Unveiling the Structure and Dissociation of Interfacial Water on RuO₂ for Efficient Acidic Oxygen Evolution Reaction

Abstract Understanding the structure and dynamic process of interfacial water molecules at the catalyst‐electrolyte interface on acidic oxygen evolution reaction (OER) kinetics is highly desirable for the development of proton exchange membrane water electrolyzers. Herein, we construct a series of p ‐block metal elements (Ga, In, Sn) doped RuO 2 catalysts with manipulated electronic structure and Ru−O covalency to investigate the effect of electrochemical interfacial engineering on the improvement of acidic OER activity. Associated with operando attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements and theoretical analysis, we uncover the free‐H 2 O enriched local environment and dynamic evolution from 4‐coordinated hydrogen‐bonded water and 2‐coordinated hydrogen‐bonded water to free‐H 2 O on the surface of Ga−RuO 2 , are responsible for the optimized connectivity of hydrogen bonding network in the electrical double layer by promoting solvent reorganization. In addition, the structurally ordered interfacial water molecules facilitate high‐efficiency proton‐coupled electron transfer across the interface, leading to reduced energy barrier of the follow‐up dissociation process and enhanced acidic OER performance. This work highlights the key role of structure and dynamic process of interfacial water for acidic OER, and demonstrates the electrochemical interfacial engineering as an efficient strategy to design high‐performance electrocatalysts.

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