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High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings


Crystalline molecular sieves with large pores and high adsorption capacities have many potential applications1,2,3,4. Of these materials, zeolites are of particular interest owing to their stability in a wide range of experimental conditions. An aluminophosphate with very large circular channels5 containing 18 oxygen atoms (18-ring channels) has been synthesized, but in the search for large-pore zeolites, most of the materials which have been synthesized up to now contain only 14-ring channels; the synthesis of zeolites with larger ring structures has been believed to be hindered by the low Si-O-Si bond angles available. A silicogaloaluminate (ECR-34) with unidirectional 18-ring channels12 was recently reported, but exhibited low micropore volume, thus rendering the material less attractive for catalytic applications. Here we report the structure and catalytic activity of the silicogermanate zeolite ITQ-33; this material exhibits straight large pore channels with circular openings of 18-rings along the c axis interconnected by a bidirectional system of 10-ring channels, yielding a structure with very large micropore volume. The conditions for synthesis are easily accessible, but are not typical, and were identified using high-throughput techniques.

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Figure 1
Figure 2: Rietveld refinement of the XRD pattern of ITQ-33 calcined at 823 K.
Figure 3: Description of the structure of ITQ-33.
Figure 4: Percentage propylene conversion as a function of time on-stream for ITQ-33 and BETA.


  1. Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002)

    Article  ADS  CAS  Google Scholar 

  2. Jäger, R., Schneider, A. M., Behrens, P., Henkelmann, B., Schramm, K-W. & Lenoir, D. Selective adsorption of polychlorinated dibenzo-p-dioxins and dibenzofurans by the zeosils UTD-1, SSZ-24, and ITQ-4. Chem. Eur. J. 10, (1)247–256 (2004)

    Article  Google Scholar 

  3. Corma, A. State of the art and future challenges of zeolites as catalysts. J. Catal. 216, 298–312 (2003)

    Article  CAS  Google Scholar 

  4. Ferey, G. Materials science. The simplicity of complexity-rational design of giant pores. Science 291, 994–995 (2001)

    Article  CAS  Google Scholar 

  5. Davis, M. E., Saldarriaga, C., Montes, C., Garces, J. & Crowder, C. A molecular sieve with eighteen-membered rings. Nature 331, 698–699 (1988)

    Article  ADS  CAS  Google Scholar 

  6. Freyhardt, C. C., Tsapatsis, M., Lobo, R. F., Balkus, K. J. & Davis, M. E. A high-silica zeolite with a 14-tetrahedral-atom pore opening. Nature 381, 295–298 (1996)

    Article  ADS  CAS  Google Scholar 

  7. Yoshikawa, M. et al. Synthesis, characterization, and structure solution of CIT-5, a new, high-silica, extra-large-pore molecular sieve. J. Phys. Chem. B 102, 7139–7147 (1998)

    Article  CAS  Google Scholar 

  8. Burton, A. et al. SSZ-53 and SSZ-59: two novel extra-large pore zeolites. Chem. Eur. J. 9, (23)5737–5748 (2003)

    Article  CAS  Google Scholar 

  9. Paillaud, J. L., Harbuzaru, B., Patarin, J. & Bats, N. Extra-large-pore zeolites with two-dimensional channels formed by 14 and 12 rings. Science 304, 990–992 (2004)

    Article  ADS  CAS  Google Scholar 

  10. Corma, A., Diaz-Cabanas, M. J., Rey, F., Nicolopoulus, S. & Boulahya, K. ITQ-15: the first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications. Chem. Commun. 12, 1356–1357 (2004)

    Article  Google Scholar 

  11. Cheetham, T. et al. Very open microporous materials: from concept to reality. Stud. Surf. Sci. Catal. 135, 788–795 (2001)

    CAS  Google Scholar 

  12. Strohmaier, K. G. & Vaughan, D. E. Structure of the first silicate molecular sieve with 18-ring pore openings, ECR-34. J. Am. Chem. Soc. 125, 16035–16039 (2003)

    Article  CAS  Google Scholar 

  13. Corma, A., Diaz-Cabanas, M. J., Martinez-Triguero, J., Rey, F. & Rius, J. A large-cavity zeolite with wide pore windows and potential as an oil refining catalyst. Nature 418, 514–517 (2002)

    Article  ADS  CAS  Google Scholar 

  14. Corma, A., Navarro, M. T., Rey, F. & Valencia, S. Synthesis of pure polymorph C of Beta zeolite in a fluoride-free system. Chem. Commun. 16, 1486–1487 (2001)

    Article  Google Scholar 

  15. Brunner, G. O. & Meier, W. M. Framework density distribution of zeolite-type tetrahedral nets. Nature 337, 146–147 (1989)

    Article  ADS  CAS  Google Scholar 

  16. Annen, M. J., Davis, M. E., Higgins, J. B. & Schlenker, J. L. VPI-7: the first zincosilicate molecular sieve containing three-membered T-atom rings. J. Chem. Soc. Chem. Commun. 17, 1175–1176 (1991)

    Article  Google Scholar 

  17. Zheng, N., Bu, X., Vu, H. & Feng, P. Open-framework chalcogenides as visible-light photocatalysts for hydrogen generation from water. Angew. Chem. Int. Edn Engl. 117, 5433–5437 (2005)

    Article  Google Scholar 

  18. Correll, S., Oeckler, O., Stock, N. & Schnick, W. LixH12-x-y+zP12OyN24-yClz—An oxonitridophosphate with a zeolite-like framework structure composed of 3-rings. Angew. Chem. Int. Edn Engl. 42, 3549–3552 (2003)

    Article  CAS  Google Scholar 

  19. Lawton, S. L. & Rohrbaugh, W. J. The framework topology of ZSM-18, a novel zeolite containing rings of three (Si, Al)-O species. Science 247, 1319–1322 (1990)

    Article  ADS  CAS  Google Scholar 

  20. Blasco, T. et al. Preferential location of Ge in the double four-membered ring units of ITQ-7 zeolite. J. Phys. Chem. B 106, 2634–2642 (2002)

    Article  CAS  Google Scholar 

  21. Corma, A., Rey, F., Rius, J., Sabater, M. J. & Valencia, S. Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites. Nature 431, 287–290 (2004)

    Article  ADS  CAS  Google Scholar 

  22. Wang, Y., Song, J. & Gies, H. The substitution of germanium for silicon in AST-type zeolite. Solid State Sci. 5, 1421–1433 (2003)

    Article  ADS  CAS  Google Scholar 

  23. Cantin, A., Corma, A., Diaz-Cabanas, M. J., Jorda, J. L. & Moliner, M. Rational design and HT techniques allow the synthesis of new IWR zeolite polymorphs. J. Am. Chem. Soc. 128, 4216–4217 (2006)

    Article  CAS  Google Scholar 

  24. Cejka, J. & Wichterlova, B. Acid-catalyzed synthesis of mono- and dialkyl benzenes over zeolites: active sites, zeolite topology, and reaction mechanisms. Catal. Rev. 44, 375–421 (2002)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  27. Rodriguez-Carvajal, J. FULLPROF version 3.30, 〈〉 (Laboratory Leon Brillouin, 2005)

  28. Treacy, M. M. J., Rivin, I., Balkowsky, E., Randall, K. H. & Foster, M. D. Enumeration of periodic tetrahedral frameworks. II. Polynodal graphs. Micropor. Mesopor. Mater. 74, 121–132 (2004)

    Article  CAS  Google Scholar 

  29. Corma, A. & Martinez-Triguero, J. The use of MCM-22 as a cracking zeolitic additive for FCC. J. Catal. 165, 102–120 (1997)

    Article  CAS  Google Scholar 

  30. Corma, A., Martinez-Triguero, J. & Martinez, C. The use of ITQ-7 as a FCC zeolitic additive. J. Catal. 197, 151–159 (2001)

    Article  CAS  Google Scholar 

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We thank CICYT for financial support, and Beamline BM25 (Spline) at ESRF for beam time allocation. J.L.J. thanks the Spanish MEC for a Juan de la Cierva contract and M.M. thanks CSIC for an I3P grant. We also thank F. Rey and V. Fornés for discussions.

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Correspondence to Avelino Corma.

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Supplementary information

Supplementary Methods

This file contains additional details of the conditions for the synthesis of zeolite ITQ-33, the X-ray data collection and the catalytic tests (PDF 75 kb)

Supplementary Figures

This file contains Supplementary Figures 1–5, corresponding to the characterization and synthesis conditions of zeolite ITQ-33 (PDF 189 kb)

Supplementary Tables

This file contains Supplementary Tables 1–2, corresponding to the crystallographic data and atomic coordinates of zeolite ITQ-33 (PDF 34 kb)

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Corma, A., Díaz-Cabañas, M., Jordá, J. et al. High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings. Nature 443, 842–845 (2006).

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