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A robust pyrazolate metal–organic framework for integrated perfluorooctanoic acid concentration and degradation

Nature Water volume 2, pages 1218–1225 (2024)Cite this article

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Abstract

Perfluorooctanoic acid (PFOA) poses a substantial threat to human health due to its bioaccumulation and carcinogenic nature. Current remediation strategies typically focus on either adsorption or degradation, neglecting the potential of an integrated approach. Herein, we present a pyrazolate metal–organic framework (MOF), PCN-1003, featuring a lamellar structure with one-dimensional open channels. PCN-1003 exhibits exceptional stability across a wide pH range (1–12) in aqueous solutions, achieving efficient PFOA adsorption (642 mg g−1). Mechanistic studies revealed that a PFOA–acetate exchange process dominates, representing a remarkable example of such a mechanism and enabling efficient PFOA uptake. Notably, PCN-1003 greatly facilitates PFOA degradation at a much lower temperature (90 °C) than observed in previously reported methods, with an approximately threefold catalytic acceleration effect, attributed to the coordination of PFOA and the confined environment within PCN-1003. This study pioneers integrated PFOA concentration and degradation using a single MOF, presenting a promising avenue for treating water contaminated with per- and polyfluoroalkyl substances.

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Fig. 1: Crystal structure and topology of PCN-1003.
Fig. 2: Structural characterization of PCN-1003.
Fig. 3: Performance and mechanism of PFOA adsorption in PCN-1003.
Fig. 4: Study of the decarboxylation of PFOA.

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Data availability

The X-ray crystallographic coordinates for PCN-1003 reported in this study have been deposited at the Cambridge Crystallographic Data Centre. These data can be obtained free of charge under deposition number 2358814. All other data supporting the findings of this study are available within the article and its Supplementary Information or from the corresponding author upon reasonable request.

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Acknowledgements

We gratefully acknowledge the financial support from the US Department of Energy, Office of Fossil Energy (grant no. DE-FE0032108). Additional support was provided by the Robert A. Welch Foundation through a Welch Endowed Chair to H.-C.Z (A-0030). We also acknowledge the financial support of the US Department of Energy, Office of Fossil Energy/Pennsylvania State University (grant no. S000655-DOE). Y.F. gratefully acknowledges the support of GWK for funding this project by providing computing time through the Center for Information Services and HPC (ZIH) at TU Dresden.

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Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Rong-Ran Liang, Zongsu Han, Yihao Yang, Vladimir I. Bakhmutov, Zhaoyi Liu, Joshua Rushlow & Hong-Cai Zhou

  2. Center for Advancing Electronics Dresden (CFAED) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Yubin Fu

  3. Max Planck Institute of Microstructure Physics, Halle, Germany

    Yubin Fu

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Contributions

H.-C.Z. conceived the research idea. R.-R.L. performed most of the experiments and analysed the data. Y.F. conducted the calculations. Z.H. and Y.Y. solved the single-crystal data. V.I.B. conducted the solid-state NMR experiments and analysed the data. R.-R.L. and H.-C.Z. wrote the paper. Z.L. and J.R. collected and analysed the NMR data. All authors discussed the results and commented on the paper.

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Correspondence to Hong-Cai Zhou.

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Nature Water thanks Lingxin Chen and Mario Wriedt for their contribution to the peer review of this work.

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Supplementary Information

General methods and instruments, Supplementary Figs. 1–39 and Tables 1–3.

Supplementary Data 1

Crystallographic txt file.

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Crystallographic checkcif report.

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Liang, RR., Fu, Y., Han, Z. et al. A robust pyrazolate metal–organic framework for integrated perfluorooctanoic acid concentration and degradation. Nat Water 2, 1218–1225 (2024). https://doi.org/10.1038/s44221-024-00343-1

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