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Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography

Nature Chemistry volume 4, pages 188–194 (2012)Cite this article

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Abstract

Porous materials such as zeolites contain well-defined pores in molecular dimensions and have important industrial applications in catalysis, sorption and separation. Aluminosilicates with intersecting 10- and 12-ring channels are particularly interesting as selective catalysts. Many porous materials, especially zeolites, form only nanosized powders and some are intergrowths of different structures, making structure determination very challenging. Here, we report the atomic structures of an aluminosilicate zeolite family, ITQ-39, solved from nanocrystals only a few unit cells in size by electron crystallography. ITQ-39 is an intergrowth of three different polymorphs, built from the same layer but with different stacking sequences. ITQ-39 contains stacking faults and twinning with nano-sized domains, being the most complex zeolite ever solved. The unique structure of ITQ-39, with a three-dimensional intersecting pairwise 12-ring and 10-ring pore system, makes it a promising catalyst for converting naphtha into diesel fuel, a process of emerging interest for the petrochemical industry.

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Figure 1: Reconstructed electron diffraction patterns and HRTEM images of ITQ-39.
Figure 2: Three-dimensional electron potential map and atomic structure model of the stacking disorder in ITQ-39.
Figure 3: Comparison of simulated and experimental powder X-ray diffraction patterns.
Figure 4: Three-dimensional channel system in ITQ-39A with its structure model superimposed.
Figure 5: Channel system in ITQ-39A represented using a rod model.
Figure 6: Comparison of the catalytic results of ITQ-39, beta and MWW for alkylation of naphtha with olefins.

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Acknowledgements

The authors acknowledge financial support from the Spanish MICINN, Consolider Ingenio 2010-Multicat, Generalitat Valenciana through the PROMETEO programme, the Swedish Research Council (VR), the Swedish Governmental Agency for Innovation Systems (VINNOVA) and the Göran Gustafsson Foundation for Natural Scientific and Medical Research. M. Moliner also acknowledges support from the ‘Subprograma Ramon y Cajal’ (contract RYC-2011-08972). Wei Wan is supported by postdoctoral grants from the Carl-Trygger Foundation. The EM facility was supported by the Knut and Alice Wallenberg Foundation. Gunnel Karlsson is thanked for TEM sample preparation using ultramicrotomy.

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Authors and Affiliations

  1. and Department of Materials and Environmental Chemistry, Berzelii Centre EXSELENT on Porous Materials, Stockholm University, Stockholm, SE-106 91, Sweden

    Tom Willhammar, Junliang Sun, Wei Wan, Peter Oleynikov, Daliang Zhang & Xiaodong Zou

  2. Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia, Consejo Superior de Investigaciones Científicas, Valencia, E-46022, Spain

    Manuel Moliner, Jorge Gonzalez, Cristina Martínez, Fernando Rey & Avelino Corma

  3. Escuela de Ciencias Químicas, Universidad de Colima, Colima, 28040, Mexico

    Jorge Gonzalez

  4. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, PR China

    Daliang Zhang

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  1. Tom Willhammar
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Contributions

T.W., W.W., P.O and D.L.Z. carried out the TEM work. T.W and J.L.S. executed the structure solution and verification. M.M., J.G. and F.R. carried out the OSDA and zeolite syntheses work. C.M. performed the catalytic experiments. X.D.Z, T.W., J.L.S., M.M. and A.C. were responsible for completing the manuscript.

Corresponding authors

Correspondence to Xiaodong Zou or Avelino Corma.

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Supplementary information

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Supplementary information (PDF 1616 kb)

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Supplementary Video 1 showing part of 3D electron diffraction data collection (WMV 5880 kb)

Supplementary information

Supplementary Video 2 displaying the reconstructed 3D reciprocal lattice from 880 ED frames (WMV 6537 kb)

Supplementary information

Supplementary Video 3 showing the 3D intersecting channel system in ITQ-39A (WMV 10701 kb)

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Crystallographic data for zeolite ITQ-39A (CIF 5 kb)

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Crystallographic data for zeolite ITQ-39B (CIF 4 kb)

Supplementary information

Crystallographic data for zeolite ITQ-39C (CIF 3 kb)

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Willhammar, T., Sun, J., Wan, W. et al. Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography. Nature Chem 4, 188–194 (2012). https://doi.org/10.1038/nchem.1253

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