INTRODUCTION
EXPERIMENTAL
RESULTS
In Figs. 1-5 the anodic sweeps of the cyclic current-potential curves are
shown for some of the studied systems. The metal-ion concentration was usually
2 x 10 -4 M, except for the case of lithium, which was deposited directly from
the 1 M LiCIO4 supporting electrolyte in acetonitrile or propylene carbonate.
The current densities given in the figures refer to the geometrical electrode area,
without taking any roughness factor into account. Capacity measurements indicate
a roughness factor of about 2 for all electrodes. The large stripping peak at more
negative potentials is due to oxidative desorption of the bulk deposit, the smaller
peak at positive potentials arises from the monolayer desorption.
Some curves show a minor third peak between the other two peaks (e.g.
see TI on Au around - 4 5 0 mV and Pb on Au at - 2 6 0 mV). The charge, however,
80--
I
aJ Cd onAg
' f
]
d)Cu onAu
I
I~_ i
8O
40
0
I / 0
!
80
1"4
~b) Pb on Ag
1
~,~oo.o ~- 8O
E E
.~4o ~.o
..~
i
0
80 20
l clTI on Ag f ) TI on Au
10
0
, I i I , f , I t
-I 0 -0 5 0 -0 5 0 ÷0
UScE/V
Fxg. 1 Anodlc stripping curves for various metal deposits on Ag and A u m 1 M Na2SO4 (pH 3)
(curves a and c) and 1 M NaC104 (pH 3) (curves b, d, e and f). [ M e + I = 2 x 10 -4 M Scan rate=20 mV
s-1 The arrows indicate the peak potentials for bulk and monolayer stripping.
METAL MONOLAYERS 27
I ' I r I I ' I 2a
80
I Cd o n C u
--
_
T[ o n C u
--
_
~ 150
'~
Li on Au
-
50
_ 0
300 I -- ' I
L, on Ag
~E200
<[
,oo
0--
r I , I J I
---3 ( -20 -10 0
UscE/V
Fig 4 Ano&c stripping curve for L1 on Ag m acetomtnle (1 M L1C10,) Scan r a t e = 1 0 0 mV s - l .
l LI o n C u
200
< 100
0
, 1 I J j
-30 -2 0 -10
UscE / V
Fig 5. Anodlc strlppmg curve for L1 on Cu in propylene carbonate (1 M LxCIO4) Scan rate = 100 mV s - 1.
28 D M. KOLB, M. PRZASNYSKI, H. GERISCHER
TABLE 1
DATA FOR UNDERPOTENTIAL SHIFT AUp AND HALF WIDTH 3 OF THE MONOLAYER
STRIPPING PEAK
x. results of this work.
A g / C u 2+ 0 5 M H2SO 4 _ _ L X
Ag/Cd 2+ 1 M N a 2 S O 4 (pH 3) 0 16 0 16 x
Ag/TI + 1 M Na2SO, (pH 3) 0.27 s 0 08 x
Ag/Pb 2+ 1 M NaCIO4 (pH 3) 0.16 0.05 x
Ag/B13 + 05 M HCIO4 0.065 -- 5
monolayer stripping process indicates, that most of the adsorbed atoms are deposited
around this potential with the least variation in adsorption energy as a function
of coverage. This peak potential Up therefore seems most suitable for the characteri-
zation properties of the adatoms, while for the bulk deposit the stripping peak
potential is within some 10 mV the same as the reversible Nernst potential. The
underpotential shift AUp can be understood as representing the difference in the
bond energies between the metal adatom on a foreign substrate and on.the metal
itself. In Tables 1 and 2 all available data on the underpotential deposition concerning
the potential difference AUp between bulk and monolayer stripping peaks are.
collected with the appropriate references. Furthermore, as a characteristic quantity
for the monolayer adsorption isotherm, the half width 6 of the monolayer stripping
peak is also given in Table 1, whenever possible. The collected data are divided
into two parts, namely CI- free and C1- containing solutions; the influence of C1-
coadsorption will be discussed at the end.
TABLE2
D A T A F O R U N D E R P O T E N T I A L S H I F T AU~pl- IN C I - C O N T A I N I N G E L E C T R O L Y T E S A N D
D I F F E R E N C E tSU~pI B E T W E E N M O N O L A Y E R S T R I P P I N G P E A K P O T E N T I A L S I N C1-
C O N T A I N I N G A N D C1- F R E E S O L U T I O N S
x' results of this work
DISCUSSION
The basic information we have obtained from the experiment is, that the
chemical potential of the first monolayer*, Pad, is markedly different from that of
the bulk film metal, /~e~. The chemical potentials of bulk phase and monolayer
can be obtained from the equilibrium conditions for the reactions,
Memo+iv+ Zemet~l ~--- Memet~l (la)
* In the following we term the adsorbed layer as monolayer, as long as 0 < 1. D u e to the
logarithmic potential dependence of 0 in the monolayer isotherm 0 = 1 is not reached before the bulk
deposition potential
30 D M. KOLB, M. PRZASNYSKI, H G E R I S C H E R
with
~Me~lv -~- ~ern. . . . = ]Ameta1 (lb)
and
Meg+olv+ 2es;~trate ~-~ Mead (2a)
with
We theretore have reed to correlate the underpotential shift AUp with the
difference in the work functions of substrate and adsorbate, since the work functions
have been determined much more accurately than the electronegativities. We expected
that the ionic character of the metal-adatom bonding should increase with
increasing differences in work function of both materials and we assume that the
ionic contribution to the chemical bond of the metal-adatom complex, arising from
the partial charge transfer, is responsible for the deposition of the first monolayer
at underpotentials.
METAL MONOLAYERS 31
~.4 1 -I - f - I
1.0-- L,',ga i*
> 0.8 ~ !
_-~ 0 TI"/Au
0 2 -- Ocu.., oc¢.,co
pb**lAg
TI*IAg
BI+~IA0
Cd~lAg
T( ICu
o I J J
0 0.5 1.0 A~IeV t 5 2.0 2.5
1
Fig 6 Underpotentlal sMft AUp between bulk and monolayer stripping peak as a tunctlon of A#,
the &fferencem work functions of substrate and adsorbate material The data are taken from Table 1
(O) Aqueous soluUon,(0) acetonltnle, (A) propylene carbonate
* The ~-values for the alkah metals were taken from ref 62
32 D M. KOLB,M. PRZASNYSKI,H. GERISCHER
When we assume that the dipole moment re(O)is built up by a partial charge
( 1 - 70)e 0 of the adatom and an equivalent counter charge - ( 1 - 70) eo at the surface
atom of the substrate, separated by the bond length l, we can derive the following
expression from eqn. (7) for the change in the contact potential AUe(0) arising
from the dipole layer:
AVe(0) = (No/eeo)O(1-7o)eol (8)
The formulation of the partial charge as (1 - 70) has been chosen here to correspond
with the definition of the so-called electrosorption valency 7, given by SchmidP °
and Schultze and Vetter 37. 70 is dependent on the coverage and will normally
increase with 0. It has been shown s°-52 that the work function of a monolayer
is already that of the bulk material.
Equation (8) gives for 70 as a function of AUe(0) approximately
70 ~ 1-0.05 eAU~(O)/Ol (9)
where AU¢(0) is expressed in V, I in A, and where we have assumed No = 1.2 × 10 Is
cm-2. Since AU¢(0) is limited by the differences in work function between substrate
and bulk deposit, the 78 values of most of the couples studied in the range
of 0/>0.5 and with A ~ < 1 eV must lie between 0.8 and 1.0. 70 values for the
partial discharge below 0.8 for complete metal monolayers would cause an
unreasonably high change A~ in the work function and can therefore be excludeck
Let us consider as an example the Cu monolayer on Pt. The difference in work
functions yields a contact potential AU¢ of about 0.85 V for 0= 1, e is assumed
to be two and l= 1.5 A, approximately the radius of the adatom. This gives a
70= 1 value of about 0.94.
The question arises, to what degree can the electrostatic energy of such an
electric double layer explain the difference in binding energies between adatoms
and a foreign substrate and atoms in the bulk? However, a simple calculation
shows that the electrostatic energy is far too small to account solely for this effect,
since the electronic charge q = ( 1 - 70)eo of the adatom is rather small. The electro-
static energy per adatom is given by:
Eel.star = NoO[m(O)]2/2 eeol = NoOq2/2 C (10)
where C=eeo/1 is a formal capacity of the dipole layer. For the above mentioned
example of a Cu monolayer on Pt, Eel stat is only about 0.02 eV, while the under-
potential shift yields an energy eoAUp=0.4 eV. Besides, the contribution of the
electrostatic energy would cause a quadratic dependence of A Up on A~ which is not
found in the experiment (see Fig. 6).
In Pauling's theory of the chemical bond 53 the bond energy between two
atoms contains an additional term which increases with increasing difference in their
electronegativities. This is caused by the contribution of ionic states to the covalent
binding because resonance between ionic and covalent bond will lower the energy.
Although Pauling's theory has been derived for 2-atomic molecules, the general
conclusions should equally hold for polyatomic molecules, of course with less simple
formulations. This concept has already been used to describe adsorption processes
on metal surfaces, where the resulting metal-adatom complex had been treated
as a surface molecule 54'55. Our observation shows that the interaction of an atom
METAL MONOLAYERS 33
with a solid metal surface follows indeed a rather simple relation, quite similar
to the interaction of 2 different atoms. However, we have to assume that for all
deposits the covalent eontribution to the surface bond is approximately the same
as in the bulk metal.
We know that the chemical bond of the adsorbed metal atoms has a polar
character which increases with increasing work function difference (see eqn. 8) and
decreases with increasing coverage. This is indicated by the shift in work function
with varying coverage 5°-52 and the shift of the excess charge on an electrode
during the deposition of the first monolayer. If we assume that a partial electron
transfer from the adatom to the substrate occurs only m such cases where the
ionization energy of the adatom is lower than the work function of the substrate, no
polarized bond could be formed for all of the studied systems except the alt:ali
metals. The experimental results, however, show that in all systems with under-
potential deposition a polar bond exists with a positive charge on the adsorbed
atom 37. This cannot be explained quantitatively, even by comparing the absolute
electronegativities of atoms and substrates. Therefore we think that the electro-
negativity of a metal atom interacting with a metal surface is best characterized
by the electronegativity of this atom in a metal lattice, namely the work function.
As mentioned above the dipole moment of the surface bond depends on the
work function difference as well as on the coverage. It is largest for small coverages
and tends to a lower limit as 0 approaches unity. As a consequence the interaction
energy of the adatom is also a function of A~ and 0 and therefore different
isotherms 0 = 0(U) will result for different A¢ values.
Figure 7 shows the half width ~ of the monolayer stripping peak as a
function of A~. Since in many cases the stripping peak is rather broad and often
600
I I I I
~00~00 CiAg'Au
l L~"~J,u .
Ag*lP0t /
J0
20 0 T,.,A.
Hg..IAuO
OCd.°/ACdo'
g IAuO
Cd'*lCuO OHg+*lpt
leo ~ O *1ACu. u "OPb'÷Au l
"~t"Ikg O~t'~Cu
o I [ I I
0 05 1.0 1.5 2.0 2.5
B~/eV
Fig. 7. Half width ~ of the monolayer stripping peak as a function of A¢
34 D M KOLB, M PRZASNYSKI, H GERISCHER
unsymmetrical, 6 will only give a rough idea about the width of the adsorption
isotherm. In addition, the form of the isotherm will partly depend on the specific
interaction of the solvent molecules with the electrode material and the metal ions.
Therefore, xt is not surprising that the points m Fig. 7 scatter rather strongly.
However, a correlation is seen insofar as the width 6 will increase with increasing
A4~. The lower limit in 6 when A4~ goes to zero is about 40 mV, a value which
is typical for the half wadth, 2.3 (kT/e0)log 4, of a Langmuir isotherm. The broadening
with increasing A4~ may be explained by an increasing difference in the adsorption
energy for the adsorption sites at 0 g 0 and 0 ~ 1 (Temkin-type isotherm).
As we have shown above in our model the work function of the electrode
surface will change from 4~o (value of the substrate material) to 4~1 (value of the
adatom material) as the coverage proceeds from 0 = 0 to 0= 1 in analogy to the
results in the gas phase 5°-s2. This means that the potential of zero charge (p.z.c.)
which is proportional to the work function 4548 (given m volts),
Up z c = ~ - const. (11)
is shifted by Aq~ V during the adsorption or deposition of the monolayer. There
have been extensive investigations by various authors to determine the total amount
of an adsorbed monolayer. This was usually done by integrating the current-
potential curve for the adsorption or desorption peak between 0 = 0 and O= 1.
Then the amount for double-layer charging determined in a metal-ion-free solution
over the same potential range was subtracted. Since the p.z.c, is shifted by Aq~ V
during the deposition or dissolution of the monolayer, whereas this is not the case
m the metal-ion-free solution, the determined charge for the adsorbed monolayer
will be too small by about
Aq = CDLAUp~c = CDLA~ (12)
if this effect is not taken into account. Consequently, the partial discharge
coefficient ? which is given by the ratio of the experimentally determined and the
theoretical charge of a monolayer is somewhat in error when the experimentally
determined charge is not corrected by Aq. Unfortunately, no exact measurement
of Up z ~ is possible at the conditions of underpotential deposition.
As listed in Table 2 many of the reported experiments were performed in
C1- containing solutions where C1- coadsorption is known to take place 39. The
absolute amount of adsorbed C1- m the potential range of interest is rather small
(0 is usually less than 20%). In these electrolytes the monolayer peak is in most
cases shifted to more negative potentials, thus decreasing the underpotential shift
AUp. Qualitatively this effect can be interpreted in accordance with the well-known
shift in the p.z.c, to more cathodic potentials arising from C1- adsorption. The
specific adsorption of anions is caused by a contribution of covalent bonding and
therefore represents a partial electron transfer between the anion and the respective
surface layer. This reduces the mean electronegativity of the metal surface. If the
anions are more strongly adsorbed on the substrate than on the deposit, the apparent
difference in electronegativity will decrease. This is the normal situation because
'the more electronegative metal will usually have the larger affinity for electrons
from the adsorbed species. In accordance with the diminished difference in effective
work function between substrate and specifically adsorbed anions and submonolayer
METAL MONOLAYERS 35
and specifically adsorbed anions, the AUp values decrease in most cases. However,
if the deposit has a greater affinity for electrons than the substrate due to specific
chemical interactions, the effective difference in A4~ can also be increased resulting
in an increase of AUp in such exceptional cases. In Fig. 8 the anodic stripping
curves are shown for a Tl-deposit on Ag in a C1- free and a C1- containing
electrolyte. The influence of the C1- is seen quite clearly. Besides a change in
the underpotentlal shift A Up a considerable reduction in the width of the mono-
layer adsorption isotherm is noted. This shows that specifically adsorbed ions like
C1- introduce certain complications into the system and therefore should be
considered with caution in the interpretation of the underpotential deposition itself.
100
7
,<
~, 50
I
-1 -0 5
UScE/V
Fig 8. Ano&c stripping curves for a T1 deposit on Ag m 0.5 M NaC104 (pH 3) ( ) [Cl-]=0,
( )[CI-]=3xl0-2M [ T l + ] = 2 x l 0 - ' M . Scan rate= 20 mV s -1.
CONCLUSION
REFERENCES