Liu Xu, Yao Guo, Cheng Xinglian, Xu Jiayu, Cai Xiao, Hu Weigang, Xu Wen Wu, Zhang Chunfeng, Zhu Yan
School of Chemistry and Chemical Engineering, Nanjing University Nanjing 210093 China
School of Physics, Nanjing University Nanjing 210093 China.
Chem Sci. 2021 Jan 5;12(9):3290-3294. doi: 10.1039/d0sc05163b.
With atomically precise gold nanoclusters acting as a starting unit, substituting one or more gold atoms of the nanocluster with other metals has become an effective strategy to create metal synergy for improving catalytic performances and other properties. However, so far detailed insight into how to design the gold-based nanoclusters to optimize the synergy is still lacking, as atomic-level exchange between the surface-gold (or core-gold) and the incoming heteroatoms is quite challenging without changing other parts. Here we report a Cd-driven reconstruction of Au(DMBT) (DMBT = 3,5-dimethylbenzenethiol), in which four Au(DMBT) staples are precisely replaced by two AuCd(DMBT) staples to form AuCd(DMBT) with the face-centered cubic inner core retained. With the dual modifications of the surface and electronic structure, the AuCd(DMBT) nanocluster exhibits distinct excitonic behaviors and superior photocatalytic performances compared to the parent Au(DMBT) nanocluster.
以原子精确的金纳米团簇作为起始单元，用其他金属取代纳米团簇中的一个或多个金原子已成为一种有效的策略，可用于创造金属协同效应以改善催化性能和其他性质。然而，到目前为止，对于如何设计金基纳米团簇以优化协同效应仍缺乏详细的见解，因为在不改变其他部分的情况下，表面金（或核心金）与引入的杂原子之间的原子级交换极具挑战性。在此，我们报道了Cd驱动的Au(DMBT)（DMBT = 3,5 - 二甲基苯硫醇）的重构，其中四个Au(DMBT)配体被两个AuCd(DMBT)配体精确取代，形成了保留面心立方内核的AuCd(DMBT)。通过表面和电子结构的双重修饰，与母体Au(DMBT)纳米团簇相比，AuCd(DMBT)纳米团簇表现出独特的激子行为和优异的光催化性能。
