High affinity lanthanum doped iron oxide nanosheets for phosphate removal

Phosphorus induced eutrophication of freshwaters is one of the great global challenges. As the critical threshold concentration for eutrophication is very low, there is a strong need for development of phosphate sorbents with high affinity and selectivity. Single sheet iron oxide (SSI), a nanomaterial prepared from oxidation and exfoliation of layered iron(II)-iron(III) hydroxide (green rust), is a fast reacting and promising sorbent. Phosphate sorption affinity and selectivity may be improved by incorporation of lanthanum (La) in the structure. Lanthanum was added during SSI synthesis resulting in La-SSIs with 0 to 22.5 wt% of La content. XPS and EXAFS showed all La was present as La(OH)₃ nanoclusters between iron hydroxide layers and on the surface of SSI. The sorbent showed fast phosphate sorption with 90% completion within 30 min and high stability with minimal La leaching. All La-SSI nanomaterials showed better sorption affinity than non-doped SSI, and the La-SSI with the highest La content showed an extreme affinity with K_d of 10⁵ L/kg at solution concentration of 0.1 mg P/L. The sorption affinity was not seriously affected by pH. The La-SSIs showed high selectivity for phosphate with<10% reduction in phosphate sorption in presence of co-existing solutes (Cl^–, NO₃^–, SO₄^2-, HCO₃^– and humic acid). Similar high affinity and selectivity was seen for phosphate sorption in real natural waters. The main phosphate sorption mechanism is attributed to inner sphere Fe-O-P and La-O-P surface complexation. In conclusion La doping turns SSI into a high-affinity and selectivity sorbent that has potential for polishing low-phosphate yet eutrophying natural waters such as drainage and lake waters.