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In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6

Nature Chemistry volume 9, pages 1012–1018 (2017)Cite this article

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Abstract

The assembly–disassembly–organization–reassembly (ADOR) mechanism is a recent method for preparing inorganic framework materials and, in particular, zeolites. This flexible approach has enabled the synthesis of isoreticular families of zeolites with unprecedented continuous control over porosity, and the design and preparation of materials that would have been difficult—or even impossible—to obtain using traditional hydrothermal techniques. Applying the ADOR process to a parent zeolite with the UTL framework topology, for example, has led to six previously unknown zeolites (named IPC-n, where n = 2, 4, 6, 7, 9 and 10). To realize the full potential of the ADOR method, however, a further understanding of the complex mechanism at play is needed. Here, we probe the disassembly, organization and reassembly steps of the ADOR process through a combination of in situ solid-state NMR spectroscopy and powder X-ray diffraction experiments. We further use the insight gained to explain the formation of the unusual structure of zeolite IPC-6.

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Figure 1: In situ NMR studies of the disassembly and organization (rearrangement) steps in the ADOR process.
Figure 2: The mechanism of the ADOR process as revealed by the in situ studies.
Figure 3: In situ XRD studies of the reassembly step of the ADOR process.
Figure 4: Experimental and simulated XRD patterns and the structure of IPC-6.
Figure 5: The possibilities for sequential rearrangement and reconnection of layers during the ADOR process.

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References

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

    Article  CAS  Google Scholar 

  2. Eliasova, P. et al. The ADOR mechanism for the synthesis of new zeolites. Chem. Soc. Rev. 44, 7177–7206 (2015).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  6. 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 

  7. 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. Comm. 2004, 1356–1357 (2004).

    Article  Google Scholar 

  8. Corma, A., Rey, F., Valencia, S., Jorda, J. L. & Rius, J. A zeolite with interconnected 8-, 10- and 12-ring pores and its unique catalytic selectivity. Nat. Mater. 2, 493–497 (2003).

    Article  CAS  Google Scholar 

  9. 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 

  10. Lorgouilloux, Y. et al. IM-17: a new zeolitic material, synthesis and structure elucidation from electron diffraction ADT data and Rietveld analysis. RSC Adv. 4, 19440–19449 (2014).

    Article  CAS  Google Scholar 

  11. Kasneryk, V. et al. Expansion of the ADOR strategy for the synthesis of new zeolites: the synthesis of IPC-12 from zeolite UOV. Angew. Chem. Int. Ed. https://doi.org/10.1002/anie.201700590 (2017).

  12. 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 

  13. Proffen, T. & Neder, R. B. DISCUS: A program for diffuse scattering and defect-structure simulation. J. Appl. Crystallogr. 30, 171–175 (1997).

    Article  CAS  Google Scholar 

  14. Slawinski, W. A., Wragg, D. S., Akporiyae, D. & Fjellvag, H. Intergrowth structure modelling in silicoaluminophosphate SAPO-18/34 family. Micropor. Mesopor. Mater. 195, 311–318 (2014).

    Article  CAS  Google Scholar 

  15. Smith, R. L. et al. Nanoporous intergrowths: how crystal growth dictates phase composition and hierarchical structure in the CHA/AEI system. Chem. Mater. 27, 4205–4215 (2015).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  17. Dawson, C. J., Kapko, V., Thorpe, M. F., Foster, M. D. & Treacy, M. M. J. Flexibility as an indicator of feasibility of zeolite frameworks. J. Phys. Chem. C 116, 16175–16181 (2012).

    Article  CAS  Google Scholar 

  18. Massiot, D. et al. Modelling one- and two-dimensional solid-state NMR spectra. Magn. Reson. Chem. 40, 70–76 (2002).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

R.E.M. and M.N. thank the Royal Society and the Engineering and Physical Sciences Research Council (EPSRC) (Grants EP/L014475/1, EP/K025112/1 and EP/K005499/1) for funding work in this area. R.E.M. and J.Č. acknowledge the Czech Science Foundation for the 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. would like to thank the European Research Council (EU FP7 Consolidator Grant 614290 “EXONMR”) and the Royal Society and Wolfson Foundation for a merit award. We thank C. Tang for his assistance with the synchrotron PXRD work carried out at the Diamond Light Source, UK. The UK 850 MHz solid-state NMR Facility used in this research was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF). Collaborative assistance from the 850 MHz facility manager (D. Iuga, University of Warwick) is acknowledged. W.A.S. and D.S.W. acknowledge the Research Council of Norway for providing the computer time at the Norwegian supercomputer facilities (under the project number NN2875k).

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Authors and Affiliations

  1. EaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK

    Samuel A. Morris, Giulia P. M. Bignami, Yuyang Tian, Marta Navarro, Daniel S. Firth, Paul S. Wheatley, Daniel M. Dawson, Russell E. Morris & Sharon E. Ashbrook

  2. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejškova 3, Prague 8, 182 23, Czech Republic

    Jiří Čejka

  3. Department of Physical and Macromolecular Chemistry, Faculty of Sciences, Charles University in Prague, Hlavova 8, Prague 2, 128 43, Czech Republic

    Jiří Čejka & Russell E. Morris

  4. Department of Chemistry, University of Oslo, Sem Sælandsvei 26, Oslo, 0371, Norway

    Wojciech A. Slawinski & David S. Wragg

  5. ISIS Facility, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, OX11 0QX, Oxfordshire, UK

    Wojciech A. Slawinski

Authors
  1. Samuel A. Morris
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Contributions

P.S.W. designed the route and synthesized the enriched UTL samples. S.A.M., P.S.W. and D.S.F. completed the in situ PXRD. Y.T. and M.N. completed the initial ADOR synthesis. W.A.S. and D.S.W. simulated the PXRD using computational approaches. G.P.M.B., D.M.D. and S.E.A. designed and completed the NMR experiments. J.Č. collaborated on the design of the project, and R.E.M. and S.E.A coordinated the project and wrote the paper.

Corresponding authors

Correspondence to Russell E. Morris or Sharon E. Ashbrook.

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The authors declare no competing financial interests.

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Morris, S., Bignami, G., Tian, Y. et al. In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6. Nature Chem 9, 1012–1018 (2017). https://doi.org/10.1038/nchem.2761

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