Simple organic structure directing agents for synthesizing nanocrystalline zeolites

[EN] The synthesis of the ZSM-5 and beta zeolites in their nanosized form has been achieved by using simple alkyl-substituted mono-cationic cyclic ammonium cations as OSDA molecules. The particular combination of a cyclic fragment and a short linear alkyl-chain group (preferentially C4) within the monocationic OSDA molecules allows directing the crystallization of nanosized zeolites with excellent solid yields (above 90%). Interestingly, the formation of the nanosized ZSM-5 and beta zeolites mostly depends on the size and nature of the cyclic fragment of the OSDA molecule, resulting in all cases in nanocrystalline solids with homogeneous distributions of particle sizes (similar to 10-25 nm) and controlled Si/Al molar ratios (similar to 15-30). The achieved nanosized ZSM-5 and beta zeolites have been extensively characterized by different techniques to study their physico-chemical properties, such as chemical composition, pore accessibility or Bronsted acidity, among others. Moreover, the catalytic properties of the nanosized ZSM-5 and beta zeolites have been evaluated for different chemical reactions, including methanol-to-olefins (MTO) in the case of ZSM-5, and alkylation of benzene with propylene to obtain cumene and oligomerization of light olefins to liquid fuels in the case of beta, observing in all cases improved catalytic activity and product selectivity towards target products when compared to related catalysts.This work has been supported by the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), MAT2015-71261-R and CTQ2015-70126-R, by the European Union through ERC-AdG-2014-671093 (SynCatMatch) and by the Fundacion Ramon Areces through a research contract of the "Life and Materials Science" program. E. M. G. and M. R. D-R. acknowledge "La Caixa - Severo Ochoa" International PhD Fellowships (call 2015). M. E. M-A. thanks MINECO for economical support through pre-doctoral fellowship (BES-2013-066800). The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization.Gallego-Sánchez, EM.; Paris-Carrizo, CG.; Díaz-Rey, MDR.; Martínez Armero, ME.; Martínez-Triguero, J.; Martínez, C.; Moliner Marin, M.... (2017). Simple organic structure directing agents for synthesizing nanocrystalline zeolites. Chemical Science. 8(12):8138-8149. https://doi.org/10.1039/c7sc02858j81388149812Davis, M. E. (2013). Zeolites from a Materials Chemistry Perspective. Chemistry of Materials, 26(1), 239-245. doi:10.1021/cm401914uMoliner, M., Martínez, C., & Corma, A. (2015). Multipore Zeolites: Synthesis and Catalytic Applications. Angewandte Chemie International Edition, 54(12), 3560-3579. doi:10.1002/anie.201406344Martínez, C., & Corma, A. (2011). Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes. Coordination Chemistry Reviews, 255(13-14), 1558-1580. doi:10.1016/j.ccr.2011.03.014Čejka, J., Centi, G., Perez-Pariente, J., & Roth, W. J. (2012). Zeolite-based materials for novel catalytic applications: Opportunities, perspectives and open problems. Catalysis Today, 179(1), 2-15. doi:10.1016/j.cattod.2011.10.006Gallego, E. M., Portilla, M. T., Paris, C., León-Escamilla, A., Boronat, M., Moliner, M., & Corma, A. (2017). «Ab initio» synthesis of zeolites for preestablished catalytic reactions. Science, 355(6329), 1051-1054. doi:10.1126/science.aal0121Brandenberger, S., Kröcher, O., Tissler, A., & Althoff, R. (2008). The State of the Art in Selective Catalytic Reduction of NOxby Ammonia Using Metal‐Exchanged Zeolite Catalysts. Catalysis Reviews, 50(4), 492-531. doi:10.1080/01614940802480122Tosheva, L., & Valtchev, V. P. (2005). Nanozeolites: Synthesis, Crystallization Mechanism, and Applications. Chemistry of Materials, 17(10), 2494-2513. doi:10.1021/cm047908zValtchev, V., & Tosheva, L. (2013). Porous Nanosized Particles: Preparation, Properties, and Applications. Chemical Reviews, 113(8), 6734-6760. doi:10.1021/cr300439kSarazen, M. L., Doskocil, E., & Iglesia, E. (2016). Effects of Void Environment and Acid Strength on Alkene Oligomerization Selectivity. ACS Catalysis, 6(10), 7059-7070. doi:10.1021/acscatal.6b02128Mintova, S., Gilson, J.-P., & Valtchev, V. (2013). Advances in nanosized zeolites. Nanoscale, 5(15), 6693. doi:10.1039/c3nr01629cCamblor, M. A., Corma, A., & Valencia, S. (1998). Characterization of nanocrystalline zeolite Beta. Microporous and Mesoporous Materials, 25(1-3), 59-74. doi:10.1016/s1387-1811(98)00172-3Mintova, S., Valtchev, V., Onfroy, T., Marichal, C., Knözinger, H., & Bein, T. (2006). Variation of the Si/Al ratio in nanosized zeolite Beta crystals. Microporous and Mesoporous Materials, 90(1-3), 237-245. doi:10.1016/j.micromeso.2005.11.026Schoeman, B. J. (2001). Journal of Porous Materials, 8(1), 13-22. doi:10.1023/a:1026566116805Van Grieken, R., Sotelo, J. L., Menéndez, J. M., & Melero, J. A. (2000). Anomalous crystallization mechanism in the synthesis of nanocrystalline ZSM-5. Microporous and Mesoporous Materials, 39(1-2), 135-147. doi:10.1016/s1387-1811(00)00190-6Iwakai, K., Tago, T., Konno, H., Nakasaka, Y., & Masuda, T. (2011). Preparation of nano-crystalline MFI zeolite via hydrothermal synthesis in water/surfactant/organic solvent using fumed silica as the Si source. Microporous and Mesoporous Materials, 141(1-3), 167-174. doi:10.1016/j.micromeso.2010.11.001Bellussi, G., & Pollesel, P. (2005). Industrial applications of zeolite catalysis: production and uses of light olefins. Studies in Surface Science and Catalysis, 1201-1212. doi:10.1016/s0167-2991(05)80466-5Yilmaz, B., & Müller, U. (2009). Catalytic Applications of Zeolites in Chemical Industry. Topics in Catalysis, 52(6-7), 888-895. doi:10.1007/s11244-009-9226-0Zones, S. I. (2011). Translating new materials discoveries in zeolite research to commercial manufacture. Microporous and Mesoporous Materials, 144(1-3), 1-8. doi:10.1016/j.micromeso.2011.03.039Larlus, O., Mintova, S., Wilson, S. T., Willis, R. R., Abrevaya, H., & Bein, T. (2011). A powerful structure-directing agent for the synthesis of nanosized Al- and high-silica zeolite Beta in alkaline medium. Microporous and Mesoporous Materials, 142(1), 17-25. doi:10.1016/j.micromeso.2010.08.025Choi, M., Na, K., & Ryoo, R. (2009). The synthesis of a hierarchically porous BEA zeolite via pseudomorphic crystallization. Chemical Communications, (20), 2845. doi:10.1039/b905087fZhu, J., Zhu, Y., Zhu, L., Rigutto, M., van der Made, A., Yang, C., … Xiao, F.-S. (2014). Highly Mesoporous Single-Crystalline Zeolite Beta Synthesized Using a Nonsurfactant Cationic Polymer as a Dual-Function Template. Journal of the American Chemical Society, 136(6), 2503-2510. doi:10.1021/ja411117yChoi, M., Na, K., Kim, J., Sakamoto, Y., Terasaki, O., & Ryoo, R. (2009). Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. Nature, 461(7261), 246-249. doi:10.1038/nature08288Kim, Y., Kim, K., & Ryoo, R. (2017). Cooperative Structure Direction of Diammonium Surfactants and Sodium Ions to Generate MFI Zeolite Nanocrystals of Controlled Thickness. Chemistry of Materials, 29(4), 1752-1757. doi:10.1021/acs.chemmater.6b05338Mintova, S., Grand, J., & Valtchev, V. (2016). Nanosized zeolites: Quo Vadis? Comptes Rendus Chimie, 19(1-2), 183-191. doi:10.1016/j.crci.2015.11.005Martínez-Franco, R., Paris, C., Martínez-Armero, M. E., Martínez, C., Moliner, M., & Corma, A. (2016). High-silica nanocrystalline Beta zeolites: efficient synthesis and catalytic application. Chemical Science, 7(1), 102-108. doi:10.1039/c5sc03019fChiappe, C., Pomelli, C. S., & Rajamani, S. (2011). Influence of Structural Variations in Cationic and Anionic Moieties on the Polarity of Ionic Liquids. The Journal of Physical Chemistry B, 115(31), 9653-9661. doi:10.1021/jp2045788Corma, A., Martı́nez-Soria, V., & Schnoeveld, E. (2000). Alkylation of Benzene with Short-Chain Olefins over MCM-22 Zeolite: Catalytic Behaviour and Kinetic Mechanism. Journal of Catalysis, 192(1), 163-173. doi:10.1006/jcat.2000.2849KOKOTAILO, G. T., LAWTON, S. L., OLSON, D. H., & MEIER, W. M. (1978). Structure of synthetic zeolite ZSM-5. Nature, 272(5652), 437-438. doi:10.1038/272437a0Emeis, C. A. (1993). Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts. Journal of Catalysis, 141(2), 347-354. doi:10.1006/jcat.1993.1145Treacy, M. M. J., & Newsam, J. M. (1988). Two new three-dimensional twelve-ring zeolite frameworks of which zeolite beta is a disordered intergrowth. Nature, 332(6161), 249-251. doi:10.1038/332249a0Stöcker, M. (1999). Methanol-to-hydrocarbons: catalytic materials and their behavior. Microporous and Mesoporous Materials, 29(1-2), 3-48. doi:10.1016/s1387-1811(98)00319-9Tian, P., Wei, Y., Ye, M., & Liu, Z. (2015). Methanol to Olefins (MTO): From Fundamentals to Commercialization. ACS Catalysis, 5(3), 1922-1938. doi:10.1021/acscatal.5b00007Martín, N., Li, Z., Martínez-Triguero, J., Yu, J., Moliner, M., & Corma, A. (2016). Nanocrystalline SSZ-39 zeolite as an efficient catalyst for the methanol-to-olefin (MTO) process. Chemical Communications, 52(36), 6072-6075. doi:10.1039/c5cc09719cVermeiren, W., & Gilson, J.-P. (2009). Impact of Zeolites on the Petroleum and Petrochemical Industry. Topics in Catalysis, 52(9), 1131-1161. doi:10.1007/s11244-009-9271-8Margarit, V. J., Martínez-Armero, M. E., Navarro, M. T., Martínez, C., & Corma, A. (2015). Direct Dual-Template Synthesis of MWW Zeolite Monolayers. Angewandte Chemie International Edition, 54(46), 13724-13728. doi:10.1002/anie.201506822Peratello, S. (1999). Olefins oligomerization: thermodynamics and kinetics over a mesoporous silica–alumina. Catalysis Today, 52(2-3), 271-277. doi:10.1016/s0920-5861(99)00081-4Corma, A., Martínez, C., & Doskocil, E. (2013). Designing MFI-based catalysts with improved catalyst life for oligomerization to high-quality liquid fuels. Journal of Catalysis, 300, 183-196. doi:10.1016/j.jcat.2012.12.029Pater, J. P. G., Jacobs, P. A., & Martens, J. A. (1998). 1-Hexene Oligomerization in Liquid, Vapor, and Supercritical Phases over Beidellite and Ultrastable Y Zeolite Catalysts. Journal of Catalysis, 179(2), 477-482. doi:10.1006/jcat.1998.2250Tabak, S. A., Krambeck, F. J., & Garwood, W. E. (1986). Conversion of propylene and butylene over ZSM-5 catalyst. AIChE Journal, 32(9), 1526-1531. doi:10.1002/aic.69032091