Amphiphilic Perfluoropolyether Copolymers for the Effective Removal of Polyfluoroalkyl Substances from Aqueous Environments

Tan, Xuecai; Zhong, Jiexi; Fu, Changkui; Dang, Huy; Han, Yanxiao; Guo, Jianhua; Yuan, Zhiguo; Zhang, Cheng; Whittaker, Andrew K.

doi:10.1021/acs.macromol.1c00096

Cited by 25 publications

(41 citation statements)

References 52 publications

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“…The 19 F resonances due to PFOA in Figure 4 broaden upon the addition of polymer (Table S1), mainly due to the restriction of mobility of the fluorinated segments on interacting with the polymer through fluorine−fluorine hydrophobic interactions and/or electrostatic attraction. 17,22,39 With increasing PFOA concentration >0.3 mM (still below the CMC), the 19 F NMR resonances of PFOA in the presence of the polymer shift back and approach the chemical shifts of free PFOA, indicating the effects of fast chemical exchange (Figures S7−S9). 19 F DOSY NMR provides additional understanding of the nature of fluorine−fluorine and electrostatic interactions by providing measurements of the self-diffusion coefficients (D f ) of PFOA and the polymer sorbent upon mixing.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

Revealing the Molecular-Level Interactions between Cationic Fluorinated Polymer Sorbents and the Major PFAS Pollutant PFOA

et al. 2022

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The development of new technologies for the removal of a family of manufactured chemicals, the per- and polyfluoroalkyl substances (PFAS), from the environment is urgently needed to safeguard public and environmental health. Here we report a fundamental study of the binding mechanisms driven by fluorine–fluorine and electrostatic interactions between perfluorooctanoic acid (PFOA), an important PFAS molecule, and three types of block copolymer sorbents containing individually perfluoropolyether (PFPE) or quaternized ammonium groups, or both functional segments in combination. The results show that both the fluorine–fluorine interactions between the PFPE segment of the block copolymer and the fluorinated tail of the PFOA as well as electrostatic attraction between the quaternized ammonium group and the anionic PFOA headgroup are crucial to achieve effective PFOA sorption from aqueous solutions. The fluorine–fluorine interactions contribute to recognition of PFOA molecules via fluorophilicity, with fast exchange between bound and free PFOA being observed, while the electrostatic interactions can tightly bind PFOA, thus precluding such exchange. Both types of interaction are observed to be rapidly established within 5 min. We show that the sorbents containing both fluorinated and cationic groups have a higher PFOA removal efficiency with potentially improved sorption capacity compared with the sorbents with a single functional group and that the electrostatic attraction is stronger and dominates the fluorine–fluorine interactions when the sorbent is highly charged. Overall, these results provide important insights into designing novel sorbents for rapid and efficient PFAS removal from contaminated environments.

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Section: ■ Results and Discussionmentioning

confidence: 98%

Revealing the Molecular-Level Interactions between Cationic Fluorinated Polymer Sorbents and the Major PFAS Pollutant PFOA

et al. 2022

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“…The synthetic details and characterization data for the copolymers are shown in the experimental section and Table S1. [25][26][27][28][29][30][31][32][33][34] Fig. 1a illustrates the chemical structures of PFPE polymer (EO10-PFPE) and control polymer (EO10-CTRL).…”

Section: Resultsmentioning

confidence: 99%

Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes

et al. 2022

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Rechargeable batteries paired with sodium (Na)-metal anodes are considered as one of the most promising high energy and low-cost energy storage systems. However, the use of highly reactive Na metal and the formation of Na dendrites during battery operation have caused signi cant safety concerns, especially when highly ammable liquid electrolytes are used. Herein, we design and develop a solventfree solid polymer electrolytes (SPEs) based on a per uoropolyether (PFPE) terminated polyethylene glycol (PEG)-based block copolymer for safe and stable all-solid-state Na-metal batteries. Compared with traditional poly(ethylene oxide) (PEO) or PEG SPEs, our results suggest that block copolymer design allows for the formation of self-assembled microstructures leading to high storage modulus at elevated temperatures with the PEG domains providing transport channels even at high salt concentration (EO/Na + = 8:2). Moreover, it is demonstrated that the incorporation of PFPE segments enhances the Na + transference number of the electrolyte to 0.46 at 80 o C. Finally, the proposed SPE exhibits highly stable symmetric cell cycling performance with high current density (0.5 mA cm -2 and 1.0 mAh cm -2 , up to 1300 hours). The assembled all-solid-state Na-metal batteries with Na 3 V 2 (PO 4 ) 3 cathode demonstrate outstanding rate performance, high capacity retention and long-term charge/discharge stability (CE = 99.91%) after more than 900 cycles.

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“…[27-30, 32, 34, 35] Many emerging PFAS remediation technologies have demonstrated efficient PFAS removal in batch studies conducted in pure water at low to moderate PFAS concentrations, but few have been studied in real water matrices or in flow-through columns. In general, emerging PFAS remediation technologies leverage intermolecular interactions such as ion exchange, [36][37][38][39][40] hydrophobic or fluorous interactions, [39][40][41][42][43][44][45] or encapsulation by supramolecular receptors [46][47][48][49][50][51][52] to bind PFAS.…”

Section: Introductionmentioning

confidence: 99%

Hydrolytically Stable Ionic Fluorogels for High‐Performance Remediation of Per‐ and Polyfluoroalkyl Substances (PFAS) from Natural Water

et al. 2022

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PFAS are known bioaccumulative and persistent chemicals which pollute natural waters globally. There exists a lack of granular sorbents to efficiently remove both legacy and emerging PFAS at environmentally relevant concentrations. Herein, we report a class of polymer networks with a synergistic combination of ionic and fluorous components that serve as granular materials for the removal of anionic PFAS from water. A library of Ionic Fluorogels (IFs) with systematic variation in charge density and polymer network architecture was synthesized from hydrolytically stable fluorous building blocks. The IFs were demonstrated as effective sorbents for the removal of 21 legacy and emerging PFAS from a natural water and were regenerable over multiple cycles of reuse. Comparison of one IF to a commercial ion exchange resin in mini-rapid smallscale column tests demonstrated superior performance for the removal of short-chain PFAS from natural water under operationally relevant conditions.

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Amphiphilic Perfluoropolyether Copolymers for the Effective Removal of Polyfluoroalkyl Substances from Aqueous Environments

Cited by 25 publications

References 52 publications

Revealing the Molecular-Level Interactions between Cationic Fluorinated Polymer Sorbents and the Major PFAS Pollutant PFOA

Revealing the Molecular-Level Interactions between Cationic Fluorinated Polymer Sorbents and the Major PFAS Pollutant PFOA

Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes

Hydrolytically Stable Ionic Fluorogels for High‐Performance Remediation of Per‐ and Polyfluoroalkyl Substances (PFAS) from Natural Water

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