water
indicated that S–ZrO2 retains a high activity at 300 °C [102]. S–ZrO2 with a
high atomic ratio of S/Zr has high proton conductivity: the proton
conductivity of the S–ZrO2 with S/Zr=0.35 was 5 10- 2 S cm − 1 at 60–
150 °C [103]. Moreover, S–ZrO2 has a high hydrophilicity. These
characterstics make S–ZrO2 a suitable support for fuel cell catalysts. In
particular, due to its high proton conductivity, it is expected that the
content of the recast electrolyte ionomer in PEMFC electrodes could be
reduced using S–ZrO2 as catalyst support. The reduction of ionomer might
result in the improvement of the gas diffusion and water transportation.
In addition, the increase of platinum utilization is also expected. Because
the perfluorosulfonated ionomer (PFSI) cannot soak into small pores in
the carbon support, platinum particles that are deposited in the small
pores may have little contact with a proton conductor. As a result, the
platinum utilization becomes low. S–ZrO2 has acid sites over the surface
in even such small pores, so that the platinum on S–ZrO2 can donate and
accept a proton and the platinum utilization would increase. Moreover,
considering its high hydrophilicity, the S–ZrO2 might improve the cell
performance under a low relative humidity. On this basis, Suzuki et al.
[104] tested sulphate zirconia as Pt support for use in PEMFC. They used
commercially available S–ZrO2 powder (Wako Pure Chemical Co., ca.
80 m2 g − 1) as a support. Pt was deposited on S–ZrO2 by using ultrasonic
spray pyrolysis. The Pt content of the Pt/S–ZrO2 was 53 wt.%. Fig. 6 [104]
shows SEM images of the S–ZrO2 and the Pt/S–ZrO2 particles. The particle
size of the S–ZrO2 was approximately 50-100 nm (Fig. 6a). As shown in
Fig. 6b, highly dispersed nanoparticles were observed on the Pt/S–ZrO2.
The composition image (Fig. 6c) shows that the nanoparticles were
platinum. Therefore, it was found that platinum was highly dispersed on
the S–ZrO2 surface as nanoparticles. Regarding the electrocatalytic
activity of Pt/S–ZrO2, in the presence of Nafion ionomer, PEMFC
performance of the Pt/S–ZrO2 cathode was lower than that of the Pt/C.
Because the slope of the voltage-current curve for the Pt/S–ZrO2 was
similar to that of Pt/C in the high current density range (1.5–2.5 A cm − 2),
there was no large iR loss caused by low electric conductivity of S–ZrO2.
Conversely, in the absence of Nafion ionomer, the cell performance of Pt/
S–ZrO2 cathode was higher than that of Pt/C. Because the lack of Nafion
ionomer decreased the proton conductivity in the catalyst layer, the cell
performance decreased in both cathodes without Nafion ionomer.
However, the decrease of the cell performance on the Pt/S–ZrO2 was
smaller than that on the Pt/C. For instance, although the voltage decrease
of Pt/C at 1 A cm − 2 was approximately 0.22 V, the decrease of Pt/S–ZrO2
was 0.10 V. The ratio of the cell voltage decrease for Pt/S–ZrO2 was 16%,
lower than the 33% for Pt/C. This result suggests that Pt/S–ZrO2 support
provided enough protons to obtain a large current and the content of the
757
ionomer in the catalyst layer might be able to be reduced using S–ZrO2 as
the support.
As it is well known, the proton conductivity of the proton exchange
membranes, such as Nafion or sulfonated poly(ether ether ketone)
(SPEEK) membranes, depend on the water content [105]. The unsatu-
rated-humidification or non-humidification of reactant gases prior to
entry into a fuel cell may lead to a decreased water content, and
accordingly reduced proton conductivity of the membranes. The
reduction in membrane thickness has facilitated water back diffusion
from the cathode to the anode, accordingly resulting in not significantly
impaired proton conductivity of the operating membrane. However, this
also increased the reactant crossover because of the thinner membrane,
which may reduce the cell performance and accelerate the membrane
degradation. To overcome these problems, Uchida et al. [106] proposed
the use of self-humidifying membranes with highly dispersed nan-
ometer-sized Pt and a hygroscopic oxide (TiO2). The Pt nanoparticles in
the membrane could suppress the reactant crossover by catalytic
recombination of the crossover H2 and O2, and the hygroscopic oxide
contributed to maintain the membrane water equilibrium. On this basis,
a different use of the Pt/S–ZrO2 catalyst than an electrode material was
proposed by Zhang et al. [107]. They prepared SPEEK/Pt/S–ZrO2 self-
humidifying membranes based on a sulfonated poly(ether ether ketone)
hybrid with sulfated zirconia supported Pt catalyst. The single cell
performance employing the SPEEK/Pt/S–ZrO2 membrane was evaluated
and the resistance of the operating membrane under wet or dry H2/O2
operations was also investigated, and compared to that of the plain
SPEEK membrane. A single cell employing the SPEEK/Pt/S–ZrO2
membrane exhibited higher cell OCV values and performance than the
plain SPEEK membrane cell under both dry and wet conditions.
Furthermore, the performance of the single cell with a SPEEK/Pt/S–
ZrO2 membrane was only slightly influenced by the humidification
conditions compared to that of the plain SPEEK membrane. The higher
OCV values and the lower resistance for the SPEEK/Pt/S–ZrO2
membrane under dry operation, as compared to of the plain SPEEK
membrane, were attributed to the incorporation of catalytic, hygroscopic
and proton-conductive Pt/S–ZrO2 catalyst inside the self-humidifying
membrane. However, no comparison was made with Nafion membrane.
2.6. SiO2
Silicon dioxide, also known as silica, is an oxide of silicon with a
chemical formula of SiO2 and has been known for its hardness since
antiquity. SiO2 has a number of distinct crystalline forms in addition to
amorphous forms. With the exception of stishovite and fibrous silica,
all of the crystalline forms involve tetrahedral SiO4 units linked
together by shared vertices in different arrangements.
Firstly, as in the case of Pt/S–ZrO2, Zhu et al. [108] and Wang et al.
[109] used silica supported Pt to prepare self-humidifying mem-
branes. Zhu et al. [108] prepared a self-humidifying membrane with a
sandwich structure with Nafion-impregnated porous PTFE composite
as the central layer and nanosized SiO2 supported Pt catalyst
embedded into the Nafion as the two side layers. Wang et al. [109],
instead, dispersed Pt/SiO2 catalyst particles uniformly into the Nafion
resin, and then a Pt/SiO2/Nafion/PTFE reinforced composite mem-
brane was prepared using a solution-cast method. The Pt/SiO2 catalyst
was prepared from H2PtCl6 and silicon dioxide (particle size of 20 nm)
by an impregnation/reduction method (Pt loading 1 wt.%, [108]) of
silicon oxide or via a microwave-assisted polyol process (Pt loading
2 wt.%, [109]). In both cases, the self-humidifying membrane
outperformed the plain Nafion/PTFE membrane. The self-humidifying
composite membranes could minimize membrane conductivity loss
under dry conditions. According to the authors, this is due to the
presence of Pt/SiO2 in the membrane.
More recently, Seger et al. [110] tested silica supported Pt as
cathode material in PEMFCs. They prepared platinum nanoparticles by
reduction of a Pt(IV) precursor with sodium borohydride on a
758 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
colloidal silica substrate. By controlling the ratio of platinum to silica,
they obtained a well dispersed catalyst surface with minimal
conductivity loss. At low Pt concentrations (Pt:SiO2 ratio of 1:1 and
2:1), Pt dispersion is quite uniform and form an interconnected
particle-network. The current interruption method was employed to
determine any possible ohmic voltage losses arising from the presence
of silica in the fuel cell. The Pt/SiO2 samples showed ohmic losses
similar to that of the commercial Pt-black sample. These results
confirm that the silica support does not contribute to any significant
increase in the overall resistivity. The performance of Pt/SiO2
composite particles in H2-fuel cell were compared to that of a Pt-
black catalyst. All these systems exhibit losses due to polarization and
further efforts are necessary to overcome these effects. The normal-
ized power density curves highlighted the beneficial aspects of Pt/
SiO2 catalysts, and the Pt/SiO2 sample at the 2:1 ratio exhibited the
highest power density values.
2.7. Indium tin oxide (ITO, Sn–In2O3)
Indium tin oxide (ITO) is essentially formed by substitutional doping
of In2O3 with Sn which replaces In3+ atoms in the cubic bixbyite
structure of indium oxide [111]. In the In2O3 crystalline structure, the
replacement of In3+ by Sn4+ affects the optical and electrical properties
of the ITO films. The replacement produces free electrons that contribute
to enhancing the conductivity (N103 S cm − 1) [112]. Chhina et al. [113]
studied the electrochemical stability of indium tin oxide supported
platinum. Pt was deposited on ITO by the reflux method, and both the
thermal and electrochemical stability were compared with that of a
commercially available 40 wt.% Pt/C catalyst (Hispec 4000). The
crystallite sizes calculated from XRD were 38 nm and 13 nm for ITO
and Pt/ITO, respectively. The total currents in the cyclic voltammetry
tests for Pt/ITO were much lower than those for Pt/Hispec 4000,
because the active surface area of the Pt particles on the ITO is much
lower than that in Hispec 4000. The ITO support was more stable to
oxidation than Vulcan XC-72R carbon. The ITO supported catalyst had a
lower electrochemically active surface area loss under an accelerated
voltage cycling test, and lower mass loss in TGA experiments compared
to the Pt/carbon catalyst.
3. Carbides
Carbides are compounds composed of carbon and a less electro-
negative element. Carbides can be generally classified by chemical
bonding type as follows: (i) salt-like, (ii) covalent compounds,
(iii) interstitial compounds, and (iv) “intermediate” transition metal
carbides. The carbides of silicon and boron are described as “covalent
carbides”, although virtually all compounds of carbon exhibit some
covalent character. Silicon carbide has two similar crystalline forms,
which are both related to the diamond structure. Boron carbide, B4C,
on the other hand has an unusual structure which includes ico-
sahedral boron units linked by carbon atoms. In this respect boron
carbide is similar to the boron rich borides. Both silicon carbide, SiC,
(carborundum) and boron carbide, B4C are very hard materials and
refractory. The carbides of the group 4, 5 and 6 transition metals (with
the exception of chromium) are often described as interstitial
compounds. These carbides are chemically quite inert, have metallic
properties and are refractory. Some exhibit a range of stoichiometries,
e.g. titanium carbide, TiC. Titanium carbide and tungsten carbide are
important industrially and are used to coat metals in cutting tools. The
carbides of transition metals, especially tungsten carbides, exhibited
Pt-like catalytic properties because near the Fermi level, the electronic
density of states of tungsten carbides resembles that of noble metal
platinum [114]. This means that these carbides are expected to be used
as electrocatalysts by themselves or as catalyst supports, which might
promote catalytic activity through synergistic effects.
3.1. Earlier works on metal carbides as fuel cell catalyst supports
Firstly in the 1960s at General Electric, boron carbides were tested
as a catalyst support in phosphoric acid [115] and alkaline [116] fuel
cells. Grubb and McKee [115] investigated boron carbide supported
platinum as the anode material in propane/oxygen PAFCs. A
commercial boron carbide powder was impregnated with a Pt
precursor, and then Pt was reduced with H2 at high temperature. Pt
crystallite size ranged from 1.6 to 4.7 nm, and increased with
increasing Pt loading. They found that Pt on boron carbide is more
resistant to sintering than platinum black or platinum on graphite at
equal surface coverage. Tests in PAFCs showed that the slopes of the
−1
current density vs. RHE/Pt loading plot are 5 mA mgPt for platinum
−1
on boron carbide and 0.6 mA mgPt for platinum black diluted with
boron carbide. This improvement by a factor of 9 is partially due to a
higher platinum surface area for the supported Pt. Then, the current
density was plotted against the real Pt area per unit electrode area.
The slopes of these straight lines were 9.3 and 3.5 μA cm − 2 for boron
carbide supported platinum and unsupported platinum black,
respectively. According to the authors, this factor of improvement
could indicate an enhancement of the Pt activity by the support.
Platinum iridium alloy catalysts supported on boron carbide were
investigated as anode materials in ammonia/oxygen alkaline fuel cells
at 100 –120 °C using 54% potassium hydroxide as electrolyte [116].
Platinum and iridium were deposited together on boron carbide and
graphite substrates by thermal decomposition of mixed solutions of a
platinum salt, Pt(NH3)2(NO2)2, and iridium chloride, IrCl3. The
catalysts were reduced in flowing hydrogen at 125 °C for 3 h. Cell
resistances were about 0.3–0.35 Ω for boron carbide anodes and 0.2–
0.25 Ω for graphite anodes. Satisfactory electrodes were obtained
using both boron carbide and graphite as the catalyst substrate. Boron
carbide-based anodes were, however, generally less reproducible than
those prepared from graphite.
Then, in the end of 1980 s, silicon and titanium carbides were
investigated as supports for H2/O2 PAFC catalysts [117,118]. SiC is
stable in hot phosphoric acid, but it is not electronically conducting.
Honji et al. [117] evaluated silicon carbide as a candidate catalyst
support material, achieving electronic conduction by incorporation of
carbon black in the catalyst layer during the fabrication of the
electrode. Platinum supported on silicon carbide was prepared by
reduction of chloroplatinic acid with methanol in the presence of
silicon carbide powder and a surface active agent. The platinum
content was in the range 5–23 wt.%. The average particle diameter of
the silicon carbide powder was about 0.3 μm and its specific surface
area about 10 m2 g − 1. Pt particles were well dispersed on the SiC
surface. Pt particle size was 4.3, 5.7, and 7.8 nm in 5, 10, and 23 wt.%
platinum, respectively. The potential-current density plots for oxygen
reduction on an electrode using Pt/SiC electrocatalysts depended on
the platinum content, and 23 wt.% Pt/SiC shows the lowest
polarization, that is about 0.7 V vs. RHE at 220 mA cm − 2 (iR
corrected), though the platinum particle size of 23 wt.% Pt/SiC was
larger than those of other Pt loadings. This value was almost the same
as that of platinum supported on carbon. Titanium carbide was
identified as a satisfactory electrical conductor and appeared to be
stable in hot phosphoric acid at oxygen electrode potentials in a fuel
cell. However, commercially available titanium carbide has a relatively
low surface area (b1 m2 g − 1) and therefore is not generally useful as
a catalyst support. Jalan and Frost [118] prepared titanium carbide
supports having a crystallite size in the range of about 5–50 nm and
relatively large average surface areas of 25–125 m2 g − 1 by contacting
titanium tetrachloride in the vapor phase with a gaseous unsaturated
hydrocarbon (ethylene, acetylene) and hydrogen at 500–1250 °C.
They found that the titanium carbide support has a desirable chain-
like structure which maintains electrical contact and has an open
porosity providing for an oxygen diffusion path and thus providing an
improved electrode, particularly for a fuel cell. Pt was supported on TiC
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
by impregnation/reduction methods, and the platinum surface area
was in the range of 20–90 m2 g − 1. The supports were characterized
by improved electrochemical corrosion resistance and the catalytic
activity of Pt/TiC in fuel cells was similar to that of electrodes made
with carbon black supports.
3.2. Tungsten carbides as PEMFC/DMFC catalyst support materials
More recently, the use of tungsten carbides as support for low
temperature fuel cells has received considerable attention. As
electrocatalysts, they are known to be highly resistant to CO poisoning
and stable in acidic and basic solutions, yet their electrocatalytic
activity for methanol oxidation is very low. However, this low activity
of tungsten carbide could be improved dramatically by adding a small
amount of platinum to tungsten carbide. Indeed, the methanol
oxidation on tungsten carbide films, modified by low coverages of
Pt, shows a promoting effect of Pt for the dissociation of methoxy
[119]. Analogously, the presence of tungsten carbide promotes the
electrochemical activity for oxygen reduction on platinum: the
overpotential is significantly reduced on a tungsten carbide nano-
crystal modified Pt catalyst, showing a synergic effect to improve the
ORR activity [120]. Generally, tungsten carbide exists in different
phases, of which the most important are tungsten monocarbide (WC)
and subcarbide (W2C). WC has the lowest electrical resistivity
(conductivity = 105 S cm − 1 at 20 °C) of any interstitial carbides, and
therefore qualifies as the most metallic carbide. A major drawback
preventing WC from being widely used as a catalyst support, however,
is the low surface area of tungsten carbide produced by traditional
metallurgical routes. WC can be made by direct carburisation of W
metal with carbon or graphite at 1400–2000 °C in hydrogen or
vacuum. The carbide formation process can also use tungsten oxide,
tungstic acid, or ammonium tungstates as the starting materials.
Carburization at high temperatures leads to low specific surface area
carbides.
As in the case of WOx, various papers report the use of tungsten
carbide dispersed on a high surface area carbon (WC/C) as catalyst
support: WC is synthesized on a carbon support and then Pt is
deposited to produce a Pt/WC/C [121–123]. In this review, we do not
consider this type of support, because it is not a carbon substitute.
Zellner and Chen [119] investigated the stability of WC and W2C by the
combination of electrochemical CV measurements in 0.5 M H2SO4 and
XPS measurements. They found that the WC film is stable at anode
potentials below 0.6 V, demonstrating the potential use of WC as an
anodic electrocatalyst in the DMFC. In contrast, W2C does not have a
stable region, suffering immediate oxidation to form WxOy species
when exposed to air or in an electrochemical environment. Zhang et
al. [124] compared the electrochemical activity and stability in PEMFC
environment of WxCy supported Pt with that of carbon supported Pt.
The tungsten carbide support was prepared through the carbonization
method using Vulcan XC-72 and H2WO4 as precursors. Pt was
deposited on the tungsten carbide and Vulcan XC-72 by the
formaldehyde reduction method. The Pt loading of the catalyst was
10 wt.%. XRD patterns showed the various diffraction peaks of WC,
W2C, and W2C0.85, and obvious peaks of Pt. The initial electrochemi-
cally active surface areas (ESA) of the Pt/C and Pt/WxCy catalysts were
16.1 and 10.2 m2 g − 1, respectively. This difference has to be ascribed
to the higher surface area of Vulcan XC-72 than that of the calcined
tungsten carbide. The ESA loss of the Pt/WxCy during the stability test
in 0.5 M H2SO4 at various potentials was much lower than that of Pt/C.
Furthermore, the Pt/C and Pt/WxCy catalysts were applied to single
cells both as anode and cathode materials to compare their
performance degradation. Before stability test, the PEMFC cell with
Pt/C better performed than that with Pt/WxCy. After stability test,
instead, the single cell prepared with the Pt/WxCy catalyst showed a
better performance than the cell with Pt/C, indicative of a high
oxidation resistance of the Pt/WxCy catalyst. Chhina et al. [125,126]
759
compared the stability of Pt supported on commercial WC
(BET = 1.6 m2 g − 1) with that of home made Vulcan XC-72 supported
Pt [125] and a commercial Pt/C [126]. In both works, the stability of
Pt/WC was higher than that of Pt/C. In the first work, similar amounts
of Pt (40 wt.%) were dispersed onto tungsten oxide and carbon
supports. However, due to the density difference between C and WC,
1.8 g cm − 3 and 15.6 g cm − 3, respectively, a comparison between
40 wt.% Pt on WC and 40 wt.% Pt on C results in a tendency towards the
observation of a lower stability of the WC, as the volumetric loading of
the catalyst on WC will be higher than that on C for the same
gravimetric loading. Therefore, an additional comparison was also
made with a smaller volumetric loading of the catalyst on the WC
support. In this comparison, 40 wt.% Pt was dispersed on C, and a
similar volume fraction of Pt was dispersed on the WC support
material. Equal solid volume ratios result in 6 wt.% Pt on WC. In both
cases, Pt/WC was more stable than Pt/C. The electrochemical activity
of the Pt/WC remained nearly constant over 100 accelerated oxidation
cycles, while the activity of Pt/C was almost completely lost after only
approximately 20 oxidation cycles. The high stability of Pt/WC was
ascribed to the surface oxidation of W during the first scan, changing
the structure of the support from Pt supported on WC to Pt supported
on a WOx shell encapsulating a WC core. Tungsten oxide, by reacting
with hydrogen, can form two stable hydrogen tungsten bronzes,
H0.18WO3 and H0.35WO3, or sub-stoichiometric tungsten oxides. Since
tungsten oxide exhibits fairly high electrochemical stability, its
formation is less deleterious to the electrochemical performance of
the cell than the oxidation of a carbon catalyst support, which leads to
irreversible platinum detachment and corresponding complete
activity loss. However, the initial activity of the Pt/WC supported
catalyst is much lower than that of Pt/C at comparable volumetric
catalyst loadings, indicating that higher surface area WC supports and
better platinum dispersion techniques are still required in order to
enhance the catalyst layer activity. Synthesis of tungsten carbide with
higher surface area was reported by Koc and Kodambaka [127]. They
prepared tungsten carbide powders from novel carbon coated
precursors. The process has two steps in which the oxide powders
were first coated with carbon by cracking of a hydrocarbon gas,
propylene (C3H6), secondly mixed with a substantial amount of
carbon black, and finally treated at temperatures in the range of 600–
1400 °C to synthesize WC. A preparation method consisted in
depositing 7.6 wt.% pyrolytic carbon on tungsten oxides and mixing
these composite particles with carbon black. The initial surface area
was about 32 m2 g − 1. Surface area increases with temperature to a
maximum of about 50 m2 g − 1 at 900 °C and then linearly decreases as
the temperature increases. During the reduction process, oxide
particles were reduced to tungsten and oxygen was removed in the
form of CO or CO2. The increase in surface area was ascribed to the
reduction of the oxides and the formation of fine W particles. At
temperatures above 1000 °C, the decrease in the surface area was
explained by the carburization of tungsten and the formation of necks
among some of the particles. To prepare high surface are WC, Chhina
et al. [126] used high surface area carbon as a template upon which
tungsten was dispersed. They synthesized WC on a high surface area
carbon using three different routes: aqueous tungstate dispersion on
carbon, an incipient wetness technique to disperse tungstate on
carbon, and DC magnetron sputtering of tungsten on carbon. The
synthesis of high surface area WC using the aqueous reduction
technique led to a low yield (10%) of W deposition, and the incipient
wetness technique led to the formation of dense WC particles with
agglomerates of 5–9 μm. DC magnetron sputtering of W onto C,
instead, proved to be a promising technique for high surface area WC
synthesis, leading to porous agglomerates that were not as dense as
those obtained by either of the other two techniques. Ganesan and Lee
[128] synthesized W2C microspheres by heating mixtures of resorci-
nol-formaldehyde polymer and ammonium metatungstate salt
(AMT). XRD analysis of the microsphere indicated W2C as the major
760 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
phase, and WC and WC1−x as minor phases. The BET surface area of the
W2C microspheres was about 176 m2 g − 1 (compared to 635 m2 g − 1 for
carbon microspheres). Platinum particles were supported on these W2C
and Pt–Ru particles on carbon microspheres by the conventional
borohydride reduction method. The crystallite sizes from XRD were
6 nm for 7.5 wt.% Pt on W2C, 14 nm for 15 wt.% Pt on W2C, and 14 nm
for 20 wt.% PtRu on carbon microspheres. By CV measurements, the
electrochemical surface area of platinum supported on W2C was
several-times higher than those of Pt–Ru supported on carbon
microspheres and commercial (E-TEK) 20 wt.% PtRu(1:1)/C carbon.
This result indicates that the platinum particles were better dispersed
on the W2C spheres than on the other supports. The electrochemical
activity towards methanol oxidation of both 7.5 wt.% and 15 wt.% Pt
supported on W2C microspheres was higher than that of PtRu
supported on carbon microspheres and the PtRu/C catalyst by E-TEK.
The mass activity of platinum supported on W2C microspheres
(7.5 wt.% Pt) was higher by factors of 2.6 and 2.4 than those of PtRu on
carbon microspheres and the commercial PtRu catalyst, respectively.
These results clearly showed that Pt supported on W2C microspheres
provides much better utilization of platinum than in the PtRu/C
catalysts and that ruthenium could be entirely replaced. According to
the authors, there are several reasons why Pt/W2C-microsphere
catalyst performs better than the commercial catalyst even with the
smaller platinum loadings and in the absence of ruthenium. The first
is the ability of W2C to stabilize the high dispersion of platinum
relative to carbon supports as discussed above. Second, in the
presence of platinum, W2C is active in the electrochemical methanol
oxidation and water decomposition. The formation of hydroxy
groups from water activation is essential for the removal of metal-
poisoning CO from the surface. This is the main role played by
ruthenium in conventional Pt–Ru catalysts and this role can be played
by W2C. Finally, W2C showed high CO resistance. The CO desorption
temperature for pure platinum is 187 °C. It decreases to 147 °C, when
the platinum is supported on W2C. This feature would decrease the
poisoning of the catalyst surface by CO and increase the activity for
electrooxidation of methanol. The stability of the Pt/W2C-micro-
sphere catalyst was tested by repeating electrochemical reaction
cycles in a H2SO4/CH3OH solution. The specific activity increased
initially, but stabilized after around 30 cycles. The authors believe
that surface oxygen species formed on the catalyst are removed
during this transient period. Once a steady state is established, there
was no sign of deactivation during 100 consecutive reaction cycles.
Jeon et al. [129] synthesized a WC supported platinum catalyst
(20 wt.% Pt) for methanol oxidation by a conventional impregnation
method and compared its MOR activity with that of a commercial (E-
TEK) Pt/C. Commercial WC powder was used as a support. Average
particle sizes of Pt in Pt/WC and Pt/C were 7.5 and 2.9 nm,
respectively. Pt particles were dispersed on WC surface uniformly,
however, most of the WC surface was covered with Pt particles despite
the small mass ratio of Pt. This result was caused by the spherical
structure and larger density of WC. The electrochemically active
surface areas (EAS) calculated from the H+ desorption were 11.2 and
5.74 m2 g − 1 for the Pt/WC and Pt/C catalysts, respectively. EAS of Pt/
WC was about twice that of Pt/C although the particle size of Pt in Pt/
WC was 2.6 times of that Pt/C. EAS calculated from CO stripping were
4.42 and 6.30 m2 g − 1 for the Pt/WC and Pt/C catalysts, respectively.
In the case of Pt/C, the difference between EAS (H+) and EAS (CO) was
within 10%, while EAS (H+) was 2.5 times of EAS (CO) in the case of
Pt/WC. The large EAS (H+) of Pt/WC was explained by the spill-over
phenomenon of H+ from Pt to WC. Spill-over of H+ creates fresh Pt
surface resulting in large EAS (H+). CO stripping showed another
interesting result: the CO electro-oxidation peak potential shifted
from 0.80 V in Pt/C to 0.68 V in Pt/WC. The improved CO oxidation
activity originated from the formation of OH by water discharge on the
WC surface. Mass activities for methanol oxidation at 0.5 V were 831
−1
and 910 mA gPt for the Pt/WC and Pt/C catalysts, respectively.
Specific activities, calculated dividing mass activity by EAS (CO) were
188 and 144 mA m − 2 for the Pt/WC and Pt/C catalysts, respectively.
Hara et al. [130] prepared a WC promoted with a small amount of
Pt metal by a wet impregnation method. Pt metal loadings were fixed
at 10 wt.%. The catalyst was prepared using a WC (surface area of
25.6 m2 g − 1) support, obtained by carburization of W2N, which was
synthesized from WO3. Pt particles were fairly aggregate with around
20 nm in size probably due to the low surface area of WC. The mass
activity of Pt/WC was lower than that of a commercial Pt/C (E-TEK), due
to its lower ESA. The specific activity of Pt/WC (about 10 A m − 2), instead,
was higher than that of the commercial Pt/C catalyst (2.5 A m − 2). The
same research group [131] prepared new WCs with high surface area by
the carburizing of W2N and WS2 precursors, which were prepared from
starting materials other than WO3, such as W(CO)6, WCl6 and the like. In
particular, the BET surface areas of WCs derived from W(CO)6/S and
(NH4)2WS4 were around 80 m2 g − 1, which is the highest value among
α-WCs reported. This is probably due to a unique structural change
forming small crystalline WC particles with a plate-like structure in the
carburization of WS2 and W2N. WC supported Pt metal was prepared by a
wet impregnation method and was evaluated as an anode catalyst for the
electrochemical hydrogen oxidation reaction. The activity of a binary Pt–
WC catalyst was greatly improved by choosing a favorable WC and by
modifying the preparative method. As a result, it turned out that the
mass activity of the Pt–WC catalyst system was superior to that of the
commercial Pt/C catalyst. The interaction of Pt metal with WC is
concluded to lead to remarkable improvement in terms of activity, and
there is a strong synergistic effect between them. The following
mechanism of H2 oxidation on Pt/WC was postulated. The hydrogen
adsorption at WC is slower and the exchange current density is smaller as
compared to hydrogen at Pt. He concluded that the reaction H2ad → 2Had
is the rate-determining step for the adsorption of H2 at the WC anode. On
the other hand, Pt metal is well known to readily dissociate the H2
molecule to Had which diffuse into the catalyst surface as a spillover
phenomenon. Therefore, it is postulated that Pt plays the role of
accelerating the process of dissociative adsorption of H2, the rate-
determining step for the WC, and WC could take over the rest of steps in
the process of the hydrogen electro-oxidation.
Ganesan et al. [132] and Ham et al. [133] tested mesoporous
tungsten carbide as a support for Pt catalysts. Ganesan et al. [132]
synthesized a mesoporous tungsten carbide by using ammonium
metatungstate as a tungsten precursor and resorcinol-formaldehyde
polymer as a carbon source in the presence of a surfactant. They
prepared two-types of WC powders by controlling the amount of
mesopores. The synthesis of both WC samples involved polyconden-
sation of resorcinol–formaldehyde in the presence of AMT, followed
by heat treatment at 900 °C. A difference in the preparation methods
for the two WC samples was the presence or absence of a surfactant
(CTABr) during the polycondensation step. The preparation with
CTABr gave WC with ample mesoporosity (denoted as meso-WC)
whereas that without CTABr yielded WC nanoparticles with a small
pore volume (denoted as part-WC). Average pore sizes were similar,
4.6 nm for part-WC and 4.3 nm for meso-WC. The BET surface areas
were also similar, 95 m2 g− 1 for part-WC and 76 m2 g− 1 for meso-WC.
The most significant difference between two samples was the pore
volume. The part-WC showed a very small volume of 0.086 cm3 g – 1,
while that of meso-WC was ca. 3-fold higher at 0.24 cm3 g − 1. Thus the
surfactant CTABr introduced during the polycondensation reaction
increased the pore volume of the sample. The XRD pattern of the
meso-WC sample showed the presence of WC as the major phase, and
minor amounts of W2C and WC1−x. The HRTEM images of meso-WC
sample are shown in Fig. 7 [132]. The WC samples are a collection of WC
nanoparticles of ca. 20 nm, which appears highly crystalline as evidenced
by clean lattice fringes. The spacing of the lattice fringes was about
0.25 nm (Fig. 7a) corresponding to the interplanar spacing of (100)
planes of simple hexagonal WC. Selected area electron diffraction (SAED)
patterns also show that WC is well crystallized. Pt particles were
 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763 761

Fig. 7. (a) Lattice TEM image of meso-WC (inset: SAED pattern of WC). (b) HRTEM images of Pt particles in Pt (3.5 wt.%)/meso-WC. Scale bars represent 2 nm (a) and 20 nm (b).
Reproduced from Ref. 132, copyright 2007, with permission from Elsevier.

deposited on these WC materials by the conventional borohydride 4. Conclusions

reduction method. The HRTEM image (Fig. 7b) shows that platinum
particles are finely dispersed on WC materials. The average Pt particle
size was ca. 2 nm for 3.5 wt.% Pt and ca. 6 nm for 7.5 wt.% Pt both on part-
WC and meso-WC. Pt supported on these materials shows higher activity
for electrochemical oxidation of methanol than a commercial PtRu/C
catalyst by a factor of six (per mass of Pt) even without Ru. The
mesoporosity and phase of WC appear important as Pt/meso-WC
performs better than Pt/W2C-microsphere and Pt/part-WC. It is
interesting to note that the two less active tungsten carbide catalysts
possess higher surface areas than that of Pt/meso-WC, but it is mostly
due to micropores. Thus for high electrocatalytic activity, the facile mass
transport of hydrated methanol to the reaction sites through mesoporous
appear more important than the inaccessible high surface area. Ham et
al. [133] prepared a mesoporous tungsten carbide of WC-phase by using
the same method of Ganesan et al. [132], then deposited Pt on the
mesoporous WC by the borohydride method (7.5 wt.% Pt). The Pt/WC
catalyst shows not only two times higher mass activity but also much
improved resistance to CO poisoning for hydrogen electro-oxidation
than a commercial Pt/C catalyst. The high activity for hydrogen oxidation
was attributed to the active participation of WC in the electro-oxidation
together with Pt and the high CO tolerance to facile formation of surface
hydroxyls on WC that could react away CO strongly adsorbed on Pt. It has
to be remarked that in both these works using mesoporous carbon the
Pt/WC weight ratio was b10 wt.%. A higher Pt loading in Pt/WC should
be desirable to decrease the amount of WC, and, as a consequence, the
mass and the thickness of the catalytic layer of the electrode, at a fixed Pt
content.
Different metal oxides and carbides have been tested as carbon-
substitute supports for low-temperature fuel cell catalysts. The
characteristics of these ceramic material and carbon Vulcan XC-72
supports, and the catalytic activity and stability in fuel cell conditions of
relative supported catalysts are summarized in Table 1. Some materials
showed encouraging results, while others presented unsuitable proper-
ties to be used as fuel cell catalyst supports. Generally, all the materials
presented high stability in a fuel cell environment and acceptable
electrical conductivity, but most of them possess a low surface area,
resulting in a low metal dispersion and, as a consequence, in a poor
electrochemical activity. In various studies, to increase metal dispersion,
supported catalysts with a low metal/ceramic ratio (b10 wt.%) were
prepared. This way to tailor the metal/ceramic composite, however, is
not suitable for use as a fuel cell support. Indeed, a low metal/ceramic
ratio results in the presence of a large amount of ceramic material in the
catalyst layer of the electrode, increasing the electrode resistance.
Regarding the electrochemical activity, ceramic supported catalysts have
to be evaluated with care. Most papers are indeed very optimistic
regarding the potential interest of ceramic materials, due to presumable
high activity of ceramic supported metals. In many works [40,46,50–
53,67,98,110] comparison of the catalytic activity of oxide/carbide
supported metals with that of the commonly used carbon supported
metals was not made, so it is not possible establish the effectiveness of
these materials as carbon-substitutes for fuel cell catalysts. In some cases
the authors overvalued their results, for example comparing the activity
of oxide supported catalysts with that of the homologous unsupported

Table 1
Characteristics of ceramic material and carbon Vulcan XC-72 supports, and catalytic activity and stability in fuel cell conditions of relative supported catalysts.

Material Specific surface Electrical conductivity Metal dispersion, Catalytic activity of Stability in fuel Refs
area m2 g − 1 S cm − 1 particle size (d) nm supported metal cell conditions
Vulcan XC-72 254 4 High d 2.9 High Low [4]
Ebonex, Ti4O7 1–3 1, 103 Low dTi4O7 10–20 Generally low Conflicting results [40–42,46]
M–TiO2 1–1.4 (high Tsynt) 136 (low Tsynt) 10 − 1–102 High dRuTio2 3.3–5.4 dSbTiO2 3.0 High High [43,45–48]
M–SnO2 ~ 43⁎ (RuSnO2) 10 − 1–103 High dSbSnO2 2.5 dRuSnO2 4 High High [64–66]
100 (SbSnO2)
WO3 18, 86 n.d. Medium/High d 6.5 High High [85–88]
d 3–6 (nanorods)
RuO2·xH2O 125 1 n.d Low n.d. [97,98]
S–ZrO2 80 n.d. n.d. Low High [104]
Sn–In2O3 ~ 22⁎ N103 Low d 13 Low High [113]
WC 1.6 (Tsynt N 900 °C), 30–80 (Tsynt b 900 °C) 105 Low/Medium d 6–20 Low (low SA) High [124–133]
176 (microsphere) d 2–6 (meso-WC) High (high SA)

⁎Calculated from particle size.

762 E. Antolini, E.R. Gonzalez / Solid State Ionics 180 (2009) 746–763
catalysts, which obviously have low active surface area and, as a
consequence, low mass activity [40,98,110]. Doped TiO2 and SnO2, WO3
and WC are the most promising materials as catalyst supports: the
catalysts supported on these materials presented both high stability and
high activity. In addition, doped TiO2 and SnO2, WO3 and WC exhibited a
promoting effect on the electrocatalytic activity of Pt or PtM alloys,
making the ceramic supported catalyst more active than the homo-
logous carbon supported catalyst. WO3, RuO2·xH2O and S–ZrO2 present
the interesting characteristics of proton conducting materials. This
property allows the reduction of Nafion ionomer content in the
electrode catalyst layer, and increases the platinum utilization. Regard-
ing the nanostructured ceramic oxides, few works have been performed
on catalysts supported on these materials for use in low-temperature
fuel cells. For this reason, at this time, notwithstanding the encouraging
results, it is a risk to affirm that the electrochemical activity of catalysts
supported on nanostructured ceramic oxides is higher than that of
carbon supported catalysts.
Generally, the electrocatalytic activity of supported Pt and Pt–M
alloy catalysts is referred as mass activity (MA) or specific activity
(SA), i.e. it is normalized with respect to the mass (MA) or the surface
area (SA) of the catalyst in the electrode. Regarding the catalysts
supported on ceramic materials, their mass activity is generally lower
than that of the same catalysts supported on carbon, due to the lower
surface area of the ceramic substrates. The specific activity, instead, is
generally higher than that of the corresponding catalysts supported on
carbon, due to the synergistic effect between the catalyst and the
ceramic support. Due to their high specific activity, ceramic materials
show a potential interest as carbon substitute for FC catalysts. The
mass activity, however, has practical implications because the cost of
an electrode depends on the amount of catalyst used. To achieve
economic metal loadings (b1 mg cm − 2) fuel cell electrodes must be
prepared from metal nanoparticles (d b 5 nm), and low metal particle
size for catalysts with metal/support weight ratio N10 wt.% can be
obtained only using high-surface-area materials as catalysts supports.
Thus, to increase the mass activity of supported catalysts, research
goals have to be addressed to the achievement of ceramic support
with high surface area.
Summarizing, the results regarding the catalytic activity of some
oxide and carbide supported catalysts are very promising, but they are
scarce and carried out overall in acidic solution. Further tests, particularly
in a single fuel cell, have to be performed to confirm the good
performance of these ceramic materials as a support for fuel cell catalysts.
Acknowledgments
The authors thank the Conselho Nacional de Desenvolvimento
Científico e Tecnológico (CNPq, Proc. 310151/2008-2) for financial
assistance to the project.
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