Developing high-performance Pt-based alloy catalysts with strong metal-support interaction is considered an effective strategy to optimise the intrinsic activity and stability of catalysts and has received extensive attention, but still challenging. Herein, Pt₃Ni alloy nanoparticles coupled with three-dimensional N-doped graphene (Pt₃Ni/3DNG) are prepared and used for enhancing the alkaline hydrogen evolution reaction (HER). It is found that the Pt₃Ni/3DNG catalyst generates a tensile strain and give rise to a ligand effect on the surface of the active sites, which efficiently boost water dissociation and optimise H* desorption, thereby accelerating the alkaline HER kinetics. As a result, the Pt₃Ni/3DNG catalyst exhibits an exceptional alkaline HER activity with a mass activity 14 times that of commercial 40 wt.% Pt/C at 70 mV and a high stability (no decay is observed after 10,000 cycles). This work demonstrates the function of quaternary-N and pyridinic-N in the HER, and provides a novel design for Pt-based alloy catalysts with high alkaline HER performance.

开发具有强金属-载体相互作用的高性能铂基合金催化剂被认为是优化催化剂本征活性和稳定性的有效策略，受到了广泛关注，但仍具有挑战性。在此，制备了与三维N掺杂石墨烯（Pt ₃ Ni/3DNG）耦合的Pt ₃ Ni合金纳米颗粒，并将其用于增强碱性析氢反应（HER）。发现Pt ₃ Ni/3DNG催化剂产生拉伸应变并在活性位点表面产生配体效应，有效促进水解离并优化H*解吸，从而加速碱性HER动力学。因此，Pt ₃Ni/3DNG 催化剂表现出卓越的碱性 HER 活性，在 70 mV 时质量活性是商业 40 wt.% Pt/C 的 14 倍，并且具有高稳定性（10,000 次循环后未观察到衰减）。这项工作证明了季氮和吡啶氮在 HER 中的作用，并为具有高碱性 HER 性能的 Pt 基合金催化剂提供了新的设计。