Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime

Cyclic voltammetry responses are derived for two-electron, two-step homogeneous electrocatalytic reactions in the total catalysis regime. The models developed provide a framework for extracting kinetic information from cyclic voltammograms (CVs) obtained in conditions under which the substrate or cosubstrate is consumed in a multielectron redox process, as is particularly prevalent for very active catalysts that promote energy conversion reactions. Such determination of rate constants in the total catalysis regime is a prerequisite for the rational benchmarking of molecular electrocatalysts that promote multielectron conversions of small-molecule reactants. The present analysis is illustrated with experimental systems encompassing various limiting behaviors.