Oxygen evolution reaction on IrO2(110) is governed by Walden-type mechanisms

Abstract Oxygen evolution reaction (OER) is a key process for sustainable energy, although renewable sources require the use of proton exchange membrane electrolyzers, with IrO₂-based materials being the gold standard due to their high activity and stability under dynamic anodic polarization conditions. However, even for the (110) facet of a single-crystalline IrO₂ model electrode, the reaction mechanism is not settled yet due to contradictory reports in literature. In the present manuscript, we disentangle the conflicting results of previous theoretical studies in the density functional theory approximation. We demonstrate that dissimilar reaction mechanisms and limiting steps for the OER over IrO₂(110) are obtained for different active surface configurations present on the IrO₂ electrode. In contrast to previous studies, we factor Walden-type mechanisms, in which the formation of the product O₂ and adsorption of the reactant H₂O occur simultaneously, into the analysis of the elementary steps. Combining free-energy diagrams along the reaction coordinate and Bader charge analysis of the active site under constant potential, we elucidate why mononuclear- or bifunctional-Walden pathways excel the traditional OER mechanisms for the OER over IrO₂(110). Our computational methodology to identify the reaction mechanism and limiting step of proton-coupled electron transfer steps is universally applicable to electrochemical processes in the field of energy conversion and storage.