Reaction stoichiometry directs the architecture of trimetallic nanostructures produced via galvanic replacement

Galvanic replacement (GR) of monometallic nanoparticles (NPs) provides a versatile route to interesting bimetallic nanostructures, with examples such as nanoboxes, nanocages, nanoshells, nanorings, and heterodimers reported. The replacement of bimetallic templates by a more noble metal can generate trimetallic nanostructures with different architectures, where the specific structure has been shown to depend on the relative reduction potentials of the participating metals and lattice mismatch between the depositing and template metal phases. Now, the role of reaction stoichiometry is shown to direct the overall architecture of multimetallic nanostructures produced by GR with bimetallic templates. Specifically, the number of initial metal islands deposited on a NP template depends on the reaction stoichiometry. This outcome was established by studying the GR process between intermetallic PdCu (i-PdCu) NPs and either AuCl₂^- (Au¹⁺) or AuCl₄^- (Au³⁺), producing i-PdCu-Au heterostructures. Significantly, multiple Au domains form in the case of GR with AuCl₂^- while only single Au domains form in the case of AuCl₄^-. These different NP architectures and their connection to reaction stoichiometry are consistent with Stranski-Krastanov (SK) growth, providing general guidelines on how the conditions of GR processes can be used to achieve multimetallic nanostructures with different defined architectures.