Engineering synergistic intermediate interaction in metal-organic framework-derived Ru/metal oxide catalysts to boost...

The kinetics of hydrogen oxidation reaction (HOR) in alkaline media is sluggish, exhibiting a decline by several orders of magnitude in comparison to that in acidic media. While Ru presents a cost-effective alternative to benchmark Pt with comparable hydrogen binding energy and enhanced oxophilicity, its performance is limited by excessive hydroxyl (OH*) adsorption under alkaline conditions. Generally, the metal-organic framework (MOF)-derived catalytic structure facilitates high dispersion of active sites, enabling effective interfacial synergy. Herein, MOF-derived Ru-based catalysts were constructed by dispersing Ru sites onto transition metal oxide/carbon supports (Ru-MO_x/C, M = V, Mn, Fe, Co). Among them, the constructed Ru-VO_x/C achieves superior HOR performance under both acidic and alkaline conditions, and possesses the minimal acid-base kinetic gap. Experimental and theoretical analyses reveal that the prominent performance originates from interfacial charge redistribution and microenvironment modulation, induced by d-d orbital coupling and built-in electric field at the Ru-VO_x interface, which synergistically optimizes and balances the key intermediate (H^⁎, OH*, and H₂O) behaviors. Remarkably, the oxophilic VO_x species could create a local OH^--enriched microenvironment that mitigates excessive OH* adsorption on Ru sites while ensuring efficient supply of reactive species, thereby synergistically modulating the diverse intermediate behaviors and enhancing HOR performance.