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Design of zeolite by inverse sigma transformation

Abstract

Although the search for new zeolites has traditionally been based on trial and error, more rational methods are now available. The theoretical concept of inverse σ transformation of a zeolite framework to generate a new structure by removal of a layer of framework atoms and contraction has for the first time been achieved experimentally. The reactivity of framework germanium atoms in strong mineral acid was exploited to selectively remove germanium-containing four-ring units from an UTL type germanosilicate zeolite. Annealing of the leached framework through calcination led to the new all-silica COK-14 zeolite with intersecting 12- and 10-membered ring channel systems. An intermediate stage of this inverse σ transformation with dislodged germanate four-rings still residing in the pores could be demonstrated. Inverse σ transformation involving elimination of germanium-containing structural units opens perspectives for the synthesis of many more zeolites.

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Figure 1: Acid leaching of IM-12 zeolite (UTL topology) dislodges germanate four-rings (Ge-4Rs, dark blue), allowing a framework contraction whereby the Ge-4R units are shifted into the channels of Ge-COK-14.
Figure 2: Comparison of IM-12 and -COK-14.
Figure 3: Rietveld refinement of X-ray powder patterns.
Figure 4: Rietveld refinement (bottom left), observed electron density (upper left) and fitted EXAFS data (right)33,34 of Ge-COK-14.
Figure 5: Two postulated intermediate structures during inverse σ transformation, obtained by simple geometric considerations.

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Acknowledgements

J.A.M. acknowledges the Flemish government for long-term structural funding (Methusalem). C.E.A.K. and N.K. acknowledge support by BelSpo in the frames of the Prodex and visiting fellowship programs. V.V.S., M.W. and L.J. acknowledge the Research Board of the Ghent University and V.V.S. is grateful to the European Research Council for funding (FP7(2007–2013) ERC grant agreement number 240483). K.V.H., S.B. and G.V.T. acknowledge part of this work was supported by funding from the ERC grant N° 246791—COUNTATOMS. The authors acknowledge FWO/NWO for providing beamtime at the DUBBLE and SNBL beamlines (ESRF, Grenoble) and P. Abdala for her assistance during the use of the beamline. G. Fink is acknowledged for setting up the homo-decoupled 1H-NMR experiments. E.B. acknowledges a fellowship as Postdoctoral Researcher of FWO-Vlaanderen. The authors are grateful to the Hercules Foundation for financial support. The authors are collaborating in a Belgian interuniversity network (IAP-PAI) supported by the Belgian government. The computational resources and services used for the DFT calculations were provided by Ghent University (Stevin Supercomputer Infrastructure).

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Contributions

J.A.M. and C.E.A.K. conceived and directed the project. E.V. synthesized -COK-14, COK-14 and Ge-COK-14 and performed the characterization. N.K. synthesized IM-12 and initiated the degermanation work. C.E.A.K., E.G. and E.B. solved crystal structures and performed data fitting. L.J., V.V.S. and M.W. carried out the DFT calculations. K.V.H., S.B. and G.V.T. performed the TEM measurements. K.H. carried out the 29Si magic angle spinning nuclear magnetic resonance. M.H. measured XRD using synchrotron radiation. C.M. and F.T. conducted the 1H-NMR experiments and contributed to their interpretation. All authors participated in the writing of the publication.

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Correspondence to Christine E. A. Kirschhock.

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Verheyen, E., Joos, L., Van Havenbergh, K. et al. Design of zeolite by inverse sigma transformation. Nature Mater 11, 1059–1064 (2012). https://doi.org/10.1038/nmat3455

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