Breaking the H2 Pressure Dependence in Hydrogenation through Interfacial *H Reservoirs on Cu–WO3 Catalysts

Breaking the inherent H2 pressure dependence in hydrogenation demands innovative strategies for the efficient management of *H species. Herein, we report a WO3-supported catalyst that synergistically integrates atomically dispersed Pt sites and Cu nanoparticles (Pt1–Cu/WO3), enabling a significant enhancement in *H coverage for hydrogenation under ambient H2 pressure (1 bar). Mechanistic investigations reveal the tripartite functionality of Pt1–Cu/WO3: (I) Atomically dispersed Pt sites achieve barrierless H2 dissociation; (II) reducible WO3 supports serve as *H reservoirs via reversible W6+/W5+ redox transitions; and (III) Cu–WO3 interfaces concentrate *H species to promote efficient dimethyl carbonate (DMC) hydrogenation on Cu nanoparticles. The optimized Pt1–Cu/WO3 catalysts achieve a CH3OH generation rate of 23.6 mmol gcat–1 h–1 for DMC hydrogenation at 80 °C and 1 bar H2, surpassing conventional Cu catalysts by 1 order of magnitude in activity at temperatures of >150 °C and >20 bar H2. These findings establish a design strategy for pressure-independent catalysis via hydrogen spillover on reducible supports.