Controlling the Morphology of Au-Pd Heterodimer Nanoparticles by Surface Ligands

Controlling the morphology of noble-metal nanoparticles is mandatory to tune specific properties such as catalytic and optical behavior. Heterodimers consisting of two noble metals have been synthesized, so far mostly in aqueous media using selective surfactants or chemical etching strategies. We report a facile synthesis for Au@Pd and Pd@Au heterodimer nanoparticles (NPs) with morphologies ranging from segregated domains (heteroparticles) to core-shell structures by applying a seed-mediated growth process with Au and Pd seed nanoparticles in 1-octadecene (ODE), which is a high-boiling organic solvent. The as-synthesized oleylamine (OAm) functionalized Au NPs led to the formation of OAm-Au@Pd heteroparticles with a "windmill" morphology, having an Au core and Pd "blades". The multiply twinned structure of the Au seed particles (⌀ ≈ 9-11 nm) is associated with a reduced barrier for heterogeneous nucleation. This leads to island growth of bimetallic Au@Pd heteroparticles with less-regular morphologies. The reaction process can be controlled by tuning the surface chemistry with organic ligands. Functionalization of Au NPs (Ø ≈ 9-11 nm) with 1-octadecanethiol (ODT) led to the formation of ODT-Au@Pd NPs with a closed Pd shell through a strong ligand-metal binding, which is accompanied by a redistribution of the electron density. Experiments with varied Pd content revealed surface epitaxial growth of Pd on Au. For OAm-Pd and ODT-Pd seed particles, faceted, Au-rich domain NPs and impeded core-shell NPs were obtained, respectively. This is related to the high surface energy of the small Pd seed particles (⌀ ≈ 5-7 nm). The metal distribution of all bimetallic NPs was analyzed by extended (aberration-corrected) transmission electron microscopy (HR-TEM, HAADF-STEM, EDX mapping, ED). The Au and Pd NPs, as well as the ODT-Au@Pd and OAm-Pd@Au heteroparticles, catalyze the reduction of 4-nitrophenol to 4-aminophenol with borohydride. The catalytic activity is dictated by the particle structure. OAm-Au@Pd heteroparticles with faceted Au domains had the highest activity because of a mixed Au-Pd surface structure, while ODT-Au@Pd NPs, where the active Au core is covered by a Pd shell, had the lowest activity.