Facet-dependent structure and dissociation of water at pristine IrO2/water interfaces

Abstract

Understanding the microscopic structure of water at metal oxide interfaces is crucial for advancing electrocatalysis. IrO2, specifically, has shown exceptional activity for electrochemical water oxidation, but we currently lack a fundamental understanding of how the surface structure of IrO2 impacts water reactivity. In this study, we developed a machine learning potential trained to first-principles accuracy for modeling IrO2/water interfaces across different facets: (110), (100), (101), and (001). Using extensive machine learning molecular dynamics simulations, we investigated the spontaneous dissociation of water molecules at these interfaces. Our results reveal a distinct dissociation probability trend: (110) > (100) ≈ (101) > (001), which we attribute primarily to the reaction thermodynamics of surface water dissociation. A strong correlation is observed between the surface Ir–O bond distances and the dissociation probabilities, highlighting the role of surface geometry in modulating reactivity. As a consequence, the interfacial solvation structures and hydrogen bonding environments are dynamically tuned by the varying water dissociation capabilities across facets. This work elucidates how water dissociation energetics depend on surface orientation and interfacial structure, offering atomistic insights into manipulating reaction chemistry at electrocatalytic interfaces.