Wang Jie, Xu Fan, Wang Zhao-Yang, Zang Shuang-Quan, Mak Thomas C W
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China.
Angew Chem Int Ed Engl. 2022 Aug 8;61(32):e202207492. doi: 10.1002/anie.202207492. Epub 2022 Jun 28.
Subtle tailoring of gold nanoclusters (NCs) could significantly change their physicochemical properties. However, direct comparison of the catalytic performance of gold NCs with identical metal cores but distinct ligand shells is rarely elucidated. In this work, a novel gold NC, Au (C B H S) (tht) Cl (Au -S), was isolated by a facile self-reducing synthesis. Au -S adopts an identical Au metal framework to that of the reported alkynyl-protected Au -C. The different protective layers lead to distinctions in their electronic structure and optical properties. Furthermore, Au -S shows better catalytic activity for the electrochemical reduction of CO to CO. Theoretical calculations identified the active sites and shed light on the catalytic mechanism to elucidate the different catalytic performances. This work provides an ideal platform to study the protective layer-activity relationship of gold NCs, and may also provide guidance in the design of metal NC-based catalysts.
对金纳米团簇（NCs）进行精细剪裁可显著改变其物理化学性质。然而，对于具有相同金属核但配体壳不同的金纳米团簇的催化性能进行直接比较的研究却很少见。在这项工作中，通过简便的自还原合成方法分离出了一种新型金纳米团簇Au(CBHS)(tht)Cl（Au-S）。Au-S与已报道的炔基保护的Au-C具有相同的Au金属骨架。不同的保护层导致它们的电子结构和光学性质存在差异。此外，Au-S在将CO电化学还原为CO方面表现出更好的催化活性。理论计算确定了活性位点，并阐明了催化机理，以解释不同的催化性能。这项工作为研究金纳米团簇的保护层-活性关系提供了一个理想平台，也可能为基于金属纳米团簇的催化剂设计提供指导。
