In Situ Reconstruction Ni-O Octahedral Active Sites for Promoting Electrocatalytic Oxygen Evolution of Nickel Phosphate

Electrochemical activation strategy is very effective to improve the intrinsic catalytic activity of metal phosphate toward the sluggish oxygen evolution reaction (OER) for water electrolysis. However, it is still challenging to operando trace the activated reconstruction and corresponding electrocatalytic dynamic mechanisms. Herein, a constant voltage activation strategy is adopted to in situ activate Ni₂P₄O₁₂, in which the break of Ni-O-Ni bond and dissolution of PO₄³⁻ groups could optimize the lattice oxygen, thus reconstructing an irreversible amorphous Ni(OH)₂ layer with a thickness of 1.5–3.5 nm on the surface of Ni₂P₄O₁₂. The heterostructure electrocatalyst can afford an excellent OER activity in alkaline media with an overpotential of 216.5 mV at 27.0 mA cm⁻². Operando X-ray absorption fine structure spectroscopy analysis and density functional theory simulations indicate that the heterostructure follows a nonconcerted proton–electron transfer mechanism for OER. This activation strategy demonstrates universality and can be used to the surface reconstruction of other metal phosphates.