Semi-Circular Potential Sweep Voltammetry: Electrochemically Quasi-Reversible System

The novel voltammetry using a semi-circular potential wave for quasi-reversible charge transfer system on electrode is theoretically investigated. Compared with conventional voltammetry based on linear sweep such as linear sweep voltammetry (LSV), semi-circular potential sweep voltammetry (SCV) may decrease the charging current outside the center of potential range and increase the faradaic current at the midpoint due to variable scan rate. In this paper, we investigate the system based on macroelectrode where simple 1 dimensional (1 D) diffusion system is valid with various charge transfer rate constant (k₀). In order to observe the amplification at midpoint, voltammetric response with different midpoint ranging from -200 mV to 200 mV are studied. SCVs shows both the shift of peak potential and the amplification of peak current for quasi-reversible electrode reaction while only higher peak current is observed for reversible reaction. Moreover, the higher current at midpoint enable the amplification of current at low overpotential region which may assist the determination of onset potential as a figure-of-merit in electrocatalyst.