Electrochemistry Communications 6 (2004) 105–109

www.elsevier.com/locate/elecom

New palladium alloys catalyst for the oxygen reduction

reaction in an acid medium
a,b,*
O. Savadogo , K. Lee a, K. Oishi a, S. Mitsushima a, N. Kamiya a, K.-I. Ota a

a
Department of Energy and Safety Engineering Yokohama, National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
b  
Laboratoire d’Electrochimie et de Materiaux, Energ
etiques, Ecole Polytechnique de Montreal, C. P. 6079,
Succ. Centre-Ville, Montreal, QC, Canada H3C 3A7

Received 3 October 2003; received in revised form 20 October 2003; accepted 20 October 2003
Published online: 14 November 2003

Abstract

Extremely active palladium-based alloys catalysts without platinum for the oxygen reduction reaction (ORR) in an acid medium
were shown for the first time. The palladium alloys were prepared by sputtering under a vacuum of less than 10 4 Pa from a
palladium target and an alloying metal sheets on a glassy carbon support. Their electrochemical characteristics for ORR were
determined at 30 °C in sulphuric acid. It was demonstrated that the base voltammograms (CVs) of Pd–Co alloys did not show
significant change in the shape or size during the whole measurements procedure. Furthermore the Pd–Co alloy CV were found to be
completely different from those of Pd and Co alone and they never changed to become more Pd-like or Co-like. The Pd–Co alloy
catalysts are stable under the applied experimental conditions. The interesting properties of the alloys for the ORR were attributed
to an appropriate electronic stabilisation of the alloying element atom in the alloy which may prevent its corrosion and which allows
the enhancement of its catalytic activity. It was further demonstrated that an improvement of at least 250 mV, based only on a
theoretical estimation from Tafel slope, in ORR over-voltage could be obtained if a Pd–Co 28% catalyst is used at 30 °C instead of
Pt for PEFC or acid Solid Polymer Electrolyser Applications.
Ó 2003 Elsevier B.V. All rights reserved.

Keywords: New palladium alloys; Oxygen reduction reaction; Acid medium; More active than platinum

1. Introduction K. The current densities of order of 60–80 mA cm 2 for

Even, though it has been shown that the oxygen re-
duction reaction (ORR) on palladium proceeds via the
4-electron pathway, as is the case on platinum [1, and
references], there is no data available in the literature on
the ORR on Pd-alloys in an acid medium. The main
reason for this is probably that Pd is not an active
material for ORR in an acid medium. By contrast al-
loying elements like Co, Cr, Ni, etc. are known to be
unstable in acid media. Electrochemical investigations
on carbon supported palladium catalysts have been
shown [2]. The galvanostatic steady-state polarisation
curves were obtained for the ORR in 6.0 M KOH at 353
*
Corresponding author. Tel.: +1-415-340-4725; fax: +1-514-340-
4468.
E-mail address: osavadogo@polymtl.ca (O. Savadogo).
the ORR was obtained at –200 mV vs. Hg, HgO/OH .
Electrochemical reduction of oxygen was studied at the
epitaxially grown ultra thin Pd layers of various thick-
ness on Au (1 1 1) and Au (1 0 0) single crystal surfaces in
5 mM HClO4 solution saturated by oxygen [3]. At the
palladium monolayer, oxygen reduction proceeded in
relatively positive potential region than that at the
multilayers of palladium at the both substrates. The
oxide reduction of the Pd layers seemed to be important
for efficient oxygen reduction. The ORR on theses
electrodes is still seriously small when compared to that
on Pt or Pt-alloys. Kinetics of the ORR in 0.5 M HClO4
on an epitaxial film of palladium on Pt(1 1 1) was studied
using the rotating disc electrodes [4]. The ORR activity
on Pd was lower than on Pt(1 1 1). In 0.5 M H2 SO4 the
inhibition of the reaction was greater on the pseudo-
morphic monolayer of Pd than on the unmodified

1388-2481/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2003.10.020
106 O. Savadogo et al. / Electrochemistry Communications 6 (2004) 105–109
Pt(1 1 1) surface. The ORR has been also investigated on
Pd particles inserted into polythiophene films [5]. The
palladium-modified electrode exhibits a considerable
catalytic activity although it is smaller than that of Pt.
The Tafel values for potentials below 0.8 V was about
120 mV decade 1 . It was observed that above 0.3 V,
only formation of hydrogen peroxide occurs, leading to
the ORR mechanism involving only two electrons. For
smaller electrode potentials, further reduction of H2 O2
to water occurs, resulting in a process involving four
electrons. These various results show that Pd modified
electrodes or thin films of Pd deposited on platinum
exhibit better catalytic properties than those of palla-
dium alone. In contrary these electrodes are less active
than platinum for the ORR in acid medium. On the
other hands, the electrodes used in these studies are not
based on Pd-alloys. The challenge is to develop appro-
priate Pd-alloys with specific compositions, which may
exhibit: (i) very good activity for oxygen reduction (at
least the same as platinum); and (ii) excellent stability in
an acid medium for PEFC applications. This is very
important because Pd is at least 50 times more available
in the earth than Pt, and each of the alloying elements is
more available than Pd itself. We report here on Pd-
alloy catalysts for oxygen reduction reaction in an acid
medium. The family of alloys includes: Pd–Co, Pd–Cr,
Pd–Ni, Pd–Ta, etc. This work deals with some results
obtained with some alloys of this first family.
2. Experimental
The alloys are fabricated by a R-F sputtering method
using the MUE-ECO-EV type of sputtering machine
manufactured by ULVAC, Japan. Each alloy was
sputtered from a palladium target of 2 in. in diameter on
which one, two or three pieces of the alloying element of
about 1 cm2 each were deposited, depending of the alloy
composition to be fabricated. The palladium target was
purchased from Tanaka Kikinzoku Corp. (Japan); the
cobalt and nickel sheets were purchased from Nilaco
Corp. (Japan) and the chromium sheet was purchased
from Furuchi Chemical Corp. (Japan) and the glassy
carbon rods were purchased from Nisshibo Corp. (Ja-
pan). The alloy was sputtered on a glassy carbon rod
support (5 mm of diameter and 5 mm of length) at 10 5
Pa, 100 W during 30 min. The nominal film thickness of
sputtered Pt and palladium alloys determined by Auger
spectroscopy and scanning electron microscopy was 1
lm. The exact composition of the alloys was obtained
from EDX analysis [6]. The oxygen reduction reaction
performance was evaluated in a 0.1 M solution of sul-
phuric acid at 30 °C, using a potentiostat/galvanostat
model PS-16 (Toho Technical Research, Japan) to make
the following electrochemical measurements: (i) cyclic
voltammetry (100 mV/s) (CV) curves in a nitrogen at-
mosphere; (ii) slow scan (1 mV/s) (SSV) current–voltage
curves in an oxygen medium; (iii) Tafel plot (TP) pa-
rameters of the ORR; etc. The curves were compared to
those of poly crystalline platinum and sputtered plati-
num. The surface area of polycrystalline Pt and
sputtered electrodes was determined from CVs mea-
surements and calculation by assuming a coulombic
charge of 220 lC for hydrogen adsorbed on a smooth Pt
surface [7–10]. From some preliminary results it was
shown that the electrode surface area of all the sputtered
electrodes was similar. Accordingly, the current densities
are expressed against the geometric surface area of the
electrodes because all the catalysts were deposited on the
same type and size of glassy carbon in the same condi-
tions. The electrochemical measurements were made in a
classical electrochemical cell with a three-electrode
configuration. The reference electrode was a reversible
hydrogen electrode (RHE) and the working electrode
was the alloy deposited on the glassy carbon support
which is connected to the potentiostat through a gold
wire attached to the glassy carbon. For CV measure-
ments, argon gas was allowed to flow into the cell at a
rate of 50 ml/min for 4 h before recording the curves
under the same flow rate. The SSV current–voltages or
TP curves were plotted under a 50 ml/min oxygen flow, 4
h after introducing the oxygen into the cell.
3. Results and discussion
The exact composition of the sputtered Pd-alloys was
determined by EDX. It was found that alloys of Pd–Co
28% a/o and Pd–Cr 30% a/o were obtained for alloys
deposited under a vacuum of 4  10 5 Pa, over a period
of 30 min (5 min out off the support to clean up the
target from surface contamination and 25 min on the
support) and a power of 100 W. The amorphous nature
of the sputtered films has been confirmed by X-ray dif-
fraction. To understand the role of the possible redox
reactions on the electrochemical reduction of oxygen,
the cyclic voltammetric response of all the electrodes
was analysed in the potential range between 0.05 and 1.2
V at 30 °C. Fig. 1 shows the CVs of R-F sputtered Pt,
polycrystalline Pt and sputtered Pd. The typical Pt-
peaks obtained on sputtered Pt and polycrystalline are
similar and are around 0.1 and 0.25 V for the hydrogen
under-potential deposition (Hupd ) and around 0.15 and
0.20 V for the oxidation of hydrogen. The peak current
densities of the polycrystalline Pt CV are 2 times higher
than those of the sputtered Pt. This difference is well
pronounced in the Pt–oxides formation and reduction
areas. The peaks are also less defined for the sputtered
Pt. This is related to the amorphous nature of the
sputtered Pt which was confirmed by X-ray diffraction.
The range of current density obtained with the poly-
crystalline Pt is similar to that obtained elsewhere
 O. Savadogo et al. / Electrochemistry Communications 6 (2004) 105–109 107

double-layer (between 0.3 and 0.8 V) is constant and the

2 B oxide formation potential starts in the same potential
range (0.8 V) as that of polycrystalline Pt. No hysteresis
1 was observed in the double-layer region, indicating that
no formation and reduction of oxides is observed in this
A
-2

region. The peak of reduction observed at around 0.72 V

i / mA cm

0 C can be attributed to the alloy oxide formed at 0.8 V.

This peak is not seen on the CV of Co alone, and for the
-1 alloy its position is related to the Co content. The reason
A bulk-Pt
of this shift might be related to the change of the ORR
B sputtered-Pd
-2 activity with the variation of the Co content. It has also
C sputtered-Pt
been verified experimentally that either the potential
-3
value of this peak does not change with time or the
0,0 0,2 0,4 0,6 0,8 1,0 1,2 number of cycles, or both. Furthermore the sputtered
Pd–Co alloy CV are completely different from those of
Fig. 1. Base voltammograms at 100 mV/s and 30 °C in nitrogen sat- sputtered Pd or Co alone. They never change and be-
urated 0.1M H2 SO4 of a sputtered Pd on glassy carbon disc, sputtered come more sputtered Pd-like or Co-like. The sputtered
platinum on glassy carbon disc and bulk-platinum. Pd–Co and sputtered Pd–Cr alloy catalysts are stable
under the applied experimental conditions. This is sup-
ported by our preliminary XPS measurements which
[1,11,12, and references]. As shown in Fig. 1, the CV of
have shown that in the case of sputtered Pd–Co alloy,
sputtered Pd is completely different from both CVs of
the ratios of the cobalt oxides (2% a/o of CoO, Co3 O4 )
Pt, indicating that Pd has no significant oxide formation
and Pd oxides (6% a/o of PdO, PdO2 ), which were
in the same potential range. Fig. 2 shows that the pro-
found at low concentrations at the catalyst surface be-
files for under-potential deposition and oxidation of
fore and after CV and SSV measurements, do not sig-
hydrogen are very pronounced on the sputtered Pd–Co
nificantly change. More significant studies related to
28% a/o, indicating a strong Hupd region which is more
XPS measurements and analysis are under active in-
visible than that even in the case of polycrystalline Pt.
vestigations. The behaviour of these alloys might be due
Better results might be obtained with the optimised
to an appropriate electronic stabilisation of the alloying
composition of this alloy i.e with Pd–Co  30% a/o. The
element atom in the alloys which may prevent their
current density exhibited by the oxidation and the re-
corrosion and leads also to the enhancement of its sur-
duction peaks of the sputtered Pd–Co alloy are about
face catalytic activity due to a synergetic effect based on
ten times higher than those of polycrystalline Pt or
the interactive and substantially inter-ionic bonding
sputtered Pd–Cr alloy. This might indicate a greater
theory [13,14] supported by a bi-functional or co-cata-
activity of this alloy than polycrystalline Pt or sputtered
lytic behaviour of the alloying element [15], or both. In
Pt–Cr for the ORR and also for the hydrogen evolution
such approaches, the nature of the alloying element, its
reaction (HER) in an acid medium The current in the
composition and surface properties are very important
[15]. The high degree of activity of the Pd–Co alloy for
the ORR is supported by the slow scan potential rate
2 curves of this reaction at 5 mV/s and 30 °C of bulk-Pt,
sputtered Pd–Co 28% a/o and sputtered Pd–Cr 30% a/o
C
1 (Fig. 3). Fig. 3 shows that, in the activation region, the
current density of the ORR on sputtered Pd–Co 28% a/o
-2

B
i / mA cm

0 alloy is significantly higher than that of the ORR on

A bulk-Pt. The confirmation of these results using rotating
-1 disk electrode (RDE) technique is under active investi-
gation. The Tafel plots of the ORR at the high current
-2 AA Pd-Cr density regions for sputtered Pd–Co 28% a/o, sputtered
B bulk-Pt Pd–Cr 30% a/o and bulk-Pt are shown in Fig. 4. The
-3
C Pd-Co corresponding Tafel slope and exchange current density
are shown in Table 1. The Tafel slopes of sputtered Pt,
0,0 0,2 0,4 0,6 0,8 1,0 1,2 and sputtered Pd are also indicated in Table 1. The
values of the Tafel slopes and the exchange current
Fig. 2. Base voltammograms at 100 mV/s and 30 °C in nitrogen sat- densities of the ORR on bulk-Pt and sputtered Pt are
urated 0.1M H2 SO4 of sputtered Pd–Co 28% a/o, sputtered Pd–Cr similar to those indicated in the literature at room
30% a/o and bulk-Pt. temperature [1,11]. The lowest Tafel slope is obtained
108 O. Savadogo et al. / Electrochemistry Communications 6 (2004) 105–109

0,90
0,0 A
0,88

C 0,86
-0,4
-2

E / V vs. RHE
i / mA cm

0,84

B 0,82
-0,8
0,80
A Pd-Cr 30%
B Pd-Co 28% 0,78
-1,2 (bulk-Pt)
C Bulk-Pt
0,76 (Pd-Cr30%)
0,74
(Pd-Co28%)
-1,6
0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,1 1,2 1,3 -1,6 -1,4 -1,2 -1,0 -0,8 -0,6 -0,4

Fig. 3. Slow scan voltage rate curves of the oxygen reduction reaction
at 5 mV/s and 30 °C oxygen saturated 0.1M H2 SO4 on bulk-Pt,
sputtered Pd–Co 28% a/o and sputtered Pd–Cr 30% a/o.
Fig. 4. Tafel Plots of the ORR at 5 mV/s and 30 °C for the sputtered
Pd–Co 28% a/o; sputtered Pd–Cr 30% a/o. and bulk-Pt from the slow
scan voltage rate curves in the anodic sweep direction in the activation
region from Fig. 3.

Table 1
Tafel slope (b), specific activity at 800 mV (i800 ) and exchange current density of the ORR in 0.1 M H2 SO4 at 30 °C on bulk-Pt; sputtered Pd; Pd–Co
28% a/o and Pd–Cr 30% a/o
Bulk-Pt Sput. Pt Sput. Pd Pd–Co 28% a/o Pd–Cr 30% a/o
b (mV/decade) 115 117 95 70 70
i800 (mA cm 2 ) 0.25 0.29 0.01 0.58 0.07
io (mA cm 2 ) 1  10 4
9.1  10 5
2.2  10 7
5.1  10 6
2.2  10 7

with the new catalyst (Pd–Co 28% a/o) for the ORR.
The exchange current density of Pd–Co 28% a/o is 20
times higher than the exchange current density of Pd.
The same exchange current density is about 20 times les
than that of Pt. Because the Tafel slope of the Pd-28%
a/o is very small compared to that of Pt, the improve-
ment in over-voltage, based only on a theoretical esti-
mation, will be significant if Pd–Co 28% a/o catalyst is
used in the place of Pt. As an example, with the data
shown in Table 1, this improvement could be at least
250 mV at 30 °C if the ORR is performed at 1 A cm 2 .
The high specific activity of the ORR at 800 mV of Pd–
Co 28% a/o (0.58 mA cm 2 ) compared to that of bulk-Pt
(0.25 mA cm 2 ) supports the excellent catalytic activity
of Pd-alloys for the oxygen reduction in acid medium.
Such an improvement may help to recover the maximum
of voltage loss at the oxygen reduction cathode for
PEFC applications.
4. Conclusion
These preliminary results show that Pd–Co28% alloy
may exhibit better performances for the ORR than Pt.
This type of alloys has many advantages over platinum
and opens new fundamental and applied avenues in the
oxygen reduction studies. Future aspects to be devel-
oped include: (i) searches of optimised composition of
Pd–Co, Pd–Ni, Pd–Cr, Pd–Ta, etc. alloys for the ORR;
(ii) development of new formulations of binary and/or
ternary Pd–(Ni, Co, Cr, W, Ta, etc.) alloys for ORR;
(iii) development of fundamental electro-catalytic stud-
ies of the ORR on these alloys; (iv) development of
other non-platinum and palladium alloys for ORR in
acid medium, etc.
Acknowledgements
This work has been partially supported by CREST of
JST (Japan Science and Technology) and Ecole Poly-
technique de Montreal, Canada.
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