Diffusion and seed shape: intertwined parameters in the synthesis of branched metal nanostructures

Branched nanocrystals display interesting optical and catalytic properties on account of their high surface areas and tips with small radii of curvatures. However, many synthetic routes toward branched nanocrystals result in inhomogeneous samples on account of asymmetric branching. Seed-mediated coreduction is a recently developed route to symmetrically branched nanocrystals where the symmetry of the seeds is transferred to the final stellated morphologies. Here, general guidelines to stellated nanocrystals are outlined by surveying coreduction of Au and Pd precursors in the presence of a variety of shape-controlled Au seeds to achieve Au/Pd nanostructures. Single-crystalline, twinned, and anisotropic seeds were analyzed to expand the classes of stellated nanostructures synthetically accessible. Significantly, single-crystalline Au seeds adopt {100}-terminated intermediates prior to branching, regardless of initial seed shape. We compared these results with those obtained with shape-controlled Pd seeds, and seed composition was identified as an important synthetic parameter, with Pd seeds being more resistant to shape changes during overgrowth. This difference is attributed to the greater diffusion rate of Au atoms on Au seeds compared to Au atoms on Pd seeds. These results provide guidelines for the seeded synthesis of symmetrically branched nanocrystals and architecturally defined bimetallic nanostructures in general.