钌基单原子和团簇催化剂在电催化反应中的竞争和协同效应

Competition and synergistic effects of Ru-based single-atom and cluster catalysts in electrocatalytic reactions

单原子和团簇催化剂在电催化领域,尤其是可持续能源存储和转化领域的重要性,得到越来越多地认可.单原子催化剂具有低金属负载和高原子利用效率的优点,但由于其表面自由能常常使得单个原子不稳定而发生聚集.团簇催化剂则因为其高原子利用率以及多样的活性位点,能够克服单原子催化剂在中间体吸附和活化等方面的局限性.钌基催化剂在电催化中有着十分重要的应用前景.然而,准确设计钌基单原子和团簇催化剂的几何和电子结构,并揭示它们之间的结构-性质关系,仍然面临着巨大的挑战.因此,我们对钌基催化剂进行了分类和比较(同源/异源),重点总结了钌基单原子和团簇在电催化领域的竞争和协同效应.近年来,钌基催化剂在析氢反应(HER)方面取得了显著进展,因此着重介绍钌基催化剂在HER中的应用,并涵盖了其他电催化反应、双功能反应(HER/OER、HER/HOR)和电化学有机反应.此外,本文还探讨了钌基单原子和团簇在HER过程中的催化机理.最后,我们指出了在复杂钌基催化剂的工业应用开发策略中所面临的挑战和前景.

Single-atom catalysts(SACs)and cluster cata-lysts are increasingly recognized as powerful materials for electrocatalysis,especially in the field of sustainable energy storage and conversion.SACs have the advantages of low metal loading and high atom utilization efficiency,but the free energy of the surface area tends to make individual atom unstable,making them prone to agglomeration during synthesis and catalytic reactions.Cluster catalysts with high atom utilization and different active sites can overcome the limitations of single-atom catalysts for continuous and col-lective adsorption as well as activation of reactants or inter-mediates.The synergistic effect resulting from the competition between single-atom and cluster catalysts can significantly improve the performance of the catalysts.Ru-based catalysts have important application prospects in cata-lysis.Accurate design of the geometrical and electronic structures of Ru-based single-atom and cluster catalysts and the unraveling of their structure-property relationships face great challenges.Herein,we classify and compare these cata-lysts,with a special focus on Ru-based homologous and het-erologous catalysts.Next,we show several major breakthroughs in electrocatalysis catalyzed by Ru-based sin-gle-atom and clusters.In recent years,Ru-based catalysts have made significant progress in hydrogen evolution reaction(HER),so we focus on the application of Ru-based catalysts in HER and cover other electrocatalytic reactions,bifunctional reactions(HER/oxygen evolution reaction,HER/hydroxide oxidation reaction),and electrochemical organic reactions.In addition,the review summarizes the catalytic mechanism of HER on Ru-based single-atom and clusters.Finally,challenges and prospects in the development of strategies for complex Ru-based catalysts for industrial applications are highlighted.