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

Breaking the inherent H 2 pressure dependence in hydrogenation demands innovative strategies for the efficient management of *H species. Herein, we report a WO 3 -supported catalyst that synergistically integrates atomically dispersed Pt sites and Cu nanoparticles (Pt 1 –Cu/WO 3 ), enabling a significant enhancement in *H coverage for hydrogenation under ambient H 2 pressure (1 bar). Mechanistic investigations reveal the tripartite functionality of Pt 1 –Cu/WO 3: (I) Atomically dispersed Pt sites achieve barrierless H 2 dissociation; (II) reducible WO 3 supports serve as *H reservoirs via reversible W 6+ /W 5+ redox transitions; and (III) Cu–WO 3 interfaces concentrate *H species to promote efficient dimethyl carbonate (DMC) hydrogenation on Cu nanoparticles. The optimized Pt 1 –Cu/WO 3 catalysts achieve a CH 3 OH generation rate of 23.6 mmol g cat –1 h –1 for DMC hydrogenation at 80 °C and 1 bar H 2, surpassing conventional Cu catalysts by 1 order of magnitude in activity at temperatures of >150 °C and >20 bar H 2 . These findings establish a design strategy for pressure-independent catalysis via hydrogen spillover on reducible supports.