The Sensitivity of Metal Oxide Electrocatalysis to Bulk Hydrogen Intercalation: Hydrogen Evolution on Tungsten Oxide

Metal oxides are attracting increased attention as electrocatalysts owing to their affordability, tunability, and reactivity. However, these materials can undergo significant chemical changes under reaction conditions, presenting challenges for characterization and optimization. Herein, we combine experimental and computational methods to demonstrate that bulk hydrogen intercalation governs the activity of tungsten trioxide (WO₃) toward the hydrogen evolution reaction (HER). In contrast to the focus on surface processes in heterogeneous catalysis, we demonstrate that bulk oxide modification is responsible for experimental HER activity. Density functional theory (DFT) calculations reveal that intercalation enables the HER by altering the acid-base character of surface sites and preventing site blocking by hydration. First-principles microkinetic modeling supports that the experimental HER rates can only be explained by intercalated HWO₃, whereas nonintercalated WO₃ does not catalyze the HER. Overall, this work underscores the critical influence of hydrogen intercalation on aqueous cathodic electrocatalysis at metal oxides.