In this report, the theory based on thin-layer cyclic voltammetry (TLCV) for consecutive electron transfer (ET) across the interface between two immiscible electrolyte solutions (ITIES) is well developed and experimentally verified. The voltammetric responses to multistep electron transfer at the ITIES are predicted by numerical simulations. Moreover, the impact of empirical parameters on the shape of the multistep current-voltage curve has been examined. The results obtained not only give information regarding the effect of the concentration ratio of the reactants in two phases and the thin-layer thickness on multistep electron transfer, but also prove the excellent agreement between simulations and experiments. The model system of two-step electron transfer of ZnTPP/[Fe(CN)₆]⁴⁻ was studied, indicating that the Bulter-Volmer (B-V) theory is suitable for the consecutive electron transfer. Thus, TLCV is demonstrated to be a useful means for investigating the kinetics of heterogeneous consecutive ET.

KEYWORDSThin layer cycle voltammetry is one of the most efficient methods to investigate liquid/liquid interface. The advantages of this approach lie on its simplicity and effectiveness. The paper represents the progress that has been made in experiments and theories, analyzing the factors that affect rate constants and discussing how to get steady-state currents.