V-doped Ni12P5 nanoflowers boost alkaline hydrogen evolution

Developing efficient and low-cost non-precious metal electrocatalysts for the alkaline HER is crucial for green hydrogen production. Nickel-rich phosphides (Ni 12 P 5 ) offer high conductivity but suffer from strong hydrogen adsorption, limiting their activity. This work presents a V doping strategy to directly modulate the electronic structure of pure-phase Ni 12 P 5 . V doping induces lattice distortion and drives the formation of a hierarchical porous nanoflower morphology, increasing the active surface area. More importantly, it optimizes the ΔG H* by downshifting the Ni d-band center and reduces the water dissociation barrier, enhancing intrinsic activity. The resulting V-Ni 12 P 5 /NF exhibits outstanding HER performance in 1 M KOH, with low overpotentials of 81 and 117 mV at 10 and 100 mA cm −2 , a Tafel slope of 60 dec −1 , and remarkable stability for over 230 h. This work demonstrates that rational heteroatom doping is an effective strategy for designing high-performance, stable, and cost-effective HER electrocatalysts.