Reduction of a Tetrafluoroterephthalonitrile-β-Cyclodextrin Polymer to Remove Anionic Micropollutants and Perfluorinated Alkyl Substances from Water

Organic micropollutants (MPs) are anthropogenic substances that contaminate water resources at trace concentrations. Many MPs, including per- and polyfluorinated alkyl substances (PFASs), have come under increased scrutiny because of their environmental persistence and association with various health problems. A beta-cyclodextrin polymer linked with tetrafluoroterephthalonitrile (TFN-CDP) has high affinity for cationic and many neutral MPs from contaminated water because of anionic groups incorporated during the polymerization. But TFN-CDP does not bind many anionic MPs strongly, including anionic PFASs. To address this shortcoming, we reduced the nitrile groups in TFN-CDP to primary amines, which reverses its affinity towards charged MPs. TFN-CDP exhibits adsorption distribution coefficients (log K-D values) of 2-3 for cationic MPs and -0.5-1.5 for anionic MPs, whereas the reduced TFN-CDP exhibits log K-D values of -0.5-1.5 for cationic MPs and 2-4 for anionic MPs, with especially high affinity towards anionic PFASs. Kinetic studies of the removal of 10 anionic PFASs at environmentally relevant concentrations showed 80-98 % removal of all contaminants after 30 min and was superior to commercial granular activated carbon. These findings demonstrate the scope and tunability of CD-based adsorbents derived from a single polymerization and the promise of novel adsorbents constructed from molecular receptors.