Site-Selective Doping and Oxidation State Control of Copper in Gold Nanorods

Abstract We report the synthesis of plasmonic gold–copper nanostructures with tunable copper spatial distribution and oxidation state. Au–Cu alloy shells were deposited in aqueous solution onto colloidal gold nanorods that functioned as seeds, and the resulting shell morphology was found to depend strongly on the nanorod aspect ratio. For relatively fat gold nanorods (16 × 31 nm), Au–Cu growth was preferentially localized near the rod midsections, forming belt-like structures, whereas for skinnier nanorods (9 × 32 nm), Au–Cu growth produced patchy surface coverage around the entire rod. The shell thickness was tuned from 1 to 4 nm; upon air exposure, thicker shells exhibited a higher Cu(I) fraction compared to the initial shell. Incorporation of the Au–Cu shell led to pronounced shifts in the plasmonic features of the gold nanorods. These tunable plasmonicAu–Cu nanorods provide a materials basis for Cu-based plasmonic materials in the context of electrochemical CO2 reduction.