@article{Huang2022, 
author = {Baoyu Huang and Xiaomei Zhao and Yong Pei},
title = {Three-stage alloying of [Ag44(p-MBA)30]4− cluster with [Au2(p-NTP)2Cl]−},
year = {2022},
journal = {Nano Research},
volume = {15},
number = {8},
pages = {7742-7751},
keywords = {metal cluster, alloying mechanism, density functional theory (DFT) calculations, metal exchange},
url = {https://www.sciopen.com/article/10.1007/s12274-022-4364-9},
doi = {10.1007/s12274-022-4364-9},
abstract = {Precise control of alloying sites has long been a challenge, yet little has been achieved in the atomic-level manipulation of metallic nanomaterials. This study reported a three-stage metal and motif exchange mechanism of alloying reaction of an atomically precise ligand-protected [Ag44(p-MBA)30]4− (p-MBA = para-mercaptobenzoic acid) cluster with [Au2(p-NTP)2Cl]− (p-MBA = para-mercaptobenzoic acid). During the first stage (Stage I), an exchange of ligand-shell metal atoms took place. During the second stage (Stage II), the motif exchanged on the [AuAg43(p-MBA)30]4− cluster. During the third stage (Stage III), the Au(I) atom in the ligand-shell was swapped with a Ag(0) atom of the icosahedral Ag12-core. The density functional theory (DFT) calculation results demonstrated that the metal exchange proceeded via different mechanisms at the different reaction stages. In reaction Stages I and II, the metal exchange proceeded via formation of a dianionic [Ag44(p-MBA)30]4−-[Au2(p-NTP)2Cl]− intermediate and then broke and recombined with the ligand-shell. In Stage III, the diffusion of the Au(I) to icosahedral Ag12-core (Stage III) was proceeded via a motif catalyzed heterometal atom diffusion mechanism. We hope that this work will provide a new perspective for the precise control of alloy position in alloyed nanomaterials.}
}