Cu基金属纳米晶：结构调控和催化Ullmann反应研究

Ullmann reaction, as an important way to build aromatic carbon-carbon and carbon-hybrid bond, has been a hot area of research in organic synthesis. It has important scientific significance and industrial applications to develop new efficient catalysts for improving the Ullmann reaction. Compared to traditional Cu-based metal complex catalysts, Cu-based metal nanocrystal catalysts have some advantages including free of complexes, easy recovery, and easy control on catalytic activity and selectivity. This project focuses on: (1) developing synthetic methods for Cu-based metal nanocrystals and achieving controllable preparation of a series of Cu-based bimetallic and multi-metallic nanocrystals; (2) achieving structural control for Cu-based metal nanocrystals, investigating the influence of microstructure of nanocrystal catalysts on their catalytic performance for Ullmann reaction, and achieving control on catalytic activity and selectivity; (3) discovering new Ullmann reaction based on understanding the mechanism of nanocrystalline catalysts. This project helps to exploit novel Cu-based metal nanocrystal catalysts for Ullmann reaction and reveal the mechanism of nanocrystalline catalysts, and has scientific significance and practical value in developing Ullmann reaction and promoting its industrial applications.

Ullmann反应作为构建芳香碳-碳和碳-杂键的重要途径，一直是有机合成的研究热点之一。发展新型高效催化剂对于改进Ullmann反应具有重要的科学意义和工业应用价值。Cu基金属纳米晶催化剂相对于传统的Cu基金属配合物催化剂具有无配体、易回收、催化活性及选择性易于调控等优势。本项目拟：（1）发展Cu基金属纳米晶的合成方法，实现系列Cu基双金属及多金属纳米晶的可控制备；（2）实现Cu基金属纳米晶的结构调控，探索纳米晶催化剂结构对于催化Ullmann反应性能的影响，从而实现对Ullmann反应催化活性和选择性的调控；（3）在认识纳米晶催化剂作用机理的基础上发现新的Ullmann反应。本项目对于开发新型Cu基金属纳米晶催化剂、深入研究Cu催化Ullmann反应机理、扩展Ullmann反应类型及推动Ullmann反应的工业化应用具有重要意义。

Cu基金属纳米晶催化剂相对于传统的Cu基金属配合物催化剂具有无配体、易回收、催化活性及选择性易于调控等优势。该项目拟围绕Cu基金属材料合成方法学、组成与尺寸调控、微观结构表征、以及催化剂构效关系开展研究。项目的实施取得了系列重要进展：1，发展了系列合成方法学，实现了Cu-基金属纳米晶材料的可控合成，并进一步发展到Cu单原子及团簇材料的合成；2，通过典型探针反应，研究了具有不同结构特征的Cu-基金属材料的反应活性，明确了Cu-基金属材料微观结构和催化性能之间的关系，从原子层次上认识了Cu-基金属材料催化作用机理；3，针对Ullmann反应及其它重要的催化反应，实现了高性能Cu-基金属催化剂的设计和制备，并在此基础上探索了新的催化反应。项目执行期间共发表学术论文44篇，包括Proc. Natl. Acad. Sci. USA 1篇，Sci. Adv.1篇，Nature Commun.5篇，J. Am. Chem. Soc.7篇，Angew. Chem. Int. Ed.5篇，Adv. Mater.5篇，Energy Environ. Sci.1篇，Joule1篇等。项目研究成果对于开发新型Cu基金属纳米催化剂、深入研究Cu基金属催化剂作用机理及推动新型金属催化剂工业化应用具有重要意义。