New design to enhance phosphonate selective removal from water by MOF confined in hyper-cross-linked resin

Although polymeric anion exchange resins can remove phosphonates, they lack selectivity for target phosphonates and are susceptible to interference by anions and other substances. Here, we developed a novel strategy via confining MIL-101(Fe)-NH2 inside commercial resins IRA-900 for high-efficient and precise phosphonate removal, accompanying with the improvement of the stability and recovery of MIL-101(Fe)-NH2. The obtained nanocomposite MIL-101(Fe)-NH2@IRA-900 (MFNI) exhibited significantly enhanced phosphonate removal in the presence of competing anions (Cl−, SO42−, NO3− and CO32−) and natural organic matter (humic acid) at high concentrations (2–4 times of phosphonate concentration). Moreover, MFNI displayed the highest phosphonate adsorption capacity (12.9 mg P/g) and the fastest adsorption kinetics (120 min) than hydrated ferric oxides modified IRA-900 (HFOI) (6.7 mg P/g, 180 min), MIL-101(Fe)-NH2 (7.6 mg P/g, 240 min) and IRA-900 (5.6 mg P/g, 360 min). Such higher adsorption affinity and anti-interference ability came from the synergistic effect of the host IRA-900 (hydrogen-bond interaction and electrostatic attraction) and the embedded MIL-101(Fe)-NH2 (ligand exchange). The depleted MFNI could be regenerated with a binary NaOH-NaCl solution and reused without significant loss of capacity. Column adsorption runs by using MFNI indicated the fresh MFNI could achieve 100 % removal of PPOA in 10.5 h continuously feeding, which offered the possibility of achieving potential large-scale applications. In general, a new MOF-confined design approach was practiced to achieve selective elimination of phosphates and to improve the stability and recovery of MOF.