Síntesis de nuevos materiales zeolíticos empleando agentes directores de estructura fosforados

[EN] This thesis is focused on the synthesis of new zeolitic structures using phosphorus containing compounds as structure directing agents, and the study of the influence of the presence of phosphorus in the adsorption capacity and acid properties of the zeolites. The phosphazene bases and aminophosphonium cations used in this work have yielded to zeolites with new crystalline structures (ITQ-45, ITQ-52, ITQ-58), as well as have developed new routes of synthesis of already known zeolites, but broadening their range of compositions (DON, RTH, ITE, STF), and these have allowed obtaining the synthetic analogue (ITQ-47) of the natural zeolite boggsite (BOG) by first time.[ES] La presente tesis doctoral se centra en la síntesis de nuevas estructuras zeolíticas empleando como agentes directores de estructura compuestos que contienen fósforo y el estudio de la influencia de la presencia de fósforo en la capacidad de adsorción y en las propiedades ácidas de las zeolitas. Las bases de fosfaceno y cationes aminofosfonio empleados en este trabajo han permitido obtener zeolitas con nuevas estructuras cristalinas (ITQ-45, ITQ-52 e ITQ-58), así como desarrollar nuevas rutas de síntesis de zeolitas conocidas ampliando el rango de composiciones (DON, RTH, ITE, STF) y obtener por primera vez el análogo sintético (ITQ-47) de la zeolita natural boggsita (BOG).[CA] La present tesi doctoral es centra en la síntesi de noves estructures zeolítiques emprant com agents directors d'estructura compostos que continguen fòsfor, i la influència de la presència de fòsfor en la capacitat d'adsorció i en la fortalesa àcida de les zeolites. Les bases de fosfazè i cations aminofosfoni emprats en aquest treball han permès obtindre zeolites amb noves estructures cristal¿lines (ITQ-45, ITQ-52 e ITQ-58), així com desenvolupar noves rutes de síntesi de zeolites conegudes ampliant el rang de composicions (DON, RTH, ITE, STF) i obtindre per primera vegada l'anàleg sintètic (ITQ-47) de la zeolita natural boggsita (BOG).Simancas Coloma, R. (2015). Síntesis de nuevos materiales zeolíticos empleando agentes directores de estructura fosforados [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/52025TESI

Synthesis and structure determination via ultra-fast electron diffraction of the new microporous zeolitic germanosilicate ITQ-62

[EN] Here, we present the synthesis and structure determination of the new zeolite ITQ-62. Its structure was determined via ultra-fast electron diffraction tomography and refined using powder XRD data of the calcined material. This new zeolite contains a tridirectional channel system of highly distorted 8-rings, as well as a monodirectional 12-ring channel system.The authors gratefully acknowledge financial support from the Spanish Government (MAT2015-71842-P and MAT2015-71261-R MINECO/FEDER and Severo Ochoa SEV-2016-0683). The authors thank ALBA Light Source for beam allocation at the beamline MSPD, and specially thank the Electron Microscopy Service of the Universitat Politecnica de Valencia. Finally, the authors thank Dr Alejandro Vidal and Dr Teresa Blasco for helping in the NMR data discussion.Bieseki, L.; Simancas Coloma, R.; Jorda Moret, JL.; Bereciartua-Pérez, PJ.; Cantin Sanz, A.; Simancas-Coloma, J.; Pergher, SB.... (2018). Synthesis and structure determination via ultra-fast electron diffraction of the new microporous zeolitic germanosilicate ITQ-62. Chemical Communications. 54(17):2122-2125. https://doi.org/10.1039/c7cc09240gS212221255417Barrer, R. M., & Denny, P. J. (1961). 201. Hydrothermal chemistry of the silicates. Part IX. Nitrogenous aluminosilicates. Journal of the Chemical Society (Resumed), 971. doi:10.1039/jr9610000971Kerr, G. T. (1966). Chemistry of Crystalline Aluminosilicates. II. The Synthesis and Properties of Zeolite ZK-4. Inorganic Chemistry, 5(9), 1537-1539. doi:10.1021/ic50043a015Burton, A. W., & Zones, S. I. (2007). Organic Molecules in Zeolite Synthesis: Their Preparation and Structure-Directing Effects. Introduction to Zeolite Science and Practice, 137-179. doi:10.1016/s0167-2991(07)80793-2Zones, S. I., Nakagawa, Y., Lee, G. S., Chen, C. Y., & Yuen, L. T. (1998). Searching for new high silica zeolites through a synergy of organic templates and novel inorganic conditions. 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W., Lobo, R. F., Weckhuysen, B. M., & Beale, A. M. (2011). Isolated Cu2+ions: active sites for selective catalytic reduction of NO. Chem. Commun., 47(2), 800-802. doi:10.1039/c0cc04218hMoliner, M., Franch, C., Palomares, E., Grill, M., & Corma, A. (2012). Cu–SSZ-39, an active and hydrothermally stable catalyst for the selective catalytic reduction of NOx. Chemical Communications, 48(66), 8264. doi:10.1039/c2cc33992gBereciartua, P. J., Cantín, Á., Corma, A., Jordá, J. L., Palomino, M., Rey, F., … Casty, G. L. (2017). Control of zeolite framework flexibility and pore topology for separation of ethane and ethylene. Science, 358(6366), 1068-1071. doi:10.1126/science.aao0092Dodin, M., Paillaud, J.-L., Lorgouilloux, Y., Caullet, P., Elkaïm, E., & Bats, N. (2010). A Zeolitic Material with a Three-Dimensional Pore System Formed by Straight 12- and 10-Ring Channels Synthesized with an Imidazolium Derivative as Structure-Directing Agent. 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SÍNTESIS DE NUEVOS MATERIALES ZEOLÍTICOS EMPLEANDO AGENTES DIRECTORES DE ESTRUCTURA FOSFORADOS

La catálisis heterogénea, en la actualidad, resulta de gran importancia en la industria farmacéutica, química fina y petroquímica. Debido a esto, la síntesis de nuevos materiales resulta prácticamente indispensable para su aplicación como catalizadores más activos y selectivos en dichos procesos. La variable de síntesis más importante a tener en cuenta en la obtención de nuevos materiales zeolíticos es la naturaleza del agente director de estructura utilizado en la síntesis. En este trabajo se propone el uso de agentes directores de estructura fosforados, en concreto las bases de fosfaceno. Los resultados más relevantes han sido obtenidos utilizando las bases de fosfaceno 1,1,1,3,3,3Hexakis( dimetilamino)difosfaceno y tertButiliminotris( dimetilamino)fosforano como agentes directores de estructura, obteniéndose las zeolitas UTD1 e ITQ3, respectivamente. Estos materiales han sido exhaustivamente caracterizados.Simancas Coloma, R. (2009). SÍNTESIS DE NUEVOS MATERIALES ZEOLÍTICOS EMPLEANDO AGENTES DIRECTORES DE ESTRUCTURA FOSFORADOS. http://hdl.handle.net/10251/14187Archivo delegad

Pd-Catalyzed Borylative Cyclization of 1,6-Enynes

Pd-catalyzed cyclization of 1,6-enynes in the presence of bis(pinacolato)diboron affords homoallylic alkylboronates. The reaction is general and proceeds with differently substituted alkenes and with both internal and terminal alkynes. It tolerates the presence of β-hydrogens and is stereoselective in the formation of both the new stereogenic centers and the alkene. This synthesis of alkylboronates avoids the use of highly nucleophilic reagents and is compatible with most functional groups.Marco-Martinez, J.; Lopez-Carrillo, V.; Bunuel, E.; Simancas Coloma, R.; Cardenas, D. (2007). Pd-Catalyzed Borylative Cyclization of 1,6-Enynes. Journal of the American Chemical Society. 129(7):1874-1875. doi:10.1021/ja0685598S18741875129

Material ITQ-62, su procedimiento de obtención y su uso

[EN] The invention relates to a microporous crystalline material, a method for obtaining same and the use thereof, the material having composition: x X2O3: y YO2: z ZO2, wherein X is a trivalent element such as Al, B, Fe, In, Ga, Cr or mixtures thereof, (y+z)/x being able to take values between 9 and infinity; Y corresponds to a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, z/y being able to take values between 10 and infinity; and Z corresponds to a tetravalent element selected from Si and Ge or mixtures thereof.[ES] En la presente invención, se presenta un material cristalino microporoso, su procedimiento de obtención y uso, que tiene una composición: x X2O3: y YO2: z ZO2 en la que X es un elemento trivalente tal como Al, B, Fe, In, Ga, Cr, o mezclas de estos, donde (y+z)/x puede tomar valores entre 9 e infinito; Y corresponde a un elemento tetravalente tal como Ti, Sn, Zr, V o mezclas de ellos, donde z/y puede tomar valores entre 10 e infinito; Z corresponde a un elemento tetravalente seleccionado entre Si y Ge o mezclas de ellos.Consejo Superior de Investigaciones Científicas (España), Universitat Politécnica de ValènciaA1 Solicitud de patente con informe sobre el estado de la técnic

ITQ-62 material, method for obtaining same and use thereof

[ES] En la presente invención, se presenta un material cristalino microporoso, su procedimiento de obtención y uso, que tiene una composición: x X2O3: y YO2: z ZO2 en la que X es un elemento trivalente tal como Al, B, Fe, In, Ga, Cr, o mezclas de estos, donde (y+z)/x puede tomar valores entre 9 e infinito; Y corresponde a un elemento tetravalente tal como Ti, Sn, Zr, V o mezclas de ellos, donde z/y puede tomar valores entre 10 e infinito; Z corresponde a un elemento tetravalente seleccionado entre Si y Ge o mezclas de ellos.[EN] The invention relates to a microporous crystalline material, a method for obtaining same and the use thereof, the material having composition: x X2O3: y YO2: z ZO2, wherein X is a trivalent element such as Al, B, Fe, In, Ga, Cr or mixtures thereof, (y+z)/x being able to take values between 9 and infinity; Y corresponds to a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, z/y being able to take values between 10 and infinity; and Z corresponds to a tetravalent element selected from Si and Ge or mixtures thereof.Consejo Superior de Investigaciones Científicas (España), Universitat Politécnica de ValènciaA1 Solicitud de patente con informe sobre el estado de la técnic

Modular organic structure-directing agents for the synthesis of zeolites

[EN] Organic structure-directing agents (OSDAs) are used to guide the formation of particular types of pores and channels during the synthesis of zeolites. We report that the use of highly versatile OSDAs based on phosphazenes has been successfully introduced for the synthesis of zeolites. This approach has made possible the synthesis of the elusive boggsite zeolite, which is formed by 10- and 12-ring intersecting channels. This topology and these pore dimensions present interesting opportunities for catalysis in reactions of industrial relevance.The authors thank the Spanish government (projects MAT2009-14528-C02-01, PLE2009-0054, and CONSOLIDER INGENIO 2010) and Generalitat Valenciana (Project Prometeo) for financial support. R. S. and N.V. thank UPV and CSIC for Programa de Formacion de Personal Investigador and Junta para la Ampliacion de Estudios predoctoral fellowships, respectively. Further details on the crystal structure may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen, Germany [fax: (+49) 7247-808-666; e-mail: [email protected]], on quoting the depository number CDS-422193.Simancas Coloma, R.; Dari, D.; Velamazan, N.; Navarro Villalba, MT.; Cantin Sanz, A.; Jorda Moret, JL.; Sastre Navarro, GI.... (2010). Modular organic structure-directing agents for the synthesis of zeolites. Science. 330(6008):1219-1222. https://doi.org/10.1126/science.119624012191222330600