Understanding the Selective Removal of Perfluoroalkyl and Polyfluoroalkyl Substances via Fluorine–Fluorine Interactions: A Critical Review

As regulatory standards for per- and polyfluoroalkyl substances (PFAS) become increasingly stringent, innovative water treatment technologies are urgently demanded for effective PFAS removal. Reported sorbents often exhibit limited affinity for PFAS and are frequently hindered by competitive background substances. Recently, fluorinated sorbents (abbreviated as fluorosorbents) have emerged as a potent solution by leveraging fluorine-fluorine (F···F) interactions to enhance selectivity and efficiency in PFAS removal. This review delves into the designs and applications of fluorosorbents, emphasizing how F···F interactions improve PFAS binding affinity. Specifically, the existence of F···F interactions results in removal efficiencies orders of magnitude higher than other counterpart sorbents, particularly under competitive conditions. Furthermore, we provide a detailed analysis of the fundamental principles underlying F···F interactions and elucidate their synergistic effects with other sorption forces, which contribute to the enhanced efficacy and selectivity. Subsequently, we examine various fluorosorbents and their synthesis and fluorination techniques, underscore the importance of accurately characterizing F···F interactions through advanced analytical methods, and emphasize the significance of this interaction in developing selective sorbents. Finally, we discuss challenges and opportunities associated with employing advanced techniques to guide the design of selective sorbents and advocate for further research in the development of sustainable and cost-effective treatment technologies leveraging F···F interactions.