Synthesis, Physical Properties and Electrocatalytic Performance of Nickel Phosphides for Hydrogen Evolution Reaction of Water Electrolysis

Nickel phosphides have been investigated as an alternative to noble metals and have emerged as potential catalysts that can efficiently catalyze the hydrogen evolution reaction (HER). However, the impacts of facet morphology and crystal structure of the nickel phosphides on their catalytic reactivity have not been systematically investigated. Herein, nickel phosphides with different crystalline states were prepared through a facile calcination treatment. It was found that the calcination treatment had important effects on the phase compositions, morphologies, and crystallinity of nickel phosphides, which are closely related to their HER activity. Generally, the crystallized Ni-P catalysts exhibited faster kinetics than the amorphous Ni-P. In particular, the Ni-P 300 showed remarkable HER performance with ${\eta }_{10}$ of ca. 65 mV, along with a very low Tafel slope of ca. 44 mV dec⁻¹ due to the increased catalytically active sites. Furthermore, the Ni-P 300 exhibited negligible decay during the 140 h galvanostatic electrolysis, showing better catalytic stability than the commercial Pt/C catalyst. Compared with the amorphous Ni-P, the boosted HER activity of the Ni-P 300 could benefit from the mixed nanocrystalline Ni₂P and Ni₃P, which could contribute to the H_ads adsorption/desorption abilities and helped provide more activity sites, promoting the HER performance.