Examination of electrocatalysis in the anodic O2 evolution reaction at Pt through evaluation of the adsorption behaviour of kinetically involved intermediate states

In regular heterogeneous catalytic reactions, evaluation of the adsorption behaviour of the ephemeral intermediates that participate kinetically in the main reaction pathway is often inaccessible experimentally. In electrocatalysis, on the other hand, electrochemical transient methods can provide such information. In the present paper, potential-relaxation transients are used to derive information on the electroactive, kinetically significant adsorbed intermediate states that are involved in the anodic O2 evolution reaction (OER) at Pt electrodes. By means of such transients, digitally recorded over 5–6 decades of time from microseconds to seconds, the adsorption capacitance of the intermediate states in the reaction is evaluated as a function of potential over a range corresponding to appreciable current densities for O2 evolution. Anodic O2 evolution takes place at Pt, as at all other metal anodes, on an oxide film. A well-defined state of such a film must be established by a pre-conditioning programme to make meaningful and reproducible kinetic studies on the OER. The state of the oxide film is conveniently characterized by means of cyclic-voltammetry. The intermediate surface states in the reaction can be two or more oxidation states of Pt atoms in the oxide and OH or O species at the oxide’s surface. Two distinct types of adsorption behaviour are distinguished for potentials above and below ca. 1.85 V against the reversible H2 electrode (RHE), and are related to the observed kinetics of the OER.