Multielectron, Multistep Molecular Catalysis of Electrochemical Reactions: Benchmarking of Homogeneous Catalysts

Abstract Current–potential responses in cyclic voltammetry and in preparative‐scale electrolysis are established for two‐electron two‐step homogeneous molecular catalysis after systematic categorization of the various possible reaction schemes. They allow the derivation of catalytic Tafel plots, reflecting the intrinsic properties of the catalysts independent of contingent electrolysis parameters. They serve as a rational basis for benchmarking catalysts of the same electrochemical reaction within the same log(turnover frequency) versus overpotential plane of merit.