Rationalizing Acidic Oxygen Evolution Reaction over IrO2: Essential Role of Hydronium Cation

The development of active, stable, and more affordable electrocatalysts for acidic oxygen evolution reaction (OER) is of great importance for the practical application of electrolyzers and the advancement of renewable energy conversion technologies. Currently, IrO2 is the only catalyst with high stability and activity, but a high cost. Further optimization of the catalyst is limited by the lack of understanding of catalytic behaviors at the acid‐IrO2 interface. Here, in strong interaction with the experiment, we develop an explicit model based on grand‐canonical density function theory (GC‐DFT) calculations to describe acidic OER over IrO2. Compared to the explicit models reported previously, hydronium cations (H3O+) are introduced at the electrochemical interface in the current model. As a result, a variation in stable IrO2 surface configuration under the OER operating condition from previously proposed complete *O‐coverage to a mixture coverage of *OH and *O is revealed, which is well supported by in situ Raman measurements. In addition, the accuracy of predicted overpotential is increased in comparison with the experimentally measured. More importantly, an alteration of the potential limiting step from previously identified *O→*OOH to *OH→*O is observed, which opens new opportunities to advance the IrO2‐based catalysts for acidic OER. Hydronium cation (H3O+) was found to be critical to regulating the observed behaviors of IrO2 during acidic oxygen evolution reaction. The H3O+ cation induced an internal electric field at the interface, enabling selective bond‐tuning to the reaction intermediates. As a result, 0.5 monolayer of *OH species was stabilized under OER operational condition, and the overall conversion was revealed to be hindered by *OH→*O.