We report on a method for the preparation of uniform and length-variable Ag nanorods through anisotropic Ag overgrowth on high-purity Au nanobipyramids. The rod diameters can be roughly tailored from ∼20 nm to ∼50 nm by judicious selection of differently sized Au nanobipyramids. The rod lengths can be tuned from ∼150 nm to ∼550 nm by varying the Ag precursor amount during the overgrowth process and/or by anisotropic shortening through mild oxidation. The controllable aspect ratios, high purity, and high dimensional uniformity of these Ag nanorods enable the observation of Fabry-Pérot-like multipolar plasmon resonance modes in the colloidal suspensions at the ensemble level, which has so far been demonstrated only on Au nanorods prepared electrochemically with anodic aluminum oxide templates. Depending on the mode order and geometry of the Ag nanorods, the multipolar plasmon wavelengths can be readily tailored over a wide spectral range from the visible to near-infrared region. We have further elucidated the relationships between the multipolar plasmon wavelengths and the geometric dimensions of the Ag nanorods at both the ensemble and single-particle levels. Our results indicate that the Au nanobipyramid-directed, dimensionally controllable Ag nanorods will be an attractive and promising candidate for developing multipolar plasmon-based devices and applications.

Silver nanostructures with narrow plasmon linewidths and good chemical stability are strongly desired for plasmonic applications. Herein, a facile method is discussed for the preparation of Ag nanostructures with narrow plasmon linewidths and improved chemical stability through Ag overgrowth on monodispersed Au nanobipyramids. Structural evolution from bipyramid through rice to rod is observed, indicating that Ag atoms are preferentially deposited on the side surfaces of Au nanobipyramids. The resultant (Au nanobipyramid)@Ag nanostructures possess high size and shape uniformities, and much narrower plasmon linewidths than other Ag nanostructures. The spectral evolution of the supported Ag nanostructures is ascertained by both ensemble and single‐particle characterizations, together with electrodynamic simulations. Systematic measurements of the refractive index sensing characteristics indicate that Ag nanostructures in this study possess high index sensitivities and figure of merit (sensitivity divided by linewidth) values. Moreover, Ag nanostructures in this study exhibit greatly improved chemical stability. The superior sensing capability of Ag nanostructures in this study is further demonstrated by the detection of sulfide ions at a relatively low detection limit. Taken together, results of this study show that the Au‐nano­bipyramid‐supported Ag nanostructures will be an outstanding candidate for the design of ultrasensitive plasmonic sensing devices as well as for the development of other plasmon‐enabled technological applications.

The synthesis of anisotropic metal nanostructures is strongly desired for exploring plasmon-enabled applications. Herein, the preparation of anisotropic Au/SiO 2 and Au/SiO 2 /Pd nanostructures is realized through selective silica coating on Au nanobipyramids. For silica coating at the ends of Au nanobipyramids, the amount of coated silica and the overall shape of the coated nanostructures exhibit a bell-shaped dependence on the cationic surfactant concentration. For both end and side silica coating on Au nanobipyramids, the size of the silica component can be varied by changing the silica precursor amount. Silica can also be selectively deposited on the corners or facets of Au nanocubes, suggesting the generality of this method. The blockage of the predeposited silica component on Au nanobipyramids enables further selective Pd deposition. Suzuki coupling reactions carried out with the different bimetallic nanostructures functioning as plasmonic photocatalysts indicate that the plasmonic photocatalytic activity is dependent on the site of Pd nanoparticles on Au nanobipyramids. Taken together, these results suggest that plasmonic hot spots play an important role in hot-electron-driven plasmonic photocatalysis. This study opens up a promising route to the construction of anisotropic bimetallic nanostructures as well as to the design of bimetallic plasmonic-catalytic nanostructures as efficient plasmonic photocatalysts.

The synthesis of metal nanostructures with plasmon wavelengths beyond ∼1000 nm is strongly desired, especially for those with small sizes. Herein we report on a AgPd-tipping process on Au nanobipyramids with the resultant red plasmon shifts reaching up to ∼900 nm. The large red plasmon shifts are ascribed to the deposition of the metal at the tips of Au nanobipyramids, which is verified by electrodynamic simulations. The method has been successfully applied to Au nanobipyramids and nanorods with different longitudinal dipolar plasmon wavelengths, demonstrating that the plasmon wavelengths of these Au nanocrystals can be extended to the entire near-infrared region. Pt can also induce the tipping on Au nanobipyramids and nanorods to realize red plasmon shifts, suggesting the generality of our approach. We have further shown that the metal-tipped Au nanobipyramids possess a high photothermal conversion efficiency and good photothermal therapy performance. This study opens up a route to the construction of Au nanostructures with plasmon resonance in a broad spectral region for plasmon-enabled technological applications.