W Doping in Ni₁₂P₅ as a Platform to Enhance Overall Electrochemical Water Splitting

Bifunctional electrocatalysts for efficient hydrogen generation from water splitting must overcome both the sluggish water dissociation step of the alkaline hydrogen evolution half-reaction (HER) and the kinetic barrier of the anodic oxygen evolution half-reaction (OER). Nickel phosphides are a promising catalysts family and are known to develop a thin active layer of oxidized Ni in an alkaline medium. Here, Ni₁₂P₅ was recognized as a suitable platform for the electrochemical production of γ-NiOOH─a particularly active phase─because of its matching crystallographic structure. The incorporation of tungsten by doping produces additional surface roughness, increases the electrochemical surface area (ESCA), and reduces the energy barrier for electron-coupled water dissociation (the Volmer step for the formation of H_ads). When serving as both the anode and cathode, the 15% W-Ni₁₂P₅ catalyst provides an overall water splitting current density of 10 mA cm^-2 at a cell voltage of only 1.73 V with good durability, making it a promising bifunctional catalyst for practical water electrolysis.