Eletrochemical ozone production: influence of the supporting electrolyte on kinetics and current efficiency

The nature of the electrolyte strongly influences the electrode kinetics of the oxygen evolution reaction (OER) and electrochemical ozone production (EOP) mainly by affecting the degree of coverage by the intermediates of both processes. The anomalous behaviour of the Tafel coefficient, b, as a function of temperature was attributed to surface adsorption of the electrolyte species, and the competition between them, as well as gas bubble adherence. Comparison of the current efficiencies of the EOP, Phi(EOP), determined for different temperatures and supporting electrolyte compositions, showed the presence of fluorinated anions increases Phi(EOP). The influence of the anion nature on Phi(EOP), When analysed in the light of the proposed electrode mechanism, reveals introduction into the electrolyte of anions having a high electronegativity changes the double layer structure resulting in an increase of surface concentration of the active centres leading to EOP. The inhibition of the OER in the high overpotential domain during EOP provoked by fluoro-anion adsorption is supported by the activation energy data. In situ surface characterisation before and after EOP investigation revealed that even under drastic conditions (high current density, low interfacial pH) beta-PbO2 can be considered an inert electrode material. (C) 2002 Elsevier Science Ltd. All rights reserved.