State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Engineering Research Center for Nano-Preparation Technology of Fujian Province, and National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
J Am Chem Soc. 2017 Feb 15;139(6):2122-2131. doi: 10.1021/jacs.6b10978. Epub 2017 Jan 26.
Surface coordination chemistry of nanomaterials deals with the chemistry on how ligands are coordinated on their surface metal atoms and influence their properties at the molecular level. This Perspective demonstrates that there is a strong link between surface coordination chemistry and the shape-controlled synthesis, and many intriguing surface properties of metal nanomaterials. While small adsorbates introduced in the synthesis can control the shapes of metal nanocrystals by minimizing their surface energy via preferential coordination on specific facets, surface ligands properly coordinated on metal nanoparticles readily promote their catalysis via steric interactions and electronic modifications. The difficulty in the research of surface coordination chemistry of nanomaterials mainly lies in the lack of effective tools to characterize their molecular surface coordination structures. Also highlighted are several model material systems that facilitate the characterizations of surface coordination structures, including ultrathin nanostructures, atomically precise metal nanoclusters, and atomically dispersed metal catalysts. With the understanding of surface coordination chemistry, the molecular mechanisms behind various important effects (e.g., promotional effect of surface ligands on catalysis, support effect in supported metal nanocatalysts) of metal nanomaterials are disclosed.
纳米材料的表面配位化学研究的是配体在表面金属原子上的配位方式以及它们在分子水平上如何影响其性质。本文展示了表面配位化学与形貌可控合成之间存在着紧密的联系，以及金属纳米材料的许多有趣的表面性质。在合成过程中引入的小分子吸附物可以通过在特定晶面上优先配位来最小化表面能，从而控制金属纳米晶的形状，而在金属纳米粒子上适当配位的表面配体则可以通过空间位阻和电子修饰来促进其催化作用。纳米材料表面配位化学研究的难点主要在于缺乏有效的工具来表征其分子表面配位结构。本文还重点介绍了几个模型材料体系，这些体系有助于表面配位结构的表征，包括超薄纳米结构、原子精确的金属纳米团簇和原子分散的金属催化剂。通过对表面配位化学的理解，可以揭示金属纳米材料中各种重要效应（例如表面配体对催化的促进作用、负载型金属纳米催化剂中的载体效应）的分子机制。
