Although multicomponent core-shell type nanomaterials are one of the highly desired structural motifs due to their simultaneous multifunctionalities, the fabrication strategy for such nanostructures is still in a primitive stage. Here, we present a redox-transmetalation process that is effective as a general protocol for the fabrication of high quality and well-defined core-shell type bimetallic nanoparticles on the sub-10 nm scale. Various core-shell type nanomaterials including Co@Au, Co@Pd, Co@Pt, and Co@Cu nanoparticles are fabricated via transmetalation reactions. Compared to conventional sequential reduction strategies, this transmetalation process has several advantages for the fabrication of core-shell type nanoparticles: (i) no additional reducing agent is needed and (ii) spontaneous shell layer deposition occurs on top of the core nanoparticle surface and thus prevents self-nucleation of secondarily added metals. We also demonstrate the versatility of these core-shell structures by transferring Co@Au nanoparticles from an organic phase to an aqueous phase via a surface modification process. The nanostructures, magnetic properties, and reaction byproducts of these core-shell nanoparticles are spectroscopically characterized and identified, in part, to confirm the chemical process that promotes the core-shell structure formation.
The structure, magnetism, and phase transition of core-shell type CoPt nanoparticles en route to solid solution alloy nanostructures are systematically investigated. The characterization of Co(core)Pt(shell) nanoparticles obtained by a "redox transmetalation" process by transmission electron microscopy (TEM) and, in particular, X-ray absorption spectroscopy (XAS) provides clear evidence for the existence of a core-shell type bimetallic interfacial structure. Nanoscale phase transitions of the Co(core)Pt(shell) structures toward c-axis compressed face-centered tetragonal (fct) solid solution alloy CoPt nanoparticles are monitored at various stages of a thermally induced annealing process and the obtained fct nanoalloys show a large enhancement of their magnetic properties with ferromagnetism. The relationship between the nanostructures and their magnetic properties is in part elucidated through the use of XAS as a critical analytical tool.
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