Abstract
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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References
Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002)
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)
Corma, A. State of the art and future challenges of zeolites as catalysts. J. Catal. 216, 298–312 (2003)
Ferey, G. Materials science. The simplicity of complexity-rational design of giant pores. Science 291, 994–995 (2001)
Davis, M. E., Saldarriaga, C., Montes, C., Garces, J. & Crowder, C. A molecular sieve with eighteen-membered rings. Nature 331, 698–699 (1988)
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)
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)
Burton, A. et al. SSZ-53 and SSZ-59: two novel extra-large pore zeolites. Chem. Eur. J. 9, (23)5737–5748 (2003)
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)
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)
Cheetham, T. et al. Very open microporous materials: from concept to reality. Stud. Surf. Sci. Catal. 135, 788–795 (2001)
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)
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)
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)
Brunner, G. O. & Meier, W. M. Framework density distribution of zeolite-type tetrahedral nets. Nature 337, 146–147 (1989)
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)
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)
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)
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)
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)
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)
Wang, Y., Song, J. & Gies, H. The substitution of germanium for silicon in AST-type zeolite. Solid State Sci. 5, 1421–1433 (2003)
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)
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)
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)
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)
Rodriguez-Carvajal, J. FULLPROF version 3.30, 〈http://www-llb.cea.fr/fullweb/fp2k/fp2k.htm〉 (Laboratory Leon Brillouin, 2005)
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)
Corma, A. & Martinez-Triguero, J. The use of MCM-22 as a cracking zeolitic additive for FCC. J. Catal. 165, 102–120 (1997)
Corma, A., Martinez-Triguero, J. & Martinez, C. The use of ITQ-7 as a FCC zeolitic additive. J. Catal. 197, 151–159 (2001)
Acknowledgements
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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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). https://doi.org/10.1038/nature05238
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DOI: https://doi.org/10.1038/nature05238
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