Non-triangular potential sweep cyclic voltammetry of reversible electron transfer: Experiment meets theory

Abstract Conventionally, cyclic voltammetry is performed using triangular waveforms; however, complications can arise from the discontinuity of the capacitive current at the potential vertex in the triangular wave. Recent literature (J. Electroanal. Chem. 2017, 801, 381–387) showed theoretically the opportunities offered by non-triangular waveforms. Herein, we test this theory for the reversible aqueous system [Ru(NH 3 ) 6 ] 3+/2+ using cosine-based waves at a glassy carbon macroelectrode. The match between the theoretical and experimental results is excellent and offers an alternative and novel method to determine the formal potential E f o of the Ru 3+ /Ru 2+ system. The scan rate dependency of the voltammograms is investigated; and for the cosine wave voltammetry the peak currents are 24% higher than that obtained from the typical triangular waves, coinciding with the simulation results.