The combination of two or more metals, forming alloys, core−shells, or other complex heterometallic nanostructures, has substantially spanned the available options to finely tune electronic and structural properties, opening a myriad of opportunities that has yet to be fully explored in different fields. In catalysis, the rational exploitation and design of bimetallic and trimetallic catalysts has just started. Several major aspects such as stability, phase segregation, and alloy− dealloy mechanisms have yet to be deeply understood and correlated with intrinsic factors such as nanoparticle size, composition, and structure and with extrinsic factors, or external agents, such as temperature, reaction gases, and support. Here, by combining model catalysts based on AuCu nanoparticles supported on silica or alumina with in situ characterization techniques under redox pretreatments and CO oxidation reaction, we demonstrate the crucial role of the support with regard to determining the stable active phase of bimetallic supported catalysts. This strategy, associated with theoretical studies, could lead to the rational design of unique active sites.

We demonstrate the fabrication of various types of heterostructures, including core-shells and dimers. This is achieved by reacting platelet-shaped covellite (CuS) nanocrystals (NCs) with Au ions under various reaction conditions: the exposure of CuS NCs to Au ions, in the presence or in the absence of ascorbic acid (AA), leads to the formation of CuS@Au core-shell nanostructures; the reaction of CuS NCs with Au ions in the presence of oleylamine (OM) leads to the formation of CuS@AuS; the presence of both OM and AA leads to the formation of Au/CuS dimers. Depending on which condition is chosen, either cation exchange (CE) between gold and copper ions is predominant (leading to amorphous AuS) or the reduction of Au leads to the nucleation of metallic Au domains (which are operated by the AA). In the heterostructures achieved by CE, the AuS shell is almost entirely amorphous, and can be converted to polycrystalline upon electron beam irradiation. Finally, when both oleylamine and AA are present in the reaction environment, Au/CuS dimers are formed due to the reduction of Au to metallic Au domains which nucleate on top of the CuS seeds. The experimental dual plasmonic bands of the CuS@Au core-shells and Au/CuS dimers are in agreement with the theoretical optical simulations. The procedures described here enable the synthesis of core-shell nanostructures with tunable localized surface plasmon resonances (LSPRs) in the near-infrared (NIR) region, and of plasmonic metal/semiconductor heterostructures with LSPRs in both the NIR and the visible regions.

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We report the colloidal synthesis of dumbbell-like AuCu@FeO nanocrystals (AuCu@FeOx NCs) and the study of their properties in the CO oxidation reaction. To this aim, the as-prepared NCs were deposited on γ-alumina and pretreated in an oxidizing environment to remove the organic ligands. A comparison of these NCs with bulk FeO-supported AuCu NCs showed that the nanosized support was far more effective in preventing the sintering of the metal domains, leading thus to a superior catalytic activity. Nanosizing of the support could be thus an effective, general strategy to improve the thermal stability of metallic NCs. On the other hand, the support size did not affect the chemical transformations experienced by the AuCu NCs during the activation step. Independently from the support size, we observed indeed the segregation of Cu from the alloy phase under oxidative conditions as well as the possible incorporation of the Cu atoms in the iron oxide domain.

Au1−xCux alloy nanoparticles synthesized by one-pot colloidal method with an accurate control of composition by the temperature and insights about the mechanism.