Proceedings of September Meeting 2016 (NFM16)
Publication date: 14th June 2016
The search for a general androbust synthesis of inorganic nanoparticles is motivated by their unique size/shape-dependent electronic, optical, magnetic and catalytic properties, as well as their potential applications. Modern synthesis of nanoparticles requires clear understanding of the precursor-to nanoparticle reaction pathways, high atomic economy, and facile experimental realization, while providing compelling quality of the product (uniform and tunable morphologies and compositions). From the view-point of practical chemistry of nanomaterials, particularly attractive might be a one-pot synthesis in which the actual metal-nitrogen bonded precursor is formed in-situ.
Here we report a facile one-pot synthesis of highly monodisperse nanoparticles (5-30nm in diameter, 5-10% in standard size distribution) of various metals and metalloids such as In, Sn, Bi, Sb, Ga, Cu, Zn and their alloys (Cu6Sn5, Cu2Sb, BixSb1-x etc.) using inexpensive commercial chloride precursors. It should be noted that several of these metals (e.g. Zn) and alloys (e.g. Cu6Sn5, Cu2Sb) had not been previously obtained in the form of uniform nanoparticles. The proposed reaction mechanism has been elucidated with multinuclear (1H, 7Li, 119Sn) NMR spectroscopy combined with DFT and molecular dynamics simulations. Metal chloride is reacted with long-chain primary or secondary amine such as oleylamine and dioctylamine in the presence of strong Brønsted base (e.g. secondary amide of lithium or butyl-lithium)that deprotonates the amine and thus promotes the formation of metal-long-chain-amide. The in-situ formed amide is then reduced or thermally decomposed into corresponding metal nanoparticles. This simple methodology eliminates elaborate preparation, storage and handling of highly reactive, moisture and oxygen sensitive molecular precursors of these metals, while providing compelling quality of nanomaterials.
References: M. He, L. Protesescu, R. Caputo, F. Krumeich, and M. V. Kovalenko. A General Synthesis Strategy for Monodisperse Metallic and Metalloid Nanoparticles (In, Ga, Bi, Sb, Zn, Cu, Sn and their alloys) via In-Situ Formed Metal-Long-Chain-Amides. Chem. Mater., 2015, 27, 635-647.
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