Rapid removal of organic micropollutants from water by a porous ß-cyclodextrin polymer.

The global occurrence in water resources of organic micropollutants, such as pesticides and pharmaceuticals, has raised concerns about potential negative effects on aquatic ecosystems and human health. Activated carbons are the most widespread adsorbent materials used to remove organic pollutants from water but they have several deficiencies, including slow pollutant uptake (of the order of hours) and poor removal of many relatively hydrophilic micropollutants. Furthermore, regenerating spent activated carbon is energy intensive (requiring heating to 500-900 degrees Celsius) and does not fully restore performance. Insoluble polymers of ß-cyclodextrin, an inexpensive, sustainably produced macrocycle of glucose, are likewise of interest for removing micropollutants from water by means of adsorption. ß-cyclodextrin is known to encapsulate pollutants to form well-defined host-guest complexes, but until now cross-linked ß-cyclodextrin polymers have had low surface areas and poor removal performance compared to conventional activated carbons. Here we crosslink ß-cyclodextrin with rigid aromatic groups, providing a high-surface-area, mesoporous polymer of ß-cyclodextrin. It rapidly sequesters a variety of organic micropollutants with adsorption rate constants 15 to 200 times greater than those of activated carbons and non-porous ß-cyclodextrin adsorbent materials. In addition, the polymer can be regenerated several times using a mild washing procedure with no loss in performance. Finally, the polymer outperformed a leading activated carbon for the rapid removal of a complex mixture of organic micropollutants at environmentally relevant concentrations. These findings demonstrate the promise of porous cyclodextrin-based polymers for rapid, flow-through water treatment.

Reduction of a Tetrafluoroterephthalonitrile-ß-Cyclodextrin Polymer to Remove Anionic Micropollutants and Perfluorinated Alkyl Substances from Water.

Organic micropollutants (MPs) are anthropogenic substances that contaminate water resources at trace concentrations. Many MPs, including per- and polyfluorinated alkyl substances (PFASs), have come under increased scrutiny because of their environmental persistence and association with various health problems. A ß-cyclodextrin polymer linked with tetrafluoroterephthalonitrile (TFN-CDP) has high affinity for cationic and many neutral MPs from contaminated water because of anionic groups incorporated during the polymerization. But TFN-CDP does not bind many anionic MPs strongly, including anionic PFASs. To address this shortcoming, we reduced the nitrile groups in TFN-CDP to primary amines, which reverses its affinity towards charged MPs. TFN-CDP exhibits adsorption distribution coefficients (log KD values) of 2-3 for cationic MPs and -0.5-1.5 for anionic MPs, whereas the reduced TFN-CDP exhibits log KD values of -0.5-1.5 for cationic MPs and 2-4 for anionic MPs, with especially high affinity towards anionic PFASs. Kinetic studies of the removal of 10 anionic PFASs at environmentally relevant concentrations showed 80-98 % removal of all contaminants after 30 min and was superior to commercial granular activated carbon. These findings demonstrate the scope and tunability of CD-based adsorbents derived from a single polymerization and the promise of novel adsorbents constructed from molecular receptors.

Removal of GenX and Perfluorinated Alkyl Substances from Water by Amine-Functionalized Covalent Organic Frameworks.

Per- and polyfluorinated alkyl substances (PFAS), such as perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), and ammonium perfluoro-2-propoxypropionate (GenX), contaminate ground and surface waters throughout the world. The cost and performance limitations of current PFAS removal technologies motivate efforts to develop selective and high-affinity adsorbents. Covalent organic frameworks (COFs) are unexplored yet promising adsorbents because of their high surface area and tunable pore sizes. Here we show that imine-linked two-dimensional (2D) COFs bearing primary amines adsorb GenX rapidly at environmentally relevant concentrations. COFs with partial amine incorporation showed the highest capacity and fastest removal, suggesting that the synergistic combination of the polar group and hydrophobic surfaces are responsible for GenX binding. A COF with 28% amine loading also removed more than 90% of 12 out of 13 PFAS. These results demonstrate the promise of COFs for PFAS removal and suggest design criteria for maximizing adsorbent performance.

ß-Cyclodextrin Polymer Network Sequesters Perfluorooctanoic Acid at Environmentally Relevant Concentrations.

Per- and poly fluorinated alkyl substances (PFASs), notably perfluorooctanoic acid (PFOA), contaminate many ground and surface waters and are environmentally persistent. The performance limitations of existing remediation methods motivate efforts to develop effective adsorbents. Here we report a ß-cyclodextrin (ß-CD)-based polymer network with higher affinity for PFOA compared to powdered activated carbon, along with comparable capacity and kinetics. The ß-CD polymer reduces PFOA concentrations from 1 µg L-1 to <10 ng L-1, at least 7 times lower than the 2016 U.S. EPA advisory level (70 ng L-1), and was regenerated and reused multiple times by washing with MeOH. The performance of the polymer is unaffected by humic acid, a component of natural organic matter that fouls activated carbons. These results are promising for treating PFOA-contaminated water and demonstrate the versatility of ß-CD-based adsorbents.

Benchmarking Micropollutant Removal by Activated Carbon and Porous ß-Cyclodextrin Polymers under Environmentally Relevant Scenarios.

The cost-effective and energy-efficient removal of organic micropollutants (MPs) from water and wastewater is challenging. The objective of this research was to evaluate the performance of porous ß-cyclodextrin polymers (P-CDP) as adsorbents of MPs in aquatic matrixes. Adsorption kinetics and MP removal were measured in batch and flow-through experiments for a mixture of 83 MPs at environmentally relevant concentrations (1 µg L-1) and across gradients of pH, ionic strength, and natural organic matter (NOM) concentrations. Performance was benchmarked against a coconut-shell activated carbon (CCAC). Data reveal pseudo-second-order rate constants for most MPs ranging between 1.5 and 40 g mg-1 min-1 for CCAC and 30 and 40000 g mg-1 min-1 for P-CDP. The extent of MP removal demonstrates slower but more uniform uptake on CCAC and faster but more selective uptake on P-CDP. Increasing ionic strength and the presence of NOM had a negative effect on the adsorption of MPs to CCAC but had almost no effect on adsorption of MPs to P-CDP. P-CDP performed particularly well for positively charged MPs and neutral or negatively charged MPs with McGowan volumes greater than 1.7 (cm3 mol-1)/100. These data highlight advantages of P-CDP adsorbents relevant to MP removal during water and wastewater treatment.

The dynamics of the risk perception on a social network and its effect on disease dynamics.

The perceived infection risk changes individual behaviors, which further affects the disease dynamics. This perception is influenced by social communication, including surveying their social network neighbors about the fraction of infected neighbors and averaging their neighbors' perception of the risk. We model the interaction of disease dynamics and risk perception on a two-layer random network that combines a social network layer with a contact network layer. We found that if information spreads much faster than disease, then all individuals converge on the true prevalence of the disease. On the other hand, if the two dynamics have comparable speeds, the risk perception still converges to a value uniformly on the network. However, the perception lags behind the true prevalence and has a lower peak value. We also study the behavior change caused by the perception of infection risk. This behavior change may affect the disease dynamics by reducing the transmission rate along the edges of the contact network or by breaking edges and isolating the infectious individuals. The effects on the basic reproduction number, the peak size, and the final size are studied. We found that these two effects give the same basic reproduction number. We find edge-breaking has a larger effect on reducing the final size, while reducing the transmission rate has a larger effect on reducing the peak size, which is true for both scale-free and Poisson networks.

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.

Evaluating the effects of water matrix constituents on micropollutant removal by activated carbon and ß-cyclodextrin polymer adsorbents.

The performance of adsorbents for the removal of organic micropollutants (MPs) from water can be influenced by the presence of water matrix constituents. The objective of this research was to evaluate the influence of water matrix constituents on the performance of coconut-shell activated carbon (CCAC), porous ß-cyclodextrin polymer (CDP), and CDP coated on cellulose microcrystal (CDP@CMC) adsorbents. MP removals were measured in batch experiments for a mixture of 90 MP at 1 µg L-1 and MP breakthrough was measured in rapid small-scale column test (RSSCT) experiments for a mixture of 15 MP at 500 ng L-1. All experiments were performed first with nanopure water, and subsequently with six different water samples collected from two separate groundwater, surface water, and wastewater effluent sources. The results of batch and RSSCT experiments demonstrate more rapid adsorption kinetics and less adsorption inhibition in the presence of matrix constituents for CDP adsorbents relative to CCAC. Further, the treatment capacity of CDP@CMC in the RSSCT experiments was higher than that of CCAC, particularly in more complex water matrices. Statistical analyses were performed to investigate associations between adsorption inhibition among groups of MPs and the concentrations of specific water matrix constituents. For CCAC, adsorption inhibition was observed for all MPs and was primarily attributed to the presence of dissolved organic matter with molar weight less than 1000 Da. For CDP adsorbents, adsorption inhibition was primarily observed for cationic MPs and was attributed to the screening of the negative surface charge of CDP by inorganic ions in water samples with high ionic strength. These data further demonstrate the value of CDP as an alternative adsorbent to CCAC for the removal of MPs during water and wastewater treatment.

QSARs to predict adsorption affinity of organic micropollutants for activated carbon and ß-cyclodextrin polymer adsorbents.

The removal of organic micropollutants (MPs) from water by means of adsorption is determined by the physicochemical properties of the adsorbent and the MPs. It is challenging to predict the removal of MPs by specific adsorbents due to the extreme diversity in physicochemical properties among MPs of interest. In this research, we established Quantitative Structure-Activity Relationships (QSARs) between the physicochemical properties of a diverse set of MPs and their distribution coefficients (KD) measured on coconut shell activated carbon (CCAC) and porous ß-cyclodextrin polymer (P-CDP) adsorbents. We conducted batch experiments with a mixture of 200 MPs and used the data to calculate KD values for each MP on each adsorbent under conditions of infinite dilution (i.e., low adsorbate concentrations). We used computational software to calculate 3656 molecular descriptors for each MP. We then developed and applied a model-selection workflow to identify the most significant molecular descriptors for each adsorbent. The functional stability and predictive power of the resulting QSARs were confirmed with internal cross validation and external validation. The applicability domain of the QSARs was defined based on the most significant molecular descriptors selected into each QSAR. The QSARs are predictive tools for evaluating adsorption-based water treatment processes and provide new insights into CCAC and P-CDP adsorption mechanisms.

ß-Cyclodextrin Polymers on Microcrystalline Cellulose as a Granular Media for Organic Micropollutant Removal from Water.

Organic contaminants at low concentrations, known as micropollutants, are a growing threat to water resources. Implementing novel adsorbents capable of removing micropollutants during packed-bed adsorption is desirable for rapid water purification and other efficient separations. We previously developed porous polymers based on cyclodextrins that demonstrated rapid uptake and high affinity for dozens of micropollutants (MPs) in batch experiments. However, these polymers are typically produced as powders with irregular particle size distributions in the range of tens of micrometers. In this powdered form, cyclodextrin polymers cannot be implemented in packed-bed adsorption processes because the variable particle sizes yield insufficient porosity packing and consequently generate high back-pressure. Here we demonstrate a facile approach to remove micropollutants from water in a continuous manner by polymerizing cyclodextrin polymer networks onto cellulose microcrystals to provide a core/shell structure. Batch adsorption experiments demonstrate rapid pollutant uptake and high accessibility of the cyclodextrins on the adsorbent. Similarly, column experiments demonstrate rapid uptake of a model pollutant with minimal back-pressure, demonstrating potential for use in packed-bed adsorption processes. Furthermore, the pollutant-saturated columns were regenerated using methanol and reused three times with almost no change in performance. Column experiments conducted with a mixture of 15 micropollutants at environmentally relevant concentrations demonstrated that removal was determined by the affinity of each micropollutant for cyclodextrin polymers. The cyclodextrin polymer grafted onto cellulose microcrystals is more resistant to both anaerobic and aerobic biodegradation as compared to cyclodextrins and unmodified cellulose crystals, presumably due to the aromatic cross-linkers, demonstrating persistence. Collectively, the findings from this study demonstrate a general strategy to incorporate novel cyclodextrin adsorbents onto cellulose substrates to enable rapid and efficient removal of micropollutants during packed-bed adsorption as well as their promising long-term stability and regeneration capabilities.

Phenolation of cyclodextrin polymers controls their lead and organic micropollutant adsorption.

Porous ß-cyclodextrin polymers linked with tetrafluoroterephthalonitrile (TFN-CDPs) have shown promise for adsorbing organic micropollutants (MPs) more quickly and effectively than conventional adsorbents. Prior to their discovery, the nucleophilic aromatic substitution (SNAr) reaction used to prepare TFN-CDP was nearly unknown for the aliphatic alcohol nucleophiles, and the low isolated yields of TFN-CDP motivated model studies of the reaction between TFN and n-butanol. These experiments reveal a previously undescribed substitution reaction of TFN in which a fluorine is substituted by a hydroxyl group. This process is responsible for the low yields of the polymerization and incorporates phenolate groups into the polymer network. Phenolation and polymerization (etherification) are competing processes, and the level of phenolate incorporation was controlled by varying the rate of base addition and initial monomer concentrations. TFN-CDPs with varying phenolate content were prepared and evaluated as adsorbents for both Pb2+ ions and 83 MPs. More heavily phenolated polymers showed increased capacity to bind Pb2+ ions. Phenolation was also correlated with increased binding affinity for almost all of the 83 MPs tested, including neutral, cationic, and anionic substances. These results leverage a newly discovered side reaction during SNAr reactions of electron-poor aryl fluorides to improve both the yield and the uptake affinity for both lead and organic MPs of TFN-CDPs.

Magnetically separable core-shell structural γ-Fe2O3@Cu/Al-MCM-41 nanocomposite and its performance in heterogeneous Fenton catalysis.

To target the low catalytic activity and the inconvenient separation of copper loading nanocatalysts in heterogeneous Fenton-like reaction, a core-shell structural magnetically separable catalyst, with γ-Fe2O3 nanoparticles as the core layer and the copper and aluminum containing MCM-41 as the shell layer, has been fabricated. The role of aluminum has been discussed by comparing the copper containing mesoporous silica with various Cu contents. Their physiochemical properties have been characterized by XRD, UV-vis, FT-IR, TEM, nitrogen physisorption and magnetite susceptibility measurements. Double content Cu incorporation results in an improved catalytic activity for phenol degradation at the given condition (40°C, initial pH=4), but leads to a declined BET surface area and less ordered mesophase structure. Aluminum incorporation helps to retain the high BET surface area (785.2m(2)/g) and the regular hexagonal mesoporous structure of MCM-41, which make the catalyst possess a lower copper content and even a higher catalytic activity than that with the double copper content in the absence of aluminum. The catalysts can be facilely separated by an external magnetic field for recycle usage.