Distinguishing Heterogeneous and Homogeneous CE Mechanisms: Theoretical Insights into Square-Wave Voltammetry

A theoretical study of an electrode mechanism where the reaction (E) is preceded by a chemical that takes place solely at surface (Chet) presented under conditions square-wave voltammetry (SWV). Rigorous mathematical solutions in form integral equations derived means Laplace transforms are for concentration all species involved mechanism, yielding explicit recurrent formulas simulation voltammetric response. The theory approximately predicts starts beginning experiment, disregarding its occurrence short time period between inserting solution until starting experiment. It demonstrated SWV can differentiate common CE C homogeneous taking vicinity electrode, and current ChetE which relevant plethora electrocatalytic processes electrodes modified with catalytically active enzymes and/or noble-metal nanoparticles, as well fundamental importance such CO2, N2, O2, H+ reductions.