Plasmonic Ag nanostructures have been of great interest for such applications in cancer therapy and catalysis, etc. However, the relatively week Ag-Ag interaction and spontaneous atom diffusion make it very difficult to generate concaved or branched structures in Ag nanocrystals with sizes less than 100 nm, which has been considered very favorable for plasmonic effects. Herein, by employing a cubic Pd seed and a specific reducing agent to restrict the surface diffusion of Ag atoms, Pd@Ag core-shell nanooctapod structures where Ag atoms can be selectively deposited onto the corner sites of the Pd cubes were obtained. Such selective decoration enables us to precisely control the locations for the hot spot formation during light irradiation. We find that the branched nanooctapod structure shows strong absorption in the visible-light region and generates intense hot spots around the octapod arms of Ag. As such, the photothermal conversion efficiency could be significantly improved by more than 50% with a colloid solution containing only ppm-level nanooctapods compared with pure water. The reported nanostructure is expected to find extensive applications due to its controlled formation of light-induced hot spots at certain points on the crystal surface.

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