Enhanced activity in industrial hydrogen evolution reaction on NiS/NiCoP by sulfur vacancy coupled with transition metal doping

Ni-based chalcogenide catalysts show the weak H2O molecule adsorption and sluggish kinetics, restricting their industrial hydrogen evolution reaction (HER) in a wide pH range. Herein, a controllable fabrication strategy of NiS/NiCoP nanoparticles by simultaneously constructing sulfur vacancies and introducing the heterometallic atoms (Zn, Fe, Mn) (M-NiCoSP-Sv) is proposed. The numerous uncoordinated surface Ni centers generated by sulfur vacancies are beneficial for cleaving the HO-H bond of H2O molecule, while S sites at Sv-NiS side and P sites at Zn-NiCoP side with rich electron aggregation are used as H2-evolution centers, synergistically facilitating HER kinetics over a wide pH range. As respected, Zn-NiCoSP-Sv exhibits excellent durability and outstanding HER activity such as 41, 78 and 34 mV of 10 mA cm-2 in alkaline, neutral and acidic electrolytes, respectively. And at the industrial current density, Zn-NiCoSP-Sv also possesses outstanding HER activity and stability. This work reveals a strategy for activating NiS-based catalyst to cleave H2O and optimize Gibbs free energy of H* by vacancy and doping co-engineering.