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Role of Au(I) Intermediates in the Electrochemical Formation of Highly Anisotropic Gold Nanostructures with Near-IR SERS Applications
In
the presence of certain stabilizing ligands, such as pyridine
derivatives, the reduction of AuÂ(III) ions has been speculated to
generate AuÂ(I) intermediates that may play a key role in nanoparticle
growth. Herein, the electrochemical behavior of AuÂ(III) in the presence
of 4-methoxypyridine, Py, is reported in aqueous electrolytes. Voltammetric
analysis reveals that a spontaneously formed AuÂ(III)–Py complex
undergoes a two-step reduction process. The first reduction involves
the transfer of two electrons and produces a AuÂ(I) species. A more
cathodic one-electron transfer results in electrodeposited gold. Sustained
generation of the AuÂ(I)–Py intermediate species produced from
the first reduction step leads to disproportionation and the formation
of aggregated nanoparticle meshes that loosely adhere to the ITO electrode.
Conversely, application of more negative potentials leads to the formation
of highly anisotropic nanodaggers from the electrodeposition of the
AuÂ(I) species. The shape-directing properties of Py adsorbed on the
nucleated gold result in preferential ⟨111⟩ growth.
The length scale of the deposited dagger-like shapes is dependent
on deposition potential and deposited charge, and arms extending several
hundred nanometers are reported. Optical characterizations show extinction
extending well into the near-infrared region, which is attributed
to localized surface plasmonic resonances. Near-IR Raman sensing applications
are demonstrated using FT-Raman with 1064 nm excitation. The nanodaggers
provide SERS enhancement factors greater than 10<sup>6</sup> for monolayers
of 4-aminothiophenol