We report the seed-dependent shape evolution of gold@silver (Au@Ag) core-shell nanostructures with various morphologies through using pre-existing Au nanocrystals as nuclei in a polyvinylpyrrolidone (PVP)-assisted polyol reduction process. Au nanocrystalline seeds with different shapes such as cube, truncated-octahedron, octahedron, twinned hexagon and triangle, five-twinned decahedron and nanorod are firstly synthesized by refluxing a 1,5-pentanediol solution containing Au precursors in the presence of PVP. The Au seeds obtained in this way then serve as the nuclei for further epitaxial growth of Ag shells by using Ag precursors via the same route. Scanning transmission electron microscope (STEM) characterization of the products obtained demonstrates that the morphological evolution of the Ag shells depends completely on the shapes of the Au seeds that are used. We have observed that the Au@Ag core-shell nanostructures formed with various regular shapes such as cube, bi-triangle, and nanorod with five-twinned cross section, are mostly surrounded by {100}-type Ag crystalline facets. Our findings provide new evidence and clear evolution routines from the Au cores with well-defined shapes to the corresponding Ag shells for the Au@Ag core-shell nanostructures by the family of the PVP-assisted polyol reduction methods.

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