金团簇二十面体结构融合过程中其催化活性的演变

近年来,由有机配体保护的原子精确金属团簇在合成方面已取得了重要进展,其独特的原子结构对一些化学反应产生独特的催化效果.原子精确的团簇催化剂明显不同于纳米颗粒催化剂和单原子催化剂,是一种关联均相和多相的、原子数目确定、尺寸均一、结构精确的新型催化剂.从原子尺度上精确构筑团簇催化剂,探究亚纳米尺度的微观结构对催化性能的影响...

Evolutionofcatalyticactivitydrivenbystructuralfusionoficosahedralgoldclustercores

Atomically precise gold cluster catalysts have emerged as a new frontier in catalysis science, owing to their unexpected catalytic properties. In this work, we explore the evolution of the catalytic activ-ity of clusters formed by the structural fusion of icosahedral Au13 units, namely Au25(SR)18, Au38(SR)24, and Au25(PPh3)10(SC2H4Ph)5Cl2, in the oxidation of pyrrolidine to γ-butyrolactam. We demonstrate that the structural fusion of icosahedral Au13 units, forming vertex-fused (vf), face-fused (ff), and body-fused (bf) clusters, can induce a decrease in the catalytic activity in the following order: Aubf > Auff > Auvf. The structural fusion of icosahedral Au13 units in the clusters does not distinguish the adsorption modes of pyrrolidine over the three clusters from each other, but modulates the chemical adsorption capacity and electronic properties of the three clusters, which is likely to be the key reason for the observed changes in catalytic reactivity. Our results are expected to be extendable to study and design atomically defined catalysts with elaborate structural patterns, in order to produce desired products.