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Synthesis of ‘unfeasible’ zeolites

Abstract

Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum—why have so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such ‘unfeasible’ zeolites, IPC-9 and IPC-10, through the assembly–disassembly–organization–reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.

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Figure 1: Synthesis of ‘unfeasible’ zeolites.
Figure 2: The role of choline cations in organizing IPC-1P layers.
Figure 3: Structures of IPC-9 and IPC-10.
Figure 4: The energetics of IPC-9 and IPC-10.

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References

  1. Akporiaye, D. E. & Price, G. D. Systematic enumeration of zeolite frameworks. Zeolites 9, 23–32 (1989).

    Article  CAS  Google Scholar 

  2. Pophale, R., Cheeseman, P. A. & Deem, M. W. A database of new zeolite-like materials. Phys. Chem. Chem. Phys. 13, 12407–12412 (2011).

    Article  CAS  Google Scholar 

  3. Blatov, V. A., Ilyushin, G. D. & Proserpio, D. M. The zeolite conundrum: why are there so many hypothetical zeolites and so few observed? A possible answer from the zeolite-type frameworks perceived as packings of tiles. Chem. Mater. 25, 412–424 (2013).

    Article  CAS  Google Scholar 

  4. Cundy, C. S. & Cox, P. A. The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time. Chem. Rev. 103, 663–701 (2003).

    Article  CAS  Google Scholar 

  5. Cundy, C. S. & Cox, P. A. The hydrothermal synthesis of zeolites: precursors, intermediates and reaction mechanism. Micropor. Mesopor. Mater. 82, 1–78 (2005).

    Article  CAS  Google Scholar 

  6. Foster, M. D. et al. Chemically feasible hypothetical crystalline networks. Nature Mater. 3, 234–238 (2004).

    Article  CAS  Google Scholar 

  7. Sartbaeva, A., Wells, S. A., Treacy, M. M. J. & Thorpe, M. F. The flexibility window in zeolites. Nature Mater. 5, 962–965 (2006).

    Article  CAS  Google Scholar 

  8. Li, Y., Yu, J. & Xu, R. R. Criteria for zeolite frameworks realizable for target synthesis. Angew. Chem. Int. Ed. 52, 1673–1677 (2013).

    Article  CAS  Google Scholar 

  9. Akporiaye, D. E. & Price, G. D. Relative stability of zeolite frameworks from calculated energetics of known and theoretical structures. Zeolites 9, 321–328 (1989).

    Article  CAS  Google Scholar 

  10. Henson, N. J., Cheetham, A. K. & Gale, J. D. Computational studies of aluminum phosphate polymorphs. Chem. Mater. 8, 664–670 (1996).

    Article  CAS  Google Scholar 

  11. Henson, N. J., Cheetham, A. K. & Gale, J. D. Theoretical calculations on silica frameworks and their correlation with experiment. Chem. Mater. 6, 1647–1650 (1994).

    Article  CAS  Google Scholar 

  12. Earl, D. J. & Deem, M. W. Toward a database of hypothetical zeolite structures. Ind. Eng. Chem. Res. 45, 5449–5454 (2006).

    Article  CAS  Google Scholar 

  13. Li, X. & Deem, M. W. Why zeolites have so few seven-membered rings. J. Phys. Chem. C 118, 15835–15839 (2014).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  15. Roth, W. J. et al. A family of zeolites with controlled pore size prepared using a top-down method. Nature Chem. 5, 628–633 (2013).

    Article  CAS  Google Scholar 

  16. Wheatley, P. et al. Zeolites with continuously tuneable porosity. Angew. Chem. Int. Ed. 53, 13210–13214 (2014).

    Article  CAS  Google Scholar 

  17. Chlubna-Eliasova, P. et al. The assembly–disassembly–organization–reassembly mechanism for 3D-2D-3D transformation of germanosilicate IWW zeolite. Angew. Chem. Int. Ed. 53, 7048–7052 (2014).

    Article  CAS  Google Scholar 

  18. Roth, W. J., Nachtigall, P., Morris, R. E. & Cejka, J. Two-dimensional zeolites: current status and perspectives. Chem. Rev. 114, 4807–4837 (2014).

    Article  CAS  Google Scholar 

  19. Paillaud, J. L., Harbuzaru, B., Patarin, J. & Bats, N. Extra-large-pore zeolites with two-dimensional channels formed by 14 and 12 rings. Science 304, 990–992 (2004).

    Article  CAS  Google Scholar 

  20. Corma, A., Diaz-Cabanas, M. J., Rey, F., Nicolooulas, S. & Boulahya, K. ITQ-15: the first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications. Chem. Commun. 1356–1357 (2004).

  21. Roth, W. J. et al. Postsynthesis transformation of three-dimensional framework into a lamellar zeolite with modifiable architecture. J. Am. Chem. Soc. 133, 6130–6133 (2011).

    Article  CAS  Google Scholar 

  22. Grajciar, L., Bludsky, O., Roth, W. J. & Nachtigall, P. Theoretical investigation of layered zeolite frameworks: interaction between IPC-1P layers derived from zeolite UTL. Catal. Today 204, 15–21 (2013).

    Article  CAS  Google Scholar 

  23. Trachta, M., Bludsky, O., Cejka, J., Morris, R. E. & Nachtigall, P. From double-four-ring germanosilicates to new zeolites: in silico investigation. ChemPhysChem 15, 2972–2976 (2014).

    Article  CAS  Google Scholar 

  24. Trachta, M., Nachtigall, P. & Bludsky, O. The ADOR synthesis of new zeolites: in silico investigation. Catal. Today 243, 32–38 (2015).

    Article  CAS  Google Scholar 

  25. Moliner, M., Martinez, C. & Corma, A. Multipore zeolites: synthesis and catalytic applications. Angew. Chem. Int. Ed. 54, 3560–3579 (2015).

    Article  CAS  Google Scholar 

  26. Sanders, M., Leslie, M. & Catlow, C. Interatomic potentials for SiO2 . J. Chem. Soc. Chem. Commun. 1271–1273 (1984).

  27. Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

    Article  CAS  Google Scholar 

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Acknowledgements

R.E.M. thanks the Royal Society and the Engineering and Physical Sciences Research Council (Grants EP/L014475/1, EP/K025112/1 and EP/K005499/1) for funding work in this area. J.Č. and P.N. acknowledge the Czech Science Foundation for the project of the Centre of Excellence (P106/12/G015) and the European Union Seventh Framework Programme (FP7/ 2007–2013) under Grant Agreement No. 604307. The research leading to these results has received funding from the European Union Seventh Framework Programme under Grant Agreement No. 312483—ESTEEM2 (Integrated Infrastructure Initiative–I3). W.J.R. thanks his current institution, Jagiellonian University in Krakow, Faculty of Chemistry. We thank W. Zhou and F. Yu for their expertise in TEM and D. Dawson for help with NMR spectroscopy.

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Contributions

M.M., P.E. and W.J.R. completed the synthesis aspects of the work and P.S.W. coordinated the characterization of the prepared materials. M.P. completed the computational modelling under the supervision of P.N. M.N. and A.M. completed the aberration-corrected electron microscopy studies. J.Č. and R.E.M. coordinated the project as a whole and wrote the paper.

Corresponding authors

Correspondence to Jiří Čejka or Russell E. Morris.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 2752 kb)

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Supplementary Movie 1 (MOV 6549 kb)

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Supplementary Movie 2 (MOV 9144 kb)

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Supplementary Movie 3 (MOV 12673 kb)

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Crystallographic data for compound IPC9 (CIF 22 kb)

Supplementary information

Crystallographic data for compound IPC10 (CIF 12 kb)

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Mazur, M., Wheatley, P., Navarro, M. et al. Synthesis of ‘unfeasible’ zeolites. Nature Chem 8, 58–62 (2016). https://doi.org/10.1038/nchem.2374

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