Electronic structure regulation of NiP via metal/nonmetal co-doping for electrocatalytic hydrogen evolution reaction

Metal Fe and nonmetal S were co-doped in NiP to modulate the electronic structure of NiP. • Metal Fe doping can improve the electroconductive of the NiP, improving the electron transfer ability and reaction kinetics of HER. • Nonmetal S doping can modulate the band structure for the high electronegativity of S element. • The synthesized Fe, S-NiP exhibited an overpotential of 35 mV at the current density of 10 mA/cm 2 . Nickel phosphide (NiP) is an effective non-noble metal electrocatalyst for the hydrogen evolution reaction (HER). However, the application of NiP is limited for the poor hydrogen adsorption and slow charge transfer during HER process. Herein, metal Fe and nonmetal S were co-doped into NiP to overcome an aforementioned drawbacks of NiP. Metal Fe doping can improve the electroconductive of the NiP, improving the electron transfer ability and reaction kinetics of HER. Nonmetal S doping can modulate the band structure for the high electronegativity of S element. The optimized d-band centers of Ni site benefited the HER reaction and improved the catalytic performance of Fe, S-NiP. The synergistic effect of metal and nonmetal doping further enhanced the catalytic activity by optimizing proton adsorption and hydrogen desorption. This work provided a guidance for metal and nonmetal co-doping for transition metal-based materials’ catalytic performance improvement.