Rational Design of Highly Phosphorescent Nanoclusters for Efficient Photocatalytic Oxidation
Zhu Chen, Ze‐Le Chen, Hao Li, Luyao Lu, Xi Kang, Jun Xuan, Manzhou Zhu
Abstract
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 Au 15 nanocluster, making up a structure-correlated nanocluster series, including homogold Au 15, bimetallic Ag x Au 15– x and Cu x Au 15– x, trimetallic Ag x Cu y Au 15– x – y, and tetrametallic Pt 1 Ag x Cu y Au 15– x – y . Their structure-dependent photophysical properties were investigated due to the atomically precise structures of these nanoclusters. Cu-alloyed Cu x Au 15– x showed intense phosphorescence and the highest singlet oxygen production efficiency. Moreover, the generation of 1 O 2 species from excited nanoclusters enabled Cu x Au 15– x 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 Cu x Au 15– x catalysts toward different photocatalytic oxidations were assessed. Overall, this study presents an intriguing Au 15 -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.