Mechanistic Insights into Cyclic Voltammograms on Pt(111): Kinetics Simulations

Abstract A detailed understanding of the electrochemistry of platinum electrodes is of great importance for the electrochemical oxidation of fuels and electrochemical reduction of dioxygen in fuel cells. The Pt(111) facet is the most representative model mimicking Pt nanoparticles and polycrystals for fundamental studies. Herein, we propose a site‐specific model accompanied with the typical elementary steps of the electrochemistry of Pt(111) in non‐adsorbing electrolyte within the potential range between 0.05 and 1.15 V versus reversible hydrogen electrode. Simulations were conducted at different scanning rates based on the kinetics models. We reproduce all the anodic and cathodic peaks observed in the reported experimental curves. These results demonstrate the underlying mechanisms of the peak formation in different potential regions.