Fe3O4@SiO2 core-shell nanoparticles (NPs) were synthesized with the co-precipitation method and functionalized with NH2 amino-groups. The nanoparticles were characterized by X-ray, FT-IR spectroscopy, transmission electron microscopy, selected area electron diffraction, and vibrating sample magnetometry. The magnetic core of all the nanoparticles was shown to be nanocrystalline with the crystal parameters corresponding only to the Fe3O4 phase covered with a homogeneous amorphous silica (SiO2) shell of about 6 nm in thickness. The FT-IR spectra confirmed the appearance of chemical bonds at amino functionalization. The magnetic measurements revealed unusually high saturation magnetization of the initial Fe3O4 nanoparticles, which was presumably associated with the deviations in the Fe ion distribution between the tetrahedral and octahedral positions in the nanocrystals as compared to the bulk stoichiometric magnetite. The fluorescent spectrum of eosin Y-doped NPs dispersed in water solution was obtained and a red shift and line broadening (in comparison with the dye molecules being free in water) were revealed and explained. Most attention was paid to the adsorption properties of the nanoparticles with respect to three dyes: methylene blue, Congo red, and eosin Y. The kinetic data showed that the adsorption processes were associated with the pseudo-second order mechanism for all three dyes. The equilibrium data were more compatible with the Langmuir isotherm and the maximum adsorption capacity was reached for Congo red.
The hollow microcapsules made of silica-coated CoFe 2 O 4 nanoparticles were synthesized using chemical co-precipitation, followed by the sol-gel method. Poly(MMA-co-MAA) microspheres were used as a core template which can be completely removed after annealing at 450 °C. The microcapsules are monodisperse with the outer diameter of about 450 nm and the thickness of the shell is about 50 nm. The nanoparticles of Co-ferrite are single crystalline. The size of the nanoparticles and magnetic properties of CoFe 2 O 4 /SiO 2 hollow spheres can be tuned with high accuracy at the annealing stage. The Mössbauer data indicate that CoFe 2 O 4 ferrite is an inverse spinel, in which Fe 3+ and Co 2+ ions are distributed in both octahedral and tetrahedral sites with the inversion degree close to the bulk ferrite value. At low temperature the CoFe 2 O 4 /SiO 2 nanoparticles are in antiferromagnetic (AFM) state due to the canted or triangular magnetic structure. Under heating in the applied field, AFM structure transforms to the ferrimagnetic(FM) structure, that increases the magnetization. The Mössbauer data revealed that the small size CoFe 2 O 4 /SiO 2 particles do not show superparamagnetic behavior, but they transit to the paramagnetic state by the jump-like first order magnetic transition (JMT). This effect is a specific property of the magnetic nanoparticles isolated by inert material. The suggested method of synthesis can be modified with various bio-ligands on the silane surface, and such materials can find many applications in diagnostics and bio-separation.
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