In recent decade, Au nanoclusters of atomic precision (AunLm, where L= organic ligand: thiolate andphosphine) have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique ele...In recent decade, Au nanoclusters of atomic precision (AunLm, where L= organic ligand: thiolate andphosphine) have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique electronic properties and frameworks, providing an excellent opportunity to correlate theintrinsic catalytic behavior with the cluster's framework as well as to study the catalytic mechanismsover gold nanoclusters. In this review, we only demonstrate the important roles of the gold nanoclustersin the oxygen activation (e.g., 302 to 102) and their selective oxidations in the presence of oxygen (e.g., COto C02, sulfides to sulfoxides, alcohol to aldehyde, styrene to styrene epoxide, amines to imines, andglucose to gluconic acid). The size-specificity (Au25 (1.3 nm), Au38 (].5 nm), Au144 (1.9 nm), etc.), ligandengineering (e.g., aromatic vs aliphatic), and doping effects (e.g., copper, silver, palladium, and platinum)are discussed in details. Finally, the proposed reactions' mechanism and the relationships of clusters'structure and activity at the atomic level also are presented.展开更多
基金financial support by the Program for the Outstanding Innovative Teams of Higher Learning Institutions of Shanxi(OIT)Shanxi Province Hundred Talent Project
文摘In recent decade, Au nanoclusters of atomic precision (AunLm, where L= organic ligand: thiolate andphosphine) have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique electronic properties and frameworks, providing an excellent opportunity to correlate theintrinsic catalytic behavior with the cluster's framework as well as to study the catalytic mechanismsover gold nanoclusters. In this review, we only demonstrate the important roles of the gold nanoclustersin the oxygen activation (e.g., 302 to 102) and their selective oxidations in the presence of oxygen (e.g., COto C02, sulfides to sulfoxides, alcohol to aldehyde, styrene to styrene epoxide, amines to imines, andglucose to gluconic acid). The size-specificity (Au25 (1.3 nm), Au38 (].5 nm), Au144 (1.9 nm), etc.), ligandengineering (e.g., aromatic vs aliphatic), and doping effects (e.g., copper, silver, palladium, and platinum)are discussed in details. Finally, the proposed reactions' mechanism and the relationships of clusters'structure and activity at the atomic level also are presented.