Why the optimum thermodynamic free-energy landscape of the oxygen evolution reaction reveals an asymmetric shape

The development of oxygen evolution reaction (OER) electrocatalysts has been spurred by thermodynamic considerations on the free-energy landscape. It is a common paradigm that the optimum thermodynamic free-energy landscape reveals a symmetric shape in that all reaction intermediates are stabilized at the equilibrium potential of the reaction. However, so far, no OER electrocatalyst has been reported that corresponds to the thermodynamic ideal because of the presence of a linear scaling relationship. Therefore, the common approach builds on the breaking of the scaling relations to establish a catalytic material that is close to the symmetric picture, yet, with minor successes. Relating to the simple two-electron hydrogen evolution reaction (HER), it was recently reported that the optimum thermodynamic free-energy landscape reveals an asymmetric shape rather than a symmetric form as soon as overpotential and kinetic effects are factored in the analysis. This finding motivates scrutinizing whether the symmetric free-energy landscape as the thermodynamic ideal in the OER is justified. Transferring the knowledge from the HER to the OER results in the introduction of the electrochemical-step asymmetry index (ESAI), representing the concept of the asymmetric thermodynamic free-energy diagram. By comparing the ESAI to the symmetric picture in terms of the electrochemical-step symmetry index (ESSI), it is demonstrated herein that the asymmetric rather than the symmetric free-energy landscape corresponds to the thermodynamic ideal. This outcome suggests changing the mindset when applying the concept of free-energy diagrams for the discovery of OER materials by heuristic material-screening techniques. (C) 2021 The Author(s). Published by Elsevier Ltd.