Seeded-Growth Aqueous Synthesis of Colloidal-Stable Citrate-Stabilized Au/CeO₂ Hybrid Nanocrystals: Heterodimers, Core@Shell, and Clover- and Star-Like Structures

Well-defined colloidal-stable citrate-stabilized Au/CeO2 hybrid nanocrystals (NCs) with coherent quasi-epitaxial interfaces and unprecedented control of their architectural and morphological characteristics have been synthesized via a novel and straightforward seeded-growth aqueous approach. The synthetic strategy, based on the identification of the experimental conditions under which the heterogeneous nucleation and growth processes of CeO2 onto presynthesized Au are controlled, allows for the fine adjustment of each individual domain in the structure, particularly the size of the Au core (from 5 to 100 nm), the thickness of the CeO2 shell (from 5 to 20 nm), and the growth mode of CeO2 onto Au NCs (from core@shell to heterodimer, clover- and star-like structures). This morphological control is achieved by the rational use of sodium citrate, which plays multiple key roles, as a reducer and stabilizing agent in the preparation of Au NCs, and as a complexing agent of Ce3+ for its controlled oxidation and hydrolysis during the subsequent CeO2 deposition. The resultant Au/CeO2 NCs remain stable and well-dispersed in water, allowing us to study the impact of fine variations of the NC structure on the underlying optical response. This level of morphological control, as well as the ease by which such well-defined nanostructures are produced, opens new opportunities for systematically investigating the interactions between individual components in designing more advanced complex NCs. Remarkably, because no organic solvents are used and no toxic waste is formed during the reaction, the proposed synthesis method can be defined as sustainable, viable, and cost-effective.