On the mechanistic complexity of oxygen evolution: potential-dependent switching of the mechanism at the volcano apex
Kai S. Exner
Abstract
), a potential-dependent activity measure based on the notion of the free-energy span model. While the mononuclear description mainly describes the legs of the volcano plot, corresponding to electrocatalysts with low intrinsic activity, it is demonstrated that the preferred pathway at the volcano apex is a strong function of the applied electrode potential. The observed mechanistic complexity including a switch of the favored pathway with increasing overpotential sets previous investigations aiming at the identification of reaction mechanisms and limiting steps into question since the entire breadth of OER pathways was not accounted for. A prerequisite for future atomic-scale studies on highly active OER catalysts refers to the evaluation of several mechanistic pathways so that neither important mechanistic features are overlooked nor limiting steps are incorrectly determined.