Twin plane decoration of silver nanorods with palladium by galvanic exchange at a controlled rate

Here we describe the galvanic exchange of surface-grown Ag nanorods (NRs) and nanowires (NWs) with PdCl(4)(2-) as a function of the PdCl(4)(2-) concentration. The morphology of the resulting AgPd alloy nanostructures depends on the galvanic exchange rate, which increases with increasing PdCl(4)(2-) concentration over a specific concentration range. When the concentration of PdCl(4)(2-) exceeds 7.5 × 10(-5) M (or ratio of moles of PdCl(4)(2-) in solution to moles of Ag on the surface542), rapid galvanic exchange results in Pd deposition over the entire Ag nanostructure in the early stages of exchange. When the concentration of PdCl(4)(2-) is in the range of 1.0 × 10(-5) to 5.0 × 10(-5) M (moles of PdCl(4)(2-) in solution to moles of Ag on the surface = 13-54), Pd deposition occurs preferentially at high energy twin plane defects in the form of well-spaced nanoparticles during the early stages of exchange. In later stages, the Pd deposits grow and coalescence into a rough shell, and etching of the Ag leads to a presumably hollow nanostructure. Composition analysis by linear sweep voltammetry as a function of time shows that the galvanic exchange rate is much slower than the diffusion-limited rate and, when correlated with UV-vis spectroscopy, shows that less than 10% Pd in the nanostructure completely dampens the Ag-localized surface plasmon band.