Local Coordination Environment-Driven Structural Dynamics of Single-Atom Copper and the CO2 Electroreduction Pathway.

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Tingyu Lu, Guoshuai Shi, Yufei Liu, Xuan Luo, Yuluo Shen, Mingwei Chang, Yijie Wu, Xinyang Gao, Jing Wu, Yefei Li, Yucheng Wang, Liming Zhang
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引用次数: 0

Abstract

Structural stability is a critical factor in realizing the potential of single-atom catalysts (SACs), yet remaining a major challenge hindering their large-scale application. Understanding the operando structural dynamics of SACs is essential for elucidating the structure-activity relationship and guiding the design of high-performance SACs. In this study, we selected five well-defined mononuclear copper (Cu) complexes with varying ligand structures to explore the coordination-driven structural dynamics of Cu single atoms and their interaction with the electrochemical CO2 reduction (CO2R) pathway. Coordination environments strongly influence the reconfiguration behaviors of Cu SACs by affecting the binding energy and charge distribution between Cu and the ligands. The in situ reconstructed Cu(0) and Cu(I) sites act as active centers for carbon product formation. Specifically, Cu(0) is closely associated with CH4 generation, while a unique Cu(I)N3H-*CO intermediate promotes multicarbon production by acting as a bridge, transferring *CO to neighboring Cu(0) with abundant unsaturated sites. This work highlights the impact of coordination environments on product distribution by influencing the reconfiguration behaviors of SACs and provides theoretical insights for designing Cu SACs with enhanced stability and tailored CO2R product selectivity.

局部配位环境驱动的单原子铜结构动力学与CO2电还原途径。
结构稳定性是实现单原子催化剂(SACs)潜力的关键因素,但仍然是阻碍其大规模应用的主要挑战。了解复合材料的结构动力学对阐明结构-活性关系、指导高性能复合材料的设计具有重要意义。在这项研究中,我们选择了5种定义明确、配体结构不同的单核铜(Cu)配合物,探索Cu单原子配位驱动的结构动力学及其与电化学CO2还原(CO2R)途径的相互作用。配位环境通过影响Cu与配体之间的结合能和电荷分布,强烈影响Cu SACs的重配置行为。原位重建的Cu(0)和Cu(I)位点是碳产物形成的活性中心。具体来说,Cu(0)与CH4的生成密切相关,而一种独特的Cu(I)N3H-*CO中间体通过将*CO转移到具有丰富不饱和位点的邻近Cu(0)来促进多碳的产生。本研究强调了协调环境通过影响sac的重构行为对产品分布的影响,并为设计具有增强稳定性和定制CO2R产品选择性的Cu sac提供了理论见解。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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