Square wave voltammetry as a powerful tool for studying multi-electron molecular catalysts

Abstract

• SWV of homogeneous two-electron molecular catalysis is theoretically investigated. • The rigorous theory applies to wide mechanistic diversity and SWV parameters. • SWV signal can enable the determination of catalytic pathways and rate constants. • SWV components are remarkably valuable to elucidate the catalyst active form. • Accurate guidelines and data analysis protocols are given. A comprehensive theoretical investigation of the square wave voltammetry (SWV) of the homogeneous two-electron molecular catalysis of electrochemical reactions is carried out. The SWV signal is studied as a function of the pulse time, the SW amplitude and the mechanistic features (catalytic rate constants, substrate concentration, formal potentials), also paying attention to the SW components that are demonstrated to be remarkably helpful in the identification of the catalyst active form. Thus, the ability of the SWV technique for the elucidation of the catalytic species and pathways, and for the determination of the corresponding rate constants is assessed, establishing accurate and valuable diagnosis criteria and procedures for quantitative data analysis based on mathematical expressions that are rigorous and easy-to-implement, and that consider the influence of diffusion on the response.