H2 Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation

In an effort to standardize the determination of overpotential values for H-2-evolving catalysts in non-aqueous solvents and allow a reliable comparison of catalysts prepared and assayed by different groups, we propose to adopt the half-wave potential as reference potential. We provide a simple method for measuring it from usual stationary cyclic voltammograms, and we derive the formulas to which the measured potential should be compared, taking into account the effect of homoconjugation. We also revisit tabulated values of the standard reduction potential of protons in nonaqueous solvents, E degrees(H+H2).