In Situ Hydroxide Growth over Nickel–Iron Phosphide with Enhanced Overall Water Splitting Performances

In this work, three dimensional (3D) self‐supported Ni‐FeOH@Ni‐FeP needle arrays with core‐shell heterojunction structure are fabricated via in situ hydroxide growth over Ni‐FeP surface. The as‐prepared electrodes show an outstanding oxygen evolution reaction (OER) performance, only requiring the low overpotential of 232 mV to reach 200 mA cm−2 with the Tafel slop of 40 mV dec−1. For overall water splitting, an alkaline electrolyzer with these electrodes only requires a cell voltage of 2.14 V to reach 1 A cm−2. Mechanistic investigations for such excellent electrocatalytic performances are utilized by in situ Raman spectroscopy in conjunction with density functional theory (DFT) calculations. The computation results present that Ni‐FeOH@Ni‐FeP attains better intrinsic conductivity and the D‐band center (close to that of the ideal catalyst), thus giving superior excellent catalytic performances. Likewise, the surface Ni‐FeOH layer can improve the structural stability of Ni‐FeP cores and attenuate the eventual formation of irreversible FeOOH products. More importantly, the appearance of FeOOH intermediates can effectively decrease the energy barrier of NiOOH intermediates, and then rapidly accelerate the sluggish reaction dynamics, as well as further enhance the electrocatalytic activities, reversibility and cycling stability. Three dimensional (3D) Ni‐FeOH@Ni‐FeP needle arrays are created on Ni foams, exhibiting excellent oxygen evolution reaction (OER) and overall water splitting performance. In‐situ Raman spectroscopy and density functional thoery (DFT) calculations reveal a FeOOH intermediates to NiOOH transition on the heterojunction surface. This process reduces the energy barrier of OER, accelerating reaction dynamics and enhancing electrocatalytic activities, reversibility, and stability.