With the ever-pressing issues of global energy demand and environmental pollution, molecular hydrogen has been receiving increasing attention as a clean alternative energy carrier. For hydrogen production, the design and development of high-performance catalysts remains rather challenging. As the compositions and structures of catalyst interfaces have paramount influences on the catalytic performances, the central topic here has always been to design and engineer the interface structures via rational routes so as to boost the activities and stabilities of electrocatalysts on hydrogen evolution reaction (HER). Here in this review, we focus on the design and preparation of multi-scale catalysts specifically catering to HER applications. We start from the design and structure-activity relationship of catalytic nanostructures, summarize the research progresses related to HER nanocatalysts, and interpret their high activities from the atomistic perspective; then, we review the studies regarding the design, preparation, HER applications and structure-activity relationship of single-atom site catalysts (SASCs), and thereupon discuss the future directions in designing HER-oriented SASCs. At the end of this review, we present an outlook on the development trends and faced challenges of catalysts for electrochemical HER.

随着全球能源需求和环境污染问题的日益紧迫，分子氢作为一种清洁的替代能源载体越来越受到关注。对于制氢，高性能催化剂的设计和开发仍然颇具挑战性。由于组成和催化剂界面结构对催化性能最重要的影响，这里的中心议题向来以设计，并设计界面结构通过合理的途径，以提高电催化剂在放氢反应（HER）上的活性和稳定性。在本文中，我们重点研究专门针对HER应用的多级催化剂的设计和制备。我们从催化纳米结构的设计和构效关系开始，总结了与HER纳米催化剂相关的研究进展，并从原子学角度解释了它们的高活性。然后，我们回顾了有关单原子中心催化剂（SASC）的设计，制备，HER应用和结构-活性关系的研究，随后讨论了面向HER的SASC设计的未来方向。在本文的最后，我们对电化学HER催化剂的发展趋势和面临的挑战提出了展望。