ESTUDIO DE TRATAMIENTOS ÁCIDO/BÁSICOS EN ZEOLITAS MONODIMENSIONALES. CORRELACIÓN ENTRE PROPIEDADES TEXTURALES Y ACTIVIDAD CATALÍTICA

Las zeolitas se definen como aluminosilicatos cristalinos microporosos que presentan estructuras tridimensionales ordenadas de poros y canales. Los sistemas de canales de microporos pueden ser uni-, bi-, y tri-direccionales. El interés por nuevas zeolitas con estructura de poro jerarquizada, es decir, cristales de zeolita que contienen simultáneamente mesoporos y microporos interconectados, lleva consigo el desarrollo de nuevas técnicas post-síntesis para generar mesoporosidad. En este trabajo se va a hacer uso de una de esas técnicas, denominada desilicación. Se hará sobre la zeolita ZSM-22, una zeolita monodimensional con canales formados por anillos de 10 miembros. La someteremos a diferentes condiciones post-síntesis para generar mesoporosidad. La desilicación consiste en la eliminación selectiva de sílice de la estructura de la zeolita, para así obtener una zeolita jerarquizada. Primeramente, se somete a la zeolita a un tratamiento con una disolución básica en la que el silicio se extrae preferentemente a la disolución, mientras que el Al permanece en el sólido, quedando tras el proceso una fase amorfa fuera de la estructura que bloquea parcialmente los poros de la estructura zeolítica y una segunda etapa de lavado ácido para poder eliminarla y desbloquear la microporosidad. Con estos tratamientos conseguimos zeolitas jerarquizadas especialmente prometedoras porque presentan mejor difusión preservando la acidez para su aplicación en catálisis. Los mesoporos producidos están interconectados y son accesibles desde la superficie externa del cristal de la zeolita, con ventaja en las reacciones con limitaciones difusionales. Para poder observar estas modificaciones en las zeolitas desilicadas, haremos uso de diferentes técnicas de caracterización, como serán ICP (espectrómetro de plasma inducido), para analizar la composición química que determina relación Si/Al y la acidez, espectroscopía infrarroja (IR) de piridina, para cuantificar la acidez BrØnsted y de Lewis, y medidas de adsorción de N2, para conocer el área BET y la distribución de poros en las zeolitas obtenidas. Finalmente estudiaremos la influencia de la mesoporosidad en la actividad del craqueo catalítico, reacción que está limitada por difusión en función del tamaño del alimento. Para ello utilizaremos como alimento olefinas C5-C6-C7, n-decano y 1,3,5-triisopropilbenceno, muy diferentes en reactividad en función de la fuerza ácida y de su tamaño cinético que afectará a su accesibilidad al sistema de microporos de las zeolitas.Zeolites are defined as microporous crystalline aluminosilicates, that they having ordered three-dimensional structures of pores and channels. The micropore channel systems can be uni-, bi-, and tri-directional. The interest for new zeolites with a hierarchical pore structure, that is, zeolite crystals that simultaneously contain mesoporous and interconnected micropores, leads to the development of new post-synthesis techniques to generate mesoporosity. In this work, one of these techniques, desilication, will be used. It will be made on zeolite ZSM-22, a one-dimensional zeolite with channels formed by 10-member rings. We will submit the zeolite to different post-synthesis conditions to generate mesoporosity. Desilication consists in the selective removal of silica from the structure of the zeolite, in order to obtain a hierarchical zeolite. Firstly, the zeolite is subjected to a treatment with a basic solution in which the silicon is preferably extracted to the solution, while the Al remains in the solid, leaving behind an amorphous phase outside the structure that partially blocks the pores of the zeolitic structure and a second stage of acid washing to be able to eliminate it and unblock the microporosity. With these treatments, we get hierarchical zeolites that are particularly promising because they present better diffusion preserving the acidity for its application in catalysis. The mesopores produced are interconnected and are accessible from the outer surface of the zeolite crystal, with an advantage in the reactions with diffusional limitations. In order to observe these modifications in the desilicated zeolites, we will make use of different characterization techniques, such as ICP (induced plasma spectrometer), to analyze the chemical composition that determines Si / Al ratio and acidity with infrared (IR) pyridine spectroscopy, to quantify Brønsted and Lewis acidity, and N2 adsorption measurements, to know the BET area and the pore distribution in the zeolites obtained. We will also use the technique of transmission electron microscopy (TEM) to be able to observe at a morphological level the zeolitic structure of our samples. Finally, we will study the influence of mesoporosity on the activity of catalytic cracking, a reaction that is limited by diffusion depending on the size of the food. For this purpose, we will use olefins C5-C6-C7, n-decane and 1,3,5-triisopropylbenzene as food, very different in reactivity depending on the acid strength and its kinetic size that will affect its accessibility to the micropore system of the zeolites.Bello Jurado, E. (2018). ESTUDIO DE TRATAMIENTOS ÁCIDO/BÁSICOS EN ZEOLITAS MONODIMENSIONALES. CORRELACIÓN ENTRE PROPIEDADES TEXTURALES Y ACTIVIDAD CATALÍTICA. http://hdl.handle.net/10251/114965TFG

Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure-Directing Agents: Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx

[EN] A novel ab initio methodology based on high-throughput simulations has permitted designing unique biselective organic structure-directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well-established commercial CHA-type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties.E.B.-J., C.P., M.M. and A.C. acknowledge financial support by the Spanish Government [Grant RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE)], and by CSIC [I-link+ Program (LINKA20381)]. 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 additionally funded by the MIT Energy Fellowship. Y.R.-L acknowledges support by the U.S. Department of Energy, Office of Basic Energy Sciences under Award DE-SC0016214. E.B.-J. acknowledges the Spanish Government for an FPI scholarship (PRE2019-088360). T.W. acknowledges financial support by the Swedish Research Council (Grant No. 2019-05465). T.W. and T.U. acknowledge funding from the Swedish Strategic Res. Foundation (project nr. ITM17-0301). The Electron Microscopy Service of the UPV is also acknowledged for their help in sample characterization. Computer calculations were executed at the Massachusetts Green High-Performance Computing Center with support from MIT Research Computing, and at the Extreme Sci. and Eng. Discovery Environment (XSEDE)[33] Expanse through allocation TG-DMR200068.Bello-Jurado, E.; Schwalbe-Koda, D.; Nero, M.; Paris, C.; Uusimäki, T.; Román-Leshkov, Y.; Corma Canós, A.... (2022). Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure-Directing Agents: Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx. Angewandte Chemie International Edition. 61(28):1-6. https://doi.org/10.1002/anie.20220183716612

NH3-SCR catalysts for heavy-duty diesel vehicles: Preparation of CHA-type zeolites with low-cost templates

Computer-assistance allows selecting the most adequate low-cost organic structure directing agents (OSDAs) for the crystallization of Al-rich CHA-type zeolites. The host-guest stabilization energies of tetraethylammonium (TEA), methyltriethylammonium (MTEA) and dimethyldiethylammonium (DMDEA), in combination with Na, were first theoretically evaluated. This “ab-initio” analysis reveals that two TEA show a serious steric hindrance in a cha cavity, whereas two MTEA would present excellent host-guest confinements. The synthesis of Al-rich CHA-type zeolites has been accomplished using TEA and MTEA. Electron diffraction and high-resolution transmission electron microscopy reveal large CHA-domains with narrow faulted GME-domains in the CHA-type material synthesized with TEA, confirming the better OSDA-directing roles of MTEA cations towards the cha cavity, in good agreement with DFT calculations. Cu-exchanged Al-rich CHA-type samples achieved with MTEA and TEA show excellent catalytic activity and hydrothermal stability for the selective catalytic reduction (SCR) of NOx with ammonia under conditions relevant for future heavy duty diesel conditions.This work has been supported by Umicore and by the Spanish Government-MCIU through RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE) and PID2020-112590GB-C21 (AEI/FEDER, UE). T.W. acknowledges financial support by the Swedish Research Council (Grant No. 2019-05465). E.B. acknowledges the Spanish Government-MCIU for a FPI scholarship (PRE2019-088360). P.F. thanks ITQ for a contract. The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization. The computations were performed on the Tirant III cluster of the Servei d'Informàtica of the University of Valencia

Effect of Framework Composition and NH3 on the Diffusion of Cu+ in Cu-CHA Catalysts Predicted by Machine-Learning Accelerated Molecular Dynamics

Creative Commons Attribution License or Creative Commons Attribution Non-Commercial No Derivatives License[EN] Cu-exchanged zeolites rely on mobile solvated Cu+ cations for their catalytic activity, but the role of the framework composition in transport is not fully understood. Ab initio molecular dynamics simulations can provide quantitative atomistic insight but are too computationally expensive to explore large length and time scales or diverse compositions. We report a machine-learning interatomic potential that accurately reproduces ab initio results and effectively generalizes to allow multinanosecond simulations of large supercells and diverse chemical compositions. Biased and unbiased simulations of [Cu(NH3)2]+ mobility show that aluminum pairing in eight-membered rings accelerates local hopping and demonstrate that increased NH3 concentration enhances long-range diffusion. The probability of finding two [Cu(NH3)2]+ complexes in the same cage, which is key for SCR-NOx reaction, increases with Cu content and Al content but does not correlate with the long-range mobility of Cu+. Supporting experimental evidence was obtained from reactivity tests of Cu-CHA catalysts with a controlled chemical composition.R.M. acknowledges the Margarita Salas grant from the Ministerio de Universidades, Spain, funded by the European Union-Next Generation EU. The authors are grateful for computation time allocated on the MIT SuperCloud cluster, the MIT Engaging cluster at the Massachusetts Green High Performance Computing Center (MGHPCC), and Summit at the Oakridge Leadership Computing Facility through the 2021 ALCC DOE program. R.G-B. thanks the Jeffrey Cheah Career Development Chair. R.M thanks Gavin Winter for assistance during the training of NNP and processing of the MD simulations and Simon Axelrod for implementing PaiNN. M.B. and M.M. are grateful for financial support from the Spanish government through PID2020-112590GB-C21, PID2021-122755OB-I00, and TED2021-130739B-I00 (MCIN/AEI/FEDER, UE) and from CSIC through the I-link+ Program (LINKA20381). E.B.-J. acknowledges the Spanish government-MCIU for a FPI scholarship (PRE2019-088360).Millán-Cabrera, R.; Bello-Jurado, E.; Moliner Marin, M.; Boronat Zaragoza, M.; Gomez-Bombarelli, R. (2023). Effect of Framework Composition and NH3 on the Diffusion of Cu+ in Cu-CHA Catalysts Predicted by Machine-Learning Accelerated Molecular Dynamics. ACS Central Science. 9(11):2044-2056. https://doi.org/10.1021/acscentsci.3c008702044205691

Synthèse de l'entrecroisement CHA/AEI, procédé de synthèse et utilisation correspondante dans des applications catalytiques

[ES] En la presente invención, se describe un nuevo procedimiento de síntesis del material intercrecido CHA/AEI en su forma zeolítica utilizando un único agente director de estructura orgánico (ADEO), mucho más sencillo que las mezclas descritas hasta el momento, y en ausencia de aniones fluoruro en el medio de síntesis. En la presente invención también se describe el material obtenido con dicho procedimiento y su uso como catalizador en diversos procesos catalíticos, como metanol a olefinas, y la reducción catalítica selectiva (RCS) de distintos óxidos de nitrógeno (NOx) en emisiones gaseosas.[EN] The present invention relates to a new method for synthesising CHA/AEI intergrown material in its zeolitic form using a single organic structure-directing agent (OSDA), which is much simpler than previously described mixtures, and in which the synthesis medium is free of fluoride anions. The present invention also relates to the material obtained with said method and the use thereof as a catalyst in various catalytic processes, such as the methanol-to-olefin process, and the selective catalytic reduction (SCR) of different nitrogen oxides (NOx) in gaseous emissions.[FR] La présente invention porte sur un nouveau procédé de synthèse du matériau entrecroisé CHA/AEI dans sa forme zéolithique au moyen d'un agent directeur unique de structure organique (ADEO), beaucoup plus simple que les mélanges décrits jusqu'à ce jour, et en l'absence d'anions fluorure dans le milieu de synthèse. L'invention porte également sur le matériau obtenu au moyen dudit procédé et sur son utilisation comme cstalyseur dans divers processus catalytiques, comme la conversion de méthanol en oléfines et la réduction catalytique sélective (RCS) de différents oxydes d'azote (NOx) en émissions gazeuses.NoMassachusetts Institute of Technology, Consejo Superior de Investigaciones Científicas (CSIC), Universitat Politècnica de ValènciaA1 Solicitud de patente con informe sobre el estado de la técnic

Deactivation and regeneration studies on Pd-containing medium pore zeolites as passive NOx adsorbers (PNAs) in cold-start applications

[EN] Two Pd-containing medium pore zeolite frameworks, MFI and MWW, have been evaluated as passive NOx adsorbers (PNAs) in automotive applications. The NOx adsorption/desorption behavior of Pd-containing standard ZSM-5 and MCM-22 zeolites with analogous physico-chemical properties (Si/Al similar to 10-12, 1%wt Pd, crystal size of similar to 200-400 nm), has been first studied. Pd/ZSM-5 shows better low-temperature NOx capacity than Pd/MCM-22 (0.83 and 0.55 mu mol NOx/mu mol Pd), but, in contrast, Pd/MCM-22 is able to desorb NOx at remarkable lower temperatures (similar to 50 degrees C fewer). In order to evaluate the influence of the textural properties of the MWW-type materials on the NOx adsorption/desorption behavior, a delaminated DS-ITQ-2 and nano-MCM-22, have also been prepared. The deactivation of the different Pd-containing medium pore zeolites and their posterior regeneration have been systematically studied by subjecting the samples to CO-ageing treatments at different temperatures (from 150 to 650 degrees C) and hydrothermal treatments at 750 degrees C, respectively. Pd/ZSM-5 is able to almost fully recovery the former NOx adsorption capacity, whereas Pd/MWW materials only recuperate half of their initial NOx adsorption capacity, fact that can be explained by the larger critical sizes of part of the agglomerated metal particles on the external surface of these materials.This work has been supported by Umicore and by the Spanish Government through SEV-2016-0683 and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE). E.B. acknowledges the Spanish Government-MCIU for a FPI scholarship. E.M.G. acknowledges "La Caixa -Severo Ochoa" International PhD Fellowships (call 2015). We thank I. Millet for technical assistance. The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization.Bello-Jurado, E.; Margarit Benavent, VJ.; Gallego-Sánchez, EM.; Schuetze, F.; Hengst, C.; Corma Canós, A.; Moliner Marin, M. (2020). Deactivation and regeneration studies on Pd-containing medium pore zeolites as passive NOx adsorbers (PNAs) in cold-start applications. Microporous and Mesoporous Materials. 302:1-10. https://doi.org/10.1016/j.micromeso.2020.110222S110302Skalska, K., Miller, J. S., & Ledakowicz, S. (2010). Trends in NO abatement: A review. Science of The Total Environment, 408(19), 3976-3989. doi:10.1016/j.scitotenv.2010.06.001Beale, A. M., Gao, F., Lezcano-Gonzalez, I., Peden, C. H. F., & Szanyi, J. (2015). Recent advances in automotive catalysis for NOx emission control by small-pore microporous materials. Chemical Society Reviews, 44(20), 7371-7405. doi:10.1039/c5cs00108kMoliner, M., Martínez, C., & Corma, A. (2013). Synthesis Strategies for Preparing Useful Small Pore Zeolites and Zeotypes for Gas Separations and Catalysis. Chemistry of Materials, 26(1), 246-258. doi:10.1021/cm4015095Fickel, D. W., D’Addio, E., Lauterbach, J. A., & Lobo, R. F. (2011). The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites. Applied Catalysis B: Environmental, 102(3-4), 441-448. doi:10.1016/j.apcatb.2010.12.022Moliner, 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/c2cc33992gSchmeisser, V., Weibel, M., Sebastian Hernando, L., Nova, I., Tronconi, E., & Ruggeri, M. P. (2013). Cold Start Effect Phenomena over Zeolite SCR Catalysts for Exhaust Gas Aftertreatment. SAE International Journal of Commercial Vehicles, 6(1), 190-199. doi:10.4271/2013-01-1064Zheng, Y., Kovarik, L., Engelhard, M. H., Wang, Y., Wang, Y., Gao, F., & Szanyi, J. (2017). Low-Temperature Pd/Zeolite Passive NOx Adsorbers: Structure, Performance, and Adsorption Chemistry. The Journal of Physical Chemistry C, 121(29), 15793-15803. doi:10.1021/acs.jpcc.7b04312Moliner, M., & Corma, A. (2019). From metal-supported oxides to well-defined metal site zeolites: the next generation of passive NOxadsorbers for low-temperature control of emissions from diesel engines. Reaction Chemistry & Engineering, 4(2), 223-234. doi:10.1039/c8re00193fGu, Y., & Epling, W. S. (2019). Passive NOx adsorber: An overview of catalyst performance and reaction chemistry. Applied Catalysis A: General, 570, 1-14. doi:10.1016/j.apcata.2018.10.036Lee, J., Ryou, Y., Cho, S. J., Lee, H., Kim, C. H., & Kim, D. H. (2018). Investigation of the active sites and optimum Pd/Al of Pd/ZSM–5 passive NO adsorbers for the cold-start application: Evidence of isolated-Pd species obtained after a high-temperature thermal treatment. Applied Catalysis B: Environmental, 226, 71-82. doi:10.1016/j.apcatb.2017.12.031Khivantsev, K., Jaegers, N. R., Kovarik, L., Hanson, J. C., Tao, F. (Feng), Tang, Y., … Szanyi, J. (2018). Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small‐Pore Zeolite SSZ‐13: High‐Capacity and High‐Efficiency Low‐Temperature CO and Passive NO x Adsorbers. Angewandte Chemie International Edition, 57(51), 16672-16677. doi:10.1002/anie.201809343Vu, A., Luo, J., Li, J., & Epling, W. S. (2017). Effects of CO on Pd/BEA Passive NOx Adsorbers. Catalysis Letters, 147(3), 745-750. doi:10.1007/s10562-017-1976-xRyou, Y., Lee, J., Kim, Y., Hwang, S., Lee, H., Kim, C. H., & Kim, D. H. (2019). Effect of reduction treatments (H2 vs. CO) on the NO adsorption ability and the physicochemical properties of Pd/SSZ-13 passive NOx adsorber for cold start application. Applied Catalysis A: General, 569, 28-34. doi:10.1016/j.apcata.2018.10.016Ryou, Y., Lee, J., Lee, H., Kim, C. H., & Kim, D. H. (2019). Effect of various activation conditions on the low temperature NO adsorption performance of Pd/SSZ-13 passive NOx adsorber. Catalysis Today, 320, 175-180. doi:10.1016/j.cattod.2017.11.030Gu, Y., Zelinsky, R. P., Chen, Y.-R., & Epling, W. S. (2019). Investigation of an irreversible NOx storage degradation Mode on a Pd/BEA passive NOx adsorber. Applied Catalysis B: Environmental, 258, 118032. doi:10.1016/j.apcatb.2019.118032Khivantsev, K., Jaegers, N. R., Kovarik, L., Prodinger, S., Derewinski, M. A., Wang, Y., … Szanyi, J. (2019). Palladium/Beta zeolite passive NOx adsorbers (PNA): Clarification of PNA chemistry and the effects of CO and zeolite crystallite size on PNA performance. Applied Catalysis A: General, 569, 141-148. doi:10.1016/j.apcata.2018.10.021Ryou, Y., Lee, J., Cho, S. J., Lee, H., Kim, C. H., & Kim, D. H. (2017). Activation of Pd/SSZ-13 catalyst by hydrothermal aging treatment in passive NO adsorption performance at low temperature for cold start application. Applied Catalysis B: Environmental, 212, 140-149. doi:10.1016/j.apcatb.2017.04.077Wang, N., Sun, Q., Bai, R., Li, X., Guo, G., & Yu, J. (2016). In Situ Confinement of Ultrasmall Pd Clusters within Nanosized Silicalite-1 Zeolite for Highly Efficient Catalysis of Hydrogen Generation. Journal of the American Chemical Society, 138(24), 7484-7487. doi:10.1021/jacs.6b03518Goel, S., Zones, S. I., & Iglesia, E. (2014). Encapsulation of Metal Clusters within MFI via Interzeolite Transformations and Direct Hydrothermal Syntheses and Catalytic Consequences of Their Confinement. Journal of the American Chemical Society, 136(43), 15280-15290. doi:10.1021/ja507956mLiu, L., Lopez-Haro, M., Lopes, C. W., Li, C., Concepcion, P., Simonelli, L., … Corma, A. (2019). Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis. Nature Materials, 18(8), 866-873. doi:10.1038/s41563-019-0412-6Liu, L., Díaz, U., Arenal, R., Agostini, G., Concepción, P., & Corma, A. (2016). Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials, 16(1), 132-138. doi:10.1038/nmat4757KOKOTAILO, G. T., LAWTON, S. L., OLSON, D. H., & MEIER, W. M. (1978). Structure of synthetic zeolite ZSM-5. Nature, 272(5652), 437-438. doi:10.1038/272437a0Leonowicz, M. E., Lawton, J. A., Lawton, S. L., & Rubin, M. K. (1994). MCM-22: A Molecular Sieve with Two Independent Multidimensional Channel Systems. Science, 264(5167), 1910-1913. doi:10.1126/science.264.5167.1910Corma, 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:10.1038/24592Corma, A., Fornés, V., Guil, J. ., Pergher, S., Maesen, T. L. ., & Buglass, J. . (2000). Preparation, characterisation and catalytic activity of ITQ-2, a delaminated zeolite. Microporous and Mesoporous Materials, 38(2-3), 301-309. doi:10.1016/s1387-1811(00)00149-9Rutkowska, M., Díaz, U., Palomares, A. E., & Chmielarz, L. (2015). Cu and Fe modified derivatives of 2D MWW-type zeolites (MCM-22, ITQ-2 and MCM-36) as new catalysts for DeNO x process. Applied Catalysis B: Environmental, 168-169, 531-539. doi:10.1016/j.apcatb.2015.01.016Margarit, 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.201506822Luo, 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/c5sc01912eGallego, E. M., Paris, C., Martínez, C., Moliner, M., & Corma, A. (2018). Nanosized MCM-22 zeolite using simple non-surfactant organic growth modifiers: synthesis and catalytic applications. Chemical Communications, 54(71), 9989-9992. doi:10.1039/c8cc05356aCorma, A., Corell, C., & Pérez-Pariente, J. (1995). Synthesis and characterization of the MCM-22 zeolite. Zeolites, 15(1), 2-8. doi:10.1016/0144-2449(94)00013-iArgyle, M., & Bartholomew, C. (2015). Heterogeneous Catalyst Deactivation and Regeneration: A Review. Catalysts, 5(1), 145-269. doi:10.3390/catal501014

Síntesis del intercrecimiento CHA/AEI, procedimiento de síntesis y uso en aplicaciones catalíticas

En la presente invención, se describe un nuevo procedimiento de síntesis del material intercrecido CHA/AEI en su forma zeolítica utilizando un único agente director de estructura orgánico (ADEI), mucho más sencillo que las mezclas descritas hasta el momento, y en ausencia de aniones fluoruro en el medio de síntesis. En la presente invención también se describe en el material obtenido con dicho procedimiento y su uso como catalizador en diversos procesos catalíticos, como metanol a olefinas, y la reducción catalítica selectiva (RCS) de distintos óxidos de nitrógenos (NOx) en emisiones gaseosas.Peer reviewedMassachusetts Institute of Technology, Consejo Superior de Investigaciones Científicas (CSIC), Universitat Politècnica de ValènciaB2 Patente con examen previ

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

[EN] 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 HighPerformance Computing Center with support from MIT Research Computing and at the Extreme Science and Engineering Discovery Environment (XSEDE) (53) Expanse through allocation TG-DMR200068.Schwalbe-Koda, D.; Kwon, S.; Paris, C.; Bello-Jurado, E.; Jensen, Z.; Olivetti, E.; Willhammar, T.... (2021). A priori control of zeolite phase competition and intergrowth with high-throughput simulations. Science. 374:308-315. https://doi.org/10.1126/science.abh3350S30831537

Podcasts como ferramenta para aprender sobre Direito

La proliferación de nuevas formas de transmisión del conocimiento, así como de su difusión constituye una oportunidad que la enseñanza del Derecho no puede dejar pasar. La elaboración de podcast o podcasting con fines educativos o de aplicación a la docencia ha sido ya objeto de utilización en el contexto anglosajón y, en un nivel mucho menor, en el contexto español. Como ya alude Piñero-Otero, T. en su investigación “La utilización de los podcasts en la universidad española: entre la institución y la enseñanza”, la incorporación de los podcasts como herramienta docente en las universidades españolas fue tardía respecto a otras universidades, como las norteamericanas. Y, no sólo eso, sino que su aplicación en la práctica es escasa. Los podcasts muestran relevantes potencialidades para la formación universitaria y, en específico, para la formación en Derecho. El formato de fragmentos o episodios de audio que desarrollan conocimiento, online, público, gratuito y accesible en cualquier momento se evidencia pertinente para captar el interés del estudiantado. Evidencia que queda patente en los estudios que ya han aplicado esta herramienta. El presente proyecto busca fomentar la extensión de este instrumento en el entorno universitario como recurso formativo complementario y de apoyo a la clase magistral y práctica establecida en la regulación de las enseñanzas superiores. Tal y como se ha apuntado en numerosas ocasiones por docentes que ya han aplicado los podcasts en la educación, se trata de una fuente más que, en ningún caso, se propone como sustitutoria de las clases ordinarias. Ello supondría el desencadenamiento de efectos negativos como una insuficiencia de formación, falta de intercambio de pensamiento y debate y riesgo de asistencia y participación en el aula, entre otros. Respecto de este último aspecto, estudios como el de Parson, V., Reddy, P., Wood, J. y Senior, C. (2009), “Educating and iPod generation: undergraduate attitudes, experiences and understanding of vodcast and podcast use”, reflejan que los estudiantes consideran como un aspecto muy positivo el hecho de que los podcasts permitan aprender y revisar el contenido de la asignatura; aspecto que quedaría desvirtuado si la docencia tradicional quedará completamente subsumida al empleo del podcast.El objetivo del Proyecto de Innovación Docente es ofrecer una herramienta para el aprendizaje del Derecho, basada en la digitalización mediante podcast, que permita a los estudiantes disponer de contenidos jurídicos para su proceso formativo.The aim of the Teaching Innovation Project is to offer a tool for learning law, based on digitalisation through podcasts, which allows students to have access to legal content for their learning process.L'obiettivo del Progetto di Innovazione Didattica è quello di offrire uno strumento per l'apprendimento del diritto, basato sulla digitalizzazione attraverso i podcast, che permetta agli studenti di avere accesso a contenuti giuridici per il loro processo di formazione.O objetivo do Projeto de Inovação Didática é oferecer uma ferramenta de aprendizagem do direito, baseada na digitalização através de podcasts, que permita aos estudantes ter acesso a conteúdos jurídicos para o seu processo de formação.Depto. de Derecho del Trabajo y Seguridad SocialFac. de DerechoFALSEsubmitte