A robust method for epitaxial deposition of Au onto the surface of Ag nanostructures is demonstrated, which allows effective conversion of Ag nanostructures of various morphologies into Ag@Au counterparts, with the anisotropic ones showing excellent plasmonic properties comparable to the original Ag nanostructures while significantly enhanced stability. Sulfite plays a determining role in the success of this epitaxial deposition as it strongly complexes with gold cations to completely prevent galvanic replacement while it also remains benign to the Ag surface to avoid any ligand‐assisted oxidative etching. By using Ag nanoplates as an example, it is shown that the corresponding Ag@Au nanoplates possess remarkable plasmonic properties that are virtually Ag‐like, in clear contrast to Ag@Au nanospheres that exhibit much lower plasmonic activities than their Ag counterparts. As a result, they display high durability and activities in surface‐enhanced Raman scattering applications. This strategy may represent a general platform for depositing a noble metal on less stable metal nanostructures, thus opening up new opportunities in rational design of functional metal nanomaterials for a broad range of applications.
Plasmonic noble metal nanoparticles with defined interior nanogaps are of great significance to surface-enhanced Raman spectroscopy (SERS) applications owing to the presence of intraparticle hotspots. In this contribution, we discovered site-selective nonepitaxial growth of Au on nonmetallic AgI nanocrystals, and on the basis of this observation, we designed an unconventional route to synthesize monometallic Au nanoframes that possess ∼7 nm of interior nanogaps and ∼23 nm of overall size by templating of small AgI nanocrystals. Chemical bonding between Au and the iodide-rich surface of the AgI nanocrystals was proposed to play a critical role in the nonepitaxial growth of the Au nanoframes against the AgI nanocrystals. The Au nanoframes obtained from this synthesis showed superior SERS activity in detecting molecules of interest in low concentrations owing to the presence of intraparticle hotspots in additional to the interparticle ones, benchmarking against Au nanospheres. This intriguing synthesis may open up new opportunities toward a variety of noble metal/semiconductor nanoconjugates for a broad range of applications such as synergistic catalysis.
Noble metal nanostructures are currently of great interest for their unique plasmonic property and potential applications in catalysis and surface-enhanced spectroscopy. However, the application of plasmonic nanostructures for quantitatively in situ SERS monitoring of the catalytic reaction has been a great challenge for investigators because combining plasmonics with catalysis requires the same kind of noble metal nanoparticles (NPs) in two very different size regimes. Herein, We have demonstrated a facile wet chemical method to synthesize Au-Ag alloy plasmonic NPs that could combine the desired plasmonic and catalytic properties with same NPs. The catalytic activity of Au-Ag alloy NPs using the reduction of 4-nitrothiophenol (4-NTP) by sodium borohydride (NaBH 4) is chosen as a model reaction. The signals of the reaction processes are detected and identified through in situ SERS spectroscopy with high sensitivity. The insights gained by current study may serve as a promising and powerful technique for better investigation in the heterogeneous catalysis. Moreover, the reduction of aromatic nitro compounds with prepared Au-Ag alloy NPs also provides potential application in sewage treatment.
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