Publication date: 15th December 2025
Electrodeposition offers control over nanocrystal growth through modulation of the applied current or potential, which governs precursor reduction kinetics, nucleation behavior, and local ion concentrations. However, conventional direct electrodeposition onto the working electrode often produces nanocrystals with ill-defined morphologies and aggregated states. This study introduces seed-assisted electrodeposition to overcome these limitations, enabling growth of structurally complex and compositionally well-defined multimetallic nanocrystals. We identify lattice mismatch and metal-metal bond dissociation energy as key parameters dictating the growth mode: high values of either parameter promote island-like overgrowth, while low lattice mismatch favors layer-by-layer growth. Guided by these mechanistic insights, we achieve uniform metal shell deposition across a range of bimetallic systems, including those exhibiting significant interfacial strain. Furthermore, we demonstrate the formation of hollow-shell nanocrystals by dynamically modulating the redox environment during growth and show the future scope of these structures for electrochemical C-N coupling. Collectively, these findings establish design principles for the electrochemical synthesis of complex multimetallic nanomaterials with tailored architectures.
The authors acknowledge financial support from Indiana University and the US National Science Foundation Division of Chemistry Center for Chemical Innovation Program Grant #2221062, Center for Single-Entity Nanochemistry and Nanocrystal Design (CSENND). The authors acknowledge support from Indiana University’s Electron Microscopy Center, and Nanoscale Characterization Facility for access to instrumentation.
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