Stimulated pH‐Dependence Phosphorus Platinum–Nickel Alloy Cluster as Hydrogen Generation Electrocatalyst in Alkaline Solution

Platinum‐based catalysts play an outstanding role in alkaline hydrogen evolution reaction (HER) but with sluggish reaction kinetics. Herein, stimulated pH‐dependence phosphorus‐embedded PtNi nano‐alloy clusters (P@PtNi/C) with good alkaline HER catalytic activity are obtained. The overpotential of P@PtNi/C at a current density of 10 mA cm −2 is 26 mV in 1M KOH solution. At the overpotential of 70 mV, the mass activity of P@PtNi/C is 4.62 A mgPt −1 , which is 21 times that of commercial 20 wt% Pt/C in terms of the unit mass of Pt. Due to the doping of P elements, the electronic interface is optimized, which enhances the OH − sensitivity and enables more OH ad * to be involved in the overall alkaline cathode reaction. Density functional theory calculations suggest that PtNi 3 P/C can promote the further reduction of OH ad * to generate O ad *, which plays an important role in the decomposition of H 2 O* to form OH ad *. A closed‐looping H 2 O reduction process that exhibits the pH‐dependent characteristics of alkaline HER is proposed. OH − is appropriately integrated into the alkaline HER catalytic process based on P@PtNi/C catalyst, which provides a feasible consideration for the design of alkaline HER catalyst.