Polymerized Molecular Receptors as Adsorbents to Remove Micropollutants from Water

ConspectusOrganic micropollutants (MPs) are increasing in number and concentration in water systems as a result of human activities. Often from human origin, these micropollutants build up in the environment because organisms lack the mechanisms to metabolize these substances, which cause negative health, ecological, and economic effects. Adsorption-based remediation processes for these compounds often rely on activated carbon materials. However, activated carbons are ineffective against certain MPs, exhibit low removal efficiencies in the presence of common aqueous matrix constituents, and require energy-intensive activation and regeneration processes. To overcome the deficiencies of traditional technologies, novel adsorbents based on molecular receptors offer promising alternative solutions. This Account describes the recent development of polymer adsorbents based on molecular receptors for removing trace organic chemicals from water. Polymer networks based on molecular receptors have high binding affinities for many MPs but, unlike activated carbons, have a specific molecule-binding mechanism that prevents these polymers from being fouled by matrix constituents such as natural organic matter. The size and hydrophobic pocket of the β-cyclodextrin receptor preferentially adsorbs target molecules such as organic micropollutants in the presence of matrix constituents, and the nature of the cross-linker tunes the binding affinity and selectivity of the adsorbent for specific classes of MPs, including those of varying charge and hydrophobicity. β-cyclodextrin polymers also exhibit rapid adsorption kinetics and are easily regenerated. This Account details β-cyclodextrin polymers made with three different cross-linkers, including a polymer that is postsynthetically transformed from a negatively charged polymer to a positively charged polymer to invert the polymer's micropollutant adsorption profile. Morphological constraints have so far limited these cross-linked polymers' ability to be used in commercial applications, but two methods to create larger and more uniformly sized particles for use in flow-through applications are described here. β-Cyclodextrin polymers are useful for trapping organic micropollutants such as bisphenol A, perfluorooctanoic acid, and many kinds of pharmaceuticals and pesticides, but their binding pockets are too large to capture micropollutants that are small or of high polarity. Other molecular receptors such as resorcinarene cavitands can target lower-molecular-weight MPs, including halomethane disinfection byproducts and industrial solvents, that are not bound strongly by β-cyclodextrins. These materials demonstrate the potential of expanding the library of polymers based on molecular receptors. Overall, these emerging adsorbents show promise for the removal of legacy and emerging MPs from water, as well as the ability to rationally tune the adsorbent's structure to target the most persistent and toxic MPs.