Geometric and electronic effects of Co@NPC catalyst in chemoselective hydrogenation: Tunable activity and selectivity via N,P co-doping

Exploring the interactions among doping heteroatom, carbon and metal atoms has great potential to significantly enhance the catalytic performance and can gain an insightful understanding of the heterogeneous catalysis mechanism. Here, we present an N,P co-doped carbon-coated cobalt (Co@NPC) as a highly selective and water-durable catalyst applicable to aqueous-phase hydrogenation of cinnamaldehyde, featuring a precise control of products by adjusting N and P doping. These di-heteroatoms display a synergistic effect of geometry and electrons in Co@NPC, thus can selectively reduce CO to produce unsaturated alcohols. In contrast, Co@NC without P doping is highly active, but shows significant productivity of saturated alcohols under equivalent conditions. Theoretical calculations manifest that the electronegativity difference among N, C and P atoms leads to the interaction between electrons, thus can adjust the chemical states of the active metal and enhance the catalytic performance in hydrogenation. It provides a desirable way for regulating the catalysis of heterogeneous catalysts.