Silver nanocrystals embrace fascinating properties for a wide variety of applications, but their performance tends to deteriorate because of shape instability arising from the dissolution of Ag atoms from high-energy sites such as edges and vertices. This issue can be addressed by framing the particle with a more stable metal M for the generation of a Ag@M core-frame nanocrystal. In addition to the improvement in shape stability, the inclusion of metal M expands the functionality and capability of the Ag nanocrystals. The first part of this talk introduces two strategies for the rational synthesis of Ag-based core-frame nanocubes. The second part showcases the augmented properties of the Ag-based core-frame nanocrystals, in addition to some new functionality. The first example demonstrates how to preserve the shape of Ag nanocubes at an elevated temperature by passivating the vulnerable edges with Ir frames. The second example highlights the use of Ag-Pd core-frame nanocubes as a SERS probe for in situ monitoring the Pd-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol by NaBH<sub>4</sub> and the subsequent Ag-catalyzed oxidation of 4-ATP to <i>trans</i>-4, 4’-dimercaptoazobezene by the oxygen from air. The third example establishes a method for the transformation of Ag@Au-Au core-frame concave nanocubes into trimetallic cage cubes through a site-selective galvanic replacement reaction. Altogether, these studies demonstrate that the shape stability of Ag nanocrystals can be enhanced while introducing new functionality by framing their edges with a different metal.

Framing silver nanocrystals with a second metal to enhance shape stability and expand functionality

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