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Au nanobipyramids (NBPs) are important nanostructures which attract much attention due to their unique structure, optical, and catalytic properties. The controlled synthesis of Au NBPs and corresponding mechanistic study are highly desirable for both fundamental research and practical applications. Herein, we demonstrate a strategy that large sized Au decahedra with well-defined shape act as seeds for growing NBPs. Furthermore, through using different sized decahedra seeds with edge from 25 to 49 nm, various sized NBPs can be easily prepared (longitudinal length from 110 to 210 nm; transverse length from 36 to 70 nm). Our study provides hard evidence for the growth of NBPs that they surely stem from the overgrowth on penta-twinned decahedra. Because these used large size seeds have well-defined shape and structure, the growth of the NBPs can be easily determined. Results show that the formation of NBPs is primarily determined by the molar ratio of Au(3+) and Au seeds (MRAA). MRAA less than 4 only causes size enhancement and no significant shape change. In cases of MRAA higher than 4 and lower than 8, quasi-nanorods are produced. When MRAA range from 8 to 10, NBPs form and the yield is higher than 90%. The effect of reaction time and temperature also are vital to the growth of NBPs. These prepared NBPs are found to exhibit excellent surface enhanced Raman scattering (SERS) performance because of many present hotspots, edges, steps, and tips on their surfaces.

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