Constructed Interfacial Oxygen-Bridge Chemical Bonding in Core-Shell Transition Metal Phosphides/Carbon Hybrid Boosting Oxygen Evolution Reaction.

A designed structure which CoP nanoparticles (NPs) ingeniously connected with graphene-like carbon layer via in-situ generated interfacial oxygen-bridge chemical bonding was achieved by a mild phosphorization treatment. The results proved that the presence of phosphorus vacancies is a crucial factor enabling formation of Co-O-C bonds. The direct coupling of edge Co of CoP with the oxygen from functional groups on the carbon layer was proposed. As a catalyst for electrocatalytic water splitting, the manufactured Fe2 O3 @C@CoP core-shell structure manifested a low overpotential of 230 mV, a low Tafel slope of 55 mV dec-1 , and long-term stability. Density functional theory calculations verified that the Co-O-C bond played a critical role in decreasing the thermodynamic energy barrier of reaction rate-determining step for the oxygen evolution reaction (OER). This synthetic route might be extended to construct metal-O-C bonds in other transition metal phosphides (or selenides, sulfides)/carbon composites for highly efficient OER catalysts.