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Ordered silicon vacancies in the framework structure of the zeolite catalyst SSZ-74

Nature Materials volume 7, pages 631–635 (2008)Cite this article

Abstract

Physico-chemical characterization of the high-silica zeolite catalyst SSZ-74 (ref. 1) suggested that it, like the related materials TNU-9 (ref. 2) and IM-5 (ref. 3), has a multidimensional 10-ring channel system4. Such pore systems are ideal for many petrochemical applications, and indeed SSZ-74 has been shown to be a good catalyst for a wide variety of reactions1. The elucidation of its framework structure, however, proved to be difficult. Comparable problems were encountered with TNU-9 and IM-5, which were synthesized with related structure-directing agents. Their framework structures, which are the two most complex ones known, both have 24 Si atoms in the asymmetric unit, and were finally solved by combining high-resolution powder diffraction data with information derived from high-resolution electron microscopy images5,6. Therefore, a similar approach, using the powder charge-flipping algorithm7 to combine the two types of data and molecular modelling to help to locate the structure-directing agent, was applied to SSZ-74. This procedure eventually revealed a most unusual 23-Si-atom framework structure (|(C16H34N2)4|[Si92□4O184(OH)8]) with ordered Si vacancies.

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Figure 1: Pore information on SSZ-74 obtained from an HRTEM image.
Figure 2: The crystal structure of SSZ-74.
Figure 3: Observed (top), calculated (middle) and difference (bottom) profiles for the Rietveld refinement of SSZ-74.
Figure 4: The framework structure and channel system of SSZ-74.

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References

  1. Zones, S. I., Burton, A. W. & Ong, K. Molecular sieve SSZ-74 composition of matter and synthesis thereof. International Patent WO/2007/079038 (2007).

  2. Hong, S. B. et al. Synthesis, structure solution, characterization, and catalytic properties of TNU-10: A high-silica zeolite with the STI topology. J. Am. Chem. Soc. 126, 5817–5826 (2004).

    Article  CAS  Google Scholar 

  3. Benazzi, E., Guth, J. L. & Rouleau, L. IM-5 zeolite, method of preparation and catalytic applications thereof. Patent Cooperation Treaty WO 98/17581 (1998).

  4. Burton, A. W. et al. A comparative study of three closely related unsolved zeolite structures. Studies Surf. Sci. Catal. 170, 690–697 (2007).

    Article  Google Scholar 

  5. Gramm, F. et al. Complex zeolite structure solved by combining powder diffraction and electron microscopy. Nature 444, 79–81 (2006).

    Article  CAS  Google Scholar 

  6. Baerlocher, Ch. et al. Structure of the polycrystalline zeolite catalyst IM-5 solved by enhanced charge flipping. Science 315, 1113–1116 (2007).

    Article  CAS  Google Scholar 

  7. Baerlocher, Ch., McCusker, L. B. & Palatinus, L. Charge flipping combined with histogram matching to solve complex crystal structures from powder diffraction data. Z. Kristallogr. 222, 47–53 (2007).

    Article  CAS  Google Scholar 

  8. Baerlocher, Ch., McCusker, L. B. & Olson, D. H. Atlas of Zeolite Framework Types 6th edn (Elsevier, Amsterdam, 2007).

    Google Scholar 

  9. Hong, S. B. et al. Synthesis, crystal structure, characterization, and catalytic properties of TNU-9. J. Am. Chem. Soc. 129, 10870–10885 (2007).

    Article  CAS  Google Scholar 

  10. Serra, J. M., Guillon, E. & Corma, A. A rational design of alkyl-aromatics dealkylation-transalkylation catalysts using C8 and C9 alkyl-aromatics as reactants. J. Catal. 227, 459–469 (2004).

    Article  CAS  Google Scholar 

  11. Zones, S. I. et al. Indirect assessment of unknown zeolite structures through inference from zeolite synthesis comparisons coupled with adsorption and catalytic selectivity studies. J. Catal. 250, 41–54 (2007).

    Article  CAS  Google Scholar 

  12. Grosse-Kunstleve, R. W., McCusker, L. B. & Baerlocher, Ch. Powder diffraction data and crystal chemical information combined in an automated structure determination procedure for zeolites. J. Appl. Crystallogr. 30, 985–995 (1997).

    Article  CAS  Google Scholar 

  13. Falcioni, M. & Deem, M. W. A biased Monte Carlo scheme for zeolite structure solution. J. Chem. Phys. 110, 1754–1766 (1999).

    Article  CAS  Google Scholar 

  14. Oszlányi, G. & Sütő, A. Ab initio structure solution by charge flipping. Acta Crystallogr. A 60, 134–141 (2004).

    Article  Google Scholar 

  15. Oszlányi, G. & Sütő, A. Ab initio structure solution by charge flipping. II. Use of weak reflections. Acta Crystallogr. A 61, 147–152 (2005).

    Article  Google Scholar 

  16. Wu, J. S., Leinenweber, K., Spence, J. C. H. & O’Keeffe, M. Ab initio phasing of X-ray powder diffraction patterns by charge flipping. Nature Mater. 5, 647–652 (2006).

    Article  CAS  Google Scholar 

  17. Zhang, K. Y. J. & Main, P. Histogram matching as a new density modification technique for phase refinement and extension of protein molecules. Acta Crystallogr. A 46, 41–46 (1990).

    Article  Google Scholar 

  18. Palatinus, L. & Chapuis, G. Superflip—a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J. Appl. Crystallogr. 40, 786–790 (2007).

    Article  CAS  Google Scholar 

  19. Hovmöller, S. CRISP: Crystallographic image processing on a personal computer. Ultramicroscopy 41, 121–135 (1992).

    Article  Google Scholar 

  20. Brenner, S., McCusker, L. B. & Baerlocher, Ch. Using a structure envelope to facilitate structure solution from powder diffraction data. J. Appl. Crystallogr. 30, 1167–1172 (1997).

    Article  CAS  Google Scholar 

  21. Brenner, S., McCusker, L. B. & Baerlocher, Ch. The application of structure envelopes in structure determination from powder diffraction data. J. Appl. Crystallogr. 35, 243–252 (2002).

    Article  CAS  Google Scholar 

  22. Burton, A. W., Lee, G. S. & Zones, S. I. Phase selectivity in the syntheses of cage-based zeolite structures: An investigation of thermodynamic interactions between zeolite hosts and structure directing agents by molecular modeling. Microporous Mesoporous Mater. 90, 129–144 (2006).

    Article  CAS  Google Scholar 

  23. Lewis, D. W., Freeman, C. M. & Catlow, C. R. A. Predicting the templating ability of organic additives for the synthesis of microporous materials. J. Phys. Chem. 99, 11194–11202 (1995).

    Article  CAS  Google Scholar 

  24. Engelhardt, G. & Michel, D. High-Resolution Solid-State NMR of Silicates and Zeolites (Wiley, Chichester, 1987).

    Google Scholar 

  25. Koller, H., Lobo, R. F., Burkett, S. L. & Davis, M. E. SiO−⋯HOSi hydrogen bonds in as-synthesized high-silica zeolites. J. Phys. Chem. 99, 12588–12596 (1995).

    Article  CAS  Google Scholar 

  26. Oszlányi, G. & Sütő, A. The charge flipping algorithm. Acta Crystallogr. A 64, 123–134 (2008).

    Article  Google Scholar 

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Acknowledgements

We thank the beamline scientists at Beamline X16C at the National Synchrotron Light Source, Brookhaven, and at the Swiss Norwegian Beamlines at the European Synchrotron Radiation Facility, Grenoble, for their assistance with the powder diffraction measurements. Research was carried out in part at the National Synchrotron Light Source, Brookhaven National Laboratory, which is supported by the US Department of Energy, Division of Materials Sciences and Division of Chemical Sciences. The NMR facility at Caltech was supported by the National Science Foundation (NSF) under Grant Number 9724240 and partially supported by the MRSEC Program of the NSF under Award Number DMR-0520565. Funding from the Swiss National Science Foundation (C.B., D.X. and L.B.M.) is gratefully acknowledged.

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Authors and Affiliations

  1. Laboratory of Crystallography, ETH Zurich, CH-8093 Zurich, Switzerland

    Christian Baerlocher, Dan Xie & Lynne B. McCusker

  2. The Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA

    Son-Jong Hwang

  3. Chevron Energy Technology Co., Richmond, California 94802, USA

    Ignatius Y. Chan, Kenneth Ong, Allen W. Burton & Stacey I. Zones

Authors
  1. Christian Baerlocher
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  2. Dan Xie
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  6. Kenneth Ong
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  7. Allen W. Burton
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  8. Stacey I. Zones
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Contributions

C.B., D.X. and L.B.M. carried out the structure analysis, S.-J.H. the MAS NMR analysis, I.Y.C. the electron microscopy experiments, K.O. the initial powder diffraction data collection and analysis and S.I.Z. the synthesis of the material. A.W.B. carried out the molecular modelling and coordinated the project.

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Correspondence to Lynne B. McCusker.

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Baerlocher, C., Xie, D., McCusker, L. et al. Ordered silicon vacancies in the framework structure of the zeolite catalyst SSZ-74. Nature Mater 7, 631–635 (2008). https://doi.org/10.1038/nmat2228

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