Defect Engineering and Carbon Supporting to Achieve Ni-Doped CoP with High Catalytic Activities for Overall Water Splitting.

This work reports the use of defect engineering and carbon supporting to achieve metal-doped phosphides with high activities and stabilities for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline media. Specifically, the nitrogen-doped carbon nanofiber-supported Ni-doped CoP with rich P defects (Pv·) on the carbon cloth (p-NiCoP/NCFs@CC) is synthesized through a plasma-assisted phosphorization method. The p-NiCoP/NCFs@CC is an efficient and stable catalyst for the HER and the OER. It only needs overpotentials of 107 and 306 mV to drive 100 mA cm for the HER and the OER, respectively. Its catalytic activities are higher than those of other catalysts reported recently. The high activities of the p-NiCoP/NCFs@CC mainly arise from its peculiar structural features. The density functional theory calculation indicates that the Pv· richness, the Ni doping, and the carbon supporting can optimize the adsorption of the H atoms at the catalyst surface and promote the strong electronic couplings between the carbon nanofiber-supported p-NiCoP with the surface oxide layer formed during the OER process. This gives the p-NiCoP/NCFs@CC with the high activities for the HER and the OER. When used in alkaline water electrolyzers, the p-NiCoP/NCFs@CC shows the superior activity and excellent stability for overall water splitting.