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[EN] The former synthesis of TS-1 opened new catalytic opportunities for zeolites, especially for their application as selective redox catalysts in several fine chemistry processes. Interestingly, isolated Ti species in the framework positions of hydrophobic zeolites, such as high silica zeolites, offer unique Lewis acid sites even in the presence of protic polar solvents (such as water). Following this discovery, other transition metals (such as Sn, Zr, V, Nb, among others) have been introduced in the framework positions of different hydrophobic zeolitic structures, allowing their application in new fine chemistry processes as very active and selective redox catalysts. Recently, these hydrophobic metallozeolites have been successfully applied as efficient catalysts for several biomass-transformation processes in bulk water. The acquired knowledge from the former catalytic descriptions in fine chemistry processes using hydrophobic Lewis acid-containing zeolites has been essential for their application in these novel biomass transformations. In the present review, I will describe the recent advances in the synthesis of new transition metal-containing zeolites presenting Lewis acid character, and their unique catalytic applications in both fine chemistry and novel biomass-transformations. ; This work has been supported by the Spanish Government-MINECO (MAT2012-37160), Consolider Ingenio 2010-Multicat, and UPV through PAID-06-11 (no. 1952). Manuel Moliner also acknowledges the "Subprograma Ramon y Cajal" for the contract RYC-2011-08972. ITQ thanks the "Program Severo Ochoa" for financial support. ; Moliner Marin, M. (2014). State of the art of Lewis acid-containing zeolites: lessons from fine chemistry to new biomass transformation processes. Dalton Transactions. 43:4197-4208. https://doi.org/10.1039/C3DT52293H ; S ; 4197 ; 4208 ; 43

[EN] In the present review, we would like to cover the most fundamental advances achieved in the design of ordered titanosilicates since the earlier discovery of TS-1 reported by EniChem in the mid-eighties. The invention of the medium-pore TS-1 zeolite was a breakthrough, and this material has been applied as efficient catalyst in diverse industrial applications. However, its limited pore size (5 5.5 Å) offers diffusion limitations when working with large molecules. The design and preparation of open titanosilicates, such as large pore molecular sieves, mesoporous ordered materials, or layered-type zeolites will be described. The applicability of these titanosilicates to catalytic oxidation processes requiring bulky organic molecules will also be presented. ; This work has been supported by the Spanish GovernmentMINECO (MAT2012-37160), Consolider Ingenio 2010-Multicat, and UPV through PAID-06-11 (n.1952). Manuel Moliner also acknowledges to ''Subprograma Ramon y Cajal'' for the contract RYC-2011-08972. ITQ thanks the ''Program Severo Ochoa'' for financial support (SEV 2012 0267). ; Moliner Marin, M.; Corma Canós, A. (2014). Advances in the synthesis of titanosilicates: From the medium pore TS-1 zeolite to highly-accessible ordered materials. Microporous and Mesoporous Materials. 189:31-40. https://doi.org/10.1016/j.micromeso.2013.08.003 ; S ; 31 ; 40 ; 189

This is the peer reviewed version of the following article: Angew. Chem. Int. Ed. 2018, 57, 15330 15353, which has been published in final form at https://doi.org/10.1002/anie.201711422. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. ; [EN] Since the early reports by Barrer in the 1940s on converting natural minerals into synthetic zeolites, the use of precrystallized zeolites as crucial inorganic directing agents to synthesize other crystalline zeolites with improved physicochemical properties has become a very important research field, allowing the design, particularly in recent years, of new industrial catalysts. This Review highlights how the presence of some crystalline fragments in the synthesis media, such as small secondary building units (SBUs) or layered substructures, not only favors the crystallization of other zeolites with similar SBUs or layers, but also permits control over important parameters affecting their catalytic activity (chemical composition, crystal size, or porosity, etc.). Recent advances in the preparation of 3D and 2D zeolites through seeding and zeolite-to-zeolite transformation processes will be discussed extensively in this Review, including their preparation in the presence or absence of organic structure-directing agents (OSDAs). The aim is to introduce general guidelines for more efficient approaches for target zeolites. ; This work has been supported by the Spanish Government (MINECO through "Severo Ochoa" (SEV-2016-0683) and MAT2015-71261-R), by the European Union through ERC-AdG-2014-671093 (SynCatMatch), and by the Fundacion Ramon Areces (through the "Life and Materials Science" program). ; Li, C.; Moliner Marin, M.; Corma Canós, A. (2018). Building zeolites from precrystallized units: nanoscale architecture. Angewandte Chemie International Edition. 57(47):15330-15353. https://doi.org/10.1002/anie.201711422 ; S ; 15330 ; 15353 ; 57 ; 47 ; Cundy, C. S., & Cox, P. A. (2005). The hydrothermal ...

15330 15353 57 47 ; S Moliner, M., Martínez, C., & Corma, A. (2015). Multiporige Zeolithe: Synthese und Anwendungen bei der Katalyse. Angewandte Chemie, 127(12), 3630-3649. doi:10.1002/ange.201406344 Moliner, M., Rey, F., & Corma, A. (2013). Rationales Design von effizienten organischen strukturdirigierenden Reagentien für die Zeolithsynthese. Angewandte Chemie, 125(52), 14124-14134. doi:10.1002/ange.201304713 Jiang, J., Yu, J., & Corma, A. (2010). Zeolithe mit sehr großen Poren als Bindeglied zwischen mikro- und mesoporösen Strukturen. Angewandte Chemie, 122(18), 3186-3212. doi:10.1002/ange.200904016 C. T.Kresge W. J.Roth U.S. Patent 5266541 1993. S. I.Zones US 4544538 1985. T. V.Whittam US Pat 4397825 1983. Corma, A., Puche, M., Rey, F., Sankar, G., & Teat, S. J. (2003). Angewandte Chemie, 115(10), 1188-1191. doi:10.1002/ange.200390275 A. W.Burton WO2014/099261 2014; ; D.Xie WO2016/122724 2016. ; Sun, 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/nature07957 ; S. I.Zones Y.Nakagawa S. T.Evans G. S.Lee US 5958370 1999; ; This is the peer reviewed version of the following article: Angew. Chem. Int. Ed. 2018, 57, 15330 15353, which has been published in final form at https://doi.org/10.1002/anie.201711422. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. [EN] Since the early reports by Barrer in the 1940s on converting natural minerals into synthetic zeolites, the use of precrystallized zeolites as crucial inorganic directing agents to synthesize other crystalline zeolites with improved physicochemical properties has become a very important research field, allowing the design, particularly in recent years, of new industrial catalysts. This Review highlights how the presence of some crystalline fragments in the synthesis media, such as small secondary building units (SBUs) or layered substructures, not ...

The synthesis of chabazite with high solid yields is achieved by the rational combination of directing effects of a source of Si and Al coming from USY zeolites and the inexpensive tetraethylammonium. Moreover, Cu-CHA materials prepared by post-synthetic and "one-pot'' methodologies show high activity and stability for SCR of NOx. ; Financial support from the Spanish Government-MINECO through "Severo Ochoa'' (SEV 2012-0267), Consolider Ingenio 2010-Multicat, MAT2012-37160 and, Intramural-201480I015 is acknowledged. The authors thank Isabel Millet for technical support. ; Martin, N.; Moliner Marin, M.; Corma Canós, A. (2015). High yield synthesis of high-silica chabazite by combining the role of zeolite precursors and tetraethylammonium: SCR of NOx. Chemical Communications. 51(49):9965-9968. https://doi.org/10.1039/c5cc02670a ; S ; 9965 ; 9968 ; 51 ; 49

[EN] In the last few years, important efforts have been made to synthesize so-called "multipore" zeolites, which contain channels of different dimensions within the same crystalline structure. This is a very attractive subject, since the presence of pores of different sizes would favor the preferential diffusion of reactants and products through those different channel systems, allowing unique catalytic activities for specific chemical processes. In this Review we describe the most attractive achievements in the rational synthesis of multipore zeolites, containing small to extra-large pores, and the improvements reported for relevant chemical processes when these multipore zeolites have been used as catalysts. ; Financial support by the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), Consolider Ingenio 2010-Multicat, MAT2012-37160, MAT2012-31657 and Intramural-201480I015 is acknowledged. ; Moliner Marin, M.; Martínez, C.; Corma Canós, A. (2015). Multipore zeolites: synthesis and catalytic applications. Angewandte Chemie International Edition. 54(12):3560-3579. https://doi.org/10.1002/anie.201406344 ; S ; 3560 ; 3579 ; 54 ; 12

The combination of Cu(II) triethylenetetramine and N,N-dimethyl-3,5-dimethylpiperidinium as structure directing agents allowed the direct preparation of highly active and hydrothermally stable Cu-SAPO-18 for the selective catalytic reduction of NOx with NH3. The approach allows performing a one-pot synthesis avoiding intermediate calcination and ion exchange, while achieving complete framework Si isolation. Combination of physicochemical characterization techniques show that copper exists as extra-framework Cu2+, which have been identified as the specific active sites for the SCR of NOx. The selective presence of isolated Si species in the zeolitic framework introduces high hydrothermal stability. ; Financial support by the Spanish Government-MINECO through "Severo Ochoa" (SEV 2012-0267), Consolider Ingenio 2010-Multicat, MAT2012-37160 and, Intramural-2014801015 is acknowledged. The authors thank Isabel Millet for technical support. ; Martínez Franco, R.; Moliner Marin, M.; Corma Canós, A. (2014). Direct synthesis design of Cu-SAPO-18, a very efficient catalyst for the SCR of NOx. Journal of Catalysis. 319:36-43. https://doi.org/10.1016/j.jcat.2014.08.005 ; S ; 36 ; 43 ; 319

Metal-containing zeolites, especially Sn-Beta, perform as very efficient heterogeneous catalysts in the selective oxidation of levoglucosenone, which is considered as a platform chemical for the production of highly-valuable chemicals, towards the synthesis of the optically pure gamma-lactone(S)-gamma-hydroxymethyl-alpha,beta-butenolide (HBO) using H2O2 as an oxidizing agent. Using Sn-Beta as a catalyst, yields up to 75% of (S)-gamma-hydroxymethyl-alpha,beta-butenolide are achieved in a "one-pot" cascade reaction. When Sn-Beta is combined with an acid resin, such as Amberlyst-15, the "two-step" process allows yields up to 90%. ; This work has been supported by the Spanish Government MINECO through Consolider Ingenio 2010-Multicat and MAT2012-37160, and by UPV through PAID-06-11 (n.1952). Manuel Moliner also acknowledges "Subprograma Ramon y Cajal" for contract RYC-2011-08972. ITQ thanks the "Program Severo Ochoa" for financial support. ; Paris Carrizo, CG.; Moliner Marin, M.; Corma Canós, A. (2013). Metal-containing zeolites as efficient catalyst for the transformation of highly valuable chiral biomass-derived products. Green Chemistry. 15(8):2101-2109. https://doi.org/10.1039/c3gc40267c ; S ; 2101 ; 2109 ; 15 ; 8 ; Corma, A., Iborra, S., & Velty, A. (2007). Chemical Routes for the Transformation of Biomass into Chemicals. Chemical Reviews, 107(6), 2411-2502. doi:10.1021/cr050989d ; Huber, G. W., Iborra, S., & Corma, A. (2006). Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering. Chemical Reviews, 106(9), 4044-4098. doi:10.1021/cr068360d ; Miftakhov, M. S., Valeev, F. A., & Gaisina, I. N. (1994). Levoglucosenone: the properties, reactions, and use in fine organic synthesis. Russian Chemical Reviews, 63(10), 869-882. doi:10.1070/rc1994v063n10abeh000123 ; Bridgwater, A. V., Meier, D., & Radlein, D. (1999). An overview of fast pyrolysis of biomass. Organic Geochemistry, 30(12), 1479-1493. doi:10.1016/s0146-6380(99)00120-5 ; Lu, Q., Xiong, W.-M., Li, W.-Z., Guo, ...

[EN] Methane, the main component of natural gas, is an interesting source of chemicals and clean liquid fuels, and a promising alternative raw material to oil. Among the possible direct routes for methane conversion, its aromatization under non-oxidative conditions has received increasing attention, despite the low conversions obtained due to thermodynamic limitations, because of its high selectivity to benzene. Mo/H-ZSM-5, the first bifunctional zeolite-catalyst proposed for this reaction, is still considered as one of the most adequate and has been widely studied. Although the mono- or bifunctional nature of the MDA mechanism is still under debate, it is generally accepted that the Mo species activate the C-H bond in methane, producing the intermediates. These will aromatize on the Bronsted acid sites of the zeolite, whose pore dimensions will provide the shape selectivity needed for converting methane into benzene. An additional role of the zeolite's Bronsted acid sites is to promote the dispersion of the Mo oxide precursor. Here, we show the influence of the different preparation steps-metal incorporation, calcination and activation of the Mo/ZSM-5- on the metal dispersion and, therefore, on the activity and selectivity of the final catalyst. Metal dispersion is enhanced when the samples are calcined under dynamic conditions (DC) and activated in N-2, and the benefits are larger when the metal has been incorporated by solid state reaction (SSR), as observed by FESEM-BSE and H-2-TPR. This leads to catalysts with higher activity, increased aromatic selectivity and improved stability towards deactivation. ; This work has been supported by the Spanish Government-MICINN through "Severo Ochoa" (SEV-2016-0683, MINECO) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE), and by Generalitat Valenciana (AICO/2019/060). The authors thank B. Esparcia for technical assistance and the electron Microscopy Service of the UPV for their help in sample characterization. ; Portilla, MT.; Llopis, FJ.; Moliner Marin, M.; Martínez, C. ...