Alkaline hydrogen evolution reaction (HER) provides a promising approach for producing green hydrogen, but designing high-efficiency transition metal nanocatalysts is rather challenging. Herein, unsaturated coordination Co−M (M = P, S, Se, Te) bonds modified metallic Co are designed on Ni foam (M-Co/NF) through a facile electrodeposition strategy. The constructed Co−M bonds not only alter the local coordination condition and electron structure, but also provide an electron transfer channel, and significantly enhance the intrinsic activities. Consequently, the P-Co/NF displays an ultralow overpotential of 23 mV at 10 mA cm with excellent stability. X-ray absorption spectroscopy verifies the formation of extremely unsaturated coordination Co−P bonds, which adjusts the charge redistribution. Density functional theory calculations prove the unsaturated coordination Co−P bonds can optimize the adsorption of HO and H adsorption. This work provides novel insight into the effects of local coordination environment on activity and the rational design of efficient transition metal nanocatalysts.

中文翻译：

---

构建不饱和配位Co−M（M = P、S、Se、Te）键修饰金属Co以实现高效的碱性析氢

碱性析氢反应（HER）为生产绿色氢气提供了一种有前途的方法，但设计高效过渡金属纳米催化剂相当具有挑战性。在此，通过简单的电沉积策略在泡沫镍（M-Co/NF）上设计了不饱和配位Co−M（M = P、S、Se、Te）键修饰的金属Co。构建的Co−M键不仅改变了局域配位条件和电子结构，而且提供了电子转移通道，并显着增强了本征活性。因此，P-Co/NF 在 10 mA cm 电流下表现出 23 mV 的超低过电位，并且具有出色的稳定性。 X 射线吸收光谱验证了极度不饱和配位 Co−P 键的形成，从而调节电荷重新分布。密度泛函理论计算证明不饱和配位Co−P键可以优化H2O和H2的吸附。这项工作为局部配位环境对活性的影响以及高效过渡金属纳米催化剂的合理设计提供了新的见解。