A formalism to compare electrocatalysts for the oxygen reduction reaction by cyclic voltammetry with the thin-film rotating ring-disk electrode measurements

This report describes a general method to correlate the features determining the performance of an electrocatalyst (EC), including the accessibility of O2 to the active sites and the kinetic activation barrier, with the outcome of conventional electrochemical experiments. The method has been implemented for oxygen reduction reaction ECs by cyclic voltammetry with the thin-film rotating ring-disk electrode (CV-TF-RRDE) setup. The method: (i) does not rely on the simplifications associated with the Butler-Volmer kinetic description of electrochemical processes and (ii) does not make assumptions on the specific features of the EC, allowing to compare accurately the kinetic performance of oxygen reduction reaction ECs with completely different chemistry. Finally, with respect to other widespread figures of merit (e.g., the half-wave potential E1/2), the figure of merit here proposed, E(jPt(5%)), allows for much more accurate comparisons of the kinetic performance of ECs.