金属有機構造体由来Ru/金属酸化物触媒における協奏的中間相互作用の工学的設計による水素酸化反応の促進

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.