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Complex zeolite structure solved by combining powder diffraction and electron microscopy

Abstract

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.

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Figure 1: High-resolution transmission electron microscopy images taken along different zone axes of TNU-9.
Figure 2: The framework structure of TNU-9 (O atoms have been omitted for clarity).
Figure 3: Observed (blue), calculated (red) and difference (black) profiles for the Rietveld refinement of TNU-9.

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Acknowledgements

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.

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Correspondence to Lynne B. McCusker.

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

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Gramm, F., Baerlocher, C., McCusker, L. et al. Complex zeolite structure solved by combining powder diffraction and electron microscopy. Nature 444, 79–81 (2006). https://doi.org/10.1038/nature05200

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