Cooperative Molecular Interaction-Based Highly Efficient Capturing of Ultrashort- and Short-Chain Emerging Per- and Polyfluoroalkyl Substances Using Multifunctional Nanoadsorbents

Abstract

The short-chain (C₄ to C₇) and ultrashort-chain (C₃ to C₂) per- and polyfluoroalkyl substances (PFAS) are bioaccumulative, carcinogenic to humans, and harder to remove using current technologies, which are often detected in drinking and environmental water samples. Herein, we report the development of nonafluorobutanesulfonyl (NFBS) and polyethylene-imine (PEI)-conjugated Fe₃O₄ magnetic nanoparticle-based magnetic nanoadsorbents and demonstrated that the novel adsorbent has the capability for highly efficient removal of six different short- and ultrashort-chain PFAS from drinking and environmental water samples. Reported experimental data indicates that by capitalizing the cooperative hydrophobic, fluorophilic, and electrostatic interaction processes, NFBS-PEI-conjugated magnetic nanoadsorbents can remove ∼100% short-chain perfluorobutanesulfonic acid within 30 min from the water sample with a maximum absorption capacity q_m of ∼234 mg g^–1. Furthermore, to show how cooperative interactions are necessary for effective capturing of ultrashort and short PFAS, a comparative study has been performed using PEI-attached magnetic nanoadsorbents without NFBS and acid-functionalized magnetic nanoadsorbents without PEI and NFBS. Reported data show that the ultrashort-chain perfluoropropanesulfonic acid capture efficiency is the highest for the NFBS-PEI-attached nanoadsorbent (q_m ∼ 187 mg g^–1) in comparison to the PEI-attached nanoadsorbent (q_m ∼ 119 mg g^–1) or carboxylic acid-attached nanoadsorbent (q_m ∼ 52 mg g^–1). In addition, the role of cooperative molecular interactions in highly efficient removal of ultrashort-chain PFAS has been analyzed in detail. Moreover, reported data demonstrate that nanoadsorbents can be used for effective removal of short-chain PFAS (<92%) and ultrashort-chain PFAS (<70%) simultaneously from reservoir, lake, tape, and river water samples within 30 min, which shows the potential of nanoadsorbents for real-life PFAS remediation.