Phosphorus incorporation activates the basal plane of tungsten disulfide for efficient hydrogen evolution catalysis

The basal planes of transition metal dichalcogenides are basically inert for catalysis due to the absence of adsorption and activation sites, which substantially limit their catalytic application. Herein, a facile strategy to activate the basal plane of WS₂ for hydrogen evolution reaction (HER) catalysis by phosphorous-induced electron density modulation is demonstrated. The optimized P doped WS₂ (P-WS₂) nanowires arrays deliver a low overpotential of 88 mV at 10 mA·cm⁻² with a Tafel slope of 62 mV·dec⁻¹ for HER, which is substantially better than the pristine counterpart. X-ray photoelectron spectroscopy confirms the surface electron densities of WS₂ have been availably manipulated by P doping. Moreover, density functional theory (DFT) studies further prove P doping can redistribute the density of states (DOS) around E_F, which endow the inert basal plane of P-WS₂ with edge-like catalytic activity toward hydrogen evolution catalysis. Our work offers a facile and effective approach to modulate the catalytic surface of WS₂ toward highly efficient HER catalysis.