Synthesis and property of nanoparticles in ionic liquids and their surface modification.

摘要

This thesis describes synthesis and surface modifications of inorganic nanoparticles, including noble metal, metal oxide, and semiconductors. The first part explores synthesis of nanoparticles in 1-butyl-3-methylimidazolium bis(triflylmethyl-sulfonyl)imide ionic liquid ([BMIM][Tf2N] IL). When this IL was used as solvents in the non-hydrolytic synthesis, the growing nanoparticles underwent an auto-separation process, which would drive final products out of the IL reaction mixture during reactions. Highly uniform nanoparticles of metal oxides, noble metals, and CdSe semiconductor, could be obtained through this auto-separation approach. By controlling the composition of capping agents and reaction temperature, iron oxide nanoparticles of various shapes including cube, sphere, and rod, could be readily achieved. After the synthesis, the IL kept its good chemical and thermal stabilities, and could be recycled for the synthesis of nanoparticles. Monodispersed 10-nm iron oxide nanoparticles were repeatedly produced using recycled ILs. The biphasic mixture of ionic liquid and water also facilitated the formation of nanoparticles. In this method, hydrophobic IL was mixed with aqueous solutions of precursors and reductants under vigorous stir. The reactions were thought to take place inside water droplets or around the interfacial region between IL and water. The resultant metal nanoparticles were stabilized by ionic liquid and could be subsequently transferred into other media. Ionic liquids used in this process were also recycled and used repeatedly to obtain gold nanoparticles of controlled sizes and shapes. Platinum nanoparticles stabilized by IL were used as heterogeneous catalysts for the hydrogenation reaction of cyclohexene. This system kept its catalytic activity after several rounds of reactions. The outstanding thermal stability of [BMIM][Tf2N] IL was also utilized to obtain PtCo nanoparticles of different chemical compositions. Surface properties of hydrophobic nanoparticles protected by capping agents were modified by coating with a layer of polystyrene through surface initiated atomic transfer radical polymerization. Their surface chemistry could be altered through the formation of complexation between capping agents and alpha-cyclodextrin. These surface-modified particles exhibited a good stability in aqueous environments.