Formation of Core-Shell AuCu@Ag Nanocrystals through the Nanoscale Kirkendall Effect

Polymetallic nanocrystals (NCs) consist of multiple metal elements. A powerful platform to achieve the flexible construction of polymetallic NCs is highly desired but challenging. Herein, we devise a model system that realizes metal atom diffusion between different NCs, resulting in the formation of polymetallic NCs. The differential bond strength between different metal atoms is proposed to initiate such metal atom diffusion, and the specific high surface-to-volume ratio of the NCs can expedite the diffusion process. Taking the Au-Cu-Ag trimetallic system as an example, core-shell AuCu@Ag NCs were successfully formed by combining AgCu NCs with Au NCs. The evolution process was explored, and the gradual fusion of simple NCs into AuCu@Ag NCs was unambiguously observed, which could be attributed to the larger bond strength of Au-Cu than that of Ag-Cu. This work offers an opportunity/platform in theory and experiment to expand the synthesis framework as well as the polymetallic NC list.