Cathodic behaviour of IrO2 electrodes in alkaline solution Part I: Electrochemical surface characterization

IrO₂ electrodes prepared by thermal decomposition of IrCl₃ on a titanium support at temperatures of calcination between 300 and 500°C have been characterized by cyclic voltammetry and potential steps. Standard voltammetric curves have been recorded between –0.65 and 0.35 V vs SCE (prior to H₂ and O₂ evolution) as a fingerprint of the surface state, and the associated charge,q^*, has been used to monitor the morphology of the active layer. The effect of hydrogen evolution has been investigated by progressively decreasing the negative potential limit, and by increasingly holding the electrode under hydrogen evolution at a constant potential. Phenomena of proton penetration beneath the outer surface into an inner surface have been quantified by potential step experiments. The effect of storing the electrodes in water rather than in the open air has also been investigated. The thermal oxides lose their typical features at calcination temperature < 350° C. Cathodic load does not appear to cause macroscopic modifications of the surface state.This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.