Electrophotocatalysis: Cyclic Voltammetry as an Analytical Tool

Electrophotocatalysis (e-PC) is currently experiencing a renewed interest. By taking advantage of the highly oxidizing or reducing power of excited state of electrogenerated ion radicals, it allows thermodynamically difficult redox reactions to be performed. However, e-PC is facing various specific issues, such as its fundamentally heterogeneous nature, implying that mass transport is coupled to chemical reactions and light absorption; back electron transfer of the ion radical excited state with the electrode; and local heating near the electrode surface modifying mass transport conditions. Herein, we address these issues in the context of cyclic voltammetry as an analytical tool and we provide a rational framework for kinetic studies of electrophotocatalytic reactions under realistic conditions and hypothesis based on literature data. This approach may be beneficial to rationalize the design and the efficiency of present and future e-PC systems.