Synthesis and characterization of the all-silica pure polymorph C, and the enriched polymorph B intergrowth material of Beta zeolite

Cantin Sanz, A.; Corma Canós, A.; Díaz Cabañas, MJ.; Jorda Moret, JL.; Moliner Marin, M.; Rey Garcia, F. (2006). Synthesis and characterization of the all-silica pure polymorph C, and the enriched polymorph B intergrowth material of Beta zeolite. Angewandte Chemie International Edition. 45(47):8013-8015. doi:10.1002/anie.200603027S80138015454

Synthesis of cocrystallized USY/ZSM-5 zeolites from kaolin and its use as fluid catalytic cracking catalysts

[EN] A series of samples of cocrystallized USY/ZSM-5 zeolites were synthesized from kaolin and silica following a sequential two-step procedure with varying content of ZSM-5 (5-25 wt%). The presence of the ZSM-5 phases was confirmed by XRD and Si-29-NMR. The samples were stabilized by steaming and tested as FCC catalysts in the cracking of vacuum gasoil. The results obtained show that effectiveness of ZSM-5 as a propylene booster is enhanced when zeolites USY and ZSM-5 were synthesized in the same kaolin material, instead of using merely the physical mixtures of the two zeolites. This enhancement is attributed to the higher ability of ZSM-5 to crack larger olefins and suppress hydrogen-transfer to the gasoline fraction when the zeolites are grown together.This work has been supported by the Spanish Government MINECO through "Severo Ochoa" SEV-2016-0683, CTQ2015-67592-P and CTQ2015-68951-C3-1-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. The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization.Ghrib, Y.; Frini-Srasra, N.; Srasra, E.; Martínez-Triguero, J.; Corma Canós, A. (2018). Synthesis of cocrystallized USY/ZSM-5 zeolites from kaolin and its use as fluid catalytic cracking catalysts. Catalysis Science & Technology. 8(3):716-725. https://doi.org/10.1039/c7cy01477eS71672583Corma, A., & Wojciechowski, B. W. (1985). The Chemistry of Catalytic Cracking. 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Layered zeolitic materials: an approach to designing versatile functional solids

Relevant layered zeolites have been considered in this perspective article from the point of view of the synthesis methodologies, materials characterization and catalytic implications, considering the unique physico-chemical characteristics of lamellar materials. The potential of layered zeolitic precursors to generate novel lamellar accessible zeolites through swelling, intercalation, pillarization, delamination and/ or exfoliation treatments is studied, showing the chemical, functional and structural versatility exhibited by layered zeolites. Recent approaches based on the assembly of zeolitic nanosheets which act as inorganic structural units through the use of dual structural directing agents, the selective modification of germanosilicates and the direct generation of lamellar hybrid organic inorganic aluminosilicates are also considered to obtain layered solids with well-defined functionalities. 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Multifunctional Hybrid Organic−Inorganic Catalytic Materials with a Hierarchical System

Spectroscopic, calorimetric, and catalytic evidences of hydrophobicity on Ti-MCM-41 silylated materials for olefin epoxidations

tHydrophobic Ti-MCM-41 samples prepared by post-synthesis silylation treatment demonstrate to behighly active and selective catalysts in olefins epoxidation by using organic hydroperoxides as oxidizingagents in liquid phase reaction systems. Epoxide yields show important enhancements with increasedsilylation degrees of the Ti-mesoporous samples. Catalytic studies are combined and correlated withspectroscopic techniques (e.g. XRD, XANES, UV-Visible,29Si MAS-NMR) and calorimetric measurementsto better understand the changes in the surface chemistry of Ti-MCM-41 samples due to the post-synthesis silylation treatment and to ascertain the role of these trimethylsilyl groups incorporated inolefin epoxidation. In such manner, the effect of the organic moieties on solids, and both water and gly-col molecules contents on the catalytic activity and selectivity are analyzed in detail. Results show thatthe hydrophobicity level of the samples is responsible for the decrease in water adsorption and, conse-quently, the negligible formation of the non-desired glycol during the catalytic process. Thus, catalystdeactivation by glycol poisoning of Ti active sites is greatly diminished, this increasing catalyst stabilityand leading to practically quantitative production of the corresponding epoxide. The extended use ofthese hydrophobic Ti-MCM-41 catalysts together with organic hydroperoxides for the highly efficientand selective epoxidation of natural terpenes is also exemplified.The authors gratefully acknowledge financial support of Spanish Government (MAT2012-38567-C02-01, Consolider-Ingenio 2010-Multicat CSD-2009-00050 and Severo Ochoa SEV-2012-0267) and Generalitat Valenciana (Project Prometeo). M.E.D. also thanks funds from Spanish Government (CTQ-2011-27550) and CSIC (PIE 2009801063). J.S.A. and F.R.R. acknowledge financial support from MINECO (Projects MAT2013-45008-p and CONCERT Project-NASEMS (PCIN-2013-057), and from Generalitat Valenciana (PROMETEO2009/002).Silvestre Albero, J.; Domine ., ME.; Jorda Moret, JL.; Navarro Villalba, MT.; Rey Garcia, F.; Rodriguez-Reinoso, F.; Corma Canós, A. (2015). Spectroscopic, calorimetric, and catalytic evidences of hydrophobicity on Ti-MCM-41 silylated materials for olefin epoxidations. Applied Catalysis A: General. 507:14-25. https://doi.org/10.1016/j.apcata.2015.09.029S142550

Proyecto TIC-TAC, aprendiendo a hacer ciencia

Treball Final de Màster Universitari en Professor/a d'Educació Secundària Obligatòria i Batxillerat, Formació Professional i Ensenyaments d'Idiomes. Codi: SAP129. Curs: 2015/2016El presente Trabajo Final de Máster (TFM) está basado en la realización de un proyecto de mejora educativa haciendo uso de la metodología investigación-acción en el ámbito científico y el ambiente en el aula en la materia de Cultura Científica en el curso de 1º de bachillerato. El proyecto se ha desarrollado durante el periodo de prácticas del Máster en Profesorado de Educación Secundaria, Bachillerato, Formación Profesional y Enseñanza de Idiomas impartido en la Univeristat Jaume I (Castellón) en el centro IES Honori Garcia de la Vall d’Uixó (Castellón). Éste consiste en desarrollar una nueva perspectiva científica en el alumnado junto un proceso de socialización en el aula mediante la estimulación de las relaciones activas, debido a que se observó que el alumnado carecía de cultura científica y la comunicación en el aula era forzada y escasa. Se ha comprobado si el Aprendizaje Basado en Proyectos Colaborativos (ABPC) y las Tecnologías de la Información y la Comunicación (TIC), conocido como proyecto TIC-TAC, pueden ser una solución a dichos problemas mediante el diseño de un plan de acción que incluye un tema de actualidad, presente en el currículum e interesante para el alumnado. Con dicho objetivo se ha elaborado un proyecto que implementa prácticas educativas innovadoras que incluyen al alumno en el proceso de Enseñanza-Aprendizaje (E-A). A partir de un caso práctico trabajado desde diferentes perspectivas, en cada uno de los grupos colaborativos, permite realizar trabajos interrelacionados que se complementan entre sí. De esta forma, se espera compartir información y conocimientos con la finalidad de ofrecer una solución consensuada entre todo el grupo clase al caso práctico inicial. Para su realización se ha establecido un núcleo de trabajo en grupo, consta de cuatro tareas diferentes que permiten elaborar el trabajo de forma progresiva junto al feedback ofrecido por el docente con la evaluación formativa. No obstante, el alumnado también participa en el proceso de evaluación, evaluando su propia práctica y la de sus compañeros con una evaluación entre iguales. Por otra parte, también se han incluido actividades individuales que se centran en el aprendizaje autónomo y reflexivo y, finalmente, una evaluación final de los conocimientos. Mediante la observación y evaluación de forma triangulada del impacto de la práctica implementada, en relación con los objetivos de partida, se puede concluir que la metodología de trabajo propuesta ha podido desarrollarse de forma adecuada y que los objetivos se han alcanzado de forma excelente. Se ha conseguido mejorar el ambiente en clase, aumentando la bidireccionalidad entre el docente y el alumnado, y fomentando las interacciones entre estos últimos. Asimismo, se ha logrado construir unas bases sólidas de conocimientos científicos en el alumnado características de la presencia de cultura científica que se han podido observar a partir de calidad de sus argumentaciones y opiniones, interés, participación y actitud activa de trabajo, tanto dentro como fuera del aula

Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1∶50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here]

Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes

[EN] The increasing environmental concern and promotion of “green processes” are forcing the substitution of traditional acid and base homogeneous catalysts by solid ones. Among these heterogeneous catalysts, zeolites and zeotypes can be considered as real “green” catalysts, due to their benign nature from an environmental point of view. The importance of these inorganic molecular sieves within the field of heterogeneous catalysis relies not only on their microporous structure and the related shape selectivity, but also on the flexibility of their chemical composition. Modification of the zeolite framework composition results in materials with acidic, basic or redox properties, whereas multifunctional catalysts can be obtained by introducing metals by ion exchange or impregnation procedures, that can catalyze hydrogenation–dehydrogenation reactions, and the number of commercial applications of zeolite based catalysts is continuously expanding. In this review we discuss determinant issues for the development of zeolite based catalysts, going from zeolite catalyst preparation up to their industrial application. Concerning the synthesis of microporous materials we present some of the new trends moving into larger pore structures or into organic free synthesis media procedures, thanks to the incorporation of novel organic templates or alternative framework elements, and to the use of high-throughput synthesis methods. Post-synthesis zeolite modification and final catalyst conformation for industrial use are briefly discussed. In a last section we give a thorough overview on the application of zeolites in industrial processes. Some of them are well established mature technologies, such as fluid catalytic cracking, hydrocracking or aromatics alkylation. Although the number of zeolite structures commercially used as heterogeneous catalysts in these fields is limited, the development of new catalysts is a continuous challenge due to the need for processing heavier feeds or for increasing the quality of the products. The application of zeolite based catalysts in the production of chemicals and fine chemicals is an emerging field, and will greatly depend on the discovery of new or known structures by alternative, lower cost, synthesis routes, and the fine tuning of their textural properties. Finally, biomass conversion and selective catalytic reduction for conversion of NOx are two active research fields, highlighting the interest in these potential industrial applications.The authors acknowledge financial support from Ministerio de Ciencia e Innovacion (project Consolider-Ingenio 2010 MULTICAT).Martínez Sánchez, MC.; Corma Canós, 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.2011.03.014S1558158025513-1

Porous catalysts Separate to accumulate: A sequential templating technique yields bifunctional catalysts with controlled separation of cooperative catalytic functionalities

Corma Canós, A. (2016). Porous catalysts Separate to accumulate: A sequential templating technique yields bifunctional catalysts with controlled separation of cooperative catalytic functionalities. Nature Materials. 15(2):134-136. http://hdl.handle.net/10251/101669S13413615

Heterogeneous catalysis: understanding the fundamentals for catalyst design

[EN] Taking the chemoselective hydrogenation of substituted nitroaromatics as a base case, it will be shown that it is possible to design improved and new catalysts by attacking the problem in a multidisciplinary way. By combining molecular modeling with in situ operando spectroscopy, and with micro-kinetic and isotopic studies, it is possible to determine how and where on the catalysts the reactant molecules interact. Then, materials synthesis methods can be applied to prepare catalysts with the desired surface active sites and their selective interaction with the reactants.This work was funded by the Spanish Government (Severo Ochoa program SEV2012-0267). The support of the European Union by (ERC-AdG-2014-671093 – SynCatMatch) is also acknowledged.Corma Canós, A. (2016). Heterogeneous catalysis: understanding the fundamentals for catalyst design. Faraday Discussions of the Chemical Society. 188:9-20. https://doi.org/10.1039/c6fd00066eS92018

Superparamagnetic particles in ZSM-5-type ferrisilicates

As-synthesized, low iron content, ferrisilicates of ZSM-5-type contain well-separated Fe(III) ions in a tetrahedral environment and display paramagnetic behavior. After hydrothermal treatment, the iron ions are partially extracted from the framework, generating nanosize iron oxide or oxyhydroxide ferrimagnetic particles. This process has been studied by transmission electron microscopy (TEM), Mossbauer spectroscopy, magnetic ac susceptibility (chi(ac)), and field dependent magnetization, on samples containing up to 6.7 wt. % Fe. The experiments evidence the growth of nonaggregated particles, with a typical size around 3 nm, presumably located at the surface of the ferrisilicate crystallites, From a thorough granulometric analysis involving TEM and chi(ac) data, it is concluded that, in the range from 1.5 to 4.6 wt. % Fe, the particle size distributions are significantly independent of the iron content