Polymerized Molecular Receptors as Adsorbents to Remove Micropollutants from Water.

Organic 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 ß-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. ß-cyclodextrin polymers also exhibit rapid adsorption kinetics and are easily regenerated. This Account details ß-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. ß-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 ß-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.

ß-Cyclodextrin Polymers with Different Cross-Linkers and Ion-Exchange Resins Exhibit Variable Adsorption of Anionic, Zwitterionic, and Nonionic PFASs.

Per- and polyfluoroalkyl substances (PFASs) occur in groundwater as mixtures of anionic, cationic, zwitterionic, and nonionic species, although few remediation technologies have been evaluated to assess the removal of different types of PFASs. In this study, we evaluated the performance of three ß-cyclodextrin polymers (CDPs), an anion-exchange (AE) resin, and a cation-exchange (CE) resin for the removal of anionic, zwitterionic, and nonionic PFASs from water. We found that a CDP with a negative surface charge rapidly removes all zwitterionic PFASs with log KD values ranging between 2.4 and 3.1, and the CE resin rapidly removes two zwitterionic PFASs with log KD values of 1.8 and 1.9. The CDPs with a positive surface charge rapidly remove all anionic PFASs with log KD values between 2.7 and 4.1, and the AE resin removes all anionic PFASs relatively slowly with log KD values between 2.0 and 2.3. All adsorbents exhibited variable removal of the nonionic PFASs and some adsorption inhibition at higher pH values and in the presence of groundwater matrix constituents. Our findings provide insight into how adsorbents can be combined to remediate groundwater contaminated with complex mixtures of different types of PFASs.

Tarnishing Silver Metal into Mithrene.

Silver metal exposed to the atmosphere corrodes and becomes tarnished as a result of oxidation and precipitation of the metal as an insoluble salt. Tarnish has so poor a reputation that the word itself connotes corruption and disrespectability; however, tarnishing is a facile synthetic approach for preparing thin metal-sulfide films on silver or copper metal that might be exploited to prepare more elaborate materials with desirable optoelectronic properties. In this work, we prepare luminescent semiconducting thin films of mithrene, a metal-organic chalcogenolate assembly, by replacing the tarnish-causing atmospheric sulfur source with diphenyl diselenide. Mithrene, or silver benzeneselenolate [AgSePh]∞, is a crystalline solid that contains both an organic supramolecular phase and a two-dimensional inorganic coordination polymer phase. This compound gradually accumulates as the sole product of silver metal corrosion. The chemical reaction is carried out on metallic silver thin films and yields crystalline films with thicknesses ranging from 5 to 100 nm. We use the large-area films (>6 cm2) afforded by this method to measure the optical properties of this compound. The mild-temperature, wafer-scale processing of hybrid chalcogenolate thin films may prove useful in the application of hybrid organic-inorganic materials in semiconductor devices and hierarchical architectures.

Low-temperature mineralization of perfluorocarboxylic acids.

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative pollutants found in water resources at concentrations harmful to human health. Whereas current PFAS destruction strategies use nonselective destruction mechanisms, we found that perfluoroalkyl carboxylic acids (PFCAs) could be mineralized through a sodium hydroxide-mediated defluorination pathway. PFCA decarboxylation in polar aprotic solvents produced reactive perfluoroalkyl ion intermediates that degraded to fluoride ions (78 to ~100%) within 24 hours. The carbon-containing intermediates and products were inconsistent with oft-proposed one-carbon-chain shortening mechanisms, and we instead computationally identified pathways consistent with many experiments. Degradation was also observed for branched perfluoroalkyl ether carboxylic acids and might be extended to degrade other PFAS classes as methods to activate their polar headgroups are identified.

A Tunable Porous ß-Cyclodextrin Polymer Platform to Understand and Improve Anionic PFAS Removal.

Cross-linked polymers containing ß-cyclodextrin (ß-CD) are promising adsorbents with demonstrated removal performances for per- and polyfluoroalkyl substances (PFASs) from contaminated water sources. Despite the promising performance of some ß-CD-based adsorbents for PFAS removal, many of these materials are not amenable for rational performance improvement or addressing fundamental questions about the PFAS adsorption mechanisms. These ambiguities arise from the poorly defined structure of the cross-linked polymers, especially with respect to the random substitution patterns of the cyclodextrins as well as side reactions that modify the structures of some cross-linkers. Here, we report a new ß-CD polymer platform in which styrene groups are covalently attached to ß-CD to form a discrete monomer that is amenable to radical polymerization. This monomer was polymerized with styrene and methacrylate comonomers to provide three ß-CD polymers with high specific surface areas and high isolated yields (all >93%). A ß-CD polymer copolymerized with a methacrylate bearing a cationic functional group achieved nearly 100% removal for eight anionic PFASs (initial concentration of 1 µg/L for each compound) in nanopure water at an exceedingly low adsorbent loading of 1 mg L-1, as compared to previous cyclodextrin polymers that required loadings at least 1 order of magnitude higher to achieve an equivalent degree of PFAS removal. Furthermore, when the adsorbents were studied in a challenging salt matrix, we observed that long-chain PFAS adsorption was controlled by a complementary interplay of hydrophobic and electrostatic interactions, whereas short-chain PFASs primarily relied on electrostatic interactions. This approach demonstrates great promise for anionic PFAS removal, and we anticipate that new compositions will be tailored using the versatility of radical polymerization to simultaneously target PFASs and other classes of micropollutants in the future.

Identifying the physicochemical properties of ß-cyclodextrin polymers that determine the adsorption of perfluoroalkyl acids.

Cyclodextrin polymers (CDPs) are emerging adsorbents with demonstrated potential to remove perfluoroalkyl acids (PFAAs) from water. However, little is known about how the physicochemical properties of different types of CDPs determine PFAA adsorption on CDPs. In this study, we investigated the adsorption performance of 34 CDPs which consist of 14 different crosslinkers and exhibit a wide range of physicochemical properties. The performance metrics included adsorption kinetics, equilibrium adsorption density, and adsorption affinity for six PFAAs. We then used complementary bivariate and multivariate analyses to discover relationships between sixteen measurable physicochemical properties of the CDPs and their performance as adsorbents. We found that: (1) CDPs with a less negative or more positive surface charge will exhibit enhanced adsorption of all types of PFAAs; (2) CDPs with greater porosity and surface area will exhibit enhanced adsorption kinetics for all types of PFAAs; (3) CDPs with greater crosslinker content will exhibit enhanced adsorption of short-chain PFAAs; (4) CDPs containing more hydrophobic crosslinkers will exhibit enhanced equilibrium adsorption density and adsorption affinity for longer-chain PFAAs; and (5) CDPs with smaller particle sizes will exhibit enhanced adsorption kinetics and equilibrium adsorption density for all PFAAs. These insights will enable the further development of CDPs and other novel adsorbents to optimize their performance for removing PFAAs during water and wastewater treatment or groundwater remediation.

Exploring the factors that influence the adsorption of anionic PFAS on conventional and emerging adsorbents in aquatic matrices.

Per and polyfluoroalkyl substances (PFASs) have raised great concern due to their ubiquity in aquatic environments, and adsorption technologies are among the most promising treatment solutions. This study investigated the key factors that influence the adsorption of anionic PFASs on conventional and emerging adsorbents. Batch adsorption experiments were conducted to evaluate the removal of 20 target PFASs at environmentally relevant concentrations by three different activated carbon (AC) materials and two different ß-cyclodextrin polymers (CDPs). Experiments were conducted in Milli-Q water and in groundwater. Major physical properties of the adsorbents were measured, along with general water chemistry parameters for each groundwater sample. Principal component analysis (PCA) was subsequently employed to extract the important associations from the multivariate dataset. The distinct performances of ACs and CDPs were attributed to their different surface chemistry and the distinct nature of their adsorption binding sites. Hydrophobic interactions dominated PFAS adsorption onto ACs while CDPs mostly attracted anionic PFASs via favorable electrostatic interactions. ACs of a smaller average particle size performed better, with our data pointing to an increased external specific surface area as the likely reason. pH and the concentration of cations were the primary contributors to adsorption inhibition in groundwater. Higher pH values limit anionic PFAS adsorption by deprotonating the functional groups on adsorbent surfaces. The elevated levels of cations in some groundwater samples limited the effects of attractive electrostatic interactions. Knowledge of PFAS adsorption mechanisms gained from this study can be used to design more efficient adsorbents and to predict their performance under a range of environmental scenarios.