In Situ Reconstruction of V-Doped Ni2P Pre-Catalysts with Tunable Electronic Structures for Water Oxidation

Nickel-based electrocatalysts are promising candidates for oxygen evolution reaction (OER) but suffer from high activation overpotentials. Herein, in situ structural reconstruction of V-doped Ni2P pre-catalyst to form highly active NiV oxyhydroxides for OER is reported, during which the partial dissolution of V creates a disordered Ni structure with an enlarged electrochemical surface area. Operando electrochemical impedance spectroscopy reveals that the synergistic interaction between the Ni hosts and the remaining V dopants can regulate the electronic structure of NiV oxyhydroxides, which leads to enhanced kinetics for the adsorption of *OH and deprotonation of *OOH intermediates. Raman spectroscopy and X-ray absorption spectroscopy further demonstrate that the increased content of active beta-NiOOH phase with the disordered Ni active sites contributes to OER activity enhancement. Density functional theory calculations verify that the V dopants facilitate the generation of *O intermediates during OER, which is the rate-determining step for realizing efficient O-2 evolution. Optimization of these properties endows the NiV oxyhydroxide electrode with a low overpotential of 221 mV to deliver a current density of 10 mA cm(-2) and excellent stability in the alkaline electrolyte.

Automated summary

This study reports on the in-situ structural reconstruction of V-doped Ni2P pre-catalyst to form highly active NiV oxyhydroxides for oxygen evolution reaction (OER), showing enhanced kinetics for the adsorption of *OH and deprotonation of *OOH intermediates. Raman spectroscopy and X-ray absorption spectroscopy demonstrate that the increased content of the active beta-NiOOH phase contributes to OER activity enhancement. Density functional theory calculations verify that the V dopants facilitate the generation of *O intermediates during OER.