Manipulating all-pH hydrogen evolution kinetics on metal sulfides through one-pot simultaneously derived multi-interface engineering and phosphorus doping

Abstract

The hydrogen evolution reaction (HER) especially at all pH is very significant for the electrocatalytic production of hydrogen energy, which consists of three key processes, i.e., water dissociation, hydroxide desorption and hydrogen combination. Herein, we developed a one-pot simultaneously derived multi-interface engineering and phosphorus doping strategy to promote all-pH hydrogen evolution kinetics on metal sulfides through constructing hierarchical NiS/WS₂/Ni₃S₄ hybrid frameworks. NiS/WS₂/Ni₃S₄ is composed of strongly cross-linked WS₂ nanosheets and NiS/Ni₃S₄ nanoparticles featuring highly exposed heterogeneous interfaces and phosphorus doping. NiS/WS₂/Ni₃S₄ only requires overpotentials of about 50 mV and 61 mV to drive 10 mA cm⁻² in alkaline and acid media, respectively, thereby being classified into one of the best transition metal sulfide (TMS) electrocatalysts. The robust all-pH HER activity of NiS/WS₂/Ni₃S should originate from the rapid transfer/transport of electrons and mass triggered by the special hierarchical structures and the multi-interface electron effects induced by the collaboration of interfaces and phosphorus doping with different capabilities for the adsorption and desorption of H*, H₂O* and H⋯OH*.