Electronic transfer as a route to increase the chemical stability in gold and silver core-shell nanoparticles.

This review article presents the collected recent findings and advancements in understanding and manipulating the electronic properties of the Au/Ag NP system from the standpoint of controlling the characteristics of heterostructured core-shell NPs. The discovery of the electronic transfer effect through analysis of both Ag-Au and Au-Ag type NPs inspired the analysis of the resulting enhanced properties. First, the background on the synthesis and characterization of Ag, Au, Ag-Au, Au-Ag and Au-Ag-Au NPs, which will be used as a basis for studying the electronic transfer and stability properties is presented. Next, Mie Theory is used to inspect the optical properties of the Ag-Au NPs, revealing subtle structural characteristics in these probes, which has implications to the plasmonic properties. This is followed by the inspection of the electronic properties of the Au-Ag NPs primarily through XPS and XANES analysis, revealing the origins of the electronic transfer phenomenon. The unique electronic properties are then revealed to result in improved particle stability in terms of susceptibility to oxidation. Finally, an assessment of the resulting enhanced plasmonic sensing properties is discussed. The results are presented in terms of synthesis technique, material characterization, understanding of the electronic properties and manipulation of those properties to create Au-Ag NPs with enhanced resistance to oxidation and galvanic replacement.

Chemical stabilization of gold coated by silver core-shell nanoparticles via electron transfer.

Silver nanoparticles are notoriously susceptible to oxidation, yet gold nanoparticles coated in silver exhibit a unique electronic interaction that occurs at the interface of the two metals, leading to enhanced stability properties for the silver shell. In order to probe the phenomenon, the stability of gold nanoparticles coated by silver was studied in the presence of various chloride-containing electrolytes. It was found that a critical silver shell thickness of approximately 1 nm exists that cannot be oxidatively etched from the particle surface: this is in contrast to the observation of complete oxidative etching for monometallic silver nanoparticles. The results are discussed in terms of particle composition, structure and morphology before and after exposing the particles to the electrolytes. Raman analysis of the reporter molecule 3-amino-1,2,4-triazole-5-thiol adsorbed on the particle surface illustrates the feasibility of using gold coated by silver nanoparticle probes in sensing applications that require the presence of high levels of salt. The results provide insight into the manipulation of the electronic and stability properties for gold- and silver-based nanoparticles.