Electrochimica Acta 48 (2003) 2435
/2445

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Electrochemical behavior of palladium
gold alloys /

M. Lukaszewski a,b, A. Czerwinski a,b,*,1

a
Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
b
Industrial Chemistry Research Institute, Rydygiera 8, 01-793 Warsaw, Poland

Received 31 October 2002; received in revised form 10 January 2003; accepted 27 March 2003

Abstract

The behavior of Pd
/Au alloys, prepared by electrochemical codeposition, has been studied in acidic solutions (1 M H2SO4) using
mainly the cyclic voltammetry technique. Morphology of the alloy surface and bulk compositions were examined by SEM/EDAX
method. Various types of voltametric behavior during potential cycling in the oxygen region are presented. The influence of
hydrogen absorption on electrochemical properties of surface oxides is demonstrated. The problem of the nature of oxygen
electrochemisorbed on Pd
/Au alloys is discussed.
# 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Noble metal alloys; Palladium
/gold alloys; Surface oxides; Hydrogen absorption; Cyclic voltammetry

1. Introduction which is reflected in a dramatic transformation of

Electrochemical behavior of binary alloys of noble
metals has been widely investigated [1
/27]. Among
various systems studied there are palladium alloys,
which are of interest because of their ability to absorb
hydrogen [26
/30] as well as valuable electrocatalytic
properties [10,13,14,16,17,19,20,22,23].
Palladium and gold form a continuous series of f.c.c.
solid solutions, homogeneous at normal conditions,
with the lattice parameter varying almost linearly with
alloy composition [31,32]. According to AES data, the
surface composition of Pd
/Au alloys under vacuum
conditions is very close to their bulk composition [33
/
35].
Cyclic voltammetry experiments [4,7,9,11,14,15,21]
have revealed that in acidic solutions the surface of
Pd
/Au electrodes, polarized to high potentials, changes
significantly. Since Pd is much less resistive to oxidation
than Au [36], selective electrochemical dissolution of this
metal takes place during repetitive potential cycling
* Corresponding author. Tel.: /48-22-822-0211; fax: /48-22-822-
5996.
E-mail address: aczerw@chem.uw.edu.pl (A. Czerwinski).
1
ISE member.
0013-4686/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0013-4686(03)00270-6
voltammograms recorded.
Rand and Woods [7] have pointed out a useful in situ
technique of surface analysis of homogeneous noble
metal alloys in a cyclic voltammetry experiment. The
method is based on a linear dependence of the potential
of surface oxides reduction (oxygen desorption) peak on
alloy surface composition. Some limitations of this
method towards Pd
/Au electrodes were found by
Gossner and Mizera [15] as well as Lamy et al. [14],
according to whom the linear relationship could be used
only for alloys containing not less than 40% at. of Pd.
The investigations of thin Pd layers deposited on Au
substrate [37
/39] have demonstrated the process of
alloy formation at the metals interface occurring at
room temperature due to the relatively high value of
diffusion coefficient of Pd in Au [39].
The studies of the Pd
/Au system in the aspect of
electrocatalysis showed synergistic effects, as reported
for oxidation of such compounds as carbon monoxide
[13,16], sodium formate [14,22] and methanol [40].
Recently, we have studied voltammetrically the pro-
cess of hydrogen electrosorption into Pd
/Au alloys [27].
In this paper we report on the electrochemical behavior
of this system in the potential range where surface
oxides are formed (oxygen region). In particular, the
influence of hydrogen absorption on electrochemical
2436 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445
properties of surface oxides is shown. The discussion on
the nature of oxygen electrochemisorbed on Pd
/Au
alloys is also presented. Although the Pd
/Au system
was the subject of many investigations, our experiments
carried out in a wide composition range have revealed
some facts not reported yet in the literature.
2. Experimental
All the experiments were performed at room tem-
perature in 1 M H2SO4 solutions prepared from triply
distilled water and analytical grade reagents. The
solutions were deoxygenated with an argon stream for
25 min. A platinum gauze and Hg j Hg2SO4 j 1 M
H2SO4 were used as the auxiliary and the reference
electrodes, respectively. All potentials in the text and on
figures are referred to RHE.
Pd
/Au alloys were deposited potentiostatically on a
gold wire (0.5 mm diameter) from a bath containing
PdCl2 and HAuCl4 in 1 M HCl [4,27]. The deposition
potential was always higher than the potential of
hydrogen sorption in order to avoid hydrogen insertion
into the alloy being formed. The composition of the
alloys was altered by employing different electrolyte
compositions and deposition potentials. The thickness
of obtained electrodes was in the range 1.5
/3.0 mm. The
roughness factor of freshly deposited alloys was in the
range 100
/500. The bulk composition of Pd
/Au alloys
was obtained from the EDAX analysis (Rontec M1
analyzer coupled with LEO 435VP scanning electron
microscope). All alloy compositions are expressed in
atomic percentages.
Two methods have been applied to evaluate the real
surface area, namely based on double layer capacity and
surface oxides reduction charge measurements. The
values of double layer capacity were determined accord-
ing to the method described in the literature, see e.g.
[25,41
/44], i.e. from the slope of the dependence of
double layer charging current on scan rate in the
potential region free from faradaic processes (0.365/
0.665 V for electrodes studied). To determine the value
of the capacity of 1 cm2, necessary for the real surface
area calculating, separate experiments were carried out
for pure alloy components under identical experimental
conditions (solution, temperature) as in the case of Pd
/
Au electrodes. Double layer capacity values were
determined for Pd and Au electrodes as described above
and their real surface areas were obtained from the
charges of surface oxides reduction, which is a well-
established and generally accepted method [9]. The value
44.5 mF cm2, found for both Pd and Au, was then used
to calculate the real surface area of Pd
/Au alloys. The
method based on surface oxides reduction charge
measurements was also used independently to estimate
the real surface area of the alloys studied. The charges
corresponding to oxygen desorption signals were used to
estimate separately the amount of a given surface phase
and the total area was obtained by their sum. The real
area of each phase was calculated taking for PdO and
AuO reduction peaks the conversion factors used for
Pd and Au electrodes, respectively (corresponding to
anodic polarization to 1.565 V). The differences between
the values of real surface area obtained using both
methods were within 30%. Thus these methods are
suitable for the estimation of real surface area of Pd
/
Au alloys, although they seem to be less accurate than
those applied to pure noble metal electrodes.
3. Results and discussion
3.1. Cyclic voltammetry behavior of Pd
/Au alloys with
various compositions
The shape of initial cycles of i
/E curves recorded in
the oxygen potential region (0.365/1.565 V; scan rate 0.1
or 0.5 V s 1), reflecting the state of the electrode surface
not subjected to any forms of pretreatment, depends on
the alloy composition. For almost all samples contain-
ing more than approximately 70% of Pd in the bulk we
obtained voltammograms with a single cathodic signal
(surface oxides reduction peak) present. Its potential
was intermediate between the potentials of respective
cathodic peaks for pure alloy components. For electro-
des less rich in Pd an additional cathodic wave was
observed, at potentials close to the position of the oxides
reduction peak on the voltammogram for Au. This
current signal was particularly distinct in the case of
alloys containing below approximately 40% of Pd,
where two well-separated peaks of comparable size
could be distinguished on i
/E curves. These results are
consistent with the literature data [7,15]. According to
the results of studies on the electrochemical behavior of
noble metal alloys [7
/9], when a single oxygen deso-
rption signal is observed on the i
/E curve, the homo-
geneity of the alloy surface should be expected, while
two cathodic peaks in the oxygen region indicate the
existence of separate surface phases. The peaks appear-
ing on voltammograms of Pd
/Au alloys will be denoted
in the text and on figures as PdO and AuO signals,
respectively. The origin of both signals will be discussed
in more detail in Section 3.3.
As it was described in numerous earlier reports
[4,7,9,11,14,15,21], the voltammograms of the Pd
/Au
alloys undergo significant changes during continuous
potential cycling in acid media to sufficiently high
potentials due to selective dissolution of Pd. The alloy
surface becomes enriched with Au, which results in a
decrease in the oxides reduction peak and its shift into
the higher potentials along with a growth of a second
cathodic peak in the position typical of Au electrode.
 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445 2437

Since the removal of Pd does not proceed uniformly, the
alloy surface becomes heterogeneous in this process
[7,9].
This kind of behavior has been observed for alloys
containing less than approximately 90% Pd in the bulk.
Fig. 1a shows i
/E curves recorded in the oxygen region
for a Pd
/Au alloy with 65% of Pd. After long
electrochemical treatment (above 200 potential cycles)
voltammogram resembles the i
/E curve for pure Au.
However, the small and broad signals below 1.0 V
indicate that a certain amount of Pd is still present on
the surface. Our experiments with hydrogen absorption
[27] confirmed the existence of surface Pd atoms on Pd
/
Au alloys despite the exhaustive potential cycling; these
atoms are believed to be the active sites in hydrogen
sorption and desorption processes. Further electroche-
mical treatment of such modified alloy does not cause
any significant changes. This steady state probably
results from Pd diffusion from the bulk of alloy, as
was proposed by Gossner and Mizera [15] and/or from
partial cathodic redeposition of metal dissolved during
anodic polarization. Alloys with a smaller Pd content
exhibited similar behavior, with less potential cycles
necessary for Pd to be depleted from the surface (Fig.
1b). Such tendency was reported earlier [7]. The
existence of two oxygen desorption peaks (indicating
surface heterogeneity) on the initial i
/E curve of most
Au-rich alloys results from Pd dissolution during the
first anodic scan being sufficient to change electrode
surface characteristics [7,9].
In the case of Pd-rich alloys (mainly from the range of
70
/80% of Pd in the bulk) we have also observed
another kind of voltammogram changes, not reported
so far. As can be seen on Fig. 1c, during potential
cycling in the oxygen region third cathodic peak
appears, placed in the vicinity of oxygen desorption
peak on pure Pd. Its position alters only slightly during
further treatment. Finally, there are two peaks distin-
guishable on the i
/E curve, at potentials almost
identical with those typical of pure Pd and Au. On the

Fig. 1. Voltammograms of Pd
/Au electrodes recorded in 1 M H2SO4 during potential cycling in the oxygen region 0.365/1.565 V: (a) initial bulk Pd
content 65%, scan rate 0.1 V s 1, (b) initial bulk Pd content 40%, scan rate 0.5 V s 1, (c) initial bulk Pd content 75%, scan rate 0.1 V s 1, (d) initial
bulk Pd content 95%, scan rate 0.5 V s 1.
2438 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445
basis of Rand and Woods idea [7,9], that signal could
be linked to the existence of an additional surface phase,
composed predominantly of Pd. However, in view of
our present knowledge about the electrochemistry of
Pd
/Au alloys, the mechanism of surface segregation
leading to such surface arrangement is rather unclear.
The process of Pd redeposition, facilitated by consider-
able roughness of the electrodes investigated, might play
a certain role in this phenomenon [6].
Fig. 2a illustrates the changes of real surface area of
Pd
/Au alloys subjected to electrochemical treatment. It
is interesting that during initial potential cycles (less
than 100) an increase in the surface roughness takes
place, followed by its smoothening. SEM observations
indicated on the changes in the crystallite size upon
cycling, being in line with the conclusions drawn from
the evolution of voltammograms. The same effect was
observed when electrochemical behavior of Pt
/Au
alloys was studied [25].
For the data presented here the value of real surface
area (S) was determined from oxides reduction charges;
the shape similar to S versus number of cycles (N)
Fig. 2. The values of the ratio of real surface area of Pd
/Au alloys to
its initial value (for 1st cycle), S/Si vs. number of potential cycles, N
(potential range 0.365/1.565 V: (a) alloys with moderate initial bulk Pd
content; scan rate 0.1 V s 1; (b) alloys with high initial bulk Pd
content; scan rate 0.5 V s 1).
relationship was obtained for the double layer capacity-
N dependence, not shown here. (For the dependence of
surface Pd content on the number of cycles see Section
3.3).
The alloys very rich in Pd (containing more than ca.
90% of Pd) exhibited behavior markedly different from
that described above, as can be seen on Fig. 1d. For a
long experimental time (more than 1000 cycles) potential
cycling causes constant increase in both oxidation and
reduction currents, which reflects the process of surface
roughening (Fig. 2b). Moreover, the surface oxides
reduction peak does not change its position (only small
shifts are observed, within several mV) as well as
appearing no additional peaks. It suggests that the
surface composition of the alloy remains practically
unaltered. The high surface concentration of Pd, in-
dicated by the low peak potential, could be maintained
by Pd diffusion from the bulk of the electrode [15] and/
or partial Pd redeposition. After reaching maximum
values the currents start to decrease, together with the
rise of a small and broad signal in the potential region
typical of oxygen desorption from Au. Owing to the
exhaustive potential cycling the Au substrate becomes
visible, as confirmed by SEM observations, which
indicates that due to electrochemical dissolution of Pd
the alloy layer has been totally removed in some regions
of the electrode. It is likely that because of high initial
Pd concentration in the bulk of the alloy as well as on its
surface, a separate surface phase, rich in Au originating
from the alloy itself, is not formed until the influence of
the Au matrix becomes significant. Thus the hetero-
genization observed here has a different mechanism
from that occurring for alloys with smaller Pd content,
although it is caused by the same process, i.e. selective
dissolution of Pd. This type of voltammograms evolu-
tion resembles partly the behavior reported for Pd
/Rh
alloy [7], where a current increase without a peak shift
was observed during potential cycling experiment.
3.2. The influence of hydrogen absorption on the shape of
voltammograms in the oxygen region
The comparison of i
/E curves recorded in the oxygen
region before and after hydrogen absorption/desorption
experiments (see [27] for details) reveals that hydrogen
absorption process changes the surface properties of
Pd
/Au electrodes (Fig. 3a). A significant shift of PdO
reduction signal into negative direction, exceeding 100
mV in some cases, has been observed. This effect was the
most dramatic for alloys containing 65
/80% Pd in the
bulk (Fig. 4). The beginning of surface oxidation was
also at lower potentials in the case of electrodes
previously subjected to hydrogen saturation and deso-
rption. Together with the peak potential shift, an
increase in reduction currents in the potential range
typical of oxygen desorption signal on Au was observed.
 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445 2439

Fig. 3. Comparison of voltammograms recorded in the oxygen region (0.365/1.565 V) before (dotted line) and after (solid line) hydrogen absorption
(1 M H2SO4). Pd
/Au alloys: (a) with 73.2% of Pd in the bulk, ca. 73% on the surface; (b) with 45.1% of Pd in the bulk, ca. 60% on the surface; (c)
impoverished in Pd on the surface, ca. 41% Pd (initial bulk Pd content 69.4%); (d) strongly impoverished in Pd on the surface, ca. 6% Pd (initial bulk
Pd content 66.2%); (e) pure Pd, scan rate 0.1 V s 1 (a
/d) or 0.5 V s 1 (e).

In particular, for the alloys containing more Au there
are two distinct cathodic peaks (PdO and AuO) on
voltammograms recorded after hydrogen sorption/des-
orption experiments, instead of a single peak (PdO)
visible on i
/E curve for a fresh alloy (Fig. 3b).
The appearance of a second cathodic signal in
position similar to that of AuO reduction peak on
pure Au could suggest the formation of a gold-rich
surface phase. However, it is possible that this signal is
due to reduction of AuO formed at these regions of
electrode surface, where the exposure of gold substrate
occurred as a result of partial dropping off the alloy
coating owing to repeated hydrogen introducing and its
removal. SEM images of Pd
/Au electrodes subjected to
2440 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445

Fig. 4. Experimental values of the negative shift of PdO peak

potential, DEp PdO (for scan rate 0.5 V s 1 and anodic potential
limit 1.565 V) after hydrogen absorption vs. bulk Pd content.

hydrogen absorption/desorption procedure indicate that

it might be the case, since they show zones of naked gold
matrix (Fig. 5a).
It should be noted that the potential shift into
cathodic direction also took place for AuO reduction
peak on a Pd
/Au electrode strongly impoverished in Pd
during long cycling in the oxygen region (Fig. 3c, d).
The behavior reported above indicates that surface
oxides formed on electrode previously subjected to
hydrogen treatment can be reduced with greater diffi-
culty than oxides generated on the fresh alloy surface.
Thus, they become electrochemically more stable, since
it is necessary to apply lower potential so that they are
reduced. According to Rand and Woods observation
[7], the negative shift of the oxides reduction peak could
suggest hydrogen-induced surface enrichment with Pd.
Fig. 5. Scanning electron microscopy images of the surface of Pd
/Au
However, similar effect, although to a smaller extent alloys taken after hydrogen absorption/desorption experiments: (a)
than for most of the alloys investigated, has been found 75.8% Pd in the bulk, (b) 47.6% Pd in the bulk.
for pure Pd electrodeposits on gold (Fig. 3e). Moreover,
the potential of PdO reduction peak on i
/E curves of Further polarization does not cause a further significant
hydrogen-treated Pd
/Au alloys happened to be much shift of the oxygen desorption peaks. The changes are
lower than for Pd. This result shows that the observed the greatest after first polarization and then they do not
phenomenon needs another explanation. The increase in exceed several mV.
electrochemical stability of surface oxides might be Prolonged potential cycling in the oxygen region of
connected with the changes in alloy lattice during its hydrogen-treated Pd
/Au alloys has been found to cause
penetration by hydrogen. It is well known that hydrogen changes identical with those reported for electrode not
absorption in Pd and Pd-based alloys causes the increase subjected to polarization into the hydrogen region. The
in lattice parameter and, as a result, the increase in fact of previous hydrogen absorption did not have any
volume of the sample together with its cracking [28
/ qualitative influence on voltammogram evolution pro-
30,45]. SEM images taken after hydrogen absorption/ ceeding due to electrochemical dissolution of Pd from
desorption experiments show that there are a lot of the alloy. However, the rate of the changes of real
cracks on Pd
/Au alloy surface (Fig. 5a, b.) It is likely surface area was slower, with approximately 50 cycles
that oxygen electrosorption on such transformed surface more being necessary for surface roughness to reach its
proceeds more easily and its desorption is inhibited in maximum value.
comparison with a fresh electrode. The pronounced shift of the potential of PdO peak
It has been found that this effect occurs even if the after hydrogen absorption means that the method of
electrode is once polarized into hydrogen region. surface composition determination based on linear
 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445
dependence between peak potential and surface metal
concentration seems to be reliable only for Pd
/Au
alloys not subjected to prior polarization into hydrogen
absorption potentials. However, for electrodes pre-
viously cycled to hydrogen region the qualitative
information about the tendency of surface changes is
still available from the position of PdO signal (its shift
into higher potential values during cycling indicates that
Pd content on the surface decreases).
3.3. The nature of oxygen chemisorbed on the surface of
Pd
/Au alloys
In the literature the cathodic peak placed at lower
potentials (denoted here as PdO reduction signal) is
often directly assigned to the reduction of PdO (oxygen
desorption from Pd surface atoms), while the signal at
higher potentials (AuO) is treated as AuO reduction
(oxygen desorption from Au surface atoms) peak
[13,15,16,21,22]. Such an interpretation of these signals
means that there is a marked difference between
adsorption properties of Pd and Au atoms on the Pd
/
Au alloy surface. In accordance with the view, the
oxygen electrosorption characteristics of Pd and Au
atoms remain partly independent [22], although some
interactions between them lead to the shift of potentials
of the respective peaks. It might be true, at least for
alloys exhibiting heterogeneous behavior, i.e. where two
phases are present on the surface. However, when a
single cathodic peak is visible on the voltammogram,
this picture seems to stop working, since if the only
signal is attributed to PdO reduction, it is difficult to
explain why AuO reduction current is not observed
despite the anodic potential limit sufficient to oxidize Au
surface atoms. On the other hand, there are suggestions
[7
/9] that each of the mentioned signals corresponds to
desorption of oxygen chemisorbed on surface atoms
constituting particular phases. If it was the case, for a
given phase, atoms of both kinds (i.e. both Pd and Au)
would take part in the processes of oxygen electrosorp-
tion and desorption and the intermediate potential value
of the PdO peak would result from strong interactions,
being sufficient to make averaged the adsorption
characteristics of two metals in an alloy phase. Hence,
in the peak attributed to PdO reduction (i.e. oxygen
desorption from Pd atoms) there should be a contribu-
tion from the process of oxygen desorption from Au
atoms, mixed with Pd atoms in a single phase. It would
also mean that for superficially heterogeneous alloys
(when more than one cathodic peak could be observed
on i
/E curve) the Au atoms contained in each phase
should have different adsorption properties. Another
question is whether the linear dependence between peak
potential and surface composition concerns the compo-
sition of an individual phase (as arises from Rand and
Woods investigations [7]) or the whole alloy (as is
2441
assumed by Gossner and Mizera [15]). Below the
experimental facts are presented, being expected to
throw a light on the still largely unclear problem of
oxygen chemisorption on Pd
/Au alloys.
Fig. 6 presents the superposition of main types of i
/E
curves observed for Pd
/Au alloys at various stages of
electrochemical treatment and the curves recorded for
pure metals, Pd and Au, under identical experimental
conditions (scan rate 0.1 V s 1, anodic potential limit
1.565 V). The potential of PdO signal has been found
to have always the value intermediate between the
values of PdO and AuO reduction signals on pure
metal electrodes. The rise of anodic current due to
surface oxidation (oxygen electrosorption) process takes
place at the potential higher than on Pd but much lower
than on Au. It reflects the known fact that oxygen
electrosorption on Pd
/Au alloys is more difficult and its
desorption proceeds easier than on pure Pd [7
/9,14,15].
Thus, the oxides formed on the alloy surface seem to be
electrochemically less stable in comparison with the case
of Pd.
The position of the second cathodic peak, denoted
here as AuO signal, is close or identical to the potential
of the respective peak on pure Au. On the anodic part of
voltammogram of electrochemically treated alloys two
distinct regions of surface oxidation are distinguishable
with a sharp increase of current at approximately 1.35
V, i.e. the value typical of the beginning of the surface
oxidation process on Au electrode.
The third signal, appearing on some i
/E curves (Fig.
6d, e), is placed at the potential typical of PdO
reduction on pure Pd.
Fig. 7 shows the changes of peak potential during
cycling in the oxygen region for all mentioned oxygen
desorption signals. It should be noted that it is the PdO
reduction peak, whose position is the most affected by
the process of electrochemical treatment. Practically it is
the only cathodic signal so strongly influenced by
palladium dissolution from the alloy, (because after ca.
100 cycles the signal becomes very broad and flattened,
only those points are presented where it was possible to
define the peak potential in an unequivocal manner). On
the other hand the potentials of AuO reduction signal
as well as the third, additional peak remain almost
unaltered. The constancy of the potential of AuO
signal together with significant shift observed for PdO
signal could be explained making an assumption that
the PdO peak contains currents of simultaneous
desorption of oxygen layer generated on both Pd and
Au atoms belonging to one surface phase (alloy phase),
while the AuO signal is connected with oxygen
desorption from a second surface phase, generated
during the potential cycling experiment, much richer in
Au that the former.
On the basis of the method of surface area determina-
tion from surface oxides reduction charges (see Section
2442 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445

Fig. 6. Superposition of main types of voltammogramms observed for Pd
/Au alloys at various stages of electrochemical treatment (potential cycling
in the range 0.365/1.565 V; scan rate 0.1 V s 1, 1 M H2SO4) and voltammograms for pure metals. Pd
/Au alloy with initial bulk Pd content 65%: (a)
initial cycle, (b) after 50 cycles, (c) after 200 cycles; Pd
/Au alloy with initial bulk Pd content 75%: (d) after 50 cycles, (e) after 150 cycles.

2) it is possible to estimate the surface composition of the surface obtained in both ways as a function of
superficially heterogeneous Pd
/Au alloys and then number of potential cycles in the oxygen region applied
compare it with the values evaluated from PdO peak to the electrode, illustrating the removal of Pd from the
potential. Fig. 8 presents the atomic content of Pd on alloy surface. It demonstrates that the concentration of
 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445
Fig. 7. The values of peak potential, Ep for oxygen desorption signals
(PdO, AuO and third peak) vs. number of potential cycles, N
(potential range 0.365/1.565 V; scan rate 0.1 V s 1) for Pd
/Au alloys
with moderate initial bulk Pd content: j 65%; ' 69.4%; m 71.3%; 2
75%; /78.4%.
Fig. 8. Surface Pd content, calculated from PdO peak potential
(empty symbols) and oxides reduction charge measurements (full
symbols) vs. number of potential cycles, N (potential range 0.365/1.565
V; scan rate 0.1 V s 1) for Pd
/Au alloys with moderate initial bulk Pd
content.
Pd calculated using the value of PdO peak potential
exceeds clearly that estimated from the areas occupied
by particular surface phases. If the potential of PdO
signal reflected the Pd content in the whole alloy surface,
both values would be much closer. It should be noted
that the real value of surface Pd content could be even
smaller than the value obtained from oxides reduction
charges if PdO signal involved contribution of oxygen
desorption from Au atoms. Thus it is likely that the Pd
content calculated from PdO peak potential corre-
sponds to the amount of Pd in one of surface phases, i.e.
the phase from which oxygen desorption resulting in this
cathodic signal proceeds. The concentration of Pd in
2443
that alloy phase might be relatively high, even if its total
content on alloy surface is lower. The observation is in
line with the mechanism of Pd removal and alloys
surface heterogenization proposed by Rand and Wood
[7]. According to their explanation the loss of Pd takes
place mainly at the edges of zones with heightened Au
concentration, produced during initial potential cycles.
Subsequent dissolution of Pd leads to the formation of
surface areas very rich in Au (actually almost pure Au)
and causes the decrease in area of the regions retaining
higher Pd content (thus the decrease in PdO signal with
the number of cycles), which results in the voltammo-
gram being a sum of the i
/E curves characteristic of
pure Au and an alloy with moderate Au content [4].
These results demonstrate that the method described
by Rand and Woods allows the determination of Pd
/
Au alloys surface composition provided the surface is
homogeneous, i.e. a single cathodic peak is observed on
voltammogram recorded in the oxygen region. If not,
only the composition of one of surface phases can be
derived from the potential of PdO signal. For hetero-
geneous Pd
/Au electrodes the method based on the real
surface area of each phase seems to be more reliable,
although its accuracy is limited by the incomplete
separation of PdO an AuO peaks. Moreover, this
method allows estimating the surface composition even
if the PdO peak becomes broad and its potential is
difficult to define. The usefulness of the method invol-
ving peak areas evaluation towards Au-rich Pd
/Au
alloys was mentioned earlier [15].
The above conclusions are partly supported by the
observation that the surface composition, calculated
from the potential of PdO signal at the very beginning
of cyclic voltammetry experiment (when the surface is
believed to be unaltered) and the bulk composition,
obtained using EDAX technique agreed well (within
20% relative error) only when a single cathodic peak was
visible on the voltammogram, as could be expected for
homogeneous Pd
/Au alloys not having subjected to any
form of pretreatment. When voltammograms with two
cathodic signals (corresponding to superficially hetero-
geneous alloys) were analyzed, the surface Pd content
derived from the position of PdO peak appeared
clearly higher than that in the bulk of alloy. However,
one cannot exclude the possibility that the observed
differences between surface and bulk composition result
from the fact that the surface of freshly deposited alloys
is not in equilibrium. It should be pointed out here that
this behavior is not likely to be due to the reported
limitation of Rand and Woods method [15], since the
calculated amount of Pd in the alloy phase was far over
40%.
However, an interesting correlation has been found
between the position of PdO signal and total surface
composition of Pd
/Au alloys, calculated on the basis of
oxides reduction charge measurements. Various surface
2444 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445
compositions were obtained during continuous potential
cycling; the alloys being characterized by relatively rapid
changes of their surface were used here. The dependence
is illustrated on Fig. 9, where the values of the PdO
peak potential (believed to reflect the composition of the
alloy surface phase) are plotted versus the content of Au
on the whole alloy surface. The points refer to alloys
cycled in the very oxygen region (full symbols) as well as
to electrodes cycled after hydrogen absorption (empty
symbols). The following facts should be noted in the
context of Fig. 9. Firstly, as it has already been
mentioned, the experimental data indicate lower surface
Au content in the alloy phase than on the whole surface.
Secondly, the two kinds of points form two series, to
which straight lines can be fitted using the least-squares
method. The lines have similar slopes but are shifted
towards each other. The fact that the line obtained for
hydrogen-treated alloys lies below that obtained for
alloys not having been polarized into the hydrogen
region corresponds to the negative shift of PdO signal
observed in the case of alloys subjected to hydrogen
saturation (see Section 2). Thirdly, both slope values are
lower than the slope of the line passing through the
points for the peaks of oxygen desorption from pure Pd
and Au electrodes (obtained under identical experimen-
tal conditions, i.e. at scan rate 0.1 V s 1 and anodic
potential limit 1.565 V). This rather surprising correla-
tion suggests that the Pd (Au) content in the phase,
reflected by PdO peak potential, is somehow related to
total Pd (Au) concentration on the heterogeneous alloy
surface. However, it should be stressed that not all
investigated electrodes followed this dependence quan-
titatively, though qualitatively their behavior was simi-
Fig. 9. PdO peak potential, Ep (scan rate 0.1 V s 1, anodic potential
limit 1.565 V) vs. surface concentration of Au, calculated from oxides
reduction charge measurements for Pd
/Au alloys not polarized to
hydrogen absorption region (full symbols) as well as for electrodes
subjected to hydrogen saturation (empty symbols). Straight lines were
fitted using least-squares method. The points corresponding to the
potential values of surface oxides reduction peaks on pure Pd and Au
are linked by a dotted line. Various alloy surface compositions were
obtained by repetitive potential cycling to 1.565 V at 0.1 V s 1;
electrodes with moderate initial bulk Pd content.
lar. The origin of the correlation could be connected
with the peculiar mechanism of the alloy surface
transformation during electrochemical treatment [7].
In order to obtain more information about the nature
of oxygen electrochemisorbed on the surface of Pd
/Au
alloys, the dependence of oxides reduction charge (QO red)
on the limit potential of anodic polarization (Ea) in a
cyclic voltammetry experiment was investigated. Due to
the strong Pd dissolution, taking place for a fresh alloy
electrode under conditions applied in our experiments
and making it difficult to maintain a constant state
(composition, area, phase arrangement) of alloy surface
at each stage of electrochemical treatment, reliable
results could be obtained only for electrochemically
aged alloys. For such alloys, impoverished in Pd (ca.
15% on the surface), it is possible to obtain relatively
stable i
/E curves in the oxygen region and it can be
assumed that the surface does not change very much
during several potential cycles. Fig. 10 presents QO red
/Ea
dependences, where the oxide reduction charges are
shown separately, for two cathodic signals (i.e. AuO
signal and third cathodic peak). The plots for pure Pd
and Au are put for comparison. The fact that experi-
mental points obtained for AuO reduction peak over-
lap with those for pure Au confirms earlier findings that
on the Pd
/Au electrode subjected to long electrochemi-
cal treatment a surface phase exists with electrosorption
properties towards oxygen very similar to pure Au. On
the other hand, similar shapes of QOred
/Ea plots for third
cathodic signal and PdO reduction peak on Pd, suggest
the existence of a surface phase resembling pure Pd,
which would support the interpretation of this addi-
tional signal as originating from oxygen desorption
from a Pd-rich phase.
Fig. 10. Dependence of oxides reduction charge, QO red on anodic
potential limit, Ea in cyclic voltammetry experiment (scan rate 0.1 V
s 1, 1 M H2SO4) obtained for third cathodic peak (m) and AuO
reduction signal (/, /) as well as for oxides reduction peaks on pure
Pd (I) and Au (^); electrodes with low Pd surface concentration (ca.
15%).
 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435
/2445 2445

4. Conclusions References

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