Host-Guest and Guest-Guest Interactions of P- and N-Containing Structure Directing Agents Entrapped inside MFI-Type Zeolite by Multinuclear NMR Spectroscopy

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpcc.9b05689".[EN] Highly crystalline pure silica MFI zeolites have been synthesized using tetraethylammonium (TEA), tetraethylphosphonium (TEP), or a mixture of both cations in different proportions as organic structure directing agents (OSDAs). The zeolites have been deeply characterized in order to get insight about the guest guest interactions involving the OSDAs and the guest host interactions involving the OSDAs and the inorganic framework, as well as the main features of the resulting materials. The results show that the average size of the MFI crystals decreases when TEP is present within the zeolite and that this cation is homogeneously distributed throughout the crystallites. The multinuclear NMR investigation (H-1, C-13, N-14, F-19, Si-29, P-31) indicates that TEP interacts with the zeolite host creating higher heterogeneity of the SiO4 crystallographic sites and a diminution on the mobility of fluorine atoms incorporated into the zeolite. Moreover, the presence of TEP influences the dynamics of the nitrogen atoms of the TEA molecules, and 2D heteronuclear correlation experiments give evidence on the spatial proximity of the TEA and TEP molecules in the MFI zeolites. Then, it is concluded that TEA and TEP are intimately mixed within the zeolite voids of the pure silica MFI samples synthesized by the dual template route.Financial support by the MINECO of Spain through the Severo Ochoa (SEV-2016-0683) and RTI2018-101784-B-I00 projects is gratefully acknowledged. The authors also thank the Microscopy Service of the Universitat Politecnica de Valencia for its assistance in microscopy characterization (FESEM equipment preparation). J.M.-O. (SEV-2012-0267-02) is grateful to the Severo Ochoa Program for a predoctoral fellowship.Martinez-Ortigosa, J.; Simancas-Coloma, J.; Vidal Moya, JA.; Gaveau, P.; Rey Garcia, F.; Alonso, B.; Blasco Lanzuela, T. (2019). Host-Guest and Guest-Guest Interactions of P- and N-Containing Structure Directing Agents Entrapped inside MFI-Type Zeolite by Multinuclear NMR Spectroscopy. The Journal of Physical Chemistry C. 123(36):22324-22334. https://doi.org/10.1021/acs.jpcc.9b05689S223242233412336Davis, M. E., & Lobo, R. F. (1992). Zeolite and molecular sieve synthesis. Chemistry of Materials, 4(4), 756-768. doi:10.1021/cm00022a005Cundy, C. S., & Cox, P. A. (2003). The Hydrothermal Synthesis of Zeolites:  History and Development from the Earliest Days to the Present Time. 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From the surface Topography to the Upper mantle beneath Central-Iberian-Zone. The ALCUDIA Seismic Experiments

American Geophysical Union, Fall Meeting 15-19 December, 2014, San FranciscoMulti-seismic experiments acquired across the central and southern part of the Iberian Peninsula provide a new insight into the structure and nature of the lithosphere beneath these areas. Normal incidence and wide-angle seismic reflection data acquired in the area resolve the internal architecture and constrain the distribution of the physical properties along an almost 280 km long transect that samples the major tectonic domains of the Central Iberian Zone (CIZ) and the associated suture (e.g., the Central Unit, CU). A high quality image, ~230 km long, down to 45 km depth (~15 s TWTT) is provided by the normal incidence data set. Based on the reflectivity characteristics, the image can be divided into an upper and mid-lower crust, ~13 km and ~18 km thick, respectively. The wide-angle seismic transect extended the crustal section towards the north across the Madrid Basin. This, latter data set also sample the CIZ until the CU. This is ~280 km long profile which provides very strong constraints on the distribution of physical properties (P wave and S wave velocities, Poisson's ratio) of the upper lithosphere. The PiP and PmP seismic phases constrain two discontinuities: the brittle to ductile discontinuity at ~13-19 km and the Moho boundary at ~31-35.5 km. Currently both appear to act as decoupling surfaces and are interpreted to represent levels of lithological/rheological variations. The internal structure of the Moho is further discussed taking into account the characteristics of the PmP reflections. Furthermore, low fold wide-angle P and S wave stacks reveal a marked crust-mantle transition which is most probably 5-6 km thick and relatively complex structure. The geometrical relationships of this structure with the crustal fabrics of the normal incidence image suggest that the Moho is most probably a result of the re-equilibration and/or other lithospheric processes active after the Variscan collision

Use of Alkylarsonium Directing Agents for the Synthesis and Study of Zeolites

This is the peer reviewed version of the following article: Chem. Eur. J. 2019, 25, 16390 16396 , which has been published in final form at https://doi.org/10.1002/chem.201904043. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Expanding the previously known family of -onium (ammonium, phosphonium, and sulfonium) organic structure-directing agents (OSDAs) for the synthesis of zeolite MFI, a new member, the arsonium cation, is used for the first time. The new group of tetraalkylarsonium cations has allowed the synthesis of the zeolite ZSM-5 with several different chemical compositions, opening a route for the synthesis of zeolites with a new series of OSDA. Moreover, the use of As replacing N in the OSDA allows the introduction of probe atoms that facilitate the study of these molecules by powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (MAS NMR), and X-ray absorption spectroscopy (XAS). Finally, the influence of trivalent elements such as B, Al, or Ga isomorphically replacing Si atoms in the framework structure and its interaction with the As species has been studied. The suitability of the tetraalkylarsonium cation for carrying out the crystallization of zeolites is demonstrated along with the benefit of the presence of As atoms in the occluded OSDA, which allows its advanced characterization as well as the study of its evolution during OSDA removal by thermal treatments.Program Severo Ochoa SEV-2016-0683 and Maria de Maeztu MDM-2015-0538 are gratefully acknowledged. S.S-F. thanks MEC for his Severo Ochoa Grant SPV-2013-067884, P.O.-B. and G.M.E. thank MEC for his Ramon y Cajal contracts (RYC-2014-16620 and RYC-2013-14386). The authors thank the financial support by the Spanish Government (RTI2018-096399-A-I00, RTI2018-101784-B-I00 and CTQ2017-89528-P) and the Generalitat Valeciana (PROMETEO/2017/066). The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization. We gratefully acknowledge ESRF synchrotron for allocating beamtime (proposal CH-5193), the Italian CRG beam-line at ESRF (LISA-BM08), and Alessandro Puri for the help and technical support during our experiment. C.W.L. (Science without Frontiers-Process no. 13191/13-6) thanks CAPES for a predoctoral fellowship.Saez-Ferre, S.; Lopes, CW.; Simancas-Coloma, J.; Vidal Moya, JA.; Blasco Lanzuela, T.; Agostini, G.; Mínguez Espallargas, G.... (2019). Use of Alkylarsonium Directing Agents for the Synthesis and Study of Zeolites. Chemistry - A European Journal. 25(71):16390-16396. https://doi.org/10.1002/chem.201904043S16390163962571Sun, J., Bonneau, C., Cantín, Á., Corma, A., Díaz-Cabañas, M. J., Moliner, M., … Zou, X. (2009). The ITQ-37 mesoporous chiral zeolite. Nature, 458(7242), 1154-1157. doi:10.1038/nature07957Jiang, J., Yu, J., & Corma, A. (2010). 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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/ja061206oCorma, A., Diaz-Cabanas, M. J., Jorda, J. L., Rey, F., Sastre, G., & Strohmaier, K. G. (2008). A Zeolitic Structure (ITQ-34) with Connected 9- and 10-Ring Channels Obtained with Phosphonium Cations as Structure Directing Agents. Journal of the American Chemical Society, 130(49), 16482-16483. doi:10.1021/ja806903cCorma, 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.1003009107Hernández-Rodríguez, M., Jordá, J. L., Rey, F., & Corma, A. (2012). Synthesis and Structure Determination of a New Microporous Zeolite with Large Cavities Connected by Small Pores. Journal of the American Chemical Society, 134(32), 13232-13235. doi:10.1021/ja306013kSimancas, J., Simancas, R., Bereciartua, P. J., Jorda, J. L., Rey, F., Corma, A., … Mugnaioli, E. (2016). Ultrafast Electron Diffraction Tomography for Structure Determination of the New Zeolite ITQ-58. Journal of the American Chemical Society, 138(32), 10116-10119. doi:10.1021/jacs.6b06394Jo, C., Lee, S., Cho, S. J., & Ryoo, R. (2015). Synthesis of Silicate Zeolite Analogues Using Organic Sulfonium Compounds as Structure-Directing Agents. Angewandte Chemie International Edition, 54(43), 12805-12808. doi:10.1002/anie.201506678Jo, C., Lee, S., Cho, S. J., & Ryoo, R. (2015). Synthesis of Silicate Zeolite Analogues Using Organic Sulfonium Compounds as Structure-Directing Agents. 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The Journal of Physical Chemistry A, 119(12), 2829-2833. doi:10.1021/jp510596pArai, Y., Elzinga, E. J., & Sparks, D. L. (2001). X-ray Absorption Spectroscopic Investigation of Arsenite and Arsenate Adsorption at the Aluminum Oxide–Water Interface. Journal of Colloid and Interface Science, 235(1), 80-88. doi:10.1006/jcis.2000.7249Farquhar, M. L., Charnock, J. M., Livens, F. R., & Vaughan, D. J. (2002). Mechanisms of Arsenic Uptake from Aqueous Solution by Interaction with Goethite, Lepidocrocite, Mackinawite, and Pyrite:  An X-ray Absorption Spectroscopy Study. Environmental Science & Technology, 36(8), 1757-1762. doi:10.1021/es010216gMorin, G., Ona-Nguema, G., Wang, Y., Menguy, N., Juillot, F., Proux, O., … Brown Jr., G. E. (2008). Extended X-ray Absorption Fine Structure Analysis of Arsenite and Arsenate Adsorption on Maghemite. Environmental Science & Technology, 42(7), 2361-2366. doi:10.1021/es072057sRamírez-Solís, A., Mukopadhyay, R., Rosen, B. P., & Stemmler, T. L. (2004). Experimental and Theoretical Characterization of Arsenite in Water:  Insights into the Coordination Environment of As−O. Inorganic Chemistry, 43(9), 2954-2959. doi:10.1021/ic0351592Prieto, C., Blasco, T., Camblor, M., & Pérez-Pariente, J. (2000). Characterization of Ga-substituted zeolite Beta by X-ray absorption spectroscopy. Journal of Materials Chemistry, 10(6), 1383-1387. doi:10.1039/b001643hLamberti, C., Turnes Palomino, G., Bordiga, S., Zecchina, A., Spanò, G., & Otero Areán, C. (1999). Catalysis Letters, 63(3/4), 213-216. doi:10.1023/a:1019025206662Axon, S. A., Huddersman, K., & Klinowski, J. (1990). Gallium EXAFS and solid-state NMR studies of Ga-substituted MFI-type zeolites. Chemical Physics Letters, 172(5), 398-404. doi:10.1016/s0009-2614(90)87133-

El Perfil sísmico ALCUDIA: una imagen de la Zona Centroibérica (Varisco Ibérico meridional, España)

The 250 km long, vertical incidence seismic reflection profile ALCUDIA was acquired in spring 2007. It samples the Variscan Central Iberian Zone from Toledo to Fuenteovejuna. Its main goal was to continue the structure obtained for the crust and mantle from the IBERSEIS transect towards the N and NE. The acquisition parameters, similar to those used in the IBERSEIS profile have proven to be adequate to show a detailed image of the whole crust and upper mantle. After preliminary processing, the upper crust shows a moderate reflectivity that can be easily correlated with identifiable surface geologic features. The middle and lower part of the crust seems to be very reflective, laminated and afected by deformation, although to a different extent. The Moho is placed at approximately 10 s TWT and appears to be flat in the time section. The section can be divided into four domains of reflectivity that can be key to stablish different domains of crustal evolution. This new transect, together with the previous IBERSEIS profile, complete an almost 600 km long lithospheric section that crosses the southern half of the Iberian Variscides.El perfil sísmico de reflexión ALCUDIA , de 250 km de longitud, fue adquirido en la primavera del año 2007. Este perfil ha muestreado la Zona Centroibérica entre Toledo y Fuenteovejuna, y su objetivo principal ha sido continuar hacia el NE la estructura de corteza y manto ya obtenida mediante el perfil IBERSEIS. Los parámetros de adquisición, similares a los de IBERSEIS, han sido adecuados para mostrar una imagen detallada de toda la corteza y el manto superior. Una vez efectuado el procesado preliminar, la corteza superior presenta una reflectividad moderada que puede correlacionarse fácilmente con rasgos geológicos de superficie. Las partes media e inferior de la corteza son muy reflectivas, laminadas y afectadas por una deformación que varía a lo largo del perfil. La Moho se localiza a unos 10 s TWT y tiene geometría plana en la sección de tiempo. La variación en los patrones generales de reflectividad permite dividir el pefil sísmico en cuatro dominios, que corresponden a diferentes evoluciones corticales. Este nuevo perfil sísmico, unido al anterior perfil IBERSEIS, constituye una sección litosférica de casi 600 km de longitud, que atraviesa la parte meridional del Varisco Ibérico.Depto. de Geodinámica, Estratigrafía y PaleontologíaFac. de Ciencias GeológicasTRUEMinisterio de Ciencia e Innovación (MICINN)Generalitat de CatalunyaJunta de Comunidades de Castilla La Mancha.pu

Geología de la extremidad oriental de la zona sudportuguesa

Se ha efectuado un estudio de geología regional en la extremidad oriental de la zona Sudportuguesa estableciéndose nuevas unidades litoestratigráficas en los materiales del devonico superior y carbonífero inferior y en la cuenca del Viar. Se han estudiado los caracteres mineralógicos y geoquímicos del vulcanismo pretectónico del plutonismo sin-postectónico y del vulcanismo tardiherciano y se han establecido las deformaciones de plegamiento y la existencia de una notable cizalla frágil tardía entre ossa-morena y la zona sudportuguesa. A la luz de todos estos datos se examinan diversos modelos geodinámicos que han sido aplicados anteriormente al suroeste del macizo ibérico en tiempos del devónico superior y carbonífero inferiorUniv. de Granada, Facultad de Ciencias. Leída el 7-10-198

El Macizo Ibérico, Zona Sudportuguesa: metamorfismo

4 páginas, 2 figurasDentro del Macizo Iberíco se comenta el metamorfismo en la zona sudoeste portuguesa y en la Faja Pirítica Iberíca, presentando sus rasgos generales, donde se distinguen tres tipos de metamorfismos: hidrotermal, de contacto y regional.Peer reviewe