Synthesis of highly stable metal-containing extra-large-pore molecular sieves

[EN] The isomorphic substitution of two different metals (Mg and Co) within the framework of the ITQ-51 zeotype (IFO structure) using bulky aromatic proton sponges as organic structure-directing agents (OSDAs) has allowed the synthesis of different stable metal-containing extra-large-pore zeotypes with high pore accessibility and acidity. These metal-containing extra-large-pore zeolites, named MgITQ-51 and CoITQ-51, have been characterized by different techniques, such as powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, UV-Vis spectroscopy, temperature programmed desorption of ammonia and Fourier transform infrared spectroscopy, to study their physico-chemical properties. The characterization confirms the preferential insertion of Mg and Co atoms within the crystalline structure of the ITQ-51 zeotype, providing high Bronsted acidity, and allowing their use as efficient heterogeneous acid catalysts in industrially relevant reactions involving bulky organic molecules.Financial support by the Spanish Government-MINECO through 'Severo Ochoa' (SEV 2012-0267), Consolider Ingenio 2010-Multicat and MAT2012-37160 is acknowledged. The European Union is also acknowledged by the SynCatMatch project (ERC-AdG-2014-671093).Martínez Franco, R.; Paris-Carrizo, CG.; Moliner Marin, M.; Corma Canós, A. (2016). Synthesis of highly stable metal-containing extra-large-pore molecular sieves. Philosophical Transactions A: Mathematical, Physical and Engineering Sciences. 374(2061). https://doi.org/10.1098/rsta.2015.0075S3742061Jiang, J., Yu, J., & Corma, A. (2010). Extra-Large-Pore Zeolites: Bridging the Gap between Micro and Mesoporous Structures. Angewandte Chemie International Edition, 49(18), 3120-3145. doi:10.1002/anie.200904016Moliner, M., Rey, F., & Corma, A. (2013). Towards the Rational Design of Efficient Organic Structure-Directing Agents for Zeolite Synthesis. Angewandte Chemie International Edition, 52(52), 13880-13889. doi:10.1002/anie.201304713Davis, M. E. (1997). The Quest For Extra-Large Pore, Crystalline Molecular Sieves. Chemistry - A European Journal, 3(11), 1745-1750. doi:10.1002/chem.19970031104Davis, M. E. (2002). Ordered porous materials for emerging applications. Nature, 417(6891), 813-821. doi:10.1038/nature00785Corma, A. (2003). State of the art and future challenges of zeolites as catalysts. Journal of Catalysis, 216(1-2), 298-312. doi:10.1016/s0021-9517(02)00132-xCorma, A., Díaz-Cabañas, M. J., Jordá, J. L., Martínez, C., & Moliner, M. (2006). High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings. Nature, 443(7113), 842-845. doi:10.1038/nature05238Davis, M. E., Saldarriaga, C., Montes, C., Garces, J., & Crowdert, C. (1988). A molecular sieve with eighteen-membered rings. Nature, 331(6158), 698-699. doi:10.1038/331698a0Corma, A., & Davis, M. E. (2004). Issues in the Synthesis of Crystalline Molecular Sieves: Towards the Crystallization of Low Framework-Density Structures. ChemPhysChem, 5(3), 304-313. doi:10.1002/cphc.200300997Martinez-Franco, R., Moliner, M., Yun, Y., Sun, J., Wan, W., Zou, X., & Corma, A. (2013). Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents. Proceedings of the National Academy of Sciences, 110(10), 3749-3754. doi:10.1073/pnas.1220733110Staab, H. A., & Saupe, T. (1988). ?Proton Sponges? and the Geometry of Hydrogen Bonds: Aromatic Nitrogen Bases with Exceptional Basicities. Angewandte Chemie International Edition in English, 27(7), 865-879. doi:10.1002/anie.198808653Corma, A., Diaz-Cabanas, M. J., Jiang, J., Afeworki, M., Dorset, D. L., Soled, S. L., & Strohmaier, K. G. (2010). Extra-large pore zeolite (ITQ-40) with the lowest framework density containing double four- and double three-rings. Proceedings of the National Academy of Sciences, 107(32), 13997-14002. doi:10.1073/pnas.1003009107(s. f.). doi:10.1021/jp027447Martínez-Franco, R., Sun, J., Sastre, G., Yun, Y., Zou, X., Moliner, M., & Corma, A. (2014). Supra-molecular assembly of aromatic proton sponges to direct the crystallization of extra-large-pore zeotypes. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, 470(2166), 20140107. doi:10.1098/rspa.2014.0107Man, P. P., Briend, M., Peltre, M. J., Lamy, A., Beaunier, P., & Barthomeuf, D. (1991). A topological model for the silicon incorporation in SAPO-37 molecular sieves: Correlations with acidity and catalysis. Zeolites, 11(6), 563-572. doi:10.1016/s0144-2449(05)80006-5Wilson ST Flanigen EM. 1986 Crystalline metal aluminophosphates . U.S. Patent 4 567 029.Corà, F., Saadoune, I., & Catlow, C. R. A. (2002). Lewis Acidity in Transition-Metal-Doped Microporous Aluminophosphates. Angewandte Chemie International Edition, 41(24), 4677-4680. doi:10.1002/anie.200290013Hartmann, M., & Kevan, L. (2002). Substitution of transition metal ions into aluminophosphates and silicoaluminophosphates: characterization and relation to catalysis. Research on Chemical Intermediates, 28(7-9), 625-695. doi:10.1163/15685670260469357Šponer, J., Čejka, J., Dědeček, J., & Wichterlová, B. (2000). Coordination and properties of cobalt in the molecular sieves CoAPO-5 and -11. Microporous and Mesoporous Materials, 37(1-2), 117-127. doi:10.1016/s1387-1811(99)00258-9Singh, P. S., Shaikh, R. A., Bandyopadhyay, R., & Rao, B. S. (1995). Synthesis of CoVPI-5 with bifunctional catalytic activity. Journal of the Chemical Society, Chemical Communications, (22), 2255. doi:10.1039/c39950002255Jhung, S. H., Jin, T., Kim, Y. H., & Chang, J.-S. (2008). Phase-selective crystallization of cobalt-incorporated aluminophosphate molecular sieves with large pore by microwave irradiation. Microporous and Mesoporous Materials, 109(1-3), 58-65. doi:10.1016/j.micromeso.2007.04.031Iton, L. E., Choi, I., Desjardins, J. A., & Maroni, V. A. (1989). Stabilization of Co (III) in aluminophosphate molecular sieve frameworks. Zeolites, 9(6), 535-538. doi:10.1016/0144-2449(89)90051-1Frache, A., Gianotti, E., & Marchese, L. (2003). Spectroscopic characterisation of microporous aluminophosphate materials with potential application in environmental catalysis. Catalysis Today, 77(4), 371-384. doi:10.1016/s0920-5861(02)00381-4Yu, T., Wang, J., Shen, M., & Li, W. (2013). NH3-SCR over Cu/SAPO-34 catalysts with various acid contents and low Cu loading. Catalysis Science & Technology, 3(12), 3234. doi:10.1039/c3cy00453hYang, X., Ma, H., Xu, Z., Xu, Y., Tian, Z., & Lin, L. (2007). Hydroisomerization of n-dodecane over Pt/MeAPO-11 (Me=Mg, Mn, Co or Zn) catalysts. Catalysis Communications, 8(8), 1232-1238. doi:10.1016/j.catcom.2006.11.00

Synthesis of Al-MTW with low Si/Al ratios by combining organic and inorganic structure directing agents

[EN] A rationalized combination of alkali cations and bulky dicationic organic structure directing agents (OSDAs) has allowed the synthesis of the Al-rich MTW zeolites with Si/Al ratios of similar to 12 and large pore accessibility. Al-27 MAS NMR spectroscopy indicates that most of the aluminum atoms are in tetrahedral coordination in framework positions, and in situ infrared pyridine adsorption/desorption spectroscopy reveals strong Bronsted acidity after cationic exchange for the Al-rich MTW. In addition, another MTW material with a Si/Al ratio of 30 has been synthesized under alkali-free conditions using a bulky dicationic molecule such as OSDA, the lowest Si/Al ratio being achieved for a MTW zeolite synthesized in the absence of alkali-cations in the synthesis media. The catalytic activity of these MTW materials has been tested for the n-decane cracking reaction, achieving higher catalytic activities and olefin yields than other related large pore zeolites.Financial support from the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), Consolider Ingenio 2010-Multicat and, MAT2012-37160 is acknowledged.Paris-Carrizo, CG.; Martín-García, N.; Martínez-Triguero, J.; Moliner Marin, M.; Corma Canós, A. (2016). Synthesis of Al-MTW with low Si/Al ratios by combining organic and inorganic structure directing agents. New Journal of Chemistry. 40(5):4140-4145. https://doi.org/10.1039/C5NJ01203AS41404145405LaPierre, R. B., Rohrman, A. C., Schlenker, J. L., Wood, J. D., Rubin, M. K., & Rohrbaugh, W. J. (1985). The framework topology of ZSM-12: A high-silica zeolite. Zeolites, 5(6), 346-348. doi:10.1016/0144-2449(85)90121-6Gies, H., & Marker, B. (1992). The structure-controlling role of organic templates for the synthesis of porosils in the systems SiO2/template/H2O. Zeolites, 12(1), 42-49. doi:10.1016/0144-2449(92)90008-dFyfe, C. A., Gies, H., Kokotailo, G. T., Marler, B., & Cox, D. E. (1990). Crystal structure of silica-ZSM-12 by the combined use of hgh-resolution solid-state MAS NMR spectroscopy and synchrotron x-ray powder diffraction. The Journal of Physical Chemistry, 94(9), 3718-3721. doi:10.1021/j100372a066Reddy, K. M., Moudrakovski, I., & Sayari, A. (1994). VS-12: a novel large-pore vanadium silicate with ZSM-12 structure. Journal of the Chemical Society, Chemical Communications, (12), 1491. doi:10.1039/c39940001491Millini, R., Frigerio, F., Bellussi, G., Pazzuconi, G., Perego, C., Pollesel, P., & Romano, U. (2003). A priori selection of shape-selective zeolite catalysts for the synthesis of 2,6-dimethylnaphthalene. Journal of Catalysis, 217(2), 298-309. doi:10.1016/s0021-9517(03)00071-xPerego, C., Amarilli, S., Millini, R., Bellussi, G., Girotti, G., & Terzoni, G. (1996). Experimental and computational study of beta, ZSM-12, Y, mordenite and ERB-1 in cumene synthesis. Microporous Materials, 6(5-6), 395-404. doi:10.1016/0927-6513(96)00037-5Jones, C. (1999). m-Xylene reactions over zeolites with unidimensional pore systems. Applied Catalysis A: General, 181(2), 289-303. doi:10.1016/s0926-860x(98)00401-3Zhang, W., & Smirniotis, P. G. (1999). Catalysis Letters, 60(4), 223-228. doi:10.1023/a:1019079612655Katovic, A., Chiche, B. H., Di Renzo, F., Giordano, G., & Fajula, F. (2000). Influence of the aluminium content on the acidity and catalytic activity of MTW-type zeolites. 12th International Congress on Catalysis, Proceedings of the 12th ICC, 857-862. doi:10.1016/s0167-2991(00)81066-6Kamimura, Y., Itabashi, K., & Okubo, T. (2012). Seed-assisted, OSDA-free synthesis of MTW-type zeolite and «Green MTW» from sodium aluminosilicate gel systems. Microporous and Mesoporous Materials, 147(1), 149-156. doi:10.1016/j.micromeso.2011.05.038Kamimura, Y., Iyoki, K., Elangovan, S. P., Itabashi, K., Shimojima, A., & Okubo, T. (2012). OSDA-free synthesis of MTW-type zeolite from sodium aluminosilicate gels with zeolite beta seeds. Microporous and Mesoporous Materials, 163, 282-290. doi:10.1016/j.micromeso.2012.07.014Coulomb, J. P., & Floquet, N. (2008). Determination of zeolite closed porosity in (1D) channel systems (AFI and MTW types). Studies in Surface Science and Catalysis, 913-916. doi:10.1016/s0167-2991(08)80037-7Gopal, S., Yoo, K., & Smirniotis, P. G. (2001). Synthesis of Al-rich ZSM-12 using TEAOH as template. Microporous and Mesoporous Materials, 49(1-3), 149-156. doi:10.1016/s1387-1811(01)00412-7Araujo, A. S., Silva, A. O. S., Souza, M. J. B., Coutinho, A. C. S. L. S., Aquino, J. M. F. B., Moura, J. A., & Pedrosa, A. M. G. (2005). Crystallization of ZSM-12 Zeolite with Different Si/Al Ratio. Adsorption, 11(2), 159-165. doi:10.1007/s10450-005-4909-8Li, J., Lou, L.-L., Xu, C., & Liu, S. (2014). Synthesis, characterization of Al-rich ZSM-12 zeolite and their catalytic performance in liquid-phase tert-butylation of phenol. Catalysis Communications, 50, 97-100. doi:10.1016/j.catcom.2014.03.011Jackowski, A., Zones, S. I., Hwang, S.-J., & Burton, A. W. (2009). Diquaternary Ammonium Compounds in Zeolite Synthesis: Cyclic and PolycyclicN-Heterocycles Connected by Methylene Chains. Journal of the American Chemical Society, 131(3), 1092-1100. doi:10.1021/ja806978fCorma, A., Martı́nez-Triguero, J., Valencia, S., Benazzi, E., & Lacombe, S. (2002). IM-5: A Highly Thermal and Hydrothermal Shape-Selective Cracking Zeolite. Journal of Catalysis, 206(1), 125-133. doi:10.1006/jcat.2001.3469Marler, B., Dehnbostel, N., Eulert, H.-H., Gies, H., & Liebau, F. (1986). Studies on clathrasils VIII. Nonasils-[4158], 88SiO2 � 8M8 � 8M9 � 4M20: Synthesis, thermal properties, and crystal structure. Journal of Inclusion Phenomena, 4(4), 339-349. doi:10.1007/bf00656161Pinar, A. B., García, R., Gómez-Hortigüela, L., & Pérez-Pariente, J. (2010). Synthesis of Open Zeolite Structures from Mixtures of Tetramethylammonium and Benzylmethylalkylammonium Cations: A Step Towards Driving Aluminium Location in the Framework. Topics in Catalysis, 53(19-20), 1297-1303. doi:10.1007/s11244-010-9587-4De Baerdemaeker, T., Müller, U., & Yilmaz, B. (2011). Alkali-free synthesis of Al-MTW using 4-cyclohexyl-1,1-dimethylpiperazinium hydroxide as structure directing agent. Microporous and Mesoporous Materials, 143(2-3), 477-481. doi:10.1016/j.micromeso.2011.03.018Emeis, 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.1993.114

Efficient Oligomerization of Pentene into Liquid Fuels on Nanocrystalline Beta Zeolites

[EN] Light alkenes oligomerization, performed in the presence of heterogeneous acid catalysts, is an interesting alternative for the production of clean liquid fuels. The process, when catalyzed by zeolites, is flexible and can be directed to the formation of oligomers in the gasoline, jet fuel, or diesel range by adjusting the reaction conditions and the zeolite's structure. Herein we show how reducing the crystal size of large-pore Beta zeolites down to 10-15 nm and controlling the number and strength distribution of their Bronsted acid sites leads to highly active and stable catalysts, selective to true oligomers within the naphtha and, especially, the diesel range. The shorter diffusion path lengths in the smaller crystallites and the reduced Bronsted acid site density of the two nanosized beta zeolites (10-15 nm) synthesized with Si/Al = 15 lead to 1-pentene conversion above 80% during the 6 h time on stream (TOS) at a space time (W/F) of 2.8 g.h.mol(-1). This value is higher than the olefin conversion obtained for a commercial nanobeta (30 nm) at a 3-fold space time of 9.1 g.h.mol(-1).Financial support by the Spanish Government-MINECO through "Severn Ochoa" (SEV-2016-0683), MAT2015-71261-R and CTQ2015-70126-R, by the Fundacion Ramon Areces through a research project within the "Life and Materials Sciences" program, and by the European Union through ERC-AdG-2014-671093-Syn-CatMatch is acknowledged. M.R.D-R. acknowledges "La Caixa-Severo Ochoa" International PhD Fellowships (call 2015). The Electron Microscopy Service of the Universitat Politecnica de Valencia is acknowledged for their help in sample characterization.Díaz-Rey, MDR.; Paris-Carrizo, CG.; Martínez Franco, R.; Moliner Marin, M.; Martínez, C.; Corma Canós, A. (2017). Efficient Oligomerization of Pentene into Liquid Fuels on Nanocrystalline Beta Zeolites. ACS Catalysis. 7(9):6170-6178. https://doi.org/10.1021/acscatal.7b00817S617061787

"Ab initio" synthesis of zeolites for preestablished catalytic reactions

[EN] Unlike homogeneous catalysts that are often designed for particular reactions, zeolites are heterogeneous catalysts that are explored and optimized in a heuristic fashion. We present a methodol. for synthesizing active and selective zeolites by using org. structure-¿directing agents that mimic the transition state (TS) of preestablished reactions to be catalyzed. In these zeolites, the pores and cavities could be generated approaching a mol.-¿recognition pattern. For disproportionation of toluene and isomerization of ethylbenzene into xylenes, the TSs are larger than the reaction products. Zeolite ITQ-¿27 showed high disproportionation activity, and ITQ-¿64 showed high selectivity for the desired para and ortho isomers. For the case of a product and TS of similar size, we synthesized a catalyst, MIT-¿1, for the isomerization of endo-¿dicyclopentane into adamantane.This work has been supported by the European Union through the European Research Council (grant ERC-AdG-2014-671093, SynCatMatch) and the Spanish government through the "Severo Ochoa Program" (grant SEV 2012-0267). The Electron Microscopy Service of the Universitat Politecnica de Valencia (UPV) is acknowledged for help with sample characterization. The Red Espanola de Supercomputacion (RES) and Centre de Calcul de la Universitat de Valencia are gratefully acknowledged for computational facilities and technical assistance. E.M.G. acknowledges "La Caixa-Severo Ochoa" International Ph.D. Fellowship (call 2015). We thank I. Millet for technical assistance and V. J. Margarit and A. Cantin for helpful discussions.Gallego-Sánchez, EM.; Portilla Ovejero, MT.; Paris-Carrizo, CG.; Leon Escamilla, EA.; Boronat Zaragoza, M.; Moliner Marin, M.; Corma Canós, A. (2017). "Ab initio" synthesis of zeolites for preestablished catalytic reactions. Science. 355(6329):1051-1054. https://doi.org/10.1126/science.aal0121S105110543556329Vermeiren, W., & Gilson, J.-P. (2009). Impact of Zeolites on the Petroleum and Petrochemical Industry. Topics in Catalysis, 52(9), 1131-1161. doi:10.1007/s11244-009-9271-8Climent, M. J., Corma, A., & Iborra, S. (2011). Heterogeneous Catalysts for the One-Pot Synthesis of Chemicals and Fine Chemicals. Chemical Reviews, 111(2), 1072-1133. doi:10.1021/cr1002084De Vos, D. E., & Jacobs, P. A. (2005). Zeolite effects in liquid phase organic transformations. Microporous and Mesoporous Materials, 82(3), 293-304. doi:10.1016/j.micromeso.2005.01.038Jacobs, P. A., Dusselier, M., & Sels, B. F. (2014). Will Zeolite-Based Catalysis be as Relevant in Future Biorefineries as in Crude Oil Refineries? Angewandte Chemie International Edition, 53(33), 8621-8626. doi:10.1002/anie.201400922Dapsens, P. Y., Mondelli, C., & Pérez-Ramírez, J. (2012). Biobased Chemicals from Conception toward Industrial Reality: Lessons Learned and To Be Learned. ACS Catalysis, 2(7), 1487-1499. doi:10.1021/cs300124mDavis, M. E. (2013). Zeolites from a Materials Chemistry Perspective. Chemistry of Materials, 26(1), 239-245. doi:10.1021/cm401914uMoliner, M., Rey, F., & Corma, A. (2013). Towards the Rational Design of Efficient Organic Structure-Directing Agents for Zeolite Synthesis. Angewandte Chemie International Edition, 52(52), 13880-13889. doi:10.1002/anie.201304713Schmidt, J. E., Deem, M. W., & Davis, M. E. (2014). Synthesis of a Specified, Silica Molecular Sieve by Using Computationally Predicted Organic Structure-Directing Agents. Angewandte Chemie International Edition, 53(32), 8372-8374. doi:10.1002/anie.201404076Eliášová, P., Opanasenko, M., Wheatley, P. S., Shamzhy, M., Mazur, M., Nachtigall, P., … Čejka, J. (2015). The ADOR mechanism for the synthesis of new zeolites. Chemical Society Reviews, 44(20), 7177-7206. doi:10.1039/c5cs00045aBhan, A., Allian, A. D., Sunley, G. J., Law, D. J., & Iglesia, E. (2007). Specificity of Sites within Eight-Membered Ring Zeolite Channels for Carbonylation of Methyls to Acetyls. Journal of the American Chemical Society, 129(16), 4919-4924. doi:10.1021/ja070094dBoronat, M., Martínez-Sánchez, C., Law, D., & Corma, A. (2008). Enzyme-like Specificity in Zeolites: A Unique Site Position in Mordenite for Selective Carbonylation of Methanol and Dimethyl Ether with CO. Journal of the American Chemical Society, 130(48), 16316-16323. doi:10.1021/ja805607mHeilmann, J., & Maier, W. F. (1994). Selective Catalysis on Silicon Dioxide with Substrate-Specific Cavities. Angewandte Chemie International Edition in English, 33(4), 471-473. doi:10.1002/anie.199404711Wulff, G., Heide, B., & Helfmeier, G. (1986). Enzyme-analog built polymers. 20. Molecular recognition through the exact placement of functional groups on rigid matrixes via a template approach. Journal of the American Chemical Society, 108(5), 1089-1091. doi:10.1021/ja00265a045Ahmad, W. R., & Davis, M. E. (1996). Transesterification on ?imprinted? silica. Catalysis Letters, 40(1-2), 109-114. doi:10.1007/bf00807466Katz, A., & Davis, M. E. (2000). Molecular imprinting of bulk, microporous silica. Nature, 403(6767), 286-289. doi:10.1038/35002032Lofgreen, J. E., & Ozin, G. A. (2014). Controlling morphology and porosity to improve performance of molecularly imprinted sol–gel silica. Chem. Soc. Rev., 43(3), 911-933. doi:10.1039/c3cs60276aTsai, T. (1999). Disproportionation and transalkylation of alkylbenzenes over zeolite catalysts. Applied Catalysis A: General, 181(2), 355-398. doi:10.1016/s0926-860x(98)00396-2Čejka, J., & Wichterlová, B. (2002). ACID-CATALYZED SYNTHESIS OF MONO- AND DIALKYL BENZENES OVER ZEOLITES: ACTIVE SITES, ZEOLITE TOPOLOGY, AND REACTION MECHANISMS. Catalysis Reviews, 44(3), 375-421. doi:10.1081/cr-120005741Xiong, Y., Rodewald, P. G., & Chang, C. D. (1995). On the Mechanism of Toluene Disproportionation in a Zeolite Environment. Journal of the American Chemical Society, 117(37), 9427-9431. doi:10.1021/ja00142a007Dorset, D. L., Kennedy, G. J., Strohmaier, K. G., Diaz-Cabañas, M. J., Rey, F., & Corma, A. (2006). P-Derived Organic Cations as Structure-Directing Agents:  Synthesis of a High-Silica Zeolite (ITQ-27) with a Two-Dimensional 12-Ring Channel System. Journal of the American Chemical Society, 128(27), 8862-8867. doi:10.1021/ja061206oX. Xiao, J. Butler, C. Comeaux, K. K., U.S. Patent 20,060,211,902 (2006).J. R. Butler, X. Xiao, R. Hall, U.S. Patent 20,080,319,243 (2008).Moreau, F., Bernard, S., Gnep, N. ., Lacombe, S., Merlen, E., & Guisnet, M. (2001). Ethylbenzene Isomerization on Bifunctional Platinum Alumina–Mordenite Catalysts. Journal of Catalysis, 202(2), 402-412. doi:10.1006/jcat.2001.3294FERNANDES, L., MONTEIRO, J., SOUSAAGUIAR, E., MARTINEZ, A., & CORMA, A. (1998). Ethylbenzene hydroisomerization over bifunctional zeolite based catalysts: The influence of framework and extraframework composition and zeolite structure. Journal of Catalysis, 177(2), 363-377. doi:10.1006/jcat.1998.2111PINES, H., & GREENLEE, T. W. (1961). Alumina: Catalyst and Support. VI.1Aromatization of 1,1-Dimethylcyclohexane, Methylcycloheptane, and Related Hydrocarbons over Platinum-Alumina Catalysts2,2a. The Journal of Organic Chemistry, 26(4), 1052-1057. doi:10.1021/jo01063a020Schreyeck, L., Caullet, P., Mougenel, J. C., Guth, J. L., & Marler, B. (1996). PREFER: a new layered (alumino) silicate precursor of FER-type zeolite. Microporous Materials, 6(5-6), 259-271. doi:10.1016/0927-6513(96)00032-6Ikeda, T., Kayamori, S., & Mizukami, F. (2009). Synthesis and crystal structure of layered silicate PLS-3 and PLS-4 as a topotactic zeolite precursor. Journal of Materials Chemistry, 19(31), 5518. doi:10.1039/b905415dMillini, R., Carluccio, L. C., Carati, A., Bellussi, G., Perego, C., Cruciani, G., & Zanardi, S. (2004). ERS-12: A new layered tetramethylammonium silicate composed by ferrierite layers. Microporous and Mesoporous Materials, 74(1-3), 59-71. doi:10.1016/j.micromeso.2004.06.007Burton, A., Accardi, R. J., Lobo, R. F., Falcioni, M., & Deem, M. W. (2000). MCM-47:  A Highly Crystalline Silicate Composed of Hydrogen-Bonded Ferrierite Layers. Chemistry of Materials, 12(10), 2936-2942. doi:10.1021/cm000243qDorset, D. L., & Kennedy, G. J. (2004). Crystal Structure of MCM-65:  An Alternative Linkage of Ferrierite Layers. The Journal of Physical Chemistry B, 108(39), 15216-15222. doi:10.1021/jp040305qKnight, L. M., Miller, M. A., Koster, S. C., Gatter, M. G., Benin, A. I., Willis, R. R., … Broach, R. W. (2007). UZM-13, UZM-17, UZM-19 and UZM-25: synthesis and structure of new layered precursors and a zeolite discovered via combinatorial chemistry techniques. Studies in Surface Science and Catalysis, 338-346. doi:10.1016/s0167-2991(07)80858-5Ikeda, T., Kayamori, S., Oumi, Y., & Mizukami, F. (2010). Structure Analysis of Si-Atom Pillared Lamellar Silicates Having Micropore Structure by Powder X-ray Diffraction. The Journal of Physical Chemistry C, 114(8), 3466-3476. doi:10.1021/jp912026nRuan, J., Wu, P., Slater, B., Zhao, Z., Wu, L., & Terasaki, O. (2009). Structural Characterization of Interlayer Expanded Zeolite Prepared From Ferrierite Lamellar Precursor. Chemistry of Materials, 21(13), 2904-2911. doi:10.1021/cm900645cRöbschläger, K.-H., & Christoffel, E. G. (1979). Reaction Mechanism of Ethylbenzene Isomerization. Industrial & Engineering Chemistry Product Research and Development, 18(4), 347-352. doi:10.1021/i360072a023Q. A. Acton, Ed. Advances in Adamantane Research and Application (ScholarlyEditions, 2013).Von R. Schleyer, P. (1957). A SIMPLE PREPARATION OF ADAMANTANE. Journal of the American Chemical Society, 79(12), 3292-3292. doi:10.1021/ja01569a086Engler, E. M., Farcasiu, M., Sevin, A., Cense, J. M., & Schleyer, P. V. R. (1973). Mechanism of adamantane rearrangements. Journal of the American Chemical Society, 95(17), 5769-5771. doi:10.1021/ja00798a059Lau, G. C., & Maier, W. F. (1987). Polycyclic hydrocarbon rearrangements in zeolites. A mechanistic study. Langmuir, 3(2), 164-173. doi:10.1021/la00074a004Honna, K., Sugimoto, M., Shimizu, N., & Kurisaki, K. (1986). CATALYTIC REARRANGEMENT OF TETRAHYDRODICYCLOPENTADIENE TO ADAMANTANE OVER Y-ZEOLITE. Chemistry Letters, 15(3), 315-318. doi:10.1246/cl.1986.315Gao, Z., & Yang, X.-B. (2010). Synthesis of adamantane on zeolite catalysts. Chinese Journal of Chemistry, 12(1), 52-57. doi:10.1002/cjoc.19940120107Navrátilová, M., & Sporka, K. (2000). Synthesis of adamantane on commercially available zeolitic catalysts. Applied Catalysis A: General, 203(1), 127-132. doi:10.1016/s0926-860x(00)00477-4Von R. Schleyer, P., & Donaldson, M. M. (1960). The Relative Stability of Bridged Hydrocarbons. II. endo- and exo-Trimethylenenorbornane. The Formation of Adamantane1,2. Journal of the American Chemical Society, 82(17), 4645-4651. doi:10.1021/ja01502a050S. I. Zones, U.S. Patent 4,544,538 (1985).M. J. Diaz, M. A. Camblor, C. Corell, A. Corma, U.S. Patent 6,077,498 (2000).Corma, A., Fornes, V., Pergher, S. B., Maesen, T. L. M., & Buglass, J. G. (1998). Delaminated zeolite precursors as selective acidic catalysts. Nature, 396(6709), 353-356. doi:10.1038/24592Luo, H. Y., Michaelis, V. K., Hodges, S., Griffin, R. G., & Román-Leshkov, Y. (2015). One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent. Chemical Science, 6(11), 6320-6324. doi:10.1039/c5sc01912eMargarit, 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.201506822E. Mishani et al.,U.S. Patent 20,110,293,519 (2011).Marcoux, D., & Charette, A. B. (2008). Palladium-Catalyzed Synthesis of Functionalized Tetraarylphosphonium Salts. The Journal of Organic Chemistry, 73(2), 590-593. doi:10.1021/jo702355cM. K. Rubin, P. Chu, U.S. Patent 4,954,325 (1990).A. S. Fung, S. L. Lawton, W. J. Roth, U.S. Patent 5,362,697 (1994).Emeis, 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.1993.1145Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J., & Fiolhais, C. (1992). Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Physical Review B, 46(11), 6671-6687. doi:10.1103/physrevb.46.6671Perdew, J. P., & Wang, Y. (1992). Accurate and simple analytic representation of the electron-gas correlation energy. Physical Review B, 45(23), 13244-13249. doi:10.1103/physrevb.45.13244Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set. Physical Review B, 54(16), 11169-11186. doi:10.1103/physrevb.54.11169Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24), 17953-17979. doi:10.1103/physrevb.50.17953Grimme, S., Antony, J., Ehrlich, S., & Krieg, H. (2010). A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. The Journal of Chemical Physics, 132(15), 154104. doi:10.1063/1.3382344Narkhede, V. V., & Gies, H. (2009). Crystal Structure of MCM-22 (MWW) and Its Delaminated Zeolite ITQ-2 from High-Resolution Powder X-Ray Diffraction Data: An Analysis Using Rietveld Technique and Atomic Pair Distribution Function. Chemistry of Materials, 21(18), 4339-4346. doi:10.1021/cm901883

A priori control of zeolite phase competition and intergrowth with high-throughput simulations

Zeolites are versatile catalysts and molecular sieves with large topological diversity, but managing phase competition in zeolite synthesis is an empirical, labor-intensive task. In this work, we controlled phase selectivity in templated zeolite synthesis from first principles by combining high-throughput atomistic simulations, literature mining, human-computer interaction, synthesis, and characterization. Proposed binding metrics distilled from more than 586,000 zeolite-molecule simulations reproduced the extracted literature and rationalized framework competition in the design of organic structure-directing agents. Energetic, geometric, and electrostatic descriptors of template molecules were found to regulate synthetic accessibility windows and aluminum distributions in pure-phase zeolites. Furthermore, these parameters allowed us to realize an intergrowth zeolite through a single bi-selective template. The computation-first approach enables control of both zeolite synthesis and structure composition using a priori theoretical descriptors.D.S.-K. and R.G.-B. acknowledge the Energy Initiative (MITEI) and MIT International Science and Technology Initiatives (MISTI) Seed Funds. D.S.-K. was also funded by the MIT Energy Fellowship. C.P., E.B.-J., M.M., and A.C. acknowledge financial support by the Spanish government through the “Severo Ochoa” program (SEV-2016-0683, MINECO) and grant RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE). E.B.-J. acknowledges the Spanish government for an FPI scholarship (PRE2019-088360). Z.J., E.O., S.K., and Y.R.-L. acknowledge partial funding from Designing Materials to Revolutionize and Engineer our Future (DMREF) from the National Science Foundation (NSF); awards 1922311, 1922372, and 1922090; and the Office of Naval Research (ONR) under contract N00014-20-1-2280. S.K. was additionally funded by the Kwanjeong Educational Fellowship. Z.J. was also supported by the Department of Defense (DoD) through the National Defense Science Engineering Graduate (NDSEG) fellowship program. T.W. acknowledges financial support by the Swedish Research Council (grant no. 2019-05465). Computer calculations were executed at the Massachusetts Green High-Performance Computing Center with support from MIT Research Computing and at the Extreme Science and Engineering Discovery Environment (XSEDE) (53) Expanse through allocation TG-DMR200068

Procedimiento de obtención de lactonas enantioméricamente puras con catalizadores sólidos

La presente invención se refiere a procedimiento para la síntesis de lactonas cíclicas enantioméricamente puras, como por ejemplo el (S)- hidroximetil- butenólido y la (S)-4-hidroximetil- - butirolactona así como sus derivados, caracterizado porque comprende, al menos, una etapa en la que se lleva a cabo una reacción de al menos un compuesto orgánico con un agente oxidante en presencia de un tamiz molecular, preferentemente con poros de diámetro de al menos 0,52 nm, que tiene una fórmula empírica en forma calcinada y deshidratada de (MxZrySnzSi1-x-y-z)O2 en la que: M es uno o más metales de valencia +3, seleccionado entre Al, B, Ga, Fe, Cr, Sc y combinaciones de los mismos, preferentemente Al; x es una fracción molar de M y tiene un valor entre 0 y 0,15; y es una fracción molar de zirconio y tiene un valor entre 0 y 0,06; z es una fracción molar de estaño y tiene un valor entre 0 y 0,06. Con la condición de que, al menos, uno de los subíndices x, y y z sea distinto de cero.Peer reviewedConsejo Superior de Investigaciones Científicas, Universitat Politecnica de ValenciaA1 Solicitud de patente con informe sobre el estado de la técnic

Procedimiento de obtención de lactonas enantioméricamente puras con catalizadores sólidos

La presente invención se refiere a procedimiento para la síntesis de lactonas cíclicas enantioméricamente puras, como por ejemplo el (S)- hidroximetil- butenólido y la (S)-4-hidroximetil- - butirolactona así como sus derivados, caracterizado porque comprende, al menos, una etapa en la que se lleva a cabo una reacción de al menos un compuesto orgánico con un agente oxidante en presencia de un tamiz molecular, preferentemente con poros de diámetro de al menos 0,52 nm, que tiene una fórmula empírica en forma calcinada y deshidratada de (MxZrySnzSi1-x-y-z)O2 en la que: M es uno o más metales de valencia +3, seleccionado entre Al, B, Ga, Fe, Cr, Sc y combinaciones de los mismos, preferentemente Al; x es una fracción molar de M y tiene un valor entre 0 y 0,15; y es una fracción molar de zirconio y tiene un valor entre 0 y 0,06; z es una fracción molar de estaño y tiene un valor entre 0 y 0,06. Con la condición de que, al menos, uno de los subíndices x, y y z sea distinto de cero.Peer reviewedConsejo Superior de Investigaciones Científicas, Universitat Politecnica de ValenciaB1 Patente sin examen previ

Procedimiento de obtención de lactonas enantioméricamente puras con catalizadores sólidos

[EN] The invention relates to a method for the synthesis of enantiomerically pure cyclic lactones, such as (S)-y-hydroxymethyl-α,β-butenolide and (S)-4-hydroxymethyl-y-butyrolactone and the derivatives thereof, characterised in that it comprises at least one step wherein a reaction is carried out between at least one organic compound and an oxidant agent in the presence of a molecular sieve, preferably having pores with a diameter of at least 0.52 nm, that has an empirical formula, in a calcined and dehydrated form, of (MxZrySnzSi1-x-y-z)O2, wherein M is at least one metal of valency +3, selected from between Al, B, Ga, Fe, Cr, Sc and combinations of same, preferably Al; x is a molar fraction of M and has a value of between 0 and 0.15; y is a molar fraction of zirconium and has a value of between 0 and 0.06; and z is a molar fraction of tin and has a value of between 0 and 0.06, on the proviso that at least one of the subindices x, y and z is different from zero.[FR] La présente invention concerne un procédé de synthèse de lactones cycliques énantiomériquement pures, comme par exemple le (S)-y-hydroxyméthyl-α,β-buténolide et la (S)-4-hydroxyméthyl-γ-butyrolactone, ainsi que leurs dérivés, ce procédé étant caractérisé en ce qu'il comprend au moins une étape consistant à mettre en oeuvre une réaction d'au moins un composé organique avec un agent oxydant en présence d'un tamis moléculaire présentant de préférence des pores d'un diamètre inférieur à 0,52 nm, ayant une formule empirique à l'état calciné et déshydraté de (MxZrySnzSi1-x-y-z)O2 dans laquelle: M représente un ou plusieurs métaux de valence +3, choisis parmi Al, B, Ga, Fe, Cr, Sc et des combinaisons de ceux-ci, de préférence Al; x représente une fraction molaire de M et a une valeur comprise entre 0 et 0,15; y représente une fraction molaire de zirconium et a une valeur comprise entre 0 et 0,06; z représente une fraction molaire d'étain et a une valeur comprise entre 0 et 0,06, à condition qu'au moins un des indices x, y et z soit différent de zéro.[ES] La presente invención se refiere a procedimiento para la síntesis de lactonas cíclicas enantioméricamente puras, como por ejemplo el (S)-y-hidroximetil-α,β-butenólido y la (S)-4-hidroximetil-y-butirolactona así como sus derivados, caracterizado porque comprende, al menos, una etapa en la que se lleva a cabo una reacción de al menos un compuesto orgánico con un agente oxidante en presencia de un tamiz molecular, preferentemente con poros de diámetro de al menos 0,52 nm, que tiene una fórmula empírica en forma calcinada y deshidratada de (MxZrySnzSi1-x-y-z)O2 en la que: M es uno o más metales de valencia +3, seleccionado entre Al, B, Ga, Fe, Cr, Sc y combinaciones de los mismos, preferentemente Al; x es una fracción molar de M y tiene un valor entre 0 y 0, 15; y es una fracción molar de zirconio y tiene un valor entre 0 y 0,06; z es una fracción molar de estaño y tiene un valor entre 0 y 0,06. Con la condición de que, al menos, uno de los subíndices x, y y z sea distinto de cero.Peer reviewedConsejo Superior de Investigaciones Científicas, Universitat Politecnica de ValenciaA1 Solicitud de patente con informe sobre el estado de la técnic

Metal-containing zeolites as efficient catalyst for the transformation of highly valuable chiral biomass-derived products

Metal-containing zeolites, especially Sn-Beta, perform as very efficient heterogeneous catalysts in the selective oxidation of levoglucosenone, which is considered as a platform chemical for the production of highly-valuable chemicals, towards the synthesis of the optically pure gamma-lactone(S)-gamma-hydroxymethyl-alpha,beta-butenolide (HBO) using H2O2 as an oxidizing agent. Using Sn-Beta as a catalyst, yields up to 75% of (S)-gamma-hydroxymethyl-alpha,beta-butenolide are achieved in a "one-pot" cascade reaction. When Sn-Beta is combined with an acid resin, such as Amberlyst-15, the "two-step" process allows yields up to 90%.This work has been supported by the Spanish Government MINECO through Consolider Ingenio 2010-Multicat and MAT2012-37160, and by UPV through PAID-06-11 (n.1952). Manuel Moliner also acknowledges "Subprograma Ramon y Cajal" for contract RYC-2011-08972. ITQ thanks the "Program Severo Ochoa" for financial support.Paris Carrizo, CG.; Moliner Marin, M.; Corma Canós, A. (2013). Metal-containing zeolites as efficient catalyst for the transformation of highly valuable chiral biomass-derived products. Green Chemistry. 15(8):2101-2109. https://doi.org/10.1039/c3gc40267cS2101210915

Synthesis of highly stable metal-containing extra-large-pore molecular sieves

The isomorphic substitution of two different metals (Mg and Co) within the framework of the ITQ-51 zeotype (IFO structure) using bulky aromatic proton sponges as organic structure-directing agents (OSDAs) has allowed the synthesis of different stable metal-containing extra-large-pore zeotypes with high pore accessibility and acidity. These metalcontaining extra-large-pore zeolites, named MgITQ-51 and CoITQ-51, have been characterized by different techniques, such as powder X-ray diffraction, scanning electron microscopy, energy dispersive Xray spectrometry, UV-Vis spectroscopy, temperature programmed desorption of ammonia and Fourier transform infrared spectroscopy, to study their physico-chemical properties. The characterization confirms the preferential insertion of Mg and Co atoms within the crystalline structure of the ITQ-51 zeotype, providing high Brønsted acidity, and allowing their use as efficient heterogeneous acid catalysts in industrially relevant reactions involving bulky organic molecules.Financial support by the Spanish Government-MINECO through ‘Severo Ochoa’ (SEV 2012–0267), Consolider Ingenio 2010-Multicat and MAT2012–37160 is acknowledged. The European Union is also acknowledged by the SynCatMatch project (ERC-AdG-2014-671093).Peer Reviewe