[Preparation of Catalyst Cyclodextrin-Fe-TAML to Activate H 2 O 2 and Oxidize Organic Micropollutants in Water].

In order to improve the stability and catalytic activity of Fe-TAML, mono-6-oxy-cyclodextrin bonded Fe-TAML catalyst (CD-Fe-TAML) was prepared by bonding Fe-TAML with cyclodextrin (CD) through chlorosulfonylation reaction, metal chelation reaction, and nucleophilic substitution reaction. The catalytic activity and stability of CD-Fe-TAML and the oxidation degradation efficiencies of 34 organic micropollutants such as antibiotics and pesticides by activation of H ₂ O ₂ in water were studied. Compared with that of Fe-TAML, CD-Fe-TAML at pH 7.0 had a 49-fold and 25-fold increase in the rate of activating H ₂ O ₂ to produce iron (Ⅴ/Ⅳ)-oxo intermediates and the degradation rate of the substrate, respectively, and its self-oxidation rate was reduced by 70%. The stability of CD-Fe-TAML was 0.7-699 times higher than that of Fe-TAML in the pH range of 3.0-10.0. Specifically, the stability of CD-Fe-TAML was 33-699 times higher than that of Fe-TAML in the pH range of 3.0-7.0. The sulfonic acid group in the molecular structure of CD-Fe-TAML had an electrophilic effect, which could increase the positive charge density of Fe in the active center, accelerate the O-O bond cleavage of H ₂ O ₂ and the generation of iron(Ⅴ/Ⅳ)-oxo intermediates, improve the catalytic activity of Fe-TAML, and also improve its hydrolysis stability. Meanwhile, the CD group in the molecular structure had the "electron shuttle" effect and inclusion effect. The former could accelerate the electron transfer between the active center Fe-TAML and H ₂ O ₂ to improve the catalytic activity of Fe-TAML. The latter could inhibit the hydrolysis and self-oxidation of the active center Fe-TAML by inclusion or binding of the hydrolysis sites and oxidation sites, thus improving its stability. The degradation efficiencies of micropollutants by CD-Fe-TAML/H ₂ O ₂ under weakly acidic and neutral conditions (in the pH range of 5.0-7.0) were 0.4-59 times higher than those of Fe-TAML/H ₂ O ₂ . The degradation efficiencies of CD-Fe-TAML/H ₂ O ₂ on nine micropollutants with a molar volume less than 0.20 L·mol ^-1 , such as acetamiprid and sulfadiazine, were 0.3-1.1 times higher than that of Fe-TAML/H ₂ O ₂ at pH 8.0, and there were no significant differences between CD-Fe-TAML/H ₂ O ₂ and Fe-TAML/H ₂ O ₂ for micropollutants with a molar volume greater than 0.20 L·mol ^-1 . The results of iodide oxidation by CD-Fe-TAML/H ₂ O ₂ showed that I ^- was not oxidized to produce iodo-disinfection byproducts (I-DBPs). The degradation of micropollutants by CD-Fe-TAML/H ₂ O ₂ in the surface water sample was not disturbed by water components. The CD-Fe-TAML/H ₂ O ₂ system has a potential application in the removal of organic micropollutants from water.