Core–shell Ag@Au nanoprisms are prepared through a surfactant‐free seed‐mediated approach by taking advantage of the anisotropic structure of silver nanoprisms as seeds. The gold coating on the silver nanoprism surface is achieved by using hydroxylamine as a mild reducing agent, and the final fully gold‐coated prism structures are confirmed by microscopic and spectroscopic characterization. The resulting Ag@Au core–shell structure preserves the optical signatures of nanoprisms and offers versatile functionality and particularly better stability against oxidation than the bare silver nanoprism. The surface plasmon resonances of the core–shell Ag@Au nanoprisms can be tuned throughout the visible and near‐IR range as a function of the Au shell thickness. Such tailorable optical features and surfactant‐free gold shells have great potential applications in biosensing and bioimaging.
Ultrathin triangular gold nanoframes are synthesized in high yield through selective gold deposition on the edges of triangular silver nanoprisms and subsequent silver etching with mild wet etchants. These ultrathin gold nanoframes are surfactant-free with tailorable ridge thickness from 1.8 to 6 nm and exhibit adjustable and distinct surface plasmon resonance bands in the visible and near-IR region. In comparison, etching of the nanoprism template by galvanic replacement can only create frame structures with much thicker ridges, which have much lower catalytic activity for 4-nitrophenol reduction than the ultrathin gold nanoframes.
Bimetallic hollow, porous noble metal nanoparticles are of broad interest for biomedical, optical and catalytic applications. The most straightforward method for preparing such structures involves the reaction between HAuCl and well-formed Ag particles, typically spheres, cubes, or triangular prisms, yet the mechanism underlying their formation is poorly understood at the atomic scale. By combining in situ nanoscopic and atomic-scale characterization techniques (XAFS, SAXS, XRF, and electron microscopy) to follow the process, we elucidate a plausible reaction pathway for the conversion of citrate-capped Ag nanospheres to AgAu nanocages; importantly, the hollowing event cannot be explained by the nanoscale Kirkendall effect, nor by Galvanic exchange alone, two processes that have been previously proposed. We propose a modification of the bulk Galvanic exchange process that takes into account considerations that can only occur with nanoscale particles. This nanoscale Galvanic exchange process explains the novel morphological and chemical changes associated with the typically observed hollowing process.
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