Acid-Base Chemistry of a Model IrO2 Catalytic Interface

Abstract

Iridium oxide (IrO₂) is one of the most efficient catalytic materials for the oxygen evolution reaction (OER), yet the atomic scale structure of its aqueous interface is largely unknown. Herein, the hydration structure, proton transfer mechanisms, and acid-base properties of the rutile IrO₂(110)-water interface are investigated using ab initio based deep neural-network potentials and enhanced sampling simulations. The proton affinities of the different surface sites are characterized by calculating their acid dissociation constants, which yield a point of zero charge in agreement with experiments. A large fraction (≈80%) of adsorbed water dissociation is observed, together with a short lifetime (≈0.5 ns) of the resulting terminal hydroxy groups, due to rapid proton exchanges between adsorbed H₂O and adjacent OH species. This rapid surface proton transfer supports the suggestion that the rate-determining step in the OER may not involve proton transfer across the double layer into solution, as indicated by recent experiments.