Ligand‐Guided Growth of Alloyed Shells on Intermetallic Seeds as a Route toward Multimetallic Nanocatalysts with Shape‐Control

Abstract Shape‐controlled core@shell PdCu@PtCu nanoparticles (NPs) were synthesized by seed‐mediated co‐reduction. Specifically, cubic‐shaped NPs were achieved by selecting tetraoctylammonium bromide (TOAB) and triphenylphosphine (TPP) as capping ligands. Their roles were investigated by incorporating independently each ligand into the reaction and analyzing the products by transmission electron microscopy (TEM). This analysis revealed that the quasi‐spherical PdCu seeds acquired cubic shapes during the synthesis and directed shell deposition. This process was mediated by TPP, which was central to achieving monodisperse NPs with shape‐control. The synthesis conditions were modified to tune both the thickness and composition of the shells. Evaluation of the NPs as catalysts for the electrooxidation of formic acid found that the NPs with the thinnest Pt‐rich shells gave the highest specific activity, with the nanocubic shape also enhancing performance with respect to the spherical counterpart. These results highlight the benefits of integrating compositional, architectural, and shape‐control all in one NP construct.