Operando Unveiling of Hydrogen Spillover Mechanisms on Tungsten Oxide Surfaces

Hydrogen spillover is a significant process in catalytic hydrogenation reactions, facilitating H₂ activation and modulating surface chemistry of reducible oxide catalysts. This study focuses on operando monitoring of platinum-induced hydrogen spillover on tungsten trioxide (WO₃), employing ambient pressure X-ray photoelectron spectroscopy (APXPS), density functional theory calculations and microkinetic modeling to investigate the dynamic evolution of surface states at varied temperatures. Facilitated by Pt metal clusters, hydrogen spillover results in the formation of W⁵⁺ and hydrogen intermediates (hydroxyl species and adsorbed water) on surfaces of WO₃ at room temperature. With increasing temperature, water desorption, reverse hydrogen spillover and surface-to-bulk diffusion of hydrogen atoms compete with each other, leading initially to reoxidation and then further reduction of W atoms in the near-surface. The combined experimental results and simulations provide a comprehensive understanding of the mechanisms underlying hydrogen interaction with reducible metal oxides, lending insights of relevance to the design of enhanced hydrogenation catalysts.