Constructing Unsaturated Coordination Co−M (M=P, S, Se, Te) Bonds Modified Metallic Co for Efficient Alkaline Hydrogen Evolution

Alkaline hydrogen evolution reaction (HER) provides a promising approach for producing green hydrogen, but designing high-efficiency transition metal nanocatalysts is rather challenging. Herein, unsaturated coordination Co−M (M = P, S, Se, Te) bonds modified metallic Co are designed on Ni foam (M-Co/NF) through a facile electrodeposition strategy. The constructed Co−M bonds not only alter the local coordination condition and electron structure, but also provide an electron transfer channel, and significantly enhance the intrinsic activities. Consequently, the P-Co/NF displays an ultralow overpotential of 23mV at 10mAcm−2 with excellent stability. X-ray absorption spectroscopy verifies the formation of extremely unsaturated coordination Co−P bonds, which adjusts the charge redistribution. Density functional theory calculations prove the unsaturated coordination Co−P bonds can optimize the adsorption of H2O and H adsorption. This work provides novel insight into the effects of local coordination environment on activity and the rational design of efficient transition metal nanocatalysts.