Insights into the relationship between Nitrilotri(methylphosphonic acid) (NTMP) adsorption and physicochemical properties of iron oxides

Non-reactive phosphorus (e.g., phosphonate) contributes to eutrophication, while little attention has been paid to its control. The iron-based materials are highly efficient in orthophosphate removal from water, while the correlation between their physicochemical properties and selective phosphonate (e.g. Nitrilotri(methylphosphonic acid) (NTMP)) adsorption is still unclear. In this study, Fe₃O₄ (magnetite), FeOOH (goethite) and Fe₂O₃ (hematite) with different crystal structures, particle sizes and surface area were synthesized for NTMP adsorption. The physicochemical properties of the three kinds of iron oxides were characterized. The batch experiments were applied to explore the NTMP adsorption and desorption performance. The maximum adsorption capacity of NTMP on Fe₃O₄, FeOOH and Fe₂O₃ were 4.14, 1.91 and 0.99 mg-P/g, respectively. Results implied the crystal structure and surface area of iron oxides determined the maximum NTMP adsorption capacity. The NTMP adsorption on the three iron oxides was spontaneous, endothermic and randomness increase. The iron oxides showed high selectivity towards NTMP adsorption in water containing anions, while the co-existing Ca²⁺ and Mg²⁺ remarkably increased the adsorption capacity. The successive adsorption-desorption cycles suggested a favorable reusability of the above iron oxides and a high NTMP desorption efficiency. The specific NTMP adsorption capacity followed the sequence of FeOOH > Fe₂O₃ > Fe₃O₄, and was highly dependent on surface OH⁻ proportion. The NTMP adsorption mechanism was mainly attributed to inner-sphere complexation. This study provides insights into the iron-based adsorbents design for selective phosphonate adsorption in the future.