Reverse hydrogen spillover enhances selective hydrogenolysis of CO bonds

H 2 activates at Co sites; isolated Rh rather than Rh particles enables C2-O bond hydrogenolysis. • Reverse hydrogen spillover promoting C2-O hydrogenolysis with a 60.3% 1,5-pentanediol yield. • Reverse hydrogen spillover prevents precious metal poisoning by active H species during hydrogenation. The selective activation and cleavage of C O bonds through directional hydrogenation play a critical role in numerous industrial catalytic applications. Traditional noble metal catalysts often face challenges due to their strong propensity for active H₂ dissociation, leading to active site occupation by hydrogen atoms and subsequently hindering the efficiency of selective C O bond cleavage. Furthermore, achieving selective cleavage of high-bond-energy C O bonds while preserving lower-energy ones remains a significant challenge requiring further exploration. Herein, we present the design of a Rh single-atom catalyst anchored on Co for the selective cleavage of the high-bond-energy C2 O bond in furfural, serving as a model reaction. Through combined experimental investigations and density functional theory calculations, we demonstrate that Rh 1 Co single-atom alloys effectively lower the activation barrier for furfural hydrogenation, converting the C O bond cleavage process from an endothermic reaction to an exothermic one. This catalytic behavior is notably absent in conventional Rh catalysts. The strong interactions within the Rh 1 Co alloy significantly promotes the hydrogenolysis of the C2 O bond and achieving a 1,5-pentanediol yield of 60.3%, surpassing most previously reported catalysts. Most importantly, Co sites facilitate H 2 activation, while isolated Rh sites serve as the centers for C O bond cleavage, introducing a reverse hydrogen spillover mechanism distinct from traditional hydrogenation processes. This reverse hydrogen spillover mechanism addresses the issue of hydrogen-induced deactivation of precious metal active sites, offering a promising pathway for broader application across diverse catalytic hydrogenation systems. Download: Download high-res image (138KB) Download: Download full-size image