Promotion of catalytic reactions by electrochemical polarization

Electrochemical polarization of metal electrodes on solid electrolytes may result in a pronounced promotion of their catalytic activity. A phenomenological analysis of this promotion effect is developed from simple thermodynamic and kinetic arguments and is compared with existing models. The strong modification of catalytic activity is related to the electrochemically controlled change of the chemical potential of a mobile component at the electrode interface within the (solid state) galvanic cell. Empirical relations reported in the literature are interpreted in terms of this chemical potential change.