1.

498 Surface Science 201 (1988) IA98-L506

North-Holland, Amsterdam

SURFACE SCIENCE LETTERS

INFLUENCE OF THE CRYSTALLOGRAPHIC ORIENTATION

OF THE SURFACE ON THE POTENTIAL OF ZERO CHARGE
OF SILVER ELECTRODES

A. HAMELIN, L STOICOVICIU
Laboratoire d'Electrochimie Interfaciale du CNRS, 1, place A. Brianr~ 92195 Meudon Cedex, Prance

L. DOUBOVA
Institute of Polarography and Preparative Electrochemistry of the CNR, 4, Corso Stati Uniti (Camin),
Padua, Italy

and

S. TRASATTI
Department of Physical Chemistry and Electrochemistry, University of Milan,
via Venezian 21, 20133 Milan, ~mly

Received 14 January 1988; accepted for publication 8 April 1988

The variation of the potential of zero charge of silver electrodes with the crystallographic
orientation of the metal surface was determined for 13 faces of low and high indices. The possible
interference ot the reaction of electrolytic hydrogen evolution (thermodynamically possible ha the
range of potential where zero charge potentials are measured) with the precise determ~ation of
the v',d,aes of the zero charge potential and its influence on the shape of the capacity potential
curves are discussed. The variation of the potential of zero charge with the crystallographic
orientation is found to parallel that of the surface energy.

1. Introduction

The importance of investigating the behaviour of single crystal faces to

understand the factors governing the structure of solid metal/aqueous solu-
tion interfaces can hardly be overemphasized [1,2]. The dependence of the
potential of zero charge (PZC) of solid electrode surfaces on the crystal!o-
graphic orientation (c.o.) has been found to parallel that of other surface
properties, e.g. the electronic work function [3-6] and the surface energy
[1,3,7]. A collection of PZC values for the main faces of silver was published in
1983 [2]. Data for a few higher index faces have been added in a recent paper
[7], in which a plot of PZC's versus c.o. has been given using for the (210) and

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 A. H , mei;.~:et al. / Po.tential of zero charge of silver electrodes 1.499

(331) faces some ,.~ues obtain¢ i in a dilute solution of sodium fluoride. Since
the influer~ce of fl~oride ion specific adsorption cannot be ruled out [8,9], the
aim of this ~ork has bee~l ~o redetermine the PZC of these faces in a
non-specifically ~dsorbed dect:olyte (KPF6), and to extend the measurements
to other faces tbz-~ far tmexplorexl. Alto~ehter, 13 different c.o.'s of silver were
investigated in a 5raM KPF6 solution a~ 22°C ± 1°C. 12 of the 13 c.o.'s used
are on the three main zones of ~he unit projected stereograplfic triangle, while
the (531) face is not. This face, with a face centered cubic structure, is a kinked
face which might give an extreme behaviour.
The sensitivity of the potential of the capacitance minimum to the experi-
mental conditions is well known. Due. to the negative values of the PZC's of
silver faces, electrolytic hydrogen evolution by reduction of solvated protons is
thermodynamically possible over a large part of the potential range explored
for these measurements [10]. Although this reaction shows high over-potential
on silver electrodes, some interference cannot be excluded for the faces which
have the most negative PZC's. Since as a rule buffered solutions would
introduce problems of specific adsorption, these cannot be used in the present
study. On the other hand, it is already known that strong hydrogen evolution
could damage the distribution of atoms of the top layer(s) of the metal surface
[10], thus affecting the determination of the PZC. Such a possibility will be
taken into account in the discussion of the PZC values. Comparisons to the
electronic work functions and the calculated surface energies of the silver faces
will be discussed.

2. Experimental

The experimental conditions are: basically the same as those adopted for the
study of the silver (111) face ix~ KPF 6 [10]. A few details are however
necessary.
Solutions were prepared immediately before each run using ultrapure water
(Patent LEI-CNRS No. 865103). KPF~ was carefully purified according to the
method described in ref. [11] (which for gold faces gave very reproducible
results). All experiments were carried out at room temperature in de-aerated
solutions. It is worth noting that the pH of these de-aerated solutions varies
slightly with the electrolyte concentration: from 5.5 for 2mM to 5.1 for
100mM.
Silver crystals were grown in a graphite crucible, oriented by the Lane
X-ray back d l f f r ~ t l n n method, ~m and mecha_n_i~_liypolished acc_ordi_n_geither
to a procedure already described on page 32 of ref. [1], or to another
procedure [12] ensuring that the face is cut with a precision better than 1 / 4 of
a degree.
Just before the electrochemical experiment, the side walls and the face of
the crystal were polished by a procedure based on CrO3 [13]. The crystal was
L500 A. Hamelin et at / Potential of zero charge of silver electrodes

then dipped in concentrated sulphuric acid, and rinsed thotoug,hly. in order to

check if traces of chromium compounds remain on the crystal, one of ~he
samples (a (210) face), was soak~ overnight in 50% sulphuric acid, treated in
a gas flame, and cooled in an ~rgon atmosphere [14]. All other conditions
being similar, the potential of the capacitance minimum (En~,) was not
observed to depend on the prepara~ion conditions.
All potentials were measured ax~(~reported on the saturated calomel elec-
trode (SCE) scale.

3. Results

The experimental conditions were as follows: (a) permanent potential

cycling (80 mV/s when not recording and 8 m V / s when recording the C(E)
curves), (b) superimposed AC signal of 20 Hz, and (c) temperature in the
range 21 to 23 ° C.
The thermodynamic potential for the electrolytic hydrogen evolution ~ at
-0.56 V in 5raM KPF6 solution. In the most negative range of potential
explored for this study (from -1.05 to -1.40 V), the faradaic current related
to the reaction of hydrogen evolution becomes larger than the capacitive
current (fig. 1). Thus, special attention has to be paid to the conditions of the
solution adjacent to the electrode surface, which are related to the value of the
negative potential limit, and to the fact that the solution is unbuffered (any
buffer would introduce specific adsorption).
The results obtained with faces which should have an extreme electrochem-
ical behaviour, according to their calculated surface energies [15] and to
previous results for silver [8,9,16] (and for gold, which also crystallizes into the

~ H,/H"
/PA.cm "~ ~ rev
9.o ..- ...... ........ !

. ' -0!s, ' _i-Esc^/V

' '
.:. , ,, x 5
'7
/. i;
// ',
50
/
i Ag(210) 5mMKPF~
/.
f
I00 i
$.

i'
F;g. 1. Cyclic voltammogram for the (210) silver face in 5raM KPF6 for two negative potential
limits. An entarged cyclic voltammogram ( × 5) is also shown. The arrow marks the position of the
reversible potential for the hydrogen reaction.
 A. Hamelin et al. / Potential of zero charge of silver electrodes L501

C~pFcm-~
50

25

I I I I
-1.0 -0.5.
Fig. 2. C(E) curves for the silver (100) faces in 5mM KPFe; ( ) results of ref. [9], ( . . . . . . )
this work.

fcc structure [1-4]) are first discussed in what follows.

The (Ill)face. The potential at the capacitance minimum (Em~n) appears to
be independent of the negative limit of the potential scan (if this is kept
between - 1.0 and - 1.3 V) and of solution stirring. This may be related to the
fact that E m ~ is - 0.3 V more positive than the negative potential limit (this
means the electrode potential goes through En~ m o r t than one minute after
the most negative potential has been reached). However, if the potential limit
is more negative than - 1.4 V, the shape of the C(E) turns out to be modified
(by the appearance of a " b u m p " between - 1 . 1 and - 1 . 0 V on the C(E)
curve, see fig. 7 of ref. [10]), presumably because the occurrence of electrolytic
hydrogen evoh. a disturbs the structure of the top layers of the silver
surface. For t~.- (111) samples the capacitance minimum, in 5raM KPF 6, was
observed at - 6 9 5 + 5 mV, the same value as at other KPF 6 concentrations
[101.
The (100)face. Two samples were used. In 5raM K P F 6 our results (fig. 2)
agree with those of the literature [9]. With two different negative potential
limits, - 1 . 0 and - 1 . 4 5 V, respectively, Em~n was found to be about 15 m~ ~
more positive in the former case, in a quiescent solution (stirring stopped at
the negative limit). In a stirred solution no effect of the potential limit was
observed.
The (210)face. This face has the most negative value of Emi.. If the solution
was gently s t ~ e d while recording the C(E) curves (to homogeneize the

than - 1 . 4 V the minimum,was always observed at - 9 9 5 inV.

The (1 lO~ face. No ~' ~ evidence of any influence of the negative limit of
potential was found, as long as this limit was kept less negative than - 1.25 V
with a slight sti~,ing of the solution. E ~ , was observed at - 9 7 5 mV, in
excelle,~ agreement with published data [8].
L502 A. Hamelin et al. / Potential of zero charge of silver electrodes

.(111)
O.775
a) (755)~ 0 . 8 0

/ :332)
/-_<O::o
(311 1331)
(530 (550
(100) ,, (410) (210)(320) :(110)
0-S94~ I.o.949

2KY
0-962 l.~g

Fig. 3. (a) Unit stereographic projected triangle with the (100) face at the center of the projection.
(b) Surface energy contours based on broken nearest-neighbour bonds in a face centered cubic

second-nearest.aeighbour bonds in a face centered cubic crystal; the unit is 7(m)

crystal; the unit is 7(2zo)=1 [15]. (c) Surface energy contours based on broken nearest- and
- 1 [17].

Esce/V
G.O

-0.7

-08

-0.~

- 19[
I
v v

Fig. 4. Variations of the relative surface energy ( ) (from fig. 3b) and PZC (fl) of silver faces
at room temperature with the c.o. plotted as a continuously varying parameter.
 A. Hamelin et al. / Potential of zero charge of silver electrodes L503

40' C/#Ecm-a

30

20

I
-I.0 -05

Fig. 5. C(E) curves for the silver (755) face in 5raM KPFt, 20 Hz, 23 ° C.

The (311)face. In 5raM KPF~, Emin was observed at - 9 0 7 mY. It was

previously found at - 9 0 5 + 5 mV by extrapolation to zero electrolyte con-
centration [7].
Other faces located in the three main zones of the unit projected stereo-
graphic triangle (fig. 3a), with e.o.'s between the five above mentioned faces,
showed intermediate values of Emi~ (fig. 4). A C(E) curve for the (755) face is
shown in fig. 5.
The (531)face. This face is not in one of the three main zones of the
projected triang/e (fig. 3a). Emin was observed to be about 100 mV less
negative than for the (210) face. All determined Emin values are summarized
in table 1.

Table 1
Potentials of zero charge of silver single crystal faces in 5mM KPF6 solution

Face Emin versus SCE (mV) Ref.

(100) - 870 + 5 This work, [9]
(110) -975 This work, [7,81
(111) -695 This work, [10,18]
(210) - 995 This work
(311) -907 Tiffs work, [71
(320) a) - 970 This w o r k
(331) a) -915 This w o r k
(332) a) - 805 This w o r k
(410) a; - 940 • lu~ WU~tI~

(511) a) -. 915 This work

(531) a) - 895 This work
(551) a} - 935 This work
(755) a) - 755 This work

a) Only one sample of this c.o. was prepared.

L504 A. Hamelin et al. / Potential of zero charge of silver electrodes

4. Discussion

The values of En~n observed in 5mM KPFt, for the main low index faces of
silver, are in excellent agreement with literature data. Experimental data have
been found to be slightly affected by the reaction of electrolytic hydrogen
evolution which at the pH of 5raM KPF6 solutions becomes thermodynami-
caly feasible from -0.56 V.
Indirect influence is possible if changes in the solution composition take
place in the layer adjacent to the electrode surface as the most negative
potentials are scanned (as already reported in the literature [19]).
At more negative potentials than the range where our C ( E ) curves were
recorded, direct influence is possible if the top atomic layer(s) of the electrode
surface is damaged by the action of hydrogen evolution.
Direct or indirect influence of this reaction is possible, in principle, for all
faces, but the consequences for the C(E) curves depend on the crystal face
because of the different position of the capacitance minimum in the potential
range scanned to record the C(E) curves.
The observed indirect influence of hydrogen evolution is (a) absent for
silver face(s) with the least negative E ~ , or (b) slight and partly eliminated by
solution stirring for face(s) with the most negative Emin.
Any direct influence of hydrogen evolution is only visible when the poten-
tial scan is extended to values more negative than - 1 . 4 V. The created defects
~nay: (a) broaden the capacitance minimum, as for faces with the most
negative Emin; (b) shift E~n to more negative values, as for faces with minima
between -0.85 and -0.95 V; or (c) manifest their contribution as a "bump"
on the C(E) curve, as discussed for the (111) face.
The values of Erm have been plotted as a function of the c.o. in fig. 4.
Neglecting any possible influence of the electrolyte concentration, En~ can be
regarded as the potential of zero charge (PZC). As shown previously [7], PZC's
are linearly related to other surface properties, such as electron work functions
[20], and surface energy calculated according to the embedded atom method
(EAM) functions [21].
The PZC's for the various silver faces have been plotted in fig. 4 against the
surface energy, relative to the (210) face, calculated on the basis of the
nearest-neighbour broken-bond model (fig. 3b) [15]. The horizontal axis i~'
scaled taking into account the angular distances between the faces. The,
dependence of these two physical properties on c.o. is strikingly similar. ~t has
been shown [17] that if only the nearest-neighbour interactions are taken into
account to calculate the relative surface energy, the (210) face turns out to
possess the highest surface energy. If nearest- and second-nearest-neighl~our
interactions are taken into account, the (531) face ex~hibits the ~ghest surface
energy [17]. For silver, Emin has been found to be - 100 mV less negative for
the (531) face thai1 for the (210) face. It ensues that the surface energy is the
 A. Hamelin et al. / Potential of zero charge of sil~r electrodes L505

Emig/V a) b)

-0.8-
0.7 .,"1/"" ""/ ~-(1111---x~

- o.+ - - 7 ........ '°°' . . . .

. . . . . . . . . . (110)-7 ' 7 _~,-
- 1.0 ' ' ' , , , , __L.
4.1 z,3 4:5 600 700 800

Fig. 6. Relation-- for the three low index faces of silver between En~n and (a) electro:~c work
function [20]; (b) surface energy calculated according to the EAM functions [21].

highest for the latter face, the nearest-neighbour interactions evidently prevail-
ing in the case of silver. On the other hand, the pattern of the variation of the
PZC with the c.o. has also been found to be characteristic of the case of
prevailing ~earest-neighbour interactions (fig. 4). (For nearest- and second-
nearest-neigh0our interactions, the pattern of the dependence of the relative
surface energy on the c.o. must be different, according to fig. 3c [17].)
However, EmJn of some faces, (110) for instance, do not fit exactly these
surface energy values. But recent calculations of the surface energy for silver
(111), (100) and (110) faces using the embedded atom method functions [21]
give a go~,d linear correlation with the observed Emi~ (fig- 6b). Calculations
for high index faces are not available.
Comparison with the variations of the electron work function, ~, would be
more informative, but experimental data for silver are available only for the
three main low index faces [20]. From the linear correlation between PZC and
~b (fig. 6a), conclusions about silver/water interactions may be drama [22,23];
however this is out of the scope of this paper.
It may be concluded that the observed values of Emi~ for silver faces in
contact with aqueous solutions correspond to PZC's of nearly ideal surface
structures.

Acknowledgement

Th_is work was supported by the EEC Contract No. ST2A-0007-F and
CNRS.

References
[1] A. Hamelin, in: Modem Aspects of Electrochemistl% Vol. 16, Eds. B.E. Conway, R.E. White
and J.O'M. Bockfis (Plenum, New York, 1985) ch. 1.
L506 A. Hamelin et al. / Potential of zero charge of silver electrodes

[2] A. Hamelin, T. Vitanov, E. Sevastianov and A. Pope,v, J. Electronanal. Chem. 145 (1983) 225.
[3] A. Hamelin and J. Lecoeur, Surface Sci. 57 (1976) 771.
[4] J. Lecoeur, J. Andro and R. Parsons, Surface Sci. 114 (1982) 320.
[5] S. Trasatti, Mater. Chem. Phys. 12 (1985) 507.
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[7] M. Bachetta, S. Trasatti, L. Doubova and A. Hamelin, J. Electroanal. Chem. 200 (1986) 389.
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publication.
[11] A. Hamelin and L. Stoicoviciu, J. Electroanal. Chem. 234 (1987) 93.
[12] A. Hamelin, to be published.
[13] T. Kurasawa, Patent Japan, 35-5619, 23 May 1960.
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[15] J.K. MacKenzie, A.J.W. Moore and J. Nicholas, J. Phys. Chem. Solids 23 (1962) 185.
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[17] J.F. Nicholas, Australian J. Phys. 21 (1968) 21.
[18] G. Valette, J. Electroanal. Chem. 224 (1987) 285.
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[20] M. Chelvayohan and C.H.B. Mee, J. Phys. C (Solid State Phys.) 15 (1982) 2305.
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[23] S. Trasatti, J. Electroanal. Chem. 172 (1984) 27.