Mechanisms that control the adsorption-desorption behavior of phosphate on magnetite nanoparticles: the role of particle size and surface chemistry characteristics.

Abstract

Eutrophication caused by excessive phosphate discharge into surface water has raised wide concern, and the efficient removal of phosphates from wastewater using sorption methods is very important. In our study, magnetite particles with two different sizes and different surface characteristics were chosen as the sorbents to examine their adsorption and desorption behavior toward phosphate. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and N2 adsorption–desorption methods were used to characterize the morphological and surface chemical properties of the two differently sized magnetite particles. Adsorption kinetics and isotherm models (including the pseudo-first-order, Freundlich, Langmuir and Temkin models) were used to fit the experimental data, and to help with the mechanistic discussions. It was found that the nanometer-sized magnetite (nFe3O4) has a much higher surface area, larger pore volume, higher amounts of surface functional groups, and a lower point of zero charge (pHPZC) value than the micrometer-sized magnetite (Fe3O4). The adsorption kinetics show that reaching adsorption equilibrium in the case of nFe3O4 is much slower, and the particle size or surface characteristics of the magnetite may become the main factor determining the adsorption rate of the phosphate to magnetite in the rapid or slow adsorption step, respectively. nFe3O4 shows much stronger adsorption of phosphate compared to Fe3O4, which may be attributed to the larger surface area of the magnetite with a smaller particle size. In addition, the amount of functional groups and the surface electrical properties may also affect the adsorption of phosphate to magnetite by influencing the formation of the outer-sphere and/or inner-sphere complexes. The adsorption/desorption of phosphate to/from the magnetite decreases/increases with increasing pH, and the extent of change is more marked for nFe3O4. Increasing the ionic strength of the solution increases the adsorption of phosphate to the two differently sized magnetite particles, whereas the presence of humic acid only increases the adsorption of phosphate to Fe3O4. These trends may be caused by the different extents of change of the surface properties or the dispersion state of the two differently sized magnetite particles under different solution chemistry conditions. The results imply that when the synthesis of magnetite-based materials for phosphate sorption is performed, both the particle size and surface properties should be considered in order to realize the efficient and economical removal of phosphate from wastewater.