金原子簇催化碳-碳偶联反应的研究进展（英文）  

A Critical Review on Carbon-Carbon Coupling over Ultra-Small Gold Nanoclusters

作　　者：周洋[1,2] 李杲[1] 

机构地区：[1]中国科学院大连化学物理研究所催化基础国家重点实验室,大连116023 [2]中国科学院大学,北京100049

出　　处：《物理化学学报》2017年第7期1297-1309,共13页Acta Physico-Chimica Sinica

摘　　要：近十几年来,金原子簇(尺寸1-2 nm)逐渐发展成为一种新型的纳米材料。特别在近几年中,金原子簇催化剂广泛地应用于纳米催化中,例如选择性氧化还原以及碳-碳偶联等反应。与传统的金纳米颗粒(>2 nm)显著不同,金原子簇具有独特的电子性质和结构,能很好地关联金原子簇催化剂的结构与其催化性能,特别是对金原子簇的催化反应机理的研究。在本综述中,我们阐明了金原子簇催化剂在碳-碳偶联反应中的应用,其中包括Ullmann、Sonogashira、Suzuki和A^3-偶联等反应。并进一步揭示了金原子簇表面有机配体(例如芳香烃硫醇vs脂肪烃硫醇)对催化反应的影响,以及其它金属在金核内部的掺杂(例如铜、银、铂、钯等)改变原子簇的电子结构从而来调控其催化性能。最后,在原子层面上关联金原子簇结构和催化性能,并初步探讨催化反应机制。金原子簇催化剂的深入研究将为高效金纳米催化剂的设计提供一些建设性的思路和策略。Well-defined gold nanoclusters have been documented as new and promising materials in the field of nanoscience. They have been well explored for the nanocatalysis of reactions like selective oxidation and hydrogenation, carbon-carbon coupling, etc. These Au nanoclusters possess unique electronic properties and crystal structure, which provide an excellent opportunity to correlate atomic structure with intrinsic catalytic property and to investigate the mechanisms of reactions over Au nanoclusters. In this review, we generalize the catalytic application of gold nanoclusters in carbon-carbon coupling reactions, including UIImann, Sonogashira, Suzuki, and A3-coupling reactions. Herein, we have discussed ligand engineering （e.g., aromatic and aliphatic thiolate） as well as the effect of metal dopants （e.g., Cu, Ag, Pt, and Pd）. Finally, the tentative catalytic mechanisms and the structure-performance relationships were discussed at the atomic level, which will give some clue for the design of efficient gold cluster catalysts.

关 键 词：金原子簇 碳-碳偶联 配体效应 金属掺杂效应 Ullmann偶联 Sonogashira交叉偶联 Suzuki交叉偶联 A3-偶联 

分 类 号：O621.251[理学—有机化学]