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The synthesis of the ZSM-5 and beta zeolites in their nanosized form has been achieved by using simple alkyl-substituted mono-cationic cyclic ammonium cations as OSDA molecules. The particular combination of a cyclic fragment and a short linear alkyl-chain group (preferentially C) within the monocationic OSDA molecules allows directing the crystallization of nanosized zeolites with excellent solid yields (above 90%). Interestingly, the formation of the nanosized ZSM-5 and beta zeolites mostly depends on the size and nature of the cyclic fragment of the OSDA molecule, resulting in all cases in nanocrystalline solids with homogeneous distributions of particle sizes (∼10-25 nm) and controlled Si/Al molar ratios (∼15-30). The achieved nanosized ZSM-5 and beta zeolites have been extensively characterized by different techniques to study their physico-chemical properties, such as chemical composition, pore accessibility or Brønsted acidity, among others. Moreover, the catalytic properties of the nanosized ZSM-5 and beta zeolites have been evaluated for different chemical reactions, including methanol-to-olefins (MTO) in the case of ZSM-5, and alkylation of benzene with propylene to obtain cumene and oligomerization of light olefins to liquid fuels in the case of beta, observing in all cases improved catalytic activity and product selectivity towards target products when compared to related catalysts. ; This work has been supported by the Spanish Government MINECO through "Severo Ochoa" (SEV 2012-0267), MAT2015-71261-R and CTQ2015-70126-R, by the European Union through ERC-AdG-2014-671093 (SynCatMatch) and by the Fundación Ramón Areces through a research contract of the "Life and Materials Science" program. E. M. G. and M. R. D- R. acknowledge "La Caixa – Severo Ochoa" International PhD Fellowships (call 2015). M. E. M- A. thanks MINECO for economical support through pre-doctoral fellowship (BES-2013-066800). ; Peer Reviewed

[EN] The synthesis of the ZSM-5 and beta zeolites in their nanosized form has been achieved by using simple alkyl-substituted mono-cationic cyclic ammonium cations as OSDA molecules. The particular combination of a cyclic fragment and a short linear alkyl-chain group (preferentially C4) within the monocationic OSDA molecules allows directing the crystallization of nanosized zeolites with excellent solid yields (above 90%). Interestingly, the formation of the nanosized ZSM-5 and beta zeolites mostly depends on the size and nature of the cyclic fragment of the OSDA molecule, resulting in all cases in nanocrystalline solids with homogeneous distributions of particle sizes (similar to 10-25 nm) and controlled Si/Al molar ratios (similar to 15-30). The achieved nanosized ZSM-5 and beta zeolites have been extensively characterized by different techniques to study their physico-chemical properties, such as chemical composition, pore accessibility or Bronsted acidity, among others. Moreover, the catalytic properties of the nanosized ZSM-5 and beta zeolites have been evaluated for different chemical reactions, including methanol-to-olefins (MTO) in the case of ZSM-5, and alkylation of benzene with propylene to obtain cumene and oligomerization of light olefins to liquid fuels in the case of beta, observing in all cases improved catalytic activity and product selectivity towards target products when compared to related catalysts. ; This work has been supported by the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), MAT2015-71261-R and CTQ2015-70126-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. E. M. G. and M. R. D-R. acknowledge "La Caixa - Severo Ochoa" International PhD Fellowships (call 2015). M. E. M-A. thanks MINECO for economical support through pre-doctoral fellowship (BES-2013-066800). The Electron Microscopy Service of the UPV is acknowledged for their help in sample ...

The synthesis of crystalline microporous materials containing large pores is in high demand by industry, especially for the use of these materials as catalysts in chemical processes involving bulky molecules. An extra-large-pore silicoaluminophosphate with 16-ring openings, ITQ-51, has been synthesized by the use of bulky aromatic proton sponges as organic structure-directing agents. Proton sponges show exceptional properties for directing extra-large zeolites because of their unusually high basicity combined with their large size and rigidity. This extra-large-pore material is stable after calcination, being one of the very few examples of hydrothermally stable molecular sieves containing extra-large pores. The structure of ITQ-51 was solved from submicrometer-sized crystals using the rotation electron diffraction method. Finally, several hypothetical zeolites related to ITQ-51 have been proposed. ; The authors gratefully acknowledge Dr. Alejandro Vidal-Moya for the SUP>27 /SUP>Al MQ MAS NMR experiment. The authors also acknowledge financial support from Ministerio de Economia y Competitividad of Spain (MAT2012-37160), Consolider Ingenio 2010-MULTICAT, Generalitat Valenciana through the PROMETEO program, Universitat Politecnica de Valencia through PAID-06-11 (n.1952), the Swedish Research Council (VR), the Swedish Governmental Agency for Innovation Systems (VINNOVA), and the Goran Gustafsson Foundation. M. M. also acknowledges "Subprograma Ramon y Cajal" for Contract RYC-2011-08972. The TEM used in this study was purchased from a grant by the Knut and Alice Wallenberg Foundation. ; Martínez Franco, R.; Moliner Marin, M.; Yun, Y.; Sun, J.; Wan, W.; Zou, X.; Corma Canós, 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. https://doi.org/10.1073/pnas.1220733110 ; S ; 3749 ; 3754 ; 110 ; 10

[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/C5NJ01203A ; S ; 4140 ; 4145 ; 40 ; 5 ; LaPierre, 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)90121-6 ; Gies, 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-d ; Fyfe, 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 ...

[EN] It has been possible to efficiently synthesize high-silica ERI and AFX zeolites with nano-sized primary crystallites (30-200 nm). This was achieved by using a dicationic and rigid organic structure directing agent (OSDA) that fits within the large cavities of these zeolites, and the use of FAU zeolites as initial Si and Al-sources. Cu- and Fe-based ERI and AFX materials were prepared following both post-synthetic cation exchange and direct synthesis methodologies, showing good activity for the selective catalytic reduction (SCR) of nitrogen oxide using ammonia. Accelerated hydrothermal ageing of the zeolites at high temperature (i.e. 750 degrees C) shows the necessity of removing the alkali cations remaining in the zeolites to obtain stable materials. Furthermore, the catalytic performance of the prepared Cu- and Fe-containing AFX catalyst, both before and after ageing treatment, approaches the catalytic activity of Cu- and Fe-CHA. (C) 2017 Elsevier B.V. All rights reserved. ; This work has been supported by Haldor Topsoe A/S, by the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), and MAT2015-71261-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. N. M. thanks MINECO for economical support through pre-doctoral fellowship (BES-2013-064347). The authors thank Isabel Millet for technical support. ; Martín-García, N.; Paris, C.; Vennestrom; Peter Nicolai Ravnborg; Thogersen, JR.; Corma Canós, A.; Moliner Marin, M. (2017). Cage-based small-pore catalysts for NH3-SCR prepared by combining bulky organic structure directing agents with modified zeolites as reagents. Applied Catalysis B Environmental. 217:125-136. https://doi.org/10.1016/j.apcatb.2017.05.082 ; S ; 125 ; 136 ; 217

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 ...

A new zeolite (named as ITQ-52) having large cavities and small and medium channels has been synthesized. This was achieved by using a new family of amino-phosphonium cations as organic structure directing agents (OSDA). These cations contain P−C and P−N bonds, and therefore they lie between previously reported P-containing OSDA, such as tetraalkylphosphonium and phosphazenes. In this study, it has been found that 1,4- butanediylbis[tris(dimethylamino)]phosphonium dication is a very efficient OSDA for crystallization of several zeolites, and in some particular conditions, the new zeolite ITQ-52 was synthesized as a pure phase. The structure of ITQ-52 has been solved using high-resolution synchrotron X-ray powder diffraction data of the calcined solid. This new zeolite crystallizes in the space group I2/m, with cell parameters a = 17.511 Å, b = 17.907 Å, c = 12.367 Å, and β = 90.22°. The topology of ITQ-52 can be described as a replication of a composite building unit with ring notation [435461] that gives rise to the formation of an interconnected 8R and 10R channel system. ; We thank financial support by the Spanish Government (MAT2012-38567-C02-01, MAT2012-38567-C02-02, Consolider Ingenio 2010-Multicat CSD-2009-00050 and Severo Ochoa SEV-2012-0267). R.S. acknowledges to UPV for a FPI predoctoral fellowship. Authors thank ALBA Light Source for beam allocation at beamline MSPD. We thank G. Sastre and J. A. Vidal for computational calculations and MAS NMR experiments, respectively. ; Simancas Coloma, R.; Jorda Moret, JL.; Rey Garcia, F.; Corma Canós, A.; Cantin Sanz, A.; Peral, I.; Popescu, C. (2014). A new microporous zeolitic silicoborate (ITQ-52) with interconnected small and medium pores. Journal of the American Chemical Society. 136(9):3342-3345. doi:10.1021/ja411915c ; S ; 3342 ; 3345 ; 136 ; 9

A two-dimensional zeolite with the topol. of MWW sheets has been obtained by direct synthesis with a combination of two org. structure-directing agents. The resultant material consists of approx. 70 % single and double layers and displays a well-structured external surface area of about 300 m2 g-1. The delaminated zeolite prepd. by means of this single-step synthetic route has a high delamination degree, and the structural integrity of the MWW layers is well preserved. The new zeolite material displayed excellent activity, selectivity, and stability when used as a catalyst for the alkylation of benzene with propylene and found to be superior to the catalysts that are currently used for producing cumene. ; Financial support by the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), Consolider Ingenio 2010-Multicat, and MAT2012-31657 is acknowledged. M.E.M.-A. thanks MINECO for financial support through a pre-doctoral fellowship (BES-2013-066800). ; Margarit Benavent, VJ.; Martínez Armero, ME.; Navarro Villalba, MT.; Martínez, C.; Corma Canós, A. (2015). Direct Dual-Template Synthesis of MWW Zeolite Monolayers. Angewandte Chemie International Edition. 54(46):13724-13728. https://doi.org/10.1002/anie.201506822 ; S ; 13724 ; 13728 ; 54 ; 46

[EN] Ferrierite zeolites with nanosized crystals and external surface areas higher than 250m(2)g(-1) have been prepared at relatively low synthesis temperature (120 degrees C) by means of the collaborative effect of two organic structure directing agents (OSDA). In this way, hierarchical porosity is achieved without the use of post-synthesis treatments that usually involve leaching of Tatoms and solid loss. Adjusting the synthesis conditions it is possible to decrease the crystallite size in the directions of the 8- and 10-ring channels, [010] and [001] respectively, reducing their average pore length to 10-30nm and increasing the number of pores accessible. The small crystal size of the nano-ferrierites results in an improved accessibility of reactants to the catalytic active centers and enhanced product diffusion, leading to higher conversion and selectivity with lower deactivation rates for the oligomerization of 1-pentene into longer-chain olefins. ; This work has been supported by the European Union through the European Research Council (ERC-AdG-2014-671093, SynCatMatch) the Spanish government through the "Severo Ochoa Program" (SEV-2016-0683) and CTQ2015-70126-R, and by the Fundacion Ramon Areces through a research project within the "Life and Materials Sciences" program. 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 its help in sample characterization. We thank Dr. Manuel Moliner for helpful discussions. ; Margarit Benavent, VJ.; Díaz-Rey, MDR.; Navarro Villalba, MT.; Martínez, C.; Corma Canós, A. (2018). Direct Synthesis of Nano-Ferrierite along the 10-Ring-Channel Direction Boosts Their Catalytic Behavior. Angewandte Chemie International Edition. 57(13):3459-3463. https://doi.org/10.1002/anie.201711418 ; S ; 3459 ; 3463 ; 57 ; 13

The combination of different experimental techniques, such as solid C-13 and H-1 magic-angle spinning NMR spectroscopy, fluorescence spectroscopy and powder X-ray diffraction, together with theoretical calculations allows the determination of the unique structure directing the role of the bulky aromatic proton sponge 1,8-bis(dimethylamino)naphthalene (DMAN) towards the extra-large-pore ITQ-51 zeolite through supra-molecular assemblies of those organic molecules. ; This work has been supported by the Spanish Government through Consolider Ingenio 2010-Multicat, the 'Severo Ochoa Programme' (SEV 2012-0267), MAT2012-37160; UPV through PAID-06-11 (no. 1952); the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA). ; Martínez Franco, R.; Sun, J.; Sastre Navarro, GI.; Yun, Y.; Zou, X.; Moliner Marin, M.; Corma Canós, A. (2014). Supra-molecular assembly of aromatic proton sponges to direct the crystallization of extra-large-pore zeotypes. Proceedings of the Royal Society of London. Series A, Mathematical and physical sciences. 470:1-13. https://doi.org/10.1098/rspa.2014.0107 ; S ; 1 ; 13 ; 470 ; Moliner, 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.201304713 ; Freyhardt, C. C., Tsapatsis, M., Lobo, R. F., Balkus, K. J., & Davis, M. E. (1996). A high-silica zeolite with a 14-tetrahedral-atom pore opening. Nature, 381(6580), 295-298. doi:10.1038/381295a0 ; Wagner, P., Yoshikawa, M., Tsuji, K., Davis, M. E., Wagner, P., Lovallo, M., & Taspatsis, M. (1997). CIT-5: a high-silica zeolite with 14-ring pores. Chemical Communications, (22), 2179-2180. doi:10.1039/a704774f ; Burton, A., Elomari, S., Chen, C.-Y., Medrud, R. C., Chan, I. Y., Bull, L. M., … Vittoratos, E. S. (2003). SSZ-53 and SSZ-59: Two Novel Extra-Large Pore Zeolites. Chemistry - A European Journal, 9(23), 5737-5748. ...

A multi-dimensional extra-large pore silicogermanate zeolite, named ITQ-54, has been synthesised by in situ decomposition of the N,N-dicyclohexylisoindolinium cation into the N-cyclohexylisoindolinium cation. Its structure was solved by 3D rotation electron diffraction (RED) from crystals of ca. 1 μm in size. The structure of ITQ-54 contains straight intersecting 20 × 14 × 12-ring channels along the three crystallographic axes and it is one of the few zeolites with extra-large channels in more than one direction. ITQ-54 has a framework density of 11.1 T atoms per 1000 Å3, which is one of the lowest among the known zeolites. ITQ-54 was obtained together with GeO2 as an impurity. A heavy liquid separation method was developed and successfully applied to remove this impurity from the zeolite. ITQ-54 is stable up to 600 °C and exhibits permanent porosity. The structure was further refined using powder X-ray diffraction (PXRD) data for both as-made and calcined samples. ; This work was supported by the Spanish Government (MAT2012-38567-C02-01, Consolider Ingenio 2010-Multicat CSD-2009-00050 and Severo Ochoa SEV-2012-0267), Generalitat Valenciana (Project Prometeo), the Swedish Research Council (VR), the Swedish Governmental Agency for Innovation Systems (VINNOVA) and the Knut & Alice Wallenberg Foundation through a grant for purchasing the TEMs and the project grant 3DEM-NATUR. Y. F. Yun thanks the China Scholarship Council (CSC). The authors acknowledge ESRF, Grenoble for the use of the beamline ID31 and the mail-in system of 11-BM at the Advanced Photon Source, Argonne National Laboratory, USA. ; Jiang, J.; Yun, Y.; Zou, X.; Jorda Moret, JL.; Corma Canós, A. (2015). ITQ-54: a multi-dimensional extra-large pore zeolite with 20 × 14 × 12-ring channels. Chemical Science. 6(1):480-485. https://doi.org/10.1039/c4sc02577f ; S ; 480 ; 485 ; 6 ; 1 ; Davis, M. E. (2002). Ordered porous materials for emerging applications. Nature, 417(6891), 813-821. doi:10.1038/nature00785 ; Atienzar, P., Díaz-Cabañas, M. J., Moliner, ...

In this article I attempt to reshape the agent-structure debate in International Relations which has become increasingly confused and fruitless. I do so by first rejecting two things — (1) the agent-structure dichotomy, presupposed in the debate, in favour of the age-old classification of causative factors into mechanistic, volitional and coincidental ones; and (2) the explanation-understanding dichotomy, prevalent in the debate, in favour of the idea of `narrative intelligibilifying'. I also draw attention to narrative as a factor constitutive of agents and structures, and offer a modified version of structurationism, while rejecting a version of scientific realism sometimes associated with it. As to how one form of social structure moves towards another, I suggest that, at its most ambitious, this is a world-historical question, and that how the three causative factors are combined in addressing this question is as fascinating as it is vital for our self-understanding as human beings.