Khani Hadi, Puente Santiago Alain R, He Tianwei
Texas Materials Institute and Materials Science and Engineering Program, The, University of Texas at Austin, Austin, TX, 78712, USA.
Yunnan Key Laboratory for Micro/Nano Materials & Technology, National Center for International Research on Photoelectric and Energy Materials, Yunnan University, Kunming, 650091, China.
Angew Chem Int Ed Engl. 2023 Oct 23;62(43):e202306103. doi: 10.1002/anie.202306103. Epub 2023 Aug 3.
The identity of alkali metal cations in the electrolyte of electrocatalysis systems has been recently introduced as a crucial factor to tailor the kinetics and Faradaic efficiency of many electrocatalytic reactions. In this Minireview, we have summarized the recent advances in the molecular-level understanding of cation effects on relevant electrocatalytic processes such as hydrogen evolution (HER), oxygen evolution (OER), and CO electroreduction (CO RR) reactions. The discussion covers the effects of electrolyte cations on interfacial electric fields, structural organization of interfacial water molecules, blocking the catalytic active sites, stabilization or destabilization of intermediates, and interfacial pHs. These cation-induced interfacial phenomena have been reported to impact the performance (activity, selectivity, and stability) of electrochemical reactions collaboratively or independently. We describe that although there is almost a general agreement on the relationship between the size of alkali cations and the activities of HER, OER, and CO RR, however, the mechanism by which the performance of these electrocatalytic reactions is influenced by alkali metal cations is still in debate.
电催化系统电解质中碱金属阳离子的身份最近被认为是调整许多电催化反应动力学和法拉第效率的关键因素。在这篇迷你综述中，我们总结了在分子水平上对阳离子对相关电催化过程（如析氢反应（HER）、析氧反应（OER）和CO电还原反应（CO RR））影响的最新认识进展。讨论内容包括电解质阳离子对界面电场、界面水分子结构组织、催化活性位点的阻塞、中间体的稳定或去稳定以及界面pH值的影响。据报道，这些阳离子诱导的界面现象会协同或独立地影响电化学反应的性能（活性、选择性和稳定性）。我们描述了尽管对于碱金属阳离子大小与HER、OER和CO RR活性之间的关系几乎已达成普遍共识，然而，碱金属阳离子影响这些电催化反应性能的机制仍存在争议。
