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Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites

Nature Materials volume 18, pages 1358–1365 (2019)Cite this article

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Abstract

Emissions of SO2 from flue gas and marine transport have detrimental impacts on the environment and human health, but SO2 is also an important industrial feedstock if it can be recovered, stored and transported efficiently. Here we report the exceptional adsorption and separation of SO2 in a porous material, [Cu2(L)] (H4L = 4′,4‴-(pyridine-3,5-diyl)bis([1,1′-biphenyl]-3,5-dicarboxylic acid)), MFM-170. MFM-170 exhibits fully reversible SO2 uptake of 17.5 mmol g−1 at 298 K and 1.0 bar, and the SO2 binding domains for trapped molecules within MFM-170 have been determined. We report the reversible coordination of SO2 to open Cu(ii) sites, which contributes to excellent adsorption thermodynamics and selectivities for SO2 binding and facile regeneration of MFM-170 after desorption. MFM-170 is stable to water, acid and base and shows great promise for the dynamic separation of SO2 from simulated flue gas mixtures, as confirmed by breakthrough experiments.

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Fig. 1: Structure of MFM-170 from single-crystal X-ray diffraction data.
Fig. 2: Comparison of SO2 uptakes of reported MOFs and covalent–organic frameworks (COFs) at 1.0 bar and 298 K.
Fig. 3: Gas sorption and separation properties of MFM-170.
Fig. 4: Chemical stability tests for MFM-170.
Fig. 5: Positions of SO2 molecules located within the pores of MFM-170∙5.46SO2 from in situ single-crystal X-ray diffraction.
Fig. 6: In situ vibrational spectra of MFM-170.

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Data availability

Results of the refinements of the solvated, evacuated and SO2-loaded crystal structures of MFM-170 have been deposited as CIF files with CCDC numbers 1538125–1538126, 1538129 and 1853512–1853514. These data can be obtained free of charge from https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

We thank EPSRC (EP/I011870), ERC (AdG 742041), the Royal Society and University of Manchester for funding. We are especially grateful to Diamond Light Source, Advanced Light Source, Oak Ridge National Laboratory and STFC/ISIS Neutron Facility for access to the beamlines B22/I11, 11.3.1, VISION and TOSCA, respectively. We thank M. Kibble for help at TOSCA beamline. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by the Laboratory Directed Research and Development programme at ORNL. This research used resources of the Advanced Light Source, which is a US Department of Energy Office of Science User Facility under contract no. DE-AC02-05CH11231. J.L. and X.Z. thank the China Scholarship Council (CSC) for funding.

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Author notes

  1. These authors contributed equally: Gemma L. Smith, Jennifer E. Eyley.

Authors and Affiliations

  1. School of Chemistry, University of Manchester, Manchester, UK

    Gemma L. Smith, Jennifer E. Eyley, Xue Han, Xinran Zhang, Jiangnan Li, Nicholas M. Jacques, Harry G. W. Godfrey, Sihai Yang & Martin Schröder

  2. School of Chemistry, University of Nottingham, Nottingham, UK

    Stephen P. Argent

  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Laura J. McCormick McPherson & Simon J. Teat

  4. Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Yongqiang Cheng & Anibal J. Ramirez-Cuesta

  5. Diamond Light Source, Harwell Science Campus, Didcot, UK

    Mark D. Frogley, Gianfelice Cinque, Sarah J. Day & Chiu C. Tang

  6. School of Chemistry, Cardiff University, Cardiff, UK

    Timothy L. Easun

  7. ISIS, STFC Rutherford Appleton Laboratory, Chilton, UK

    Svemir Rudić

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Contributions

G.L.S. and J.E.E. performed the synthesis and characterization of MOF samples and measurements of adsorption isotherms. G.L.S. and X.H. performed measurements and the analysis of the breakthrough data. G.L.S., X.Z., S.P.A., L.J.M., S.J.T. and S.Y. collected and analysed the synchrotron single-crystal X-ray diffraction data. G.L.S., H.G.W.G., Y.C., S.R. and A.J.R.-C. collected and analysed the neutron scattering data. G.L.S., S.J.D. and C.C.T. collected and analysed the long-duration synchrotron X-ray diffraction data. G.L.S., J.L., N.M.J., M.D.F., G.C. and T.L.E. collected and analysed the synchrotron IR data. T.L.E. supervised the laboratory work of J.E.E. S.Y. and M.S. led the overall design and direction of the project. G.L.S., S.Y. and M.S. prepared the manuscript with help from all authors.

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Correspondence to Sihai Yang or Martin Schröder.

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Supplementary information

Supplementary Information

Supplementary Tables 1–29, Figs. 1–26 and refs. 1–12

Supplementary Data

Compressed archive file that contains six crystallographic information files corresponding to the crystal structures of MFM-170·H2O·solv (CCDC no. 1538125), MFM-170·H2O (CCDC no. 1538126), MFM-170·H2O·3.27SO2 (CCDC no. 1538129), MFM-170 (CCDC no. 1853512), MFM-170·5.46SO2 (CCDC no. 1853513) and MFM-170·0.09SO2 (CCDC no. 1853514)

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Smith, G.L., Eyley, J.E., Han, X. et al. Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites. Nat. Mater. 18, 1358–1365 (2019). https://doi.org/10.1038/s41563-019-0495-0

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