Académique Documents
Professionnel Documents
Culture Documents
www.elsevier.com/locate/electacta
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
properties of surface oxides is shown. The discussion on corresponding to oxygen desorption signals were used to
the nature of oxygen electrochemisorbed on Pd /Au estimate separately the amount of a given surface phase
alloys is also presented. Although the Pd /Au system and the total area was obtained by their sum. The real
was the subject of many investigations, our experiments area of each phase was calculated taking for PdO and
carried out in a wide composition range have revealed AuO reduction peaks the conversion factors used for
some facts not reported yet in the literature. 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
2. Experimental methods were within 30%. Thus these methods are
suitable for the estimation of real surface area of Pd /
All the experiments were performed at room tem- Au alloys, although they seem to be less accurate than
perature in 1 M H2SO4 solutions prepared from triply those applied to pure noble metal electrodes.
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 3. Results and discussion
H2SO4 were used as the auxiliary and the reference
electrodes, respectively. All potentials in the text and on 3.1. Cyclic voltammetry behavior of Pd /Au alloys with
figures are referred to RHE. various compositions
Pd /Au alloys were deposited potentiostatically on a
gold wire (0.5 mm diameter) from a bath containing The shape of initial cycles of i/E curves recorded in
PdCl2 and HAuCl4 in 1 M HCl [4,27]. The deposition the oxygen potential region (0.365/1.565 V; scan rate 0.1
potential was always higher than the potential of or 0.5 V s 1), reflecting the state of the electrode surface
hydrogen sorption in order to avoid hydrogen insertion not subjected to any forms of pretreatment, depends on
into the alloy being formed. The composition of the the alloy composition. For almost all samples contain-
alloys was altered by employing different electrolyte ing more than approximately 70% of Pd in the bulk we
compositions and deposition potentials. The thickness obtained voltammograms with a single cathodic signal
of obtained electrodes was in the range 1.5 /3.0 mm. The (surface oxides reduction peak) present. Its potential
roughness factor of freshly deposited alloys was in the was intermediate between the potentials of respective
range 100 /500. The bulk composition of Pd /Au alloys cathodic peaks for pure alloy components. For electro-
was obtained from the EDAX analysis (Rontec M1 des less rich in Pd an additional cathodic wave was
analyzer coupled with LEO 435VP scanning electron observed, at potentials close to the position of the oxides
microscope). All alloy compositions are expressed in reduction peak on the voltammogram for Au. This
atomic percentages. current signal was particularly distinct in the case of
Two methods have been applied to evaluate the real alloys containing below approximately 40% of Pd,
surface area, namely based on double layer capacity and where two well-separated peaks of comparable size
surface oxides reduction charge measurements. The could be distinguished on i/E curves. These results are
values of double layer capacity were determined accord- consistent with the literature data [7,15]. According to
ing to the method described in the literature, see e.g. the results of studies on the electrochemical behavior of
[25,41/44], i.e. from the slope of the dependence of noble metal alloys [7 /9], when a single oxygen deso-
double layer charging current on scan rate in the rption signal is observed on the i/E curve, the homo-
potential region free from faradaic processes (0.365/ geneity of the alloy surface should be expected, while
0.665 V for electrodes studied). To determine the value two cathodic peaks in the oxygen region indicate the
of the capacity of 1 cm2, necessary for the real surface existence of separate surface phases. The peaks appear-
area calculating, separate experiments were carried out ing on voltammograms of Pd /Au alloys will be denoted
for pure alloy components under identical experimental in the text and on figures as PdO and AuO signals,
conditions (solution, temperature) as in the case of Pd / respectively. The origin of both signals will be discussed
Au electrodes. Double layer capacity values were in more detail in Section 3.3.
determined for Pd and Au electrodes as described above As it was described in numerous earlier reports
and their real surface areas were obtained from the [4,7,9,11,14,15,21], the voltammograms of the Pd /Au
charges of surface oxides reduction, which is a well- alloys undergo significant changes during continuous
established and generally accepted method [9]. The value potential cycling in acid media to sufficiently high
44.5 mF cm2, found for both Pd and Au, was then used potentials due to selective dissolution of Pd. The alloy
to calculate the real surface area of Pd /Au alloys. The surface becomes enriched with Au, which results in a
method based on surface oxides reduction charge decrease in the oxides reduction peak and its shift into
measurements was also used independently to estimate the higher potentials along with a growth of a second
the real surface area of the alloys studied. The charges 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 partial cathodic redeposition of metal dissolved during
alloy surface becomes heterogeneous in this process anodic polarization. Alloys with a smaller Pd content
[7,9]. exhibited similar behavior, with less potential cycles
This kind of behavior has been observed for alloys necessary for Pd to be depleted from the surface (Fig.
containing less than approximately 90% Pd in the bulk. 1b). Such tendency was reported earlier [7]. The
Fig. 1a shows i/E curves recorded in the oxygen region existence of two oxygen desorption peaks (indicating
for a Pd /Au alloy with 65% of Pd. After long surface heterogeneity) on the initial i /E curve of most
electrochemical treatment (above 200 potential cycles) Au-rich alloys results from Pd dissolution during the
voltammogram resembles the i /E curve for pure Au. first anodic scan being sufficient to change electrode
However, the small and broad signals below 1.0 V surface characteristics [7,9].
indicate that a certain amount of Pd is still present on In the case of Pd-rich alloys (mainly from the range of
the surface. Our experiments with hydrogen absorption 70 /80% of Pd in the bulk) we have also observed
[27] confirmed the existence of surface Pd atoms on Pd / another kind of voltammogram changes, not reported
Au alloys despite the exhaustive potential cycling; these so far. As can be seen on Fig. 1c, during potential
atoms are believed to be the active sites in hydrogen cycling in the oxygen region third cathodic peak
sorption and desorption processes. Further electroche- appears, placed in the vicinity of oxygen desorption
mical treatment of such modified alloy does not cause peak on pure Pd. Its position alters only slightly during
any significant changes. This steady state probably further treatment. Finally, there are two peaks distin-
results from Pd diffusion from the bulk of alloy, as guishable on the i/E curve, at potentials almost
was proposed by Gossner and Mizera [15] and/or from 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 relationship was obtained for the double layer capacity-
be linked to the existence of an additional surface phase, N dependence, not shown here. (For the dependence of
composed predominantly of Pd. However, in view of surface Pd content on the number of cycles see Section
our present knowledge about the electrochemistry of 3.3).
Pd /Au alloys, the mechanism of surface segregation The alloys very rich in Pd (containing more than ca.
leading to such surface arrangement is rather unclear. 90% of Pd) exhibited behavior markedly different from
The process of Pd redeposition, facilitated by consider- that described above, as can be seen on Fig. 1d. For a
able roughness of the electrodes investigated, might play long experimental time (more than 1000 cycles) potential
a certain role in this phenomenon [6]. cycling causes constant increase in both oxidation and
Fig. 2a illustrates the changes of real surface area of reduction currents, which reflects the process of surface
Pd /Au alloys subjected to electrochemical treatment. It roughening (Fig. 2b). Moreover, the surface oxides
is interesting that during initial potential cycles (less reduction peak does not change its position (only small
than 100) an increase in the surface roughness takes shifts are observed, within several mV) as well as
place, followed by its smoothening. SEM observations appearing no additional peaks. It suggests that the
indicated on the changes in the crystallite size upon surface composition of the alloy remains practically
cycling, being in line with the conclusions drawn from unaltered. The high surface concentration of Pd, in-
the evolution of voltammograms. The same effect was dicated by the low peak potential, could be maintained
observed when electrochemical behavior of Pt/Au by Pd diffusion from the bulk of the electrode [15] and/
alloys was studied [25]. or partial Pd redeposition. After reaching maximum
For the data presented here the value of real surface values the currents start to decrease, together with the
area (S) was determined from oxides reduction charges; rise of a small and broad signal in the potential region
the shape similar to S versus number of cycles (N) 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.
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 pure Au could suggest the formation of a gold-rich
are two distinct cathodic peaks (PdO and AuO) on surface phase. However, it is possible that this signal is
voltammograms recorded after hydrogen sorption/des- due to reduction of AuO formed at these regions of
orption experiments, instead of a single peak (PdO) electrode surface, where the exposure of gold substrate
visible on i/E curve for a fresh alloy (Fig. 3b). occurred as a result of partial dropping off the alloy
The appearance of a second cathodic signal in coating owing to repeated hydrogen introducing and its
position similar to that of AuO reduction peak on removal. SEM images of Pd /Au electrodes subjected to
2440 M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435 /2445
dependence between peak potential and surface metal assumed by Gossner and Mizera [15]). Below the
concentration seems to be reliable only for Pd /Au experimental facts are presented, being expected to
alloys not subjected to prior polarization into hydrogen throw a light on the still largely unclear problem of
absorption potentials. However, for electrodes pre- oxygen chemisorption on Pd /Au alloys.
viously cycled to hydrogen region the qualitative Fig. 6 presents the superposition of main types of i /E
information about the tendency of surface changes is curves observed for Pd /Au alloys at various stages of
still available from the position of PdO signal (its shift electrochemical treatment and the curves recorded for
into higher potential values during cycling indicates that pure metals, Pd and Au, under identical experimental
Pd content on the surface decreases). conditions (scan rate 0.1 V s 1, anodic potential limit
1.565 V). The potential of PdO signal has been found
3.3. The nature of oxygen chemisorbed on the surface of to have always the value intermediate between the
Pd /Au alloys values of PdO and AuO reduction signals on pure
metal electrodes. The rise of anodic current due to
In the literature the cathodic peak placed at lower surface oxidation (oxygen electrosorption) process takes
potentials (denoted here as PdO reduction signal) is place at the potential higher than on Pd but much lower
often directly assigned to the reduction of PdO (oxygen than on Au. It reflects the known fact that oxygen
desorption from Pd surface atoms), while the signal at electrosorption on Pd /Au alloys is more difficult and its
higher potentials (AuO) is treated as AuO reduction desorption proceeds easier than on pure Pd [7 /9,14,15].
(oxygen desorption from Au surface atoms) peak Thus, the oxides formed on the alloy surface seem to be
[13,15,16,21,22]. Such an interpretation of these signals electrochemically less stable in comparison with the case
means that there is a marked difference between of Pd.
adsorption properties of Pd and Au atoms on the Pd / The position of the second cathodic peak, denoted
Au alloy surface. In accordance with the view, the here as AuO signal, is close or identical to the potential
oxygen electrosorption characteristics of Pd and Au of the respective peak on pure Au. On the anodic part of
atoms remain partly independent [22], although some voltammogram of electrochemically treated alloys two
interactions between them lead to the shift of potentials distinct regions of surface oxidation are distinguishable
of the respective peaks. It might be true, at least for with a sharp increase of current at approximately 1.35
alloys exhibiting heterogeneous behavior, i.e. where two V, i.e. the value typical of the beginning of the surface
phases are present on the surface. However, when a oxidation process on Au electrode.
single cathodic peak is visible on the voltammogram, The third signal, appearing on some i /E curves (Fig.
this picture seems to stop working, since if the only 6d, e), is placed at the potential typical of PdO
signal is attributed to PdO reduction, it is difficult to reduction on pure Pd.
explain why AuO reduction current is not observed Fig. 7 shows the changes of peak potential during
despite the anodic potential limit sufficient to oxidize Au cycling in the oxygen region for all mentioned oxygen
surface atoms. On the other hand, there are suggestions desorption signals. It should be noted that it is the PdO
[7 /9] that each of the mentioned signals corresponds to reduction peak, whose position is the most affected by
desorption of oxygen chemisorbed on surface atoms the process of electrochemical treatment. Practically it is
constituting particular phases. If it was the case, for a the only cathodic signal so strongly influenced by
given phase, atoms of both kinds (i.e. both Pd and Au) palladium dissolution from the alloy, (because after ca.
would take part in the processes of oxygen electrosorp- 100 cycles the signal becomes very broad and flattened,
tion and desorption and the intermediate potential value only those points are presented where it was possible to
of the PdO peak would result from strong interactions, define the peak potential in an unequivocal manner). On
being sufficient to make averaged the adsorption the other hand the potentials of AuO reduction signal
characteristics of two metals in an alloy phase. Hence, as well as the third, additional peak remain almost
in the peak attributed to PdO reduction (i.e. oxygen unaltered. The constancy of the potential of AuO
desorption from Pd atoms) there should be a contribu- signal together with significant shift observed for PdO
tion from the process of oxygen desorption from Au signal could be explained making an assumption that
atoms, mixed with Pd atoms in a single phase. It would the PdO peak contains currents of simultaneous
also mean that for superficially heterogeneous alloys desorption of oxygen layer generated on both Pd and
(when more than one cathodic peak could be observed Au atoms belonging to one surface phase (alloy phase),
on i/E curve) the Au atoms contained in each phase while the AuO signal is connected with oxygen
should have different adsorption properties. Another desorption from a second surface phase, generated
question is whether the linear dependence between peak during the potential cycling experiment, much richer in
potential and surface composition concerns the compo- Au that the former.
sition of an individual phase (as arises from Rand and On the basis of the method of surface area determina-
Woods investigations [7]) or the whole alloy (as is 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 2443
compositions were obtained during continuous potential lar. The origin of the correlation could be connected
cycling; the alloys being characterized by relatively rapid with the peculiar mechanism of the alloy surface
changes of their surface were used here. The dependence transformation during electrochemical treatment [7].
is illustrated on Fig. 9, where the values of the PdO In order to obtain more information about the nature
peak potential (believed to reflect the composition of the of oxygen electrochemisorbed on the surface of Pd /Au
alloy surface phase) are plotted versus the content of Au alloys, the dependence of oxides reduction charge (QO red)
on the whole alloy surface. The points refer to alloys on the limit potential of anodic polarization (Ea) in a
cycled in the very oxygen region (full symbols) as well as cyclic voltammetry experiment was investigated. Due to
to electrodes cycled after hydrogen absorption (empty the strong Pd dissolution, taking place for a fresh alloy
symbols). The following facts should be noted in the electrode under conditions applied in our experiments
context of Fig. 9. Firstly, as it has already been and making it difficult to maintain a constant state
mentioned, the experimental data indicate lower surface (composition, area, phase arrangement) of alloy surface
Au content in the alloy phase than on the whole surface. at each stage of electrochemical treatment, reliable
Secondly, the two kinds of points form two series, to
results could be obtained only for electrochemically
which straight lines can be fitted using the least-squares
aged alloys. For such alloys, impoverished in Pd (ca.
method. The lines have similar slopes but are shifted
15% on the surface), it is possible to obtain relatively
towards each other. The fact that the line obtained for
stable i/E curves in the oxygen region and it can be
hydrogen-treated alloys lies below that obtained for
alloys not having been polarized into the hydrogen assumed that the surface does not change very much
region corresponds to the negative shift of PdO signal during several potential cycles. Fig. 10 presents QO red /Ea
observed in the case of alloys subjected to hydrogen dependences, where the oxide reduction charges are
saturation (see Section 2). Thirdly, both slope values are shown separately, for two cathodic signals (i.e. AuO
lower than the slope of the line passing through the signal and third cathodic peak). The plots for pure Pd
points for the peaks of oxygen desorption from pure Pd and Au are put for comparison. The fact that experi-
and Au electrodes (obtained under identical experimen- mental points obtained for AuO reduction peak over-
tal conditions, i.e. at scan rate 0.1 V s 1 and anodic lap with those for pure Au confirms earlier findings that
potential limit 1.565 V). This rather surprising correla- on the Pd /Au electrode subjected to long electrochemi-
tion suggests that the Pd (Au) content in the phase, cal treatment a surface phase exists with electrosorption
reflected by PdO peak potential, is somehow related to properties towards oxygen very similar to pure Au. On
total Pd (Au) concentration on the heterogeneous alloy the other hand, similar shapes of QOred /Ea plots for third
surface. However, it should be stressed that not all cathodic signal and PdO reduction peak on Pd, suggest
investigated electrodes followed this dependence quan- the existence of a surface phase resembling pure Pd,
titatively, though qualitatively their behavior was simi- which would support the interpretation of this addi-
tional signal as originating from oxygen desorption
from a Pd-rich phase.
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 Fig. 10. Dependence of oxides reduction charge, QO red on anodic
fitted using least-squares method. The points corresponding to the potential limit, Ea in cyclic voltammetry experiment (scan rate 0.1 V
potential values of surface oxides reduction peaks on pure Pd and Au s 1, 1 M H2SO4) obtained for third cathodic peak (m) and AuO
are linked by a dotted line. Various alloy surface compositions were reduction signal (/, /) as well as for oxides reduction peaks on pure
obtained by repetitive potential cycling to 1.565 V at 0.1 V s 1; Pd (I) and Au (^); electrodes with low Pd surface concentration (ca.
electrodes with moderate initial bulk Pd content. 15%).
M. Lukaszewski, A. Czerwinski / Electrochimica Acta 48 (2003) 2435 /2445 2445
4. Conclusions References
1) Besides the behavior reported earlier in the litera- [1] M.W. Breiter, Electrochim. Acta 10 (1965) 543.
ture, some other kinds of voltammogram changes [2] A. Damjanovic, V. Brusic, J. Electroanal. Chem. 15 (1967) 29.
have been observed during continuous potential [3] R. Woods, Electrochim. Acta 14 (1969) 533.
[4] R. Woods, Electrochim. Acta 14 (1969) 632.
cycling of Pd /Au electrodes in the oxygen region.
[5] R. Woods, Electrochim. Acta 16 (1971) 655.
In the case of Pd-rich alloys (mainly 65 /80% of Pd [6] J.S. Mayell, W.A. Barber, J. Electrochem. Soc. 116 (1969) 37.
in the bulk) a third cathodic peak appears at [7] D.A.J. Rand, R. Woods, J. Electroanal. Chem. 36 (1972) 57.
potential very close or almost equal with the [8] D.A.J. Rand, R. Woods, Surf. Sci. 41 (1974) 611.
potential of oxygen desorption peak on pure Pd [9] R. Woods, in: A.J. Bard (Ed.), Electroanalytical Chemistry, vol. 9
(Ch. 1), Marcel Dekker, New York, 1976.
electrode. For alloys initially very rich in Pd (above
[10] A. Capon, R. Parsons, J. Electroanal. Chem. 65 (1975) 285.
90%) the AuO reduction signal is not observed [11] B.E. Conway, H. Angerstein-Kozlowska, G. Czartoryska, Z.
until the Pd removal from the alloys becomes Phys. Chem. Neue Folge 112 (1978) 195.
sufficient to let the Au substrate influence the i /E [12] B.G. Baker, D.A.J. Rand, R. Woods, J. Electroanal. Chem. 97
curve. (1979) 189.
[13] K. Gossner, E. Mizera, J. Electroanal. Chem. 98 (1979) 37.
2) After electrode polarization into the hydrogen
[14] B. Beden, C. Lamy, J.M. Leger, Electrochim. Acta 24 (1979) 1157.
region, surface oxides are formed and reduced at [15] K. Gossner, E. Mizera, J. Electroanal. Chem. 140 (1982) 47.
potentials lower than before applying the hydrogen [16] K. Gossner, E. Mizera, J. Electroanal. Chem. 140 (1982) 35.
sorption procedure. The enhanced electrochemical [17] F. Kadirgan, B. Beden, J.M. Leger, C. Lamy, J. Electroanal.
stability of the oxides probably results from changes Chem. 125 (1981) 89.
[18] E. Rach, J. Heitbaum, Electrochim. Acta 32 (1987) 1173.
of electrode surface properties caused by prior
[19] M. Enyo, J. Electroanal. Chem. 186 (1985) 155.
hydrogen penetration into alloy lattice. [20] K. Nishimura, K. Kunimatsu, M. Enyo, J. Electroanal. Chem.
3) Due to the significant shift of oxides reduction 260 (1989) (1989) 167.
peaks after hydrogen absorption, reliable quantita- [21] K. Nishimura, K. Machida, M. Enyo, J. Electroanal. Chem. 257
tive information about the surface composition (1988) 217.
based on the position of PdO signal can be [22] K. Nishimura, K. Machida, M. Enyo, J. Electroanal. Chem. 251
(1988) (1988) 103.
obtained only for Pd /Au electrodes not polarized [23] N. Dalbay, F. Kadirgan, Electrochim. Acta 36 (1991) 353.
to hydrogen region. [24] M. Grden, A. Paruszewska, A. Czerwinski, J. Electroanal. Chem.
4) The peak defined as PdO reduction signal can be 502 (2001) 91.
linked to oxygen desorption from both Pd and Au [25] K. Kusmierczyk, M. .Lukaszewski, Z. Rogulski, H. Siwek, J.
atoms constituting one surface phase and having Kotowski, A. Czerwinski, Polish J. Chem. 76 (2002) 607.
[26] M. Grden, A. Piascik, Z. Koczorowski, A. Czerwinski, J.
similar adsorption properties towards oxygen due to Electroanal. Chem. 532 (2002) 35.
atomic interactions occurring in the alloy. The [27] M. Lukaszewski, K. Kusmierczyk, J. Kotowski, H. Siwek, A.
AuO signal is connected with the process of Czerwinski, J. Solid State Electrochem. 7 (2003) 69.
oxygen desorption from another surface phase, [28] F.A. Lewis, The Palladium/Hydrogen System, Academic Press,
consisting of almost pure Au. New York, 1967.
[29] Y. Sakamoto, K. Yuwasa, K. Hirayama, J. Less-Common Met.
5) In some cases an additional phase, electrochemically
88 (1982) 115.
similar to Pd, seems to exist on the alloy surface. [30] T.B. Flanagan, Y. Sakamoto, Platinum Met. Rev. 37 (1993) 26.
Oxygen desorption from this phase could be re- [31] W.B. Pearson, A Handbook of Lattice Spacings and Structures of
sponsible for the third cathodic peak observed in the Alloys, Pergamon Press, London, 1958.
oxygen region. [32] M. Hansen, Constitution of Binary Alloys, McGraw-Hill, New
York, 1958.
6) The method of surface composition determination
[33] B.J. Wood, H. Wise, Surf. Sci. 52 (1975) 151.
based on the linear relationship between PdO [34] A. Jablonski, S.H. Overbury, G.A. Somorjai, Surf. Sci. 65 (1977)
reduction peak and Pd content works only when 578.
alloy surface remains homogeneous. In the case of [35] L. Hilaire, P. Legare, Y. Holl, G. Maire, Surf. Sci. 103 (1981) 125.
superficially heterogeneous Pd /Au electrodes the [36] D.A.J. Rand, R. Woods, J. Electroanal. Chem. 35 (1972) 209.
[37] D.A.J. Rand, R. Woods, J. Electroanal. Chem. 44 (1973) 83.
composition of alloy surface can be estimated from
[38] S.H. Cadle, Anal. Chem. 46 (1974) 587.
real areas occupied by each of surface phases. [39] K. Gossner, E. Mizera, J. Electroanal. Chem. 125 (1981) 359.
[40] M. Watanabe, S. Motoo, J. Electroanal. Chem. 60 (1975) 259.
[41] S. Trasatii, O.A. Petrii, Pure Appl. Chem. 63 (1991) 711.
Acknowledgements [42] P. Waszczuk, P. Zelenay, J. Sobkowski, Electrochim. Acta 40
(1995) 1717.
[43] S. Smolinski, P. Zelenay, J. Sobkowski, J. Electroanal. Chem. 442
This work was financially supported by the Polish (1998) 41.
State Committee for Scientific Research (KBN) Grant [44] S. Smolinski, J. Sobkowski, J. Electroanal. Chem. 463 (1999) 1.
3T09A 003 19. [45] F.A. Lewis, Platinum Met. Rev. 5 (1961) 21.