Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry of Systems Approaching Reversibility

Abstract

Efforts to design catalytic schemes approaching reversibility in which the catalyst is active for both the oxidation and reduction processes are attracting active attention boosted by recent successes. Kinetic analysis of such systems, by electrochemical techniques such as cyclic voltammetry (CV), would contribute to establish reliable mechanisms. So far, the relationships required to achieve this task have been restrained to irreversible catalytic schemes. The purpose of the present communication is to fill this gap. As a preliminary contribution, the analysis is limited to simple on-electron-one step schemes so as to set out the main features of the competition between catalytic reaction and diffusion transport of catalyst and substrates. Emphasis is put on S-shaped CV responses, which offer the best opportunities to accessing the detailed kinetic information forming the basis for determination of mechanisms.