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This work described a general strategy to enhance a typical organic-aqueous heterogeneous green oxidation reaction by introducing surface tunable magnetic nanoparticles into liquids to form a controllable Pickering emulsion. We synthesized cross-linked polystyrene (PS)-covered Fe3O4 nanoparticles grafted with different N-alkyl imidazoles and systematically discussed the effect of surface properties on the formation of emulsions. By loading such particles, the dichloromethane-water-based 2,2,6,6-tetramethylpiperidine-1-oxyl-mediated Montanari oxidation system was converted from the unstable millimeter-scale dispersion into a stable micrometer-scale emulsion, which significantly reduced the reactant transfer distance and resulted in a significantly high overall reaction rate. This reaction efficiency is elucidated in terms of unique properties inherent in an emulsion, including the self-assembly of Fe3O4/PS and Fe3O4/PS[im-C n]Cl ( n=1, 4, 6, and 10) nanoparticles, well ensuring a large specific surface area of the water-oil interface. [ABSTRACT FROM AUTHOR]

This study demonstrated the use of a magnetic superhydrophobic polymer nanosphere cage derived from a Pickering emulsion as a framework for miceller catalysis in biphasic media. We designed this system through the covalent stabilisation of active site (2,2,6,6-tetramethylpiperidine 1-oxyl)-grafted amphiphiles onto the magnetic hydrophobic core to form a micelle-like architecture and used it as a Pickering emulsifier to develop a new kind of micelle-catalysed biphasic system. The catalysis results reveal that these fixed micelle-tethered 2,2,6,6-tetramethylpiperidine 1-oxyl catalysts demonstrate much higher activity than their soluble counterparts in the biphasic Montanari oxidation of alcohols, which could be due to the unique properties of Pickering emulsion and miceller catalysis. In addition, the excellent magnetic response ensures the efficient recycling of the catalyst by magnetic decantation. The catalyst can be recycled at least 10 times without significant loss of activity or degradation of magnetic susceptibility. Moreover, this study demonstrates that this new Pickering emulsion-based and micelle-catalysed biphasic system is technically simple and practically applicable. [ABSTRACT FROM AUTHOR]