Herein, a novel single-atomic Pt doping and interface-rich CoS/Co(OH)₂ (Pt-CoS/Co(OH)₂/C) electrocatalyst has been successfully prepared. Benefiting from precise regulation of d-orbital electronic structure modulation on Co site, Pt-CoS/Co(OH)₂/C exhibited remarkable HER activity and high stability for hydrogen evolution in splitting both water (73 mV@10 mA·cm⁻²) and seawater (87 mV@10 mA·cm⁻²). Notably, atomic Pt doping was introduced into CoS/Co(OH)₂, which could produce local unbalanced Coulombic force and significantly increased the number of S vacancies, and then expose abundant Co sites. Meantime, Co(OH)₂ in Pt-CoS/Co(OH)₂/C could act as the adsorption sites for H₂O in hydrogen evolution reaction process. Density functional theory results also proved that atomic Pt doping, S vacancies and Co(OH)₂ coupling could result in the formation of enriched electronic Co sites and optimize \({\text d}_{{z}^{2}}\) orbital electronic structure, and then realize the depth upward shift of d-band center and enhance the adsorption of H* on Co sites.

Graphical abstract

中文翻译：

---

调节 d 轨道以实现硫化钴中丰富的电子钴位点，从而增强电催化水/海水分解中的析氢

在此，成功制备了一种新型单原子Pt掺杂和富界面CoS/Co(OH) ₂ (Pt-CoS/Co(OH) _{2 /C)电催化剂。}受益于Co位点d轨道电子结构调制的精确调控，Pt-CoS/Co(OH) ₂ /C在分解水时表现出显着的HER活性和高析氢稳定性(73 mV@10 mA·cm ^-2）和海水（87 mV@10 mA·cm ^-2）。_{值得注意的是，在CoS/Co(OH) 2}中引入原子Pt掺杂，可以产生局部不平衡的库仑力并显着增加S空位的数量，从而暴露出丰富的Co位点。同时，Pt-CoS/Co (OH) _{2 /C中的Co(OH) 2}可以作为析氢反应过程中H _{2 O的吸附位点。}密度泛函理论结果还证明原子Pt掺杂、S空位和Co(OH) ₂耦合可以导致富集电子Co位点的形成并优化\({\text d}_{{z}^{2}}\ )轨道电子结构，进而实现d带中心深度上移，增强H*在Co位上的吸附。

图形概要