Ruthenium (Ru)-based catalysts have displayed compelling hydrogen evolution activities, which hold the promising potential to substitute platinum in alkaline H2-evolution. In the challenging alkaline electrolytes, the water-dissociation process involves multistep reactions, while the profound origin and intrinsic factors of diverse Ru species on water-dissociation pathways and reaction principles remain ambiguous. Here the fundamental origin of water-dissociation pathways of Ru-based catalysts in alkaline media to be from their unique electronic structures in complex coordination environments are disclosed. These theoretical results validate that the modulated electronic structures with delocalization-localization coexistence at their boundaries between the Ru nanocluster and single-atom site have a profound influence on water-dissociation pathways, which push H2O* migration and binding orientation during the splitting process, thus enhancing the dissociation kinetics. By creating Ru catalysts with well-defined nanocluster, single-atom site, and also complex site, the electrocatalytic data shows that both the nanocluster and single-atom play essential roles in water-dissociation, while the complex site possesses synergistically enhanced roles in alkaline electrolytes. This study discloses a new electronic structure-dependent water-dissociation pathway and reaction principle in Ru-based catalysts, thus offering new inspiration to design efficient and durable catalysts for the practical production of H2 in alkaline electrolytes.
Bibliografisk noteFunding Information:
This work was financially supported by the National Key R&D Program of China (2021YFE0205000, 2019YFA0110600, and 2019YFA0110601), National Natural Science Foundation of China (Nos. 52161145402, 52173133, and 51803134), the Sichuan Science and Technology Program (Nos. 2022YFH0088, 2021YFH0087, 2021YFH0135, and 2021YFH0180), the 1·3·5 Project for Disciplines of Excellence, West China Hospital, Sichuan University (No. ZYJC21047), the innovation project of Med‐X Center for Materials, Sichuan University (No. MCM202102). C.C. acknowledges the financial support of the State Key Laboratory of Polymer Materials Engineering (Grant No. sklpme2021‐4‐02) and Fundamental Research Funds for the Central Universities. C.H. thanks the China Scholarship Council (CSC) for financial support. The authors gratefully acknowledge Dr. Mi Zhou and Dr. Minghua Zhang for their analytical support. The authors thank the Ceshigo Research Service for the technical support on XAS. The authors also thank Zhongkebaice Technology Service Co. Ltd. for the technical support on high‐resolution HAADF‐STEM.
© 2023 Wiley-VCH GmbH.