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

Abstract

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 health1,2,3,4,5. 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)6,7 and poor removal of many relatively hydrophilic micropollutants8. Furthermore, regenerating spent activated carbon is energy intensive (requiring heating to 500–900 degrees Celsius) and does not fully restore performance9,10. Insoluble polymers of β-cyclodextrin, an inexpensive, sustainably produced macrocycle of glucose, are likewise of interest for removing micropollutants from water by means of adsorption11. β-cyclodextrin is known to encapsulate pollutants to form well-defined host–guest complexes, but until now cross-linked β-cyclodextrin polymers have had low surface areas and poor removal performance compared to conventional activated carbons11,12,13. Here we crosslink β-cyclodextrin with rigid aromatic groups, providing a high-surface-area, mesoporous polymer of β-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 β-cyclodextrin adsorbent materials7,8,11,12,13. 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.

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Figure 1: β-CD polymer networks derived from nucleophilic aromatic substitution reactions.
Figure 2: Rate of bisphenol A uptake by various adsorbents.
Figure 3: Compound P-CDP rapidly adsorbs a broad range of organic micropollutants.
Figure 4: P-CDP outperforms NAC for the rapid removal of a complex mixture of pollutants at environmentally relevant concentrations.

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Acknowledgements

This work was supported by the National Science Foundation (NSF) through the Center for Sustainable Polymers (CHE-1413862). This research made use of the Cornell Center for Materials Research User Facilities, which are supported by the NSF (DMR-1120296). We acknowledge I. Keresztes for help with NMR spectroscopy, and M. Matsumoto for the design of the schematic of the polymer in Fig. 1a.

Author information

Authors and Affiliations

Authors

Contributions

A.A., B.J.S., and L.X., and W.R.D. designed, synthesized, and characterized the cyclodextrin polymers and their micropollutant uptake at high concentrations. Y.L. and D.E.H. designed and conducted experiments that quantified micropollutant uptake at low concentrations. All authors wrote the manuscript.

Corresponding authors

Correspondence to Damian E. Helbling or William R. Dichtel.

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Competing interests

Cornell University has filed a provisional patent application related to the new cyclodextrin polymers reported in this manuscript.

Extended data figures and tables

Extended Data Figure 1 Porosity measurements of commercial ACs.

These are the materials used in Fig. 2. Shown are the N2 sorption isotherm (77 K, left column) and the cumulative pore size distribution (right column) of Brita AC (a), GAC (b) and NAC (c). The cumulative pore size distributions of each adsorbent are similar to that of P-CDP (Fig. 1c).

Extended Data Figure 2 Infrared spectra of the cyclodextrin polymers and monomers.

Spectra are labelled by chemical structure or compound name (top trace is 1, second trace down is β-CD). The FT-IR spectra shown in this figure of P-CDP and NP-CDP reflect the incorporation of β-CD and 1.

Extended Data Figure 3 13C CP-MAS solid-state NMR spectra of P-CDP, NP-CDP, β-CD and 1.

The spectra of P-CDP and NP-CDP exhibit resonances associated with β-CD at δ = 72 and 100 p.p.m. (labelled a and b, respectively). Resonances at δ = 95 and 140 p.p.m. (labelled e and c) correspond to the newly formed alkoxy groups and aromatic carbons, respectively. The spectrum of 1 is broadened because of 19F–13C coupling.

Extended Data Figure 4 Characterization of the bisphenol A uptake rate by each adsorbent.

UV–vis spectra recorded at different contact times (coloured traces; left column) and pseudo-second-order plots (right column) for P-CDP (a), NP-CDP (b), EPI-CDP (c), Brita AC (d), GAC (e) and NAC (f). t (in min) is the contact time of bisphenol A solution with the adsorbent, and Qt (in mg g−1) is the amount of bisphenol A adsorbed per gram of adsorbent.

Extended Data Figure 5 Langmuir isotherm of bisphenol A adsorption by P-CDP.

The equilibrium uptake of bisphenol A, qe (in mg g−1), by P-CDP as a function of bisphenol A residual concentration (C, in mol l−1) fits the Langmuir model, which is consistent with the formation of 1:1 inclusion complexes with an association constant (K) of 56,500 L mol−1, and an 88 mg g−1 maximum equilibrium adsorption capacity (qmax,e).

Extended Data Figure 6 Uptake of other pollutants by P-CDP.

UV–vis spectra recorded as a function of contact times with P-CDP (1 mg ml−1). a, BPS (0.1 mM); b, metolachlor (0.1 mM); c, ethinyl oestradiol (0.04 mM); d, propranolol hydrochloride (0.09 mM); e, 2-NO (0.1 mM); f, 1-NA (0.1 mM); and g, 2,4-DCP (0.1 mM).

Extended Data Table 1 Water regain analysis of P-CDP and NP-CDP
Extended Data Table 2 Rates of bisphenol A uptake by each adsorbent
Extended Data Table 3 Equilibrium uptake of each pollutant by P-CDP
Extended Data Table 4 Adsorption equilibrium constants for each micropollutant onto P-CDP

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This file contains Supplementary Text and Data, Supplementary Figures 1-8 and Supplementary Tables 1-2. (PDF 1690 kb)

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Alsbaiee, A., Smith, B., Xiao, L. et al. Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer. Nature 529, 190–194 (2016). https://doi.org/10.1038/nature16185

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