Zhu Chen, Chen Ze-Le, Li Hao, Lu Luyao, Kang Xi, Xuan Jun, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui 230601, China.
J Am Chem Soc. 2024 Aug 21;146(33):23212-23220. doi: 10.1021/jacs.4c05530. Epub 2024 Jul 31.
Analyzing the molecular structure-photophysical property correlations of metal nanoclusters to accomplish function-oriented photocatalysis could be challenging. Here, the selective heteroatom alloying has been exploited to a nanocluster, making up a structure-correlated nanocluster series, including homogold , bimetallic and , trimetallic , and tetrametallic . Their structure-dependent photophysical properties were investigated due to the atomically precise structures of these nanoclusters. Cu-alloyed showed intense phosphorescence and the highest singlet oxygen production efficiency. Moreover, the generation of O species from excited nanoclusters enabled as a suitable catalyst for efficient photocatalytic oxidation of silyl enol ethers to produce α,β-unsaturated carbonyl compounds. The generality and applicability of the catalysts toward different photocatalytic oxidations were assessed. Overall, this study presents an intriguing -based cluster series enabling an atomic-level understanding of structure-photophysical property correlations, which hopefully provides guidance for the fabrication of cluster-based catalysts with customized photocatalytic performance.
分析金属纳米团簇的分子结构与光物理性质的相关性以实现功能导向的光催化可能具有挑战性。在此，已将选择性杂原子合金化应用于纳米团簇，构成了一个与结构相关的纳米团簇系列，包括纯金、双金属、三金属和四金属纳米团簇。由于这些纳米团簇具有原子精确的结构，因此研究了它们与结构相关的光物理性质。铜合金化的纳米团簇表现出强烈的磷光和最高的单线态氧产生效率。此外，激发态纳米团簇产生的氧物种使该纳米团簇成为将硅烯醇醚高效光催化氧化以生成α,β-不饱和羰基化合物的合适催化剂。评估了该纳米团簇催化剂对不同光催化氧化反应的通用性和适用性。总体而言，本研究提出了一个有趣的基于纳米团簇的系列，能够在原子水平上理解结构与光物理性质的相关性，有望为制备具有定制光催化性能的基于团簇的催化剂提供指导。
