燃料化学学报（中英文）2025，Vol.53Issue(7)：983-993,11.DOI:10.3724/2097-213X.2025.JFCT.0006
金属团簇催化剂的精准调控及其催化性能研究
Rational design and catalytic properties of atomically precise metal clusters
摘要
Abstract
Metal clusters with precise formulas and crystallographically determined structures provide an unprecedented opportunity are used as well-defined catalysts to tailor the active sites,achieving high atom efficiency and a clear understanding of the catalytic mechanisms.These metal clusters are composed of a definite number of atoms,typically featuring an outer shell containing organic ligands and metal atoms monolayer,as well as an internal metal core.Their electronic and geometric structure exhibit various tunability,which offers a vast scope for the regulation of catalytic properties.The ligands are connected to metal atoms through the covalent bonds between the coordinating atoms and metal atoms,and the steric hindrance and interactions can be effectively regulated by adjusting the types of substituents around the coordinating atoms.The core,on the other hand,exhibits diverse geometric configurations depending on the number of metal atoms and the spatial and electronic interactions of the ligands.Accurately controlling the structures of metal clusters at the atomic scale can overcome the drawbacks of size and structural polydispersity in traditional metal nanoparticles,and thus reflect the impact of microstructure on target products at the atomic level and provide fundamental information for the study of the nature of metal catalysis.In this review,we systematically summarize the advances in the structural modifications of metal clusters,delving into various crucial factors and strategies.Firstly,the strategies of metal atom number modification are explored,which involve the precise control of the number of metal atoms to obtain clusters with various sizes and the shuttling of a single atom of the core while leaving the surface structure of the metal cluster unchanged.Secondly,the alloy site regulation technique is analyzed,which entails the controllable introduction of heterometallic atoms on the surface,subsurface,and core of the cluster to construct alloy sites,allowing the creation of unique catalytic sites that can interact with specific reactants,thereby improving the selectivity and efficiency of catalytic reactions.Subsequently,the organic ligand modification is discussed,which focuses on replacing all or part of the ligands to achieve fine-tuning of catalytic performance while maintaining the metal core.By modifying the ligands,researchers can adjust the steric and electronic properties of the cluster,optimizing its interaction with reactants and products.In addition,the isomer modification is introduced,which explores the specific impact of clusters with the same chemical composition but different atomic packing configurations on catalytic performance.This modification strategy highlights the importance of atomic arrangement in the catalytic properties of metal clusters.Finally,the electronic modification strategy is elaborated,which precisely regulates the superatomic electronic configurations of metal clusters to affect the overall physicochemical properties and catalytic performance.Understanding these fundamental principles is expected to open up new horizons in the catalysis of atomically precise clusters and the development of precise heterogeneous catalysts,thus paving the way for the design of next-generation catalysts with superior performance and selectivity.The precise control of metal cluster structures offers a powerful tool for addressing the challenges in catalysis,leading to highly efficient and sustainable chemical processes.关键词
原子精确/金属团簇/精准调控/催化性能Key words
atomic precision/metal cluster/rational design/catalytic performance分类
通用工业技术引用本文复制引用
蔡潇,丁维平,祝艳..金属团簇催化剂的精准调控及其催化性能研究[J].燃料化学学报（中英文）,2025,53(7):983-993,11.基金项目
The project was supported by National Natural Science Foundation of China(22125202,92461312,U24A20487,22302091),Natural Science Foundation of Jiangsu Province(BK20220033),and China Postdoctoral Science Foundation(2024T170400,2022M721551).国家自然科学基金(22125202,92461312,U24A20487,22302091),江苏省自然科学基金(BK20220033)和中国博士后科学基金(2024T170400,2022M721551)资助 （22125202,92461312,U24A20487,22302091）
