A Single Mechanistic Platform that Unifies all Common Electrochemical Mechanism via the ECrevEC′ Reaction Scheme in Cyclic Voltammetry

A unified theoretical framework capable of describing diverse electrochemical mechanisms is of fundamental importance for the interpretation of voltammetric data. In this work, we present a single mechanistic platform based on the ECrevEC′ reaction scheme in cyclic voltammetry, which integrates a wide range of commonly encountered electrode processes within one generalized model. The proposed mechanism comprises two sequential electron-transfer steps separated by a reversible chemical transformation, coupled with a regenerative catalytic pathway.
Through systematic theoretical analysis, it is demonstrated that, under specific limiting conditions, the ECrevEC′ scheme converges to several fundamental mechanisms, including E, EE, EC, EC′, ECE, EEC’, CEC’ and related variants. This intrinsic flexibility establishes the model as a universal framework for studying complex electrochemical systems involving coupled chemical and catalytic processes. The influence of kinetic parameters, equilibrium constants, and signal parameters on voltammetric responses is examined, revealing characteristic features that enable mechanistic discrimination and kinetic evaluation.
The results highlight the potential of the ECrevEC′ platform to serve as a powerful tool for interpreting cyclic voltammetric behavior of redox-active systems, including biological, catalytic, and surface-confined processes. This unified approach provides a consistent basis for bridging theoretical analysis and experimental voltammetry, thereby facilitating deeper insight into multistep electrochemical mechanisms. Entire MATHCAD simulation file of this important mechanism adapted for cyclic voltammetry is given the readers for free.