Tuning the Fe(II)/hydroxide Ratio during Synthesis of Magnetite Nanoparticles to Maximize Cr(VI) Uptake Capacity

Abstract

The impact of hydroxyl excess as defined by the Fe(II)/hydroxide ratio during the synthesis of Fe3O4 nanoparticles by oxidative precipitation of FeSO4 was examined as a critical parameter determining the potential for Cr(VI) uptake from polluted water. Various samples were prepared by varying the OH− excess in the range of −0.10 up to +0.03 M and characterized according to their composition, morphology, and surface configuration. Their efficiency for Cr(VI) removal was evaluated by batch adsorption tests, carried out under similar conditions with drinking water purification in the concentration range below 10 mg/L. Results indicate that near the zero-excess point for hydroxyl balance, the uptake capacity for residual Cr(VI) concentration equal to 25 μg/L remains at very low levels (<0.5 mg/g). However, a small increase above +0.02 M features synthesized nanoparticles with an uptake capacity of 2.5 mg/g owed to the decrease in particles size (28 nm) and enhancement of the reducing potential (Fe2+/Fe3+ = 0.42). In addition, utilizing negative excess values below −0.05 M triggers a similar efficiency rise, although the morphology of the obtained aggregates is rather different. Such finding is attributed to a possible exchange mechanism between adsorbed sulfates and chromate anions that assist approach of Cr(VI) to the material’s surface. Overall, proper tuning of hydroxyl excess offers multiple options for the implementation of monodisperse magnetically responsive nanoparticles or larger aggregates with optimized purification efficiency in water technology.