Abstract

Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

References

  1. 1.

    Zhou, H. C., Long, J. R. & Yaghi, O. M. Introduction to metal–organic frameworks. Chem. Rev. 112, 673–674 (2012).

  2. 2.

    Sumida, K. et al. Carbon dioxide capture in metal–organic frameworks. Chem. Rev. 112, 724–781 (2012).

  3. 3.

    Suh, M. P., Park, H. J., Prasad, T. K. & Lim, D. W. Hydrogen storage in metal–organic frameworks. Chem. Rev. 112, 782–835 (2012).

  4. 4.

    McKinlay, A. C. et al. BioMOFs: metal–organic frameworks for biological and medical applications. Angew. Chem. 49, 6260–6266 (2010).

  5. 5.

    Ferey, G. & Serre, C. Large breathing effects in three-dimensional porous hybrid matter: facts, analyses, rules and consequences. Chem. Soc. Rev. 38, 1380–1399 (2009).

  6. 6.

    Burtch, N. C., Jasuja, H. & Walton, K. S. Water stability and adsorption in metal–organic frameworks. Chem. Rev. 114, 10575–10612 (2014).

  7. 7.

    Cavka, J. H. et al. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 130, 13850–13851 (2008).

  8. 8.

    Colombo, V. et al. High thermal and chemical stability in pyrazolate-bridged metal–organic frameworks withexposed metal sites. Chem. Sci. 2, 1311–1319 (2011).

  9. 9.

    DeCoste, J. B., Denny, M. S., Peterson, G. W., Mahle, J. J. & Cohen, S. M. Enhanced aging properties of HKUST-1 in hydrophobic mixed-matrix membranes for ammonia adsorption. Chem. Sci. 7, 2711–2716 (2016).

  10. 10.

    DeCoste, J. B., Peterson, G. W., Smith, M. W., Stone, C. A. & Willis, C. R. Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition. J. Am. Chem. Soc. 134, 1486–1489 (2012).

  11. 11.

    Wittmann, T. et al. Enhancing the water stability of Al-MIL-101-NH2 via postsynthetic modification. Chem. Eur. J. 21, 314–323 (2015).

  12. 12.

    Chui, S. S. Y., Lo, S. M. F., Charmant, J. P. H., Orpen, A. G. & Williams, I. D. A chemically functionalizable nanoporous material Cu3(TMA)2(H2O)3. Science 283, 1148–1150 (1999).

  13. 13.

    Peterson, G. W. et al. Ammonia vapor removal by Cu3(BTC)2 and its characterization by MAS NMR. J. Phys. Chem. C 113, 13906–13917 (2009).

  14. 14.

    DeCoste, J. B. & Peterson, G. W. Metal–organic frameworks for air purification of toxic chemicals. Chem. Rev. 114, 5695–5727 (2014).

  15. 15.

    Singh, M. P., Dhumal, N. R., Kim, H. J., Kiefer, J. & Anderson, J. A. Influence of water on the chemistry and structure of the metal organic framework Cu3(btc)2. J. Phys. Chem. C. 120, 17323–17333 (2016).

  16. 16.

    Serre, C. et al. Very large breathing effect in the first nanoporous chromium(iii)-based solids: MIL-53 or CrIII(OH)·{O2C–C6H4-CO2}·{HO2C-C6H4-CO2H}x·H2Oy. J. Am. Chem. Soc. 124, 13519–13526 (2002).

  17. 17.

    Xiao, B. et al. Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework. Nat. Chem. 1, 289–294 (2009).

  18. 18.

    Slone, C. S., Weinberger, D. A. & Mirkin, C. A. The transition metal coordination chemistry of hemilabile ligands. Prog. Inorg. Chem. 48, 233–350 (1999).

  19. 19.

    Mohideen, M. I. H. et al. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic–hydrophobic metal–organic framework. Nat. Chem. 3, 304–310 (2011).

  20. 20.

    Sato, H. et al. Self-accelerating CO sorption in a soft nanoporous crystal. Science 343, 167–170 (2014).

  21. 21.

    Dawson, D. M. et al. High-resolution solid-state 13C NMR spectroscopy of the paramagnetic metal–organic frameworks, STAM-1 and HKUST-1. Phys. Chem. Chem. Phys. 15, 919–929 (2013).

  22. 22.

    Clarke, S. J. et al. First principles methods using CASTEP. Z. Krist. 220, 567–570 (2005).

  23. 23.

    Al-Janabi, N., Alfutimie, A., Siperstein, F. R. & Fan, X. L. Underlying mechanism of the hydrothermal instability of Cu3(BTC)2 metal–organic framework. Front. Chem. Sci. Eng. 10, 103–107 (2016).

  24. 24.

    Todaro, M. et al. Decomposition process of carboxylate MOF HKUST-1 unveiled at the atomic scale level. J. Phys. Chem. C 120, 12879–12889 (2016).

  25. 25.

    Nijem, N., Fursich, K., Bluhrn, H., Leone, S. R. & Gilles, M. K. Ammonia adsorption and co-adsorption with water in HKUST-1: spectroscopic evidence for cooperative interactions. J. Phys. Chem. C 119, 24781–24788 (2015).

  26. 26.

    Mazur, M. et al. Synthesis of ‘unfeasible’ zeolites. Nat. Chem. 8, 58–62 (2016).

  27. 27.

    Morris, R. E. & Cejka, J. Exploiting chemically selective weakness in solids as a route to new porous materials. Nat. Chem. 7, 381–388 (2015).

  28. 28.

    Wu, D. & Navrotsky, A. Thermodynamics of metal–organic frameworks. J. Solid State Chem. 223, 53–58 (2015).

  29. 29.

    Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination. J. Appl. Crystallogr. 48, 3–10 (2015).

  30. 30.

    Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. C 71, 308 (2015).

  31. 31.

    Brennan, S. & Cowan, P. L. A suite of programs for calculating X-ray absorption, reflection, and diffraction performance for a variety of materials at arbitrary wavelengths. Rev. Sci. Instrum. 63, 850–853 (1992).

  32. 32.

    Farrugia, L. J. WinGX and ORTEP for Windows: an update. J. Appl. Cryst. 45, 849–854 (2012).

  33. 33.

    Skibsted, J. & Jakobsen, H. J. Variable-temperature 87Rb magic-angle spinning NMR spectroscopy of inorganic rubidium salts. J. Phys. Chem. A 103, 7958–7971 (1999).

Download references

Acknowledgements

R.E.M. thanks the Royal Society and the EPSRC (grants EP/L014475/1 and EP/K025112/1) for funding work in this area, and the Czech Science Foundation for project P106/12/G015 and OP VVV ‘Excellent Research Teams’, project no. CZ.02.1.01/0.0/0.0/15_003/0000417 – CUCAM. S.E.A. thanks the Royal Society/Wolfson Foundation for a merit award, and the European Research Council (EU FP7 Consolidator Grant 614290 ‘EXONMR’) for funding. This research used the resources of the Advanced Light Source, which is a US DOE Office of Science User Facility under contract no. DE-AC02-05CH11231, and the development of the gas cell used in this research was funded through US DOE award no. DE-SC0001015. The authors thank the Diamond Light Source and C. Tang for access to beamline I11, and S. Vornholt for help with electron microscopy and the EPSRC Capital for Great Technologies funding (EP/L017008/1).

Author information

Affiliations

  1. EaStCHEM School of Chemistry, University of St Andrews, Purdie Building, St Andrews, UK

    • Lauren N. McHugh
    • , Matthew J. McPherson
    • , Laura J. McCormick
    • , Samuel A. Morris
    • , Paul S. Wheatley
    • , David McKay
    • , Daniel M. Dawson
    • , Charlotte E. F. Sansome
    • , Sharon E. Ashbrook
    •  & Russell E. Morris
  2. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    • Laura J. McCormick
    •  & Simon J. Teat
  3. Defence Science and Technology Laboratory (Dstl), Porton Down, Salisbury, Wiltshire, UK

    • Corinne A. Stone
    •  & Martin W. Smith
  4. Department of Physical and Macromolecular Chemistry, Faculty of Sciences, Charles University in Prague, Hlavova , Prague, Czech Republic

    • Russell E. Morris

Authors

  1. Search for Lauren N. McHugh in:

  2. Search for Matthew J. McPherson in:

  3. Search for Laura J. McCormick in:

  4. Search for Samuel A. Morris in:

  5. Search for Paul S. Wheatley in:

  6. Search for Simon J. Teat in:

  7. Search for David McKay in:

  8. Search for Daniel M. Dawson in:

  9. Search for Charlotte E. F. Sansome in:

  10. Search for Sharon E. Ashbrook in:

  11. Search for Corinne A. Stone in:

  12. Search for Martin W. Smith in:

  13. Search for Russell E. Morris in:

Contributions

L.J.M. originally synthesized the material and completed the crystallography with S.A.M. and S.J.T. The adsorption and stability experiments were designed and carried out by L.N.M., P.S.W., M.J.M., C.A.S. and M.W.S. The NMR was completed and analysed by D.M.D., C.E.F.S. and S.E.A, and D.M. carried out the computational work. The paper was written by L.N.M. and R.E.M. and revised by all authors.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Russell E. Morris.

Supplementary information

  1. Supplementary Information

    Synthetic procedures for the synthesis of linker precursors and STAM-17-OEt linker; Powder diffraction; Thermogravimetric analysis; Adsorption experiments; Solid-state NMR; Crystallographic Information

  2. Crystallographic data

    CIF for hydrated STAM-17-OEt; CCDC reference: 1566114

  3. Crystallographic data

    CIF for dehydrated STAM-17-OEt; CCDC reference: 1566115

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41557-018-0104-x