Du Yuanxin, Wang Pei, Fang Yi, Zhu Manzhou
Department of Materials Science and Engineering, Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Key Laboratory of Functional Inorganic Material Chemistry of Anhui Province, Anhui University, Hefei, 230601, China.
ChemSusChem. 2025 Mar 15;18(6):e202402085. doi: 10.1002/cssc.202402085. Epub 2024 Nov 15.
Recently, atomically precise metal nanoclusters (NCs) have been widely applied in CO reduction reaction (CORR), achieving exciting activity and selectivity and revealing structure-performance correlation. However, at present, the efficiency of CORR is still unsatisfactory and cannot meet the requirements of practical applications. One of the main reasons is the difficulty in CO activation due to the chemical inertness of CO. Constructing symmetry-breaking active sites is regarded as an effective strategy to promote CO activation by modulating electronic and geometric structure of CO molecule. In addition, in the subsequent CORR process, asymmetric charge distributed sites can break the charge balance in adjacent adsorbed C intermediates and suppress electrostatic repulsion between dipoles, benefiting for C-C coupling to generate C products. Although compared to single atoms, metal nanoparticles, and inorganic materials the research on the construction of asymmetric catalytic sites in metal NCs is in a newly-developing stage, the precision, adjustability and diversity of metal NCs structure provide many possibilities to build asymmetric sites. This review summarizes several strategies of construction asymmetric charge distribution in metal NCs for boosting CORR, concludes the mechanism investigation paradigm of NCs-based catalysts, and proposes the challenges and opportunities of NCs catalysis.
近年来，原子精确的金属纳米团簇（NCs）已广泛应用于CO还原反应（CORR），展现出令人兴奋的活性和选择性，并揭示了结构-性能关系。然而，目前CORR的效率仍不尽人意，无法满足实际应用的需求。主要原因之一是由于CO的化学惰性，难以实现CO的活化。构建对称性破缺的活性位点被认为是一种通过调节CO分子的电子和几何结构来促进CO活化的有效策略。此外，在随后的CORR过程中，不对称电荷分布位点可以打破相邻吸附C中间体中的电荷平衡，并抑制偶极子之间的静电排斥，有利于C-C偶联生成C产物。尽管与单原子、金属纳米颗粒和无机材料相比，金属NCs中不对称催化位点构建的研究尚处于新发展阶段，但金属NCs结构的精确性、可调节性和多样性为构建不对称位点提供了诸多可能性。本文综述了几种在金属NCs中构建不对称电荷分布以促进CORR的策略，总结了基于NCs催化剂的机理研究范式，并提出了NCs催化面临的挑战和机遇。
