Programmable Synthesis of Monodisperse Multimetallic Alloy Nanoparticles

Multimetallic alloy nanoparticles (MMANPs) exhibit excellent properties, yet developing general colloidal routes toward monodisperse MMANPs is still challenging due to multidimensional synthetic complexity. Herein, we demonstrate a generalized Two-NP conversion strategy for the colloidal synthesis of a library of uniform MMANPs, in which parent precursor NPs with well-defined structures are clearly identified that can accommodate various metallic atoms throughout multistep transformation. This study defines two pivotal criteria for eligible parent precursors, verifying colloidal monometallic Pt, Au, and Pd NPs, as well as their bimetallic derivatives, as ideal candidates. The differential competency and rich diversity of parent precursors allow us to design a variety of rational synthetic routes, which enables that the versatile synthesis of MMANPs, including over 200 monodisperse Pt-based ternary-to-senary alloy nanocubes, to be theoretically achieved (the constituent metals studied include Pt, Au, Pd, Fe, Co, Ni, Rh, Ag, Cu, Mn, and Sn). Benefiting from the structural inheritance of parent precursor NPs, 64 representative monodisperse MMANPs with controllable constituent elements, morphology, and size are readily produced. We propose a mechanism-driven synthesis paradigm that replaces empirical screening with a reliable precursor-oriented synthetic methodology, enabling the programmable fabrication of diverse MMANPs.