The design of active, stable, and cost-effective electrocatalysts for the H₂ evolution reaction (HER) in alkaline conditions is important for electrochemical systems such as the chloro-alkaline process and H₂ production. Here we report catalysts comprising Pt on Ni single crystalline spines (Pt/Ni-SP) with high activity and stability for HER in alkaline solution with proposed mechanism. The Pt/Ni-SP catalysts are prepared by dispersing platinum nanoparticles (1.7–3.1 nm) on the single-crystalline spines (Ni-SP) of Ni urchin-like particles. The size and coverage of Pt nanoparticles on Ni-SP are increased with increases in the Pt loading amount. X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy are performed to observe the structure of the Pt/Ni-SP catalyst. The catalysts achieve the mass activity of 1.11 A mg⁻¹_(Pt), comparing favorably to Pt/C catalysts with the mass activity of 0.33 A mg⁻¹_(Pt) at 0.05 V overpotential. The Tafel slope of the Pt/Ni-SP catalyst is approximately 30 mV dec⁻¹, similar to that of Pt, while Pt/Ni-SP is very stable in alkaline solution, like Ni. The synergistic effect of Pt/Ni-SP is ascribed to H spillover from Pt to Ni.

Electrochemical and chemical phase transformations of α-Co(OH)₂ into various other cobalt hydroxides were performed, and their structures were characterized to discern the correlation between electrocatalytic activity and crystal structure.