A template-free solvothermal combined with precursor thermal transformation method has been developed for the preparation of flower-like Fe 3 O 4 nanostructured hollow microspheres. The reaction mechanism and the self-assembly evolution process were studied, and it was found that the synthetic conditions for the precursor such as reaction time, urea concentration and non-aqueous media are all crucial for the formation of the flower-like hierarchical precursors. The flower-like Fe 3 O 4 microspheres obtained by calcining the precursor in Ar gas exhibit superparamagnetic behavior and show relative high saturation magnetization at room temperature. To endow them with SERS activity, silver coating was conducted by magnetron sputtering. The obtained Fe 3 O 4 /Ag hybrid microflowers make a positive influence on the high sensitivity of SERS to 4-pyridinethiol (4-Mpy) and Rhodamine 6G (R6G) molecules when compared with the silver film substrates. More importantly, the detection limit of Fe 3 O 4 /Ag hybrid microflowers for R6G dye can reach up to 10 215 M, which meets the requirements of ultratrace detection of analytes using SERS. Thus, the SERS-active magnetic hybrids prepared in this work may possibly be used as an optical probe with magnetic function for application in high-sensitivity bioassays.

Bifunctional Au-loaded Fe3O4@C composite microspheres were controllably synthesized by coating of Au nanoparticles (NPs) on the surface of the poly(diallyldimethylammonium chloride) (PDDA) functionalized Fe3O4@C microspheres. The amount of Au loading can be effectively tuned by altering the feeding amounts of solution Au NPs or further growth. The obtained Au-loaded Fe3O4@C composite microspheres exhibit both superior surface-enhanced Raman scattering (SERS) sensitivity and catalytic degradation activity for organic dyes. The SERS signal intensity of methylene blue (MB) distinctly enhances with the increase of Au loading, which endows increased Raman 'hot spots' and provides a significant enhancement of the Raman signal through electromagnetic (EM) field enhancements. Furthermore, the catalytic experiments of the Fe3O4@C@Au composite microspheres with the highest Au loading demonstrate that the model organic dye of MB molecules could be degraded within 10 min and the catalytic activity could be recovered without sharp activity loss in six runs, which indicates their superior catalytic degradation activity. The reason could be mainly ascribed to the synergistic effects of small size of Au NPs, the good adsorption behavior of carbon layers and the excellent dispersivity of the composite microspheres induced by the sandwiched carbon layers. The results indicate that the bifunctional Au-loaded Fe3O4@C composite microspheres could be served as promising materials in wastewater treatment.