Xu Yi Ning, Li Jia-Hui, Wu Jia Chen, Li Wenbo, Yang Yuwei, Wu Haoran, Fu Huai Qin, Zhu Minghui, Wang Xue Lu, Dai Sheng, Lian Cheng, Liu Peng Fei, Yang Hua Gui
Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China.
State Key Laboratory of Chemical Engineering, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China.
Adv Mater. 2025 May;37(18):e2500343. doi: 10.1002/adma.202500343. Epub 2025 Mar 19.
Recent advancements in alloy catalysis have yield novel materials with tailored functionalities. Among these, Cu-based single-atom alloy (SAA) catalysts have attracted significant attention in catalytic applications for their unique electronic structure and geometric ensemble effects. However, selecting alloying atoms with robust dispersion stability on the Cu substrate is challenging, and has mostly been practiced empirically. The fundamental bottleneck is that the microscopic mechanism that governs the dispersion stability is unclear, and a comprehensive approach for designing Cu-based SAA systems with simultaneous dispersion stability and high catalytic activity is still missing. Here, combining theory and experiment, a simple yet intuitive d-p orbital matching mechanism is discovered for rapid assessment of the atomic dispersion stability of Cu-based SAAs, exhibiting its universality and extensibility for screening effective SAAs across binary, ternary and multivariant systems. The catalytic selectivity of the newly designed SAAs is demonstrated in a prototype reaction-acidic CO electroreduction, where all SAAs achieve single-carbon product selectivity exceeding 70%, with SbCu reaching a peak CO faradaic efficiency of 99.73 ± 2.5% at 200 mA cm. This work establishes the fundamental design principles for Cu-based SAAs with excellent dispersion stability and selectivity, and will boost the development of ultrahigh-performance SAAs for advanced applications such as electrocatalysis.
合金催化领域的最新进展已产生具有定制功能的新型材料。其中，铜基单原子合金（SAA）催化剂因其独特的电子结构和几何集合效应在催化应用中受到了广泛关注。然而，在铜基底上选择具有强分散稳定性的合金原子具有挑战性，且大多是凭经验进行。根本瓶颈在于，控制分散稳定性的微观机制尚不清楚，并且仍然缺乏一种能够同时设计出具有分散稳定性和高催化活性的铜基SAA体系的综合方法。在此，通过理论与实验相结合，发现了一种简单直观的d-p轨道匹配机制，用于快速评估铜基SAA的原子分散稳定性，展示了其在筛选二元、三元和多组分体系中有效SAA方面的通用性和可扩展性。在一个典型反应——酸性CO电还原反应中，展示了新设计的SAA的催化选择性，其中所有SAA实现了超过70%的单碳产物选择性，在200 mA cm时，SbCu的CO法拉第效率达到99.73±2.5%的峰值。这项工作确立了具有优异分散稳定性和选择性的铜基SAA的基本设计原则，并将推动用于电催化等先进应用的超高性能SAA的发展。
