T Rasatti 1984
T Rasatti 1984
S. TRASAW
Department of Physical Chemistry and Electroohemistry, University of Milan. Via Venezian 21, 20133
Milan, Italy
Abstract- Requisites for electrode materials to be suitable for technological applications are outlined and
discussed. Oxides with metallic or quasi-metallic conductivity meet these requirements best. Most of these
electrodes are prepared by thermal procedures. It is shown that the temperature of preparation affects the
catalytic activity through the surface area and the chemical composition (non-stoichiometry). The co-
variation of these parameters is best followed in situ by voltammetric curves and point of zero charge
measurements. Examples are given for pure RuO,, IrO,. CosO, and 1rQ-t RuOz mixtures. Kinetic and
mechanistic detailsare discussed for 0s evolution on RuO,,IrO, and CosOI and for Cl, evolution on RuO,
and Co30,. Finally, the electrocatalytic properties of different oxides are correlated with the energy change
involved in the lower * higher valency state transition. Experimental data for both O2 and Cl* evolution can
thus be organized into a “volcano” curve enabling predictive interpolations to be made.
The practical importance of such electrode processes Table 1. Electrodes for technological applications
as the anodic evolution of chlorine and oxygen can requisites
hardly be overemphasized. Cl, production, one of the
largest technological application of electrochemistry, (1) High surface area
is based on the direct anodic discharge ofchloride ions. (2) High electrical conduction
O2 evolution is an unavoidable side reaction in many (3) Good electrocatalytic properties
(41 Long-term mechanical and chemical stability at
anodic processes; moreover, it is the most common the support/active layer and at the active
anodic reaction coupled with most of the cathodic layer/solution interface
processes occurring in aqueous solutions (water elec- (5) Minimized gas bubble problems
trolysis, metal electrowinning, etc.). In any of these Enhanced selectivity
cases the appropriate selection of the electrode ma- ;:; Availability and low cost
terials is a prerequisite for the optimization of the (8) Health safety
electrolysis parameters.
The main requisites needed for an electrode material
choice is based on a compromise between activity,
to be useful for technological applications are listed in stability and cost[5]. While the prototype of this class
Table 1. The suitability of a material for practical
of oxides has been RuO,[6] which is most active but
problems in a result of the combination of all the
fairly expensive, the applied research is now in the
features mentioned in the table, but points (2) and (4) direction of replacing very good but expensive elec-
are those usually prevailing as large current densities
trocatalysts with cheaper materials whose electrocata-
are to be used. Nevertheless, fundamental research
lytic properties are perhaps not so excellent[7].
insists on the study of point (3) because this involves
Accordingly, an excellent electrocatalyst whose per-
the largest body of conceptual interdisciplinary
formances deteriorate with time is technologically less
implications. interesting than a material of lower electrocatalytic
The requisites outlined in Table 1 are best met by
qualities but of much better long-term stability. It may
transition metal oxides with metallic or quasi-metallic thus happen that in some applications under particu-
conductivity[l]. The discovery[2] that the perform- larly severe conditions, such as water electrolysis in
ances of some precious metal oxides are far better than SPE cells, a Poorer and much more expensive elec-
those of the corresponding precious metals has pro- trocatalyst such as IrOz is mixed with RuO, to
voked a technological jump in the large electrolytic
improve the stability of the latter[8].
industry, particularly in the chlor-alkali cell tech- Strictly, the term “electrocatalysis” implies the in-
noIogy[3]. The use of these oxide electrodes has later fluence of the electrode material on the rate of the
been extended to water electrolysis[4]. electrode reaction (primary effects, in Parsons de-
It is exceptional that all the requisites in Table 1 can fmition)[9] ie the kineticand mechanistic effects of the
be optimized in one electrocatalyst. More usuahy, the bonds formed by reactants, products and/or inter-
mediates with the electrode surface. This term has
+ Introductory lecture given al the Symposium on however acquired a wider meaning on a practical basis:
“Electrccatalysis: Practice, Theory and Further if a material shows a lower overpotential because it is
Development”, I>16 September 1983, Neunkirchen a. mainly a better conductor, this is as a whole regarded
Brandt, F. R. G. as a better electrocatalyst. Although this usage has a
I503
1504 S.T~~shln
B = Sb, Nb, Ta
I
‘00
h .,
400
T/ “C
800
f/k&
Fig. 6. Rutherford backscattering spectra of Ti/RuO, and Ti/IrOz elezrrodes prepared at 400°C.
Anodic evolution of oxygen and chlorine 1507
-M-OH-t-M-0-+H+.
Lj I
/
xm 400
11
500
r/x
600
‘1
700 800
I 1
M-H-+-M+OH- (2a)
t I
or
I I
-M-OH + Hz0 + -M-OH:+ OH-. (2b)
I
The point of zero charge is defined as the pH at which
the oxide surface carries no net electrical charge. It is a Fig. 9. Point of zero charge of Co,O, powder as a function
quantity characteristic of the given oxide and is of the temperature of decomposition of Co (NO,),.
1508 S. TRASA-ITI
4.0 -
I ,’
/ /
I
.26OT
fact predicted neither on a thermodynamic nor on a Y ,F’ ,’
5 / I’
kinetic basis. pH effects were observed by Arikado et 7 7’ /
a@393 with RuO, electrodes and were ascribed to Ci- > -1
,
J’ ..
,a. .
.
-300
containing surface complex formation. However, these E
,=
/’
,fX
,’
or chloro-complexes) whose exact nature is on the surface should be calculated from the heat of forma-
other hand not well known. Anodic reactions are tion of the solid phase. However, correlations using
usually envisaged to occur with breakage of similar data have been found unsatisfactoryC54, 553.
cation-&and bonds and formation of new bonds. It is The reason is to be sought in the fact that, if the
usual to look at heterogeneous catalysis from the adsorption of oxygen on bare metals simulates the
viewpoint of co-ordination chemistry[48-501. The formation of the corresponding bulk oxide[57], ad-
same approach can reasonably be extended to eiec- sorption of oxygen on a bulk oxide is expected to
trochemistry where the interaction of the solid surface simulate the formation of the higher oxide:
with a condensed phase increases the probability of
MO,+O-+ MO,+ ,. (4)
formation of co-ordinately saturated surface groups.
The main and most difficult task of electrocatalytic Any step of the reaction of oxygen evolution can be
studies is to organize experimental kinetic data in a envisaged as a transition of the underlying oxide to a
rational fashion. Best comparison among different higher state. Thus, for instance, for the primary water
electrode materials is made in terms of overpotential at discharge:
constant current density. Irrespective of the detailed
origin of the phenomenon, electrocatalysis can be -M-OH + H,O -+ -M ,,
I /OH +H++e. (5)
expressed, to a first approximation, in terms of bond
strength between the electrode surface and reaction
1 OH
intermediatesc51, 521. Since no in siru electrochemical This reaction can also be viewed[53] as a transition
data are available for oxides, the evaluation of the between two different configurations of the surface
electrocatalytic activity must first rely on experimental coordination complex or better still between two
data taken from neighbouring fields. Considering different complexes (the coordination number of the
oxygen evolution, bonds between surface metal ions surface hydroxy-complex is increased by one). In this
and oxygenated species can be envisaged to be formed context, the parameter which is expected to parallel the
and broken during the anodic reaction. The analogue energy change occurring during the electrochemical
in the gas phase can be found in the adsorption of reaction is the enthalpy of transition of the oxide from
oxygen on oxides. The kinetic features of this reaction a lower to a higher oxidation state[5S]. Figure 17
can be investigated by homomolecular isotopic oxygen shows that the activity for oxygen evolution changes
exchange: with the nature of the catalyst according to a volcano-
shaped curve. Oxides which are oxidized with difficulty
‘802+1602*2180’60. (3) are not very active because intermediates adsorb too
Data have been reported by Boreskov et ul.[53] and by weakly. Water discharge is the rate determining step in
Winter[54]. Figure 16 shows a plot of overpotential this case. Oxides which are oxidized too easily are also
for oxygen evolution against the activation energy for not very active because intermediates are adsorbed too
isotopic oxygen exchange[55]. Despite the scatter of strongly. Removal of oxygenated species is rate de-
data, the two reactivity scales can be seen to run termining for these electrodes.
parallel which suggests that the same energetic par- Figure 17 corroborates the old Sabatier’s principle
ameters are responsible for the observed catalytic of catalysis. It is probably only a first approximation
phenomena. Some exception is given by CoaO,. The since the plot is not at constant Tafel slope (constant
reason for this might be related to its semiconducting mechanism) nor at constant surface area, and the
characteristics but this explanation is probabiy not possibility that for some of the oxides the Tafel slope
conclusive. may be governed by the space charge behaviour
Some authors[53,56] have suggested that the bond [59, 603 is not taken explicitly into consideration.
strength of oxygen atoms adsorbed on the oxide Nevertheless the approach works satisfactorily and the
0.8
c “r
Fig. 16. Electrocatalytic activity in O2 evolution at various Fig. 17. Electrocatalytic activity in 0, evolution at various
oxide electrodes as a function of the activation energy for the oxide electrodes as a function of the enthalpy of the lower
homomokular isotopic O5 exchange in the gas phase. (0) + higher oxide transition. (0) Alkaline and (a) acid solutions
Aikaline and (0) acidic solulions are indicated. are indicated.
Anodic evolution of oxygen and chlorine 1511
plot possesses some useful predictive character. selectivity for chlorine evolution should not depend
Conceptually, the approach does not conflict with appreciably on the electrode material. Experimental
other views according to which the catalytic activity is data for chlorine evolution from concentrated brines
expressed in terms of (1) matching between the poten- appear to support this conclusion[66,67], but the
tial for oxygen evolution and the potential of oxide situation may differ at other pH values and low
further oxidation[61] or (2) variation in crystal field chlorine concentrations because of the interference
stabilization energy for the transition of the surface between the two processes.
complexes between two configurations[58].
The task of rationalizing the experimental data for Acknowl~d~~~nt-Financial support for this work from the
Cl2 evolution is in principle harder since no useful data Italian National Research Council (CNR) is gratefully
exist for adsorption of chlorine from the gas phase acknowledged.
onlo oxides. There is however ample evidence in
catalysis that the M-0 bond strength can organize the
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