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

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.

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/.

References

  1. 1.

    Rezaei, F. et al. SOx/NOx removal from flue gas streams by solid adsorbents: a review of current challenges and future directions. Energy Fuels 29, 5467–5486 (2015).

    CAS  Article  Google Scholar 

  2. 2.

    Gao, J. et al. Pilot-scale experimental study on the CO2 capture process with existing of SO2: degradation, reaction rate, and mass transfer. Energy Fuels 25, 5802–5809 (2011).

    CAS  Article  Google Scholar 

  3. 3.

    Ding, S. et al. Significant promotion effect of Mo additive on a novel Ce–Zr mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. ACS Appl. Mater. Interf. 7, 9497–9506 (2015).

    CAS  Article  Google Scholar 

  4. 4.

    Kinnunen, N. M. et al. Case study of a modern lean-burn methane combustion catalyst for automotive applications: what are the deactivation and regeneration mechanisms? Appl. Catal. B Environ. 207, 114–119 (2017).

    CAS  Article  Google Scholar 

  5. 5.

    Han, X., Yang, S. & Schröder, M. Porous metal–organic frameworks as emerging sorbents for clean air. Nat. Rev. Chem. 3, 108–118 (2019).

    CAS  Article  Google Scholar 

  6. 6.

    Raymundo-Piñero, E. et al. Factors controling the SO2 removal by porous carbons: relevance of the SO2 oxidation step. Carbon 38, 335–344 (2000).

    Article  Google Scholar 

  7. 7.

    Mathieu, Y. et al. Adsorption of SOx by oxide materials: a review. Fuel Process. Technol. 114, 81–100 (2013).

    CAS  Article  Google Scholar 

  8. 8.

    Kohl, A. L. & Nielsen, R. Gas Purification (Gulf Professional, 1997).

  9. 9.

    Nabais, A. R. et al. CO2/N2 gas separation using Fe(BTC)-based mixed matrix membranes: a view on the adsorptive and filler properties of metal-organic frameworks. Sep. Purif. Technol. 202, 174–184 (2018).

    CAS  Article  Google Scholar 

  10. 10.

    Peng, J. et al. Efficient kinetic separation of propene and propane using two microporous metal organic frameworks. Chem. Commun. 53, 9332–9335 (2017).

    CAS  Article  Google Scholar 

  11. 11.

    Chen, D.-M. et al. Tunable robust pacs-MOFs: a platform for systematic enhancement of the C2H2 uptake and C2H2/C2H4 separation performance. Inorg. Chem. 57, 2883–2889 (2018).

    CAS  Article  Google Scholar 

  12. 12.

    Zhong, R. et al. A solvent ‘squeezing’ strategy to graft ethylenediamine on Cu3(BTC)2 for highly efficient CO2/CO separation. Chem. Eng. Sci. 184, 85–92 (2018).

    CAS  Article  Google Scholar 

  13. 13.

    Zhang, Z. et al. MOFs for CO2 capture and separation from flue gas mixtures: the effect of multifunctional sites on their adsorption capacity and selectivity. Chem. Commun. 49, 653–661 (2013).

    CAS  Article  Google Scholar 

  14. 14.

    Peralta, D. et al. Comparison of the behavior of metal–organic frameworks and zeolites for hydrocarbon separations. J. Am. Chem. Soc. 134, 8115–8126 (2012).

    CAS  Article  Google Scholar 

  15. 15.

    Carter, J. H. et al. Exceptional adsorption and binding of sulfur dioxide in a robust zirconium-based metal–organic framework. J. Am. Chem. Soc. 140, 15564–15567 (2018).

    CAS  Article  Google Scholar 

  16. 16.

    Cui, X. et al. Ultrahigh and selective SO2 uptake in inorganic anion-pillared hybrid porous materials. Adv. Mater. 29, 1606929 (2017).

    Article  Google Scholar 

  17. 17.

    Glomb, S. et al. Metal–organic frameworks with internal urea-functionalized dicarboxylate linkers for SO2 and NH3 adsorption. ACS Appl. Mater. Inter. 9, 37419–37434 (2017).

    CAS  Article  Google Scholar 

  18. 18.

    Yang, S. et al. Irreversible network transformation in a dynamic porous host catalyzed by sulfur dioxide. J. Am. Chem. Soc. 135, 4954–4957 (2013).

    CAS  Article  Google Scholar 

  19. 19.

    Tan, K. et al. Mechanism of preferential adsorption of SO2 into two microporous paddle wheel frameworks M(bdc)(ted)0.5. Chem. Mater. 25, 4653–4662 (2013).

    CAS  Article  Google Scholar 

  20. 20.

    Savage, M. et al. Selective adsorption of sulfur dioxide in a robust metal-organic framework material. Adv. Mater. 28, 8705–8711 (2016).

    CAS  Article  Google Scholar 

  21. 21.

    Li, L. et al. Post-synthetic modulation of the charge distribution in a metal–organic framework for optimal binding of carbon dioxide and sulfur dioxide. Chem. Sci. 10, 1472–1482 (2019).

    CAS  Article  Google Scholar 

  22. 22.

    Lee, G.-Y. et al. Amine-functionalized covalent organic framework for efficient SO2 capture with high reversibility. Sci. Rep. 7, 557 (2017).

    Article  Google Scholar 

  23. 23.

    Thallapally, P. K. et al. Prussian blue analogues for CO2 and SO2 capture and separation applications. Inorg. Chem. 49, 4909–4915 (2010).

    CAS  Article  Google Scholar 

  24. 24.

    Fernandez, C. et al. Gas-induced expansion and contraction of a fluorinated metal−organic framework. Cryst. Growth Des. 10, 1037–1039 (2010).

    CAS  Article  Google Scholar 

  25. 25.

    Tchalala, M. R. et al. Fluorinated MOF platform for selective removal and sensing of SO2 from flue gas and air. Nat. Commun. 10, 1328 (2019).

    CAS  Article  Google Scholar 

  26. 26.

    Riboldi, L. & Bolland, O. Overview on pressure swing adsorption (PSA) as CO2 capture technology: state-of-the-art, limits and potentials. Energy Proc. 114, 2390–2400 (2017).

    CAS  Article  Google Scholar 

  27. 27.

    Riboldi, L. & Bolland, O. Evaluating pressure swing adsorption as a CO2 separation technique in coal-fired power plants. Int. J. Greenh. Gas. Control 39, 1–16 (2015).

    CAS  Article  Google Scholar 

  28. 28.

    Britt, D. et al. Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites. Proc. Natl. Acad. Sci. USA 106, 20637–20640 (2009).

    CAS  Article  Google Scholar 

  29. 29.

    Wong-Foy, A. G., Matzger, A. J. & Yaghi, O. M. Exceptional H2 saturation uptake in microporous metal-organic frameworks. J. Am. Chem. Soc. 128, 3494–3495 (2006).

    CAS  Article  Google Scholar 

  30. 30.

    Caskey, S. R., Wong-Foy, A. G. & Matzger, A. J. Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores. J. Am. Chem. Soc. 130, 10870–10871 (2008).

    CAS  Article  Google Scholar 

  31. 31.

    Britt, D., Tranchemontagne, D. & Yaghi, O. M. Metal-organic frameworks with high capacity and selectivity for harmful gases. Proc. Natl. Acad. Sci. USA 105, 11623–11627 (2008).

    CAS  Article  Google Scholar 

  32. 32.

    Guillerm, V. et al. A supermolecular building approach for the design and construction of metal–organic frameworks. Chem. Soc. Rev. 43, 6141–6172 (2014).

    CAS  Article  Google Scholar 

  33. 33.

    Park, J. et al. A versatile metal–organic framework for carbon dioxide capture and cooperative catalysis. Chem. Commun. 48, 9995–9997 (2012).

    CAS  Article  Google Scholar 

  34. 34.

    Lu, Z. et al. The utilization of amide groups to expand and functionalize metal-organic frameworks simultaneously. Chem. A Eur. J. 22, 6277–6285 (2016).

    CAS  Article  Google Scholar 

  35. 35.

    Branton, P. J., Hall, P. G., Treguer, M. & Sing, K. S. W. Adsorption of carbon dioxide, sulfur dioxide and water vapour by MCM-41, a model mesoporous adsorbent. J. Chem. Soc. Faraday Trans. 91, 2041–2043 (1995).

    CAS  Article  Google Scholar 

  36. 36.

    Tan, K. et al. Interaction of acid gases SO2 and NO2 with coordinatively unsaturated metal organic frameworks: MOF-74 (M = Zn, Mg, Ni, Co). Chem. Mater. 29, 4227–4235 (2017).

    CAS  Article  Google Scholar 

  37. 37.

    Goodman, A. L., Li, P., Usher, C. R. & Grassian, V. H. Heterogeneous uptake of sulfur dioxide on aluminum and magnesium oxide particles. J. Phys. Chem. A 105, 6109–6120 (2001).

    CAS  Article  Google Scholar 

  38. 38.

    Schneider, W. F., Li, J. & Hass, K. C. Combined computational and experimental investigation of SOx adsorption on MgO. J. Phys. Chem. B 105, 6972–6979 (2001).

    CAS  Article  Google Scholar 

  39. 39.

    Marinho, M. V. et al. Synthesis, crystal structure, and spectroscopic characterization of trans-bis[(μ-1,3-bis(4-pyridyl)propane)(μ-(3-thiopheneacetate-O))(3-thiopheneacetate-O)]dicopper(II), {[Cu2(O2CCH2C4H3S)4 μ-(BPP)2]}n: from a dinuclear paddle-wheel copper(II) unit to a 2-D coordination polymer involving monatomic carboxylate bridges. Inorg. Chem. 43, 1539–1544 (2004).

    CAS  Article  Google Scholar 

Download references

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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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.

Corresponding authors

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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