Cyclodextrin Polymers with Nitrogen-Containing Tripodal Crosslinkers for Efficient PFAS Adsorption,ACS Materials Letters

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Cyclodextrin Polymers with Nitrogen-Containing Tripodal Crosslinkers for Efficient PFAS Adsorption
ACS Materials Letters ( IF 9.6 ) Pub Date : 2020-08-20 , DOI: 10.1021/acsmaterialslett.0c00240
Anna Yang ₁ , Casey Ching ₂ , Maeghan Easler ₃ , Damian E. Helbling ₂ , William R. Dichtel ₁

Affiliation

Per- and polyfluoroalkyl substances (PFAS) are widely used industrial chemicals that are of a great concern because of their pervasive presence in water resources and association with negative health effects. Crosslinked β-cyclodextrin-containing (β-CD) polymer adsorbents have shown promising performances for sequestering PFAS. Recently, installing amino groups into the crosslinkers of a β-CD polymer network improved the binding of many anionic PFAS, including short-chain and branched derivatives. However, the relative importance of the electrostatic interactions from the amino groups and the host-guest interactions within the cavity of the β-CD for PFAS binding are unclear. Herein, β-CD-based adsorbents crosslinked with tripodal crosslinkers containing three amino or amido groups are prepared with comparable physicochemical properties to investigate the respective roles of the crosslinker and β-CD in binding affinity and capacity for anionic PFAS. β-CD polymers containing amines showed superior removal for ten anionic PFAS compared to polymers containing amido groups. Both β-CD polymers have superior performance for perfluorooctanoic acid (PFOA) removal compared to activated carbons (ACs), consistent with β-CD:PFOA inclusion complexes playing an important role. Adsorbents containing amido groups showed low binding affinity and capacity for GenX, whereas the amine-functionalized polymer had outstanding affinity and capacity for GenX (K_L = 8.8 × 10⁴ M^–1, Q_M = 222 mg g^–1), underscoring the essential role of electrostatic interactions for removing short-chain and branched PFAS. The amine-containing β-CD polymer exhibited 100-fold higher affinity and twice the capacity (K_L = 1.8 × 10⁶ M^–1, Q_M = 457 mg g^–1) for PFOA compared to GenX, which are the highest reported values for β-CD polymers. These results highlight the synergistic effects of electrostatic interactions and host-guest interactions in β-CD polymers as important design criteria for efficient removal of anionic PFAS from water. This study further demonstrates broad tunability of crosslinked β-CD polymers and their promise as adsorbents for PFAS remediation.

中文翻译：

含氮三脚架交联剂的环糊精聚合物可有效吸附PFAS

全氟烷基物质和多氟烷基物质（PFAS）是广泛使用的工业化学品，因为它们在水资源中普遍存在并与健康产生负面影响，因此备受关注。交联的含β-环糊精（β-CD）聚合物吸附剂已显示出用于隔离PFAS的有前途的性能。最近，在β-CD聚合物网络的交联剂中安装氨基改善了许多阴离子PFAS的结合，包括短链和支链衍生物。然而，对于PFAS结合，来自氨基的静电相互作用和β-CD腔内的主体-客体相互作用的相对重要性尚不清楚。在这里与具有三个氨基或酰胺基的三脚架交联剂交联的基于β-CD的吸附剂的制备具有可比的理化性质，以研究交联剂和β-CD在阴离子PFAS的结合亲和力和容量方面的各自作用。与含酰胺基团的聚合物相比，含胺的β-CD聚合物对十种阴离子PFAS的去除效果更好。与活性炭（ACs）相比，两种β-CD聚合物均具有优异的全氟辛酸（PFOA）去除性能，这与β-CD：PFOA包合物具有重要作用。含酰胺基的吸附剂对GenX的结合亲和力和容量低，而胺官能化的聚合物对GenX的亲和力和容量却很出色（与活性炭（ACs）相比，两种β-CD聚合物均具有优异的全氟辛酸（PFOA）去除性能，这与β-CD：PFOA包合物具有重要作用。含酰胺基的吸附剂对GenX的结合亲和力和容量低，而胺官能化的聚合物对GenX的亲和力和容量却很出色（与活性炭（ACs）相比，两种β-CD聚合物均具有优异的全氟辛酸（PFOA）去除性能，这与β-CD：PFOA包合物具有重要作用。含酰胺基的吸附剂对GenX的结合亲和力和容量低，而胺官能化的聚合物对GenX的亲和力和容量却很出色（K _L = 8.8×10 ⁴ M ^–1，Q _M = 222 mg g ^–1），强调了静电相互作用对去除短链和支链PFAS的重要作用。含胺的β-CD聚合物显示出100倍的高亲和力和两倍的容量（K _L = 1.8×10 ⁶ M ^–1，Q _M = 457 mg g ^–1）与GenX相比，PFOA的含量最高，这是β-CD聚合物报道的最高值。这些结果强调了β-CD聚合物中静电相互作用和主体-客体相互作用的协同效应，这是从水中有效去除阴离子PFAS的重要设计标准。这项研究进一步证明了交联的β-CD聚合物的广泛可调性及其作为PFAS修复吸附剂的前景。

更新日期：2020-09-08

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