Li Site, Du Xiangsha, Liu Zhongyu, Li Yingwei, Shao Yucai, Jin Rongchao
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
Precis Chem. 2023 Mar 15;1(1):14-28. doi: 10.1021/prechem.3c00008. eCollection 2023 Mar 27.
The emergence of ligand-protected, atomically precise gold nanoclusters (NCs) in recent years has attracted broad interest in catalysis due to their well-defined atomic structures and intriguing properties. Especially, the precise formulas of NCs provide an opportunity to study the size effects at the atomic level without complications by the polydispersity in conventional nanoparticles that obscures the relationship between the size/structure and properties. Herein, we summarize the catalytic size effects of atomically precise, thioate-protected gold NCs in the range of tens to hundreds of metal atoms. The catalytic reactions include electrochemical catalysis, photocatalysis, and thermocatalysis. With the precise sizes and structures, the fundamentals underlying the size effects are analyzed, such as the surface area, electronic properties, and active sites. In the catalytic reactions, one or more factors may exert catalytic effects simultaneously, hence leading to different catalytic-activity trends with the size change of NCs. The summary of literature work disentangles the underlying fundamental mechanisms and provides insights into the size effects. Future studies will lead to further understanding of the size effects and shed light on the catalytic active sites and ultimately promote catalyst design at the atomic level.
近年来,配体保护的、原子精确的金纳米团簇(NCs)的出现因其明确的原子结构和有趣的性质而在催化领域引起了广泛关注。特别是,NCs精确的化学式提供了一个在原子水平上研究尺寸效应的机会,而不会受到传统纳米颗粒多分散性的干扰,这种多分散性掩盖了尺寸/结构与性质之间的关系。在此,我们总结了原子精确的、硫醇盐保护的金NCs在几十到几百个金属原子范围内的催化尺寸效应。催化反应包括电化学催化、光催化和热催化。凭借精确的尺寸和结构,分析了尺寸效应背后的基本原理,如表面积、电子性质和活性位点。在催化反应中,一个或多个因素可能同时发挥催化作用,从而导致随着NCs尺寸变化出现不同的催化活性趋势。对文献工作的总结理清了潜在的基本机制,并提供了对尺寸效应的见解。未来的研究将进一步加深对尺寸效应的理解,揭示催化活性位点,并最终推动原子水平上的催化剂设计。