Monday, 14 May 2018: 08:40
Room 211 (Washington State Convention Center)
It is appealing to develop and understand new approaches to generate anisotropic metal nanoparticles (NPs) owing to their application in optical-based sensing platforms. Empirically, the formation of anisotropic NPs is typically back-rationalized by speculating that shape-directing ions or molecules preferentially adsorb on different crystallographic facets of the growing particle. An alternative strategy is described herein whereby electrochemical measurements of pyridine-derivative adsorption on different low index single crystal surfaces conclusively demonstrate preferentially adsorption on Au(100} surfaces. This serves as a starting basis for developing rational approaches to generate homogeneous and heterogeneous anisotropic NPs through chemical and electrochemical reduction of AuIII precursors. The pyridine derivatives are shown to play a critical role in the formation of Au nanopods and nanodaggers. Electrochemical evidence is provided of a two-step reduction of tetrachloroaurate involving a pyridine-stabilized AuI species which plays a key role in producing anisotropic structures. Both electrodeposited and suspended NPs have surface plasmon resonances that extend well into the near IR (λmax ≈ 1000-1350 nm). Near-IR Raman sensing applications are demonstrated using FT-Raman with 1064 nm excitation. Electrodeposited nanodaggers provide SERS enhancement factors greater than 106 for monolayers of 4-aminothiophenol (4-ATP).