Letter | Published:

Complex zeolite structure solved by combining powder diffraction and electron microscopy

Naturevolume 444pages7981 (2006) | Download Citation



Many industrially important materials, ranging from ceramics to catalysts to pharmaceuticals, are polycrystalline and cannot be grown as single crystals. This means that non-conventional methods of structure analysis must be applied to obtain the structural information that is fundamental to the understanding of the properties of these materials. Electron microscopy might appear to be a natural approach, but only relatively simple structures have been solved by this route. Powder diffraction is another obvious option, but the overlap of reflections with similar diffraction angles causes an ambiguity in the relative intensities of those reflections. Various ways of overcoming or circumventing this problem have been developed1,2, and several of these involve incorporating chemical information into the structure determination process3,4,5,6,7. For complex zeolite structures, the FOCUS algorithm8,9 has proved to be effective. Because it operates in both real and reciprocal space, phase information obtained from high-resolution transmission electron microscopy images can be incorporated directly into this algorithm in a simple way. Here we show that by doing so, the complexity limit can be extended much further. The power of this approach has been demonstrated with the solution of the structure of the zeolite TNU-9 (|H9.3|[Al9.3Si182.7O384]; ref. 10) with 24 topologically distinct (Si,Al) atoms and 52 such O atoms. For comparison, ITQ-22 (ref. 11), the most complex zeolite known to date, has 16 topologically distinct (Si,Ge) atoms.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.


  1. 1

    David, W. I. F., Shankland, K., McCusker, L. B., Baerlocher, C. (eds) Structure Determination from Powder Diffraction Data (Oxford Univ. Press, Oxford, 2002)

  2. 2

    Baerlocher, Ch., McCusker, L. B. (eds) Structure determination from powder diffraction data. Z. Kristallogr. 219, (Spec. Iss.)782–901 (2004)

  3. 3

    Harris, K. D. M., Habershon, S., Cheung, E. Y. & Johnston, R. L. Developments in genetic algorithm techniques for structure solution from powder diffraction data. Z. Kristallogr. 219, 838–846 (2004)

  4. 4

    Favre-Nicolin, V. & Cerny, R. A better FOX: using flexible modelling and maximum likelihood to improve direct-space ab initio structure determination from powder diffraction. Z. Kristallogr. 219, 847–856 (2004)

  5. 5

    Burton, A. W. Structure solution of zeolites from powder diffraction data. Z. Kristallogr. 219, 866–880 (2004)

  6. 6

    Florence, A. J. et al. Solving molecular crystal structures from laboratory X-ray powder diffraction data with DASH: the state of the art and challenges. J. Appl. Crystallogr. 38, 249–259 (2005)

  7. 7

    Brodski, V., Peschar, R. & Schenk, H. Organa – a program package for structure determination from powder diffraction data by direct-space methods. J. Appl. Crystallogr. 38, 688–693 (2005)

  8. 8

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

  9. 9

    Grosse-Kunstleve, R. W., McCusker, L. B. & Baerlocher, C. Zeolite structure determination from powder diffraction data: applications of the FOCUS method. J. Appl. Crystallogr. 32, 536–542 (1999)

  10. 10

    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)

  11. 11

    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. Nature Mater. 2, 493–497 (2003)

  12. 12

    Wagner, P. et al. Electron diffraction structure solution of a nano-crystalline zeolite at atomic resolution. J. Phys. Chem. B 103, 8245–8250 (1999)

  13. 13

    Baerlocher, C., Meier, W. M. & Olson, D. H. Atlas of Zeolite Framework Types (Elsevier, Amsterdam, 2001)

  14. 14

    Ohsuna, T., Liu, Z., Terasaki, O., Hiraga, K. & Camblor, M. Framework determination of a polytype of zeolite beta by using electron crystallography. J. Phys. Chem. B 106, 5673–5678 (2002)

  15. 15

    Dorset, D. L., Roth, W. J. & Gilmore, C. J. Electron crystallography of zeolites – the MWW family as a test of direct 3D structure determination. Acta Crystallogr. A 61, 516–527 (2005)

  16. 16

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

  17. 17

    von Schnering, H. G. & Nesper, R. Nodal surfaces of Fourier series: fundamental invariants of structured matter. Z. Phys. B 83, 407–412 (1991)

  18. 18

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

  19. 19

    Fitch, A. N. The high resolution powder diffraction beam line at ESRF. J. Res. NIST 109, 133–142 (2004)

  20. 20

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

  21. 21

    Kokotailo, G. T., Lawton, S. L., Olson, D. H. & Meier, W. M. Structure of synthetic zeolite ZSM-5. Nature 272, 437–438 (1978)

  22. 22

    Pawley, G. S. Unit-cell refinement from powder diffraction scans. J. Appl. Crystallogr. 14, 357–361 (1981)

  23. 23

    Le Bail, A., Duroy, H. & Fourquet, J. L. Ab-initio structure determination of LiSbWO4 by X-ray powder diffraction. Mater. Res. Bull. 23, 447–452 (1988)

  24. 24

    Estermann, M. A. & Gramlich, V. Improved treatment of severely or exactly overlapping Bragg reflections for the application of direct methods to powder data. J. Appl. Crystallogr. 26, 396–404 (1993)

Download references


We thank the beamline scientists at SRS, Daresbury, and A. Fitch at the ESRF, Grenoble, for their assistance with the powder diffraction measurements. Funding from the Swiss National Science Foundation (L.B.M, C.B., F.G.), the Swedish Science Research Council and the Japan Science and Technology Agency (T.O., O.T.), and the Korea Science and Engineering Foundation (S.B.H.) is acknowledged. Author Contributions F.G., C.B. and L.B.M. performed the data analysis and structure solution; S.J.W. and P.A.W. collected the synchrotron powder diffraction data and coordinated the project; Z.L., T.O. and O.T. obtained the HRTEM images; and B.H and S.B.H. synthesized and characterised TNU-9.

Author information

Author notes

    • Tetsu Ohsuna

    Present address: Department of Applied Chemistry, Waseda University, Ohkubo-3, Shinjuku-ku, Tokyo, 169-8555, Japan


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

    • Fabian Gramm
    • , Christian Baerlocher
    •  & Lynne B. McCusker
  2. School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK

    • Stewart J. Warrender
    •  & Paul A. Wright
  3. Division of Applied Chemistry and Biotechnology, Hanbat National University, Taejon, 305-719, Korea

    • Bada Han
    •  & Suk Bong Hong
  4. Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden

    • Zheng Liu
    • , Tetsu Ohsuna
    •  & Osamu Terasaki
  5. National Institute of Advanced Industrial Science & Technology (AIST), Tsukuba, Ibaraki, 3058565, Japan

    • Zheng Liu
  6. Technology (AIST), Tsukuba, Ibaraki, 3058565

    • Zheng Liu


  1. Search for Fabian Gramm in:

  2. Search for Christian Baerlocher in:

  3. Search for Lynne B. McCusker in:

  4. Search for Stewart J. Warrender in:

  5. Search for Paul A. Wright in:

  6. Search for Bada Han in:

  7. Search for Suk Bong Hong in:

  8. Search for Zheng Liu in:

  9. Search for Tetsu Ohsuna in:

  10. Search for Osamu Terasaki in:

Competing interests

Reprints and permissions information is available at www.nature.com/reprints. The authors declare no competing financial interests.

Corresponding author

Correspondence to Lynne B. McCusker.

Supplementary information

  1. Supplementary Data

    Crystallographic data for H-TNU-9 in cif format. (TXT 7 kb)

About this article

Publication history



Issue Date



Further reading


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.