The right combination: Shape and composition are two important factors governing the catalytic properties of bimetallic nanocatalysts. Combining gold and palladium in a Au‐core–Pd‐shell structure coupled with an icosahedral morphology is shown to maximize catalytic performance for the selective oxidation of the biorenewable sources glycerol and 1,2‐propanediol to glyceric and lactic acids, respectively.

Access to the full text of the published version may require a subscription. In order to develop nanocatalysts with enhanced catalytic performance, it is important to be able to synthesize nanocrystals enclosed by high-index surface facets, due to their high denisty of low coordinated atoms at step, ledge and kink sites. Here, we report a facile seed-mediated route to the synthesis of highly branched Pd nanostructures with a combination of {113}, {115} and {220} high-index surface planes. The size of these nanostructures is readily controlled by a simple manipulation of the seed concentration. The selective use of oleylamine and oleic acid was also found to be critical to the synthesis of these structures, with Pd icosahedra enclosed by low-index {111} facets being produced when hexadecylamine was employed as capping ligand. The structure-property relationship of these nanostructures as catalysts in Suzuki-cross coupling reactions was then investigated and compared, with the high-index faceted branched Pd nanostructures found to be the most effective catalysts. Rights