Reverse Hydrogen Spillover on Metal Oxides for Water‐Promoted Catalytic Oxidation Reactions

Abstract Understanding the water‐involved mechanism on metal oxide surface and the dynamic interaction of water with active sites is crucial in solving water poisoning in catalytic reactions. Herein, this work solves this problem by designing the water‐promoted function of metal oxides in the ethanol oxidation reaction. In situ multimodal spectroscopies unveil that the competitive adsorption of water‐dissociated *OH species with O2 at Sn active sites results in water poisoning and the sluggish proton transfer in CoO‐SnO2 imparts water‐resistant effect. Carbon material as electron donor and proton transport channel optimizes the Co active sites and expedites the reverse hydrogen spillover from CoO to SnO2. The water‐promoted function arises from spillover protons facilitating O2 activation on the SnO2 surface, leading to crucial *OOH intermediate formation for catalyzing C‐H and C‐C cleavage. Consequently, the tailored CoO‐C‐SnO2 showcases a remarkable 60‐fold enhancement in ethanol oxidation reaction compared to bare SnO2 under high‐humidity conditions.