Ekctrochimka Aem, Vd.38, No. 15, pp.2145-2153.

1993 0113-46116/93 $6
.00+n10
Printed in Great Bduin . © 1993. Petpmoo Ptwr Ltd

A HYDROGEN ADSORPTION AND ABSORPTION STUDY

WITH ULTRATHIN Pd OVERLAYERS ON Au(111) AND
Au(100)
M . BALDAUF and D . M . KOLB
Department of Electrochemistry, University of Ulm, D-89069 Ulm, Germany

(Received 8 March 1993)

Abstract-Pd overlayers with (111) and (100) morphology and with average thicknesses between one and
ten monolayers were deposited onto Au(l11) and Au(100), respectively . In the case of Pd on Au(11l), the
film growth was characterized by in situ STM. Due to a significant overpotential for hydrogen absorption
in the Pd thin films, adsorption of hydrogen can be studied without being masked by the absorption
reaction. H adsorption on Pd(111) films with an average thickness of about five monolayers occurs in two
steps up to a total amout of about one monolayer, whereas for thicknesses of 10 monolayers and above
as well as for all Pd"(100)" films only a single adsorption peak is observed . The H adsorption process is
strongly influenced by the anion of the supporting electrolyte with respect to its thermodynamics as well
as kinetics . The maximum amount of adsorbed hydrogen increases with the average film thickness and
the H/Pd-ratio reaches a limiting value of around 0 .6 in acid electrolytes for thicknesses well above 10
monolayers . The influence of organic molecules and of upd TI on hydrogen adsorption, absorption and
evolution is shown and briefly discussed .

Key words : hydrogen absorption, hydrogen adsorption, palladium, thin films .

1 . INTRODUCTION ers on Au(Ill) and Au(l00), the morphology of

Electrochemical studies with Pd as the electrode
material are often hampered by its extraordinary
ability to absorb hydrogen in large amounts[1] .
Unlike Pt, where hydrogen adsorption has been
studied extensively and has revealed interesting
surface phenomena, this reaction is practically
impossible to be studied with bulk Pd because it is
masked by the H absorption reaction . Secondly,
studies with Pd single crystal electrodes are very
scarce[2-7], because of the extreme difficulties con-
nected with the surface preparation . Flame annealing
and subsequent cooling in a stream of Ar seems to
be not very applicable to Pd and surface preparation
by cycles of sputtering and annealing under uhv con-
ditions requires an unusually high number of cycles
which makes this metal unconvenient to work with .
An interesting approach to circumvent the above
mentioned difficulties lies in the use of thin Pd over-
layers rather than bulk material . Attard and
Bannister[8] deposited a single monolayer of Pd
onto Pt(111) to study hydrogen and sulfate adsorp-
tion in the absence of any hydrogen absorption.
Tateishi et al.[9, 10] deposited Pd particles in the
2-10nm range onto glassy carbon to study hydrogen
adsorption, absorption and evolution. They showed
that for the Pd particles hydrogen absorption
occurred at more cathodic potentials than for a
massive Pd electrode, allowing for a study of H
adsorption which in the latter case is masked by the
absorption reaction . Similar observations had been
reported before by other groups for Pd overlayers on
polycrystalline gold[11-14] .
In this study we have investigated hydrogen
adsorption and absorption on ultrathin Pd overlay-
which reveals clear (111) and (100) textures, respec-
tively. Thus the adsorption of hydrogen on a single-
crystalline Pd surface could be studied with ease, the
corresponding cyclic current-potential curves
showing more adsorption structure than those for
Pd films on polycrystalline gold . In addition, the
blocking of adsorption sites for hydrogen by organic
molecules and metal atoms deposited at under-
potentials has been studied, as well as the maximum
amount of hydrogen which can be absorbed by these
thin Pd films .
2. EXPERIMENTAL
The electrodes were gold single crystals of either
(111) or (100) surface orientation, about 4 and 5mm
in diameter and 3mm thick in both cases, with a
gold wire attached to their rear for proper handling .
The surface was first prepared by standard crystallo-
graphic procedures such as mechanical and electro-
chemical polishing and its quality renewed by flame
annealing before each electrochemical deposition of
Pd . In some cases 200 nm thick gold films evapo-
rated onto "Robax" glass (AF 45, Berliner Glas KG)
with a 2 inn thick chromium undercoating were used
as electrodes, which have a (111) morphology when
treated properly, which is comparable in quality with
massive single-crystal electrodes[15, 16] . Pd was
deposited onto the gold surface typically from 0 .1 M
H2S0 4 + 0.1 mM H2PdCI 4 at +0.27 V vs. sce. The
amount deposited was controlled by the charge and
usually varied between 1 and 10 monolayer equiva-
lents (ML), one equivalent being defined as
440pCcm -2 for Pd deposition onto Au(Ill) and

2145


2146 M . BALDAUF and D . M. KOLA

-2
380pCcm for Pd onto Au(100) . These values cor-
respond to the number of substrate surface atoms,
taking into account the valence state of two for the
Pd ion . For the study of much thicker Pd films leg
100 monolayers), deposition was done from 1 mM
H,PdCI, in 0.1 M H,SO, onto the Au(111) film elec-
trodes rather than onto the massive single crystals in
order not to jeopardize the quality of the latter by
excessive alloying . After Pd deposition the electrode
was emersed from the electrochemical cell, rinsed
several times with Milli-Q water and immersed into
a second cell with a Pd ion-free electrolyte, mostly
0.1 M H,SO, for the study of hydrogen adsorption
and absorption in acidic solutions . For comparison,
a polycrystalline Pd wire with 0 .5 mm diameter
(Heraeus, 0.9995 purity) was used as the electrode .
The solutions were made of H,SO„ HCIO, (both
Merck, suprapure), Na,SO, (Merck, p.a.), CuO
(Fluka, puriss . p.a.), PdCl, (Merck, for synthesis) and
Milli-Q water and they were deaerated with purified
nitrogen . All potentials were measured and are
quoted against the saturated calomel electrode (see) .
3. RESULTS AND DISCUSSION
3 .1 . Morphology of Pd overlayers on Au(Ill) and
Au(100)
The morphology of the Pd overlayers on the two
different gold substrates was studied by in situ STM
and by cyclic voltammetry with the underpotential
deposition of Cu as a structural probe . The STM
studies were performed with the Au(I11) film elec-
trodes only, because both massive Au single crystals
with a gold wire attached to their rear side were not
suitable for mounting in the STM cell . A sequence of
STM images obtained before and during Pd deposi-
tion on Au(111) in 0.01M H,SO, + 0 .5 mM
H,PdCI, reveals rather surprisingly a two-
dimensional growth during the initial stages of the
deposition process (Fig . 1). We should mention here
briefly that the first monolayer of Pd is deposited at
underpotentials on Au(111) between 0 .7 and 0.5V vs .
see. This has been clearly seen in the corresponding
cyclic voltammograms and STM images and will be
reported elsewhere[17] . Hence the Pd bulk deposi-
tion occurs onto Au(111) covered already with one
monolayer of Pd which is in registry with the sub-
strate. Onto such a surface the second Pd layer tie
the 1st bulk layer) grows strictly in two-dimensional
islands, whereas the third layer is found to partly
grow in two dimensions and partly as three-
dimensional clusters . Epitaxial growth with the
result of a rather flat and continuous Pd"(111)' film
is seen up to the equivalent of several layers, before it
gradually turns into a rough, polycrystalline film at
larger thicknesses .
The (111) texture of the Pd overlayer is also reflec-
ted in the underpotential deposition (upd) of Cu, the
cyclic current-potential curve for which is shown in
Fig. 2a for a 5 ML Pd film . A comparison of this

(a) (b) (C)

(d) (e) (f)

Y n
50 nm
Fig . 1 . Sequence of STM top view images for Au(111) on glass, recorded before (a) and during (b-0 Pd
deposition from 0 .01M H 2 S0, + 0.5mM H 2 PdCl, . (a) E = +0 .70V vs- sce ; (b<)E = +0 .49V vs- sce ;
(0 E = + 0.39 V vs. see. The two-dimensional growth of the 1st and 2nd bulk layer is clearly seen . Differ-
ent heights are denoted by different shades of grey, lighter shades corresponding to higher points . Height
differences are monoatomic .


Ultrathin Pd overlayers on Au(11I) and Au(100) 2147

(a > 10
5ML 1Pd / Cu

10

Q
1
'E

1
U
0
r
-10

Au(100) / 5' ML' Pd /

10 -20 Cu _

0.0 02 0A 0 .0 0.2 0 .4

E SCE / V E SCE / V

Fig. 2. Cyclic current-potential curves for (a) 5 ML Pd on Au(111) and (b) 5 ML Pd on Au(l00) in 0.1 M

curve with the voltammograms for Cu upd on
massive single crystal electrodes[2] reveals a striking
similarity with Pd(111), whereas the corresponding
upd curve for the 100 ML film clearly shows a poly-
crystalline surface . Similar experiments with Pd
overlayers on Au(100) also indicate epitaxial growth
of the Pd, now with a (100) texture . Figure 2b shows
the cyclic voltammogram for the Cu upd on a 5 ML
Pd overlayer on Au(100), which again is practically
identical with the curve for Cu upd on massive
Pd(100) as far as number of peaks and peak poten-
tials are concerned[2, 3] .
The above described results therefore strongly
support our assumption that thin Pd overlayers on
gold single crystal surfaces exhibit single crystallinity
which can make these films a convenient substitute
of massive Pd electrodes .
3 .2. Hydrogen absorption in the Pd overlayers
Figure 3 shows a sequence of cyclic current-
potential curves comprising the region of H adsorp-
tion, absorption and evolution in 0 .1 M H,SO, for
Pd overlayers on Au(III) ranging from I to 10
monolayer equivalents (ML) in thickness . A corre-
sponding curve for polycrystalline Pd, which is
included in Fig . 3c for comparison, reveals that the
hydrogen absorption reaction is clearly shifted to

40
(a)
20
0ML(x5)

i I
3'ML'
0
- 40

1 ML
- 40

I I - 80
-0.4 -0.2 0.0 -0.4 -0 .2 0.0 -0 .4 -0 .2 0 .0
E / V E SCE / V E / V
SCE SCE
Fig. 3 . Cyclic current-potential curves for thin Pd overlayers on Au(111) in 0 .1 M H,SO, . Scan rate :
5mV s - ' . Average film thicknesses as indicated in the diagrams in terms of "monolayers" (ML). Dashed
curve in (c) corresponds to polycrystalline bulk Pd .


2 14 8 M . BALDAUF and D . M . KOLB

250 i I . '
I

200

100

50 0.20

0 0.00

i
0.0 1 .0 2.0
lop (Pd /'ML')

Fig 4 . Amount of hydrogen adsorbed on (0) and absorbed in (A) Pd thin films on Au(111) as a function
of Pd film thickness . 0.1 M H 2 SO 4 .

more cathodic potentials for the Pd overlayers, thus

unmasking the hydrogen adsorption region at
around -0.05V vs . sce[9-14] . The amount of
hydrogen absorbed in the Pd overlayer between
-0.15 and -0 .30V grows with the Pd cluster size
such, that an increase in the H 464/Pd-ratio from zero
to 0 .6 with the average Pd thickness from 1 to
100 ML is observed (Fig . 4). Under the present
experimental conditions, 0 .6 seems to be the limiting
value for the H/Pd-ratio[9, 10]. It is interesting to
note, that H absorption occurs only for Pd films
thicker than 2 ML . This suggests either that there is
a minimum of three layers required for the Pd film
to develop the ability to absorb hydrogen, or that a
larger interatomic spacing in the first two Pd layers
due to the registry with the Au substrate causes film
properties which are substantially different from
those of the Pd bulk .
Au(111) / Pd / H„

3.3 . Hydrogen adsorption on Pd overlayers with (111)

texture
I I, I

The adsorption behaviour of hydrogen on the Pd -0.1 0 .0 0 .1

overlayers changes markedly with the cluster size, as
is clearly seen in the sequence of voltammograms in
Fig . 3 and, on an enlarged scale for three different
thicknesses, in Fig . 5 . H adsorption on the under-
potentially deposited Pd monolayer (Fig . 3a) shows
one broad adsorption and desorption peak with a
-2
total charge of about 170 µC em which formally
corresponds to approximately 0.7 monolayers (ML)
of H(1 ML A 240µC cm -=). This adsorption behav-
iour is distinctly different from that for a Pd mono-
layer on Pt(111) where H adsorption seems to occur
within a rather narrow adsorption spike[8] . This
may not be too surprising, because the vastly differ-
ent chemical nature of the two substrates, Au and Pt,
will be reflected in the adlayer properties .
With the deposition of the second Pd ML which
has been shown to grow via two-dimensional islands
on top of the Pd upd layer, H adsorption and
desorption become more defined, the maximum
coverage of H being reached in two energetically
slightly different steps . This is more clearly seen for
the desorption process where the two current peaks
V
ESCE /
Fig . 5. Cyclic current-potential curves for hydrogen
adsorption on thin Pd overlayers on Au(111) . Average
thicknesses of Pd : ( ) 2 ML ; (---- ) 5 ML ; ( )
10 ML . 0.1 M H 2SO4 . 5 mV s - ' .
do not overlap as strongly as for the adsorption . For
average Pd thicknesses of 10 ML and above a single
narrow current peak for H adsorption or desorption
emerges. The overall charge for the H adsorption
region has its maximum for film thicknesses around
3 ML, but decreases for thicker layers (Fig. 4), which
most likely reflects the smoothening of the Pd
surface as the islands or clusters coalesce . The two
adsorption peaks for low thicknesses (2-5 ML) seem
to indicate the existence of two different kinds of
adsorption sites for the thin Pd overlayers, the more
anodic peak very tentatively being assigned to H
adsorption at the perimeter of the islands which
gradually disappears as the latter merge and form a
uniform overlayer.


Ultrathin Pd overlayers on Au(111) and Au(100) 2149

concentration has been measured. The result, shown

1 _\
I
Au(111) / 5'ML' Pd / H
I I I
60
-0A -0.2 0 .0
ESCE / V
Fig . 6. Cyclic current-potential curves for 5 ML Pd on
Au(Ill) in ( ) 0.1M HCIO, and (---- ) 0.1M
HCIO4 + 0.1 M Na,SO4 . 5 mV s - ' .
Hydrogen adsorption on Pd is strongly influenced
by the anion in very much the same manner as for
Pt . Sharp and energetically well-confined adsorption
peaks are seen in sulfate-containing electrolytes
whereas in perchlorate solutions a rather broad and
unstructured adsorption behaviour emerges (Fig. 6) .
For the latter case two adsorption sites seem to be
discernable in the mesa-like current peak for desorp-
tion . Not unexpectedly, the hydrogen absorption
reaction is hardly influenced by the anion . The
curves in Fig . 6 clearly show that anions can interact
strongly with adsorbed hydrogen and significantly
change the energetics . In order to verify that the
current peaks around 0 and -0 .1 V are indeed due
to hydrogen rather than sulfate adsorption, the
dependence of these peaks on proton and sulfate
in Fig . 7, confirms the assumption made above : the
potential of the current peaks assigned to hydrogen
adsorption indeed shifts linearly with the H' con-
centration in solution of constant sulfate concentra-
tion (0.1 M Na3 SO4 ), the slope being approximately
6OmV decade', whereas no potential shift is seen at
constant pH when the sulfate concentration is
altered . Such a behaviour unequivocally shows that
the current peaks are caused by the hydrogen
adsorption reaction .
Despite the rather slow scan rate of 5 mV s - ', an
appreciable asymmetry in the peak potentials for H-
adsorption and -desorption is noted (eg Fig. 5) . This
could be indicative of a two-dimensional nucleation-
and-growth process being involved in the formation
of the hydrogen adlayer instead of a purely adsorp-
tive event . Although such a two-dimensional growth
mechanism has not been found for hydrogen on Pt,
it has been observed for the underpotential deposi-
tion of metals on densely-packed (111) substrates, eg
0.2 Cu on Au(111)[18], where again a strong anion
influence was noted. Therefore, potential step experi-
ments were performed, the results of which are
shown in Figs 8 and 9 . Unlike for hydrogen on Pt,
rising transients were found for H adsorption on
Pd"(111)" in sulfuric acid solutions, which were on
the seconds time scale . The transients for the 2ML
Pd on Au(III) (Fig. 8) show a single but strongly
asymmetric current peak which could indicate the
occurrence of a combined adsorption-phase forma-
tion process for the H adlayer, whereas only falling
transients were obtained for the desorption process,
ie for potential steps in positive direction . For Pd
overlayers of 5ML average thickness, which show
two distinct current peaks in the H adsorption
region (eg Fig. 5), a double-peak transient was
observed when the potential step covered the region
of both peaks (Fig . 9). This suggests that H adsorp-
tion on both types of surface sites follows a
nucleation-and-growth behaviour. Since H adsorp-
tion on metal electrodes usually is a very fast
process, the extremely slow current response seen in
Figs 8 and 9 must reflect the behaviour of the sulfate
ion rather than the hydrogen, ie sulfate desorption

-50

-100

E -150

2
a
-200
w
-250

-300

-360
-6 -5 -4 -3 -2 0
log (o/M)
Fig . 7. Potential of the current peak assigned to hydrogen adsorption on 5ML Pd on Aultii) as a
function of sulfate (0) and proton (A) concentration . (O) : 0.1 M HC1O4 + xM Na,SO, . (A) : 0.1 M
Na,SO, + xM HCIO, . F refers to the more negative peak on the cathodic scan-


2150 M. Bu .DAUF and D. M . Kota

80

60

0 5 10 15 20 25
t/s
Fig . 8. Current transients for a two monolayer thick Pd film on Au(111) in 0 .1 M H,SO, . Potential steps
from -0 .02 V vs . see to the indicated values .

from the electrode surface similar to the case of Cu
upd on Au(111)[18] .
3 .4 . Hydrogen adsorption on Pd overlayers with (100)
texture
In Fig. 10 are shown cyclic current-potential
curves for 2, 5 and 10 ML thick Pd overlayers on
Au(100) in 0.1 M H I S04 for the potential region of
H adsorption and absorption . While the H absorp-
tion behaviour is in essence the same as that for
Pd"(111)" films, eg with respect to the H/Pd-ratio as
a function of film thickness, there are distinct differ-
ences in the hydrogen adsorption as one might have
expected . Adsorption of hydrogen on Pd"(100)"
occurs over a much wider potential range than on
Pd"(111)", adsorption and desorption being much
less reversible than in the case of Pd"(111)" .
-2
Assuming 210pCcm as the charge equivalent of
one monolayer of hydrogen on Pd(100) (as opposed
to 240pCcm -2 on Pd(111)), H adsorbs up to a full
monolayer on 5 and IOML Pd"(100)", whereas on
the 2 ML overlayer a clearly smaller amount of H, a ,
is observed, which is of the order of 0 .6 monolayers .
We stress the point that-like for Pd"(111)"-there
is practically no sign of a H absorption in the 2 ML
overlayer (Fig. 10a). Preliminary potential step
experiments indicated the occurrence of rising
current transients on the seconds time scale for H
adsorption on Pd"(100)" superimposed on purely
falling transients . We are therefore led to conclude,
that a nucleation-and-growth behaviour occurs
during the formation of a H adlayer on the (100) face
together with a purely adsorptive step .
3.5 . Influence of additives on the hydrogen adsorption
For electrochemical studies with Pd it would be
highly desirable to influence, independently from
each other, H adsorption, absorption and evolution
by an appropriate surface modification . In prelimi-
nary experiments, organic molecules such as IH-

Au(111) / 5 'ML' Pd / Hm
II

0 5 10 15 20
t/s
Fig . 9. Current transients for 5 ML Pd on Au(11I) in 0.1 M H,SO, . Potential steps from -0 .01V vs . sce
to the indicated values .


Ultrathin Pd overlayers on Au(111) and Au(100) 2 15 1

20

. 20
10' ML'

Au(100) / Pd / H

-40 \ I I I ~ I
-120
-0 .4 -0 .2 0.0 -0.4 -02 0.0
E / V E SCE / V
SCE

Fig. 10 . Cyclic current-potential curves for thin Pd overlayers on Au(100) in 0 .1 M H Z SO+ . Scan rate :
SmV s - ' . Average film thicknesses in terms of "monolayers' (ML) as indicated in the figures .

benzotriazole (BT) and crystal violet (CV) or metal
ions such as TI+ were added to the electrolyte and
their power of inhibition by adsorption or under-
potential deposition studied for 5 ML Pd overlayers .
The result for BT added in concentrations of 0 .1 and
4mM is shown in Fig . It . A clear effect on the H
adsorption reaction is found, shifting the respective
current peaks in the cathodic direction . Simulta-
neously with increasing shift, the two peaks merge
into one. No significant influence of the adsorbed
BT on H absorption or H evolution was found, the
slight but unsystematic shifts of the absorption peak
potentials being due to experimental scatter . Addi-
tion of crystal violet (CV) at a concentration of
0.1 mM completely blocks H adsorption on
Pd"(111)", but leaves the amount of absorbed hydro-
gen unaltered (Fig . 12). However, in the presence of
the additive, H absorption and desorption become

40 I I I

20

0
0

Q C
1
1

_ 40
Au(111) / 5' ML' Pd / BT Au(111) / 5'ML' Pd / CV

I I I I 1 1
_ 60
-0A -0 .2 0.0 -0 .4 -0 .2 0 .0
E SCE / V E SCE / V

Fig . 11 . Cyclic current-potential curves for 5 ML Pd on Fig 12 . Cyclic current-potential curves for 5 ML Pd on
Au(lll) in 0.1M H 2 SO,+xM 1H-benzolriazole (BT) . Au(Ill) in OA M H,SO, without (----) and with
x=0(
. ( ) ; I x 10 -4 M (- ---) ; 4 x 10 -3 M ( ) 1 x 10 - 'M crystal violet (CV) . 5 mV s - ' .
5 mV s - ' .

rA 3ra5-r

2152
i t 1 t
10 I t i t
t
1 4. SUMMARY
-l0 t In this study it is shown that thin Pd overlayers
Au(lcJ) / 5'WC Pd /
.30 CV
I and clear differences in the adsorption behaviour for
-0A -0.2
E SCE / V
Fig. 13. Cyclic current-potential curves for 5ML Pd on
Au(100) in O .IM H,SO, without (----) and with
( ) 1 x 10'4 M crystal violet (CV). 5 mV a- ' .
much more reversible, an effect already noticeable
with BT (see Fig, ll} The influence of CV on the
hydrogen absorption reaction is particularly clearly
seen with the Pd"(100)" film (Fig . 13), where in the
presence of CV a rather reversible charging behav-
iour confined to a small potential region is observed .
In addition it seems that hydrogen adsorption on
Pd"(100)" is not completely suppressed by CV, but
shifted in the negative direction, causing a broad
shoulder in the voltammogram around -150 mV vs .
see. Finally, the effect of a metal monolayer depos-
ited at underpotentials is demonstrated in Fig 14
-0.4 -02
E ME / V
Fig. 14. Cyclic current-potential curves for 5ML Pd on
Au(Ill) in O .1M H,SO, without (---- ) and with
( )5x10 5 - 'MTI,SO, .5mVs - '
M. BAIDAuF and D. M . Kola
with T1 . H adsorption again is blocked completely
and the H absorption reaction shifted to higher
overpotentials . Desorption of H out of the Pd bulk is
also hindered by the upd layer, the hydrogen oxida-
tt
tion curve extending now far more into anodic direc-
tion. In all three cases, however, an increase of the
t amount of absorbed hydrogen could not be
t achieved.
electrodeposited onto Au(111) and Au(100) elec-
trodes have surface properties very similar to those
of Pd(111) and Pd(100), respectively, as was tested by
the underpotential deposition of Cu . Adsorption of
hydrogen on such Pd"(111)" and Pd"(100)" surfaces
has been studied as a function of Pd film thickness
the two surface orientations as well as for the
OA
various film thicknesses were found . The following
observations may be noteworthy :
(a) The amount of hydrogen adsorbed onto the
first (underpotentially deposited) Pd layer on
Au(111) is only about 2/3 of a full monolayer .
(b) As for Pt(I11), hydrogen adsorption on the
Pd"(111)" overlayers is strongly influenced by
the anion of the supporting electrolyte.
(c) Formation of the hydrogen adlayer on
Pd"(111)" in sulfuric acid solutions follows a
nucleation-and-growth mechanism .
(d) A two monolayers thick Pd film does not
absorb hydrogen to any appreciable amount.
(e) The ability of Pd to absorb hydrogen starts
with a thickness of three layers. The H/Pd-
ratio then increases with Pd film thickness and
reaches a limiting value of 0 .6 in acid solu-
tions.
(f) Crystal violet suppresses hydrogen adsorption,
but influences favorably the kinetics for the
hydrogen absorption reaction, making loading
and unloading of the Pd films more reversible .
Acknowledgement-The STM images of the Pd-covered
Au(l11) surfaces were obtained by Dip]
: Phys. T. Will.
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