The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

Abstract

The characteristics of bimetallic nanomaterials are dictated by their size, shape and elemental distribution. Solution synthesis is widely utilized to form nanomaterials, such as nanoparticles, with controlled size and shape. However, the effects of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape-controlled synthesis on the final shape of the nanomaterials and the elemental distribution within the alloy. We demonstrate that this strategy can tune the size of monodisperse PtM (M=Ni or Cu) alloy nanocrystals ranging from 3 to 16 nm with an octahedral shape using acetylacetonate or halide precursors of Pt(II), Pt(IV) and Ni or Cu (II). The nanoparticles formed from halide precursors showed an enrichment of platinum on their surfaces, and the bromides could oxidatively etch the nanoparticles during synthesis with the O2/Br- pair. The two nanocrystal precursors can be uti-lized independently and can control the size with a trend of Pt(acac)2<PtCl2<PtCl4<PtBr2<PtBr4 and M(acac)2<MCl2<MBr2 for the secondary metal (copper or nickel). These results open up avenues to understand the effect of the ligand shell of a precursor during the synthesis of alloy nanoparticles as well as to control, in a scalable manner, the nanomaterial size and surface chemistry.