Rapid removal of organic micropollutants from water by a porous β

Nature volume 529, pages 190–194 (2016)Cite this article

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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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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.

Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, 14853, New York, USA

Alaaeddin Alsbaiee, Brian J. Smith, Leilei Xiao & William R. Dichtel

School of Civil and Environmental Engineering, Cornell University, Ithaca, 14853, New York, USA

Yuhan Ling & Damian E. Helbling

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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.

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

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

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).

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.

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.

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.

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).

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).

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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Received: 04 July 2015

Accepted: 26 October 2015

Published: 21 December 2015

Issue Date: 14 January 2016

DOI: https://doi.org/10.1038/nature16185

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