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

Abstract

Organic micropollutants (MPs) are anthropogenic substances that contaminate water resources at trace concentrations.M any MPs,i ncluding per-a nd polyfluorinated alkyl substances (PFASs), have come under increased scrutiny because of their environmental persistence and association with various health problems.Ab-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,i ncluding anionic PFASs.T oa ddress this shortcoming,w er educed the nitrile groups in TFN-CDP to primary amines,w hich reverses its affinity towards charged MPs.T FN-CDP exhibits adsorption distribution coefficients (log K D values) of 2-3 for cationic MPs and À0.5-1.5 for anionic MPs,w hereas the reduced TFN-CDP exhibits log K D values of À0.5-1.5 for cationic MPs and 2-4 for anionic MPs, with especially high affinity towards anionic PFASs.K inetic studies of the removal of 10 anionic PFASs at environmentally relevant concentrations showed 80-98 %r emoval 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 as ingle polymerization and the promise of novel adsorbents constructed from molecular receptors.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Emerging Functional Porous Polymeric and Carbonaceous Materials for Environmental Treatment and Energy Storage

“…Lately, to improve the adsorption performance of anionic micropollutants and perfluorinated alkyl substances from water, primary amines were preset in the tetrafluoroterephthalonitrile linked β-CD polymer, which wiped 80-98% of all contaminants within 30 min. [143] Based on the background in both porous polymers and environment control, the COF-based materials for adsorption have also been reported by Dichtel's group. A highly porous (≥1000 m 2 g −1 ) imine-linked 2D COFs bearing primary amines was employed to rapidly adsorb ammonium perfluoro-2-propoxypropionate (GenX) and other PFASs (Figure 5a).…”

“…Anionic micropollutant and PFASs [143] Amine-modified PIM-1 -Amines Amidation and nitrile reduction Selective-dye adsorption [144] Z-PAF-C -Zwitterions Ring opening reaction Antifouling salt rejection membrane [145] PAF [TEMPO]50%-NiP-COF 264 TEMPO "click" reaction Supercapacitor [142] S-CTF-1 -Sulfur Vulcanization LSB [160] S-COF-V 6 Sulfur Vulcanization LSB [161] polysulfide@ TFPPy-ETTA-COF -Sulfur Vulcanization LSB [162] CEA ( Figure 3c). The stretching/shrinking of PDMAEMA chains in different pH conditions can manipulate the aggregation state of CEA indicators, enabling the visible pH-sensitive fluorescence change.…”

Fluorinated Organic Porous Materials

“…57 In very recent work, they demonstrated that the reduction of the -CN group into -CH 2 NH 2 dramatically enhances the affinity of the material for PFOA. 58 Work on tailoring porous organic materials to capture water contaminants has recently been reviewed. 59…”

Acyclic Cucurbit[n]uril‐Type Receptors: Aromatic Wall Extension Enhances Binding Affinity, Delivers Helical Chirality, and Enables Fluorescence Sensing

“…[9c, 11] Macrocycles are at the heart of solutions to societally important problemsi ncluding the formulation of insoluble drugs, [6] the household product Febreeze TM , [12] glucose monitors, [13] sequestrants for nuclear waste ions, [14] and the removal of contaminants from water sources. [15] Amongst thesem olecular containers, cucurbit[n]urils (CB[n], Figure 1) [16] have distin-guishedt hemselves due to their ability to form high affinity CB [n]•guest complexesi nh ighly selective and stimuli responsive processes in aqueous solution. [17] Accordingly,m acrocyclic CB[n]a nd their derivatives have been extensivelyi nvestigated as componentso fs ensing ensembles, [18] molecular machines, [19] in pharmaceutical applications, [20] as catalysts, [21] and are even beginning to appear in commercial deodorizing products.…”

“…Some of the most popular classes of macrocyclic receptors include the crown ethers, [1c] cryptands, [1b] cyclodextrins, [6] calixarenes, [7] cyclophanes, [1a, 3a, 8] cavitands, [9] pillararenes, [10] as well as cages self‐assembled by H‐bonding, the hydrophobic effect, and metal–ligand interactions [9c, 11] . Macrocycles are at the heart of solutions to societally important problems including the formulation of insoluble drugs, [6] the household product Febreeze TM , [12] glucose monitors, [13] sequestrants for nuclear waste ions, [14] and the removal of contaminants from water sources [15] . Amongst these molecular containers, cucurbit[ n ]urils (CB[ n ], Figure 1) [16] have distinguished themselves due to their ability to form high affinity CB[ n ]⋅guest complexes in highly selective and stimuli responsive processes in aqueous solution [17] .…”