HER takes place on the surface of catalyst via a multi–step electrochemical process, and the electrocatalytic activity is highly correlated with synergistic chemisorption and desorption reactions on catalyst. Rational design of electrocatalysts with tailored surface chemical properties and architectures for the highly efficient hydrogen evolution reaction (HER) has received considerable interests. Herein, we report hierarchical structure constructed by the conductive carbon nanotube backbone core and the electrocatalytic active Mo-S-Ni nanosheets. Benefitting from their unique architecture and electronic modulation at the interface, the Mo-S-Ni-CNTs heterostructure delivers low overpotential of 98.8 and 78.1 mV at 10 mA cm⁻² with high stability in alkaline and acidic electrolytes. Theoretical calculations reveal that interface with optimized H-absorption sites is involved in the HER process and the electronic states at the interface are greatly changed, which enable optimal hydrogen adsorption, and contribute to the accelerating charge transfer kinetics. This work provides new sights for the design and preparation of novel co-axial hierarchical structures as highly efficient electrocatalysts toward HER.

HER通过多步电化学过程发生在催化剂表面，其电催化活性与催化剂上的协同化学吸附和解吸反应高度相关。具有定制表面化学性质和结构的用于高效析氢反应（HER）的电催化剂的合理设计已经引起了相当大的兴趣。在此，我们报告了由导电碳纳米管骨架核心和电催化活性 Mo-S-Ni 纳米片构成的分层结构。得益于其独特的结构和界面处的电子调制，Mo-S-Ni-CNTs 异质结构在 10 mA cm ^{-2下提供 98.8 和 78.1 mV 的低过电势}在碱性和酸性电解质中具有高稳定性。理论计算表明，具有优化的氢吸收位点的界面参与了 HER 过程，并且界面处的电子态发生了很大变化，从而实现了最佳的氢吸附，并有助于加速电荷转移动力学。这项工作为新型同轴分层结构的设计和制备提供了新的视角，作为高效的 HER 电催化剂。