Electrostatic Self-Assembly of Au Nanoparticles onto Thermosensitive Magnetic Core-Shell Microgels for Thermally Tunable and Magnetically Recyclable Catalysis

A facile route to fabricate a nanocomposite of Fe₃O₄@poly[N-isopropylacrylamide (NIPAM)-co-2-(dimethylamino)ethyl methacrylate (DMAEMA)]@Au (Fe₃O₄@PND@Au) is developed for magnetically recyclable and thermally tunable catalysis. The negatively charged Au nanoparticles with an average diameter of 10 nm are homogeneously loaded onto positively charged thermoresponsive magnetic core-shell microgels of Fe₃O₄@poly(NIPAM-co-DMAEMA) (Fe₃O₄@PND) through electrostatic self-assembly. This type of attachment offers perspectives for using charged polymeric shell on a broad variety of nanoparticles to immobilize the opposite-charged nanoparticles. The thermosensitive PND shell with swollen or collapsed properties can be as a retractable Au carrier, thereby tuning the aggregation or dispersion of Au nanoparticles, which leads to an increase or decrease of catalytic activity. Therefore, the catalytic activity of Fe₃O₄@PND@Au can be modulated by the volume transition of thermosensitive microgel shells. Importantly, the mode of tuning the aggregation or dispersion of Au nanoparticles using a thermosensitive carrier offers a novel strategy to adjust and control the catalytic activity, which is completely different with the traditional regulation mode of controlling the diffusion of reactants toward the catalytic Au core using the thermosensitive poly(N-isopropylacrylamide) network as a nanogate. Concurrent with the thermally tunable catalysis, the magnetic susceptibility of magnetic cores enables the Fe₃O₄@PND@Au nanocomposites to be capable of serving as smart nanoreactors for thermally tunable and magnetically recyclable catalysis.