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

Journal name:
Nature Chemistry
Volume:
4,
Pages:
188–194
Year published:
DOI:
doi:10.1038/nchem.1253
Received
Accepted
Published online

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.

At a glance

Figures

  1. Reconstructed electron diffraction patterns and HRTEM images of ITQ-39.
    Figure 1: Reconstructed electron diffraction patterns and HRTEM images of ITQ-39.

    a,b, Two perpendicular cuts of the reconstructed three-dimensional reciprocal lattice giving the h0l slice (a) and the 0kl slice (b). The h0l pattern in a can be indexed using two oblique reciprocal lattices that are related by a 180° rotation along c*; one of them is indicated. The 0kl pattern in b can be indexed using two different lattices; a rectangular one (marked b*Ac*) and an oblique one (marked b*Bc*), corresponding to two different polymorphs ITQ-39A and ITQ-39B, respectively. c,d, Structure projection reconstructed from 20 HRTEM images along b (c) and a (d), respectively. Inserts are the corresponding selected-area electron diffraction patterns. Pairwise channels are seen as ‘8’ in the thin crystal area in c. Twins can be identified from the orientation of the pairwise channels. 10-ring channels are observed in d and the channel stacking is traced by a line in d. The different stacking leads to three polymorphs A, B and C, also marked in d. The domains used for structure factor determination are outlined by rectangles.

  2. Three-dimensional electron potential map and atomic structure model of the stacking disorder in ITQ-39.
    Figure 2: Three-dimensional electron potential map and atomic structure model of the stacking disorder in ITQ-39.

    a, Three-dimensional electrostatic potential map of the building layer of ITQ-39 reconstructed from the structure factor amplitudes and phases extracted from the marked nano-domains in Fig. 1c,d. The 28 symmetry-independent silicon atoms could be located directly from the three-dimensional map and placed based on chemical knowledge. The refined structure model of ITQ-39 is superimposed and only the silicon–silicon connections are shown. b, Atomic structure model of the three polymorphs viewed along a. The building layers (highlighted) are stacked along c* either without any shift (ITQ-39C) or with a shift of −1/3b (ITQ-39B) or ±1/3b (ITQ-39A). c, Projection along b showing the unique pairwise 12-ring channels. The different polymorphs are not distinguishable from this projection because the relative layer shifts are along b.

  3. Comparison of simulated and experimental powder X-ray diffraction patterns.
    Figure 3: Comparison of simulated and experimental powder X-ray diffraction patterns.

    The experimental powder X-ray diffraction pattern was obtained from a calcined pure-silica ITQ-39 sample. The simulated powder X-ray diffraction pattern was calculated using DIFFaX34 from a model containing both the intergrowth of ITQ-39A (45%), ITQ-39B (45%) and ITQ-39C (10%) and twinning with twin domains 6 nm in thickness along c*, as estimated from HRTEM images. Translational disorder within the building layer was not included in the simulation.

  4. Three-dimensional channel system in ITQ-39A with its structure model superimposed.
    Figure 4: Three-dimensional channel system in ITQ-39A with its structure model superimposed.

    a, Projection along b showing that the 12-ring channels intersect with 10-ring channels running along three directions (indicated by arrows). b, Different view of the channel system with a cross-section of the intersecting channels, illustrating channel connectivity. The 12-ring channels along b are straight, and the 10-ring channels along a, c and a + c zig-zag. The channel systems in ITQ-39B and ITQ-39C are similar to those in ITQ-39A, except for the relative heights of the 10-ring channels.

  5. Channel system in ITQ-39A represented using a rod model.
    Figure 5: Channel system in ITQ-39A represented using a rod model.

    a, Viewed along the pairwise 12-ring channels. b, Viewed perpendicular to the pairwise 12-ring channels. The straight pairwise 12-ring channels and their connection with the zig-zag 10-ring channels are clearly shown.

  6. Comparison of the catalytic results of ITQ-39, beta and MWW for alkylation of naphtha with olefins.
    Figure 6: Comparison of the catalytic results of ITQ-39, beta and MWW for alkylation of naphtha with olefins.

    A mixture of 70 wt% heavy and 30 wt% light naphtha was used. Catalysis was performed at 230 °C and 3.5 MPa with 1.7 h contact time with respect to the olefins. TOS, time on stream.

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Author information

Affiliations

  1. Berzelii Centre EXSELENT on Porous Materials, and Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, 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, E-46022 Valencia, 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

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.

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The authors declare no competing financial interests.

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Supplementary information

PDF files

  1. Supplementary information (1,616 KB)

    Supplementary information

Movies

  1. Supplementary information (5,881 KB)

    Supplementary Video 1 showing part of 3D electron diffraction data collection

  2. Supplementary information (6,538 KB)

    Supplementary Video 2 displaying the reconstructed 3D reciprocal lattice from 880 ED frames

  3. Supplementary information (10,702 KB)

    Supplementary Video 3 showing the 3D intersecting channel system in ITQ-39A

Crystallographic information files

  1. Supplementary information (6 KB)

    Crystallographic data for zeolite ITQ-39A

  2. Supplementary information (5 KB)

    Crystallographic data for zeolite ITQ-39B

  3. Supplementary information (4 KB)

    Crystallographic data for zeolite ITQ-39C

Additional data