RESUMO
Phosphates in high concentrations are harmful pollutants for the environment, and new and cheap solutions are currently needed for phosphate removal from polluted liquid media. Iron oxide nanoparticles show a promising capacity for removing phosphates from polluted media and can be easily separated from polluted media under an external magnetic field. However, they have to display a high surface area allowing high removal pollutant capacity while preserving their magnetic properties. In that context, the reproducible synthesis of magnetic iron oxide raspberry-shaped nanostructures (RSNs) by a modified polyol solvothermal method has been optimized, and the conditions to dope the latter with cobalt, zinc, and aluminum to improve the phosphate adsorption have been determined. These RSNs consist of oriented aggregates of iron oxide nanocrystals, providing a very high saturation magnetization and a superparamagnetic behavior that favor colloidal stability. Finally, the adsorption of phosphates as a function of pH, time, and phosphate concentration has been studied. The undoped and especially aluminum-doped RSNs were demonstrated to be very effective phosphate adsorbents, and they can be extracted from the media by applying a magnet.
RESUMO
This study reports on investigation of the magnetic properties of layer-by-layer (LbL) assembled nanofilms comprising polyvinyl alcohol (PVA) and citrate-coated magnetite (cit-MAG) nanoparticles deposited onto silicon (SF sample) and glass (GF sample) substrates. DC magnetization measurements were performed over the temperature range of 4 K to 300 K, in the applied magnetic field range of ±60 kOe. The magnetic data of the as-synthesized cit-MAG nanoparticles (F sample) are also collected for comparison. The three as-fabricated samples reveal perfect superparamagnetic (SPM) behavior only around room temperature; at temperatures lower than 200 K the SPM scaling is not observed and all samples behave as interacting superparamagnetic (ISPM) materials. The evolution from the ISPM to the SPM regime is marked by a steady decrease in the hysteretic properties of all samples, with the temperature-dependence of the coercivity decreasing slower than the T1/2 behavior predicted for non-interacting superparamagnetic particles. The modified Bloch's law used to assess information on nanoparticles' surface spins gives the Bloch's exponent close to 2 (for the F and SF samples) and close to 1 (for the GF sample). Interestingly, the surface spin freezing temperature (Tf) is 8 ± 1 K for all samples. The magnetic behavior of all three samples can be described within the model picture of a core-shell structure for the cit-MAG nanoparticles; the core comprising magnetically-ordered spins whereas the shell behaving as a spin-glass-like system. However, the contribution of the shell magnetism to the effective magnetic properties is much more evident in the GF sample in which magnetic dipole-dipole interaction is three-times weaker than in the SF sample and two times weaker than in the F sample. In contrast, the strong magnetic dipole-dipole interaction in the SF sample affects the surface spins, hindering the onset of magnetically-ordered regions in the nanoparticle's shell, making the surface magnetism contribution negligible. The LbL-fabricated nanofilms herein reported and the presented analysis of their magnetic properties we envisage can support the engineering of magnetic nanofilms for multiple applications.