Suchergebnisse

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, ...

90 94 172 1 ; S ; [EN] The aim of this work is to study the activity for the nitrate catalytic reduction in natural water, using a continuous stirred tank reactor, of Pd/Cu and Pd/Sn catalysts supported on different materials. The studied supports are: -Al2O3 (commercial), active carbon, graphite, hydrotalcite and alumina synthesized in our laboratory with a high surface area. The activity and selectivity of the catalysts supported on these materials have been compared. The best results have been obtained with the Pd/Sn catalysts supported on alumina. These results show thatthe surface area ofthe supportis notthe only important characteristic for an active catalyst in this reaction, but also its acid–base properties, electrical conductivity and interaction with the metallic active sites are very significant. The adequate combination of these characteristics is necessary to obtain an active catalyst. The influence of the Pd/Sn content on the activity of the alumina supported catalysts was studied, observing that the best activity was obtained when the Pd/Sn ratio was higher than 1. This result clearly indicates that it is necessary to have both Pd and Pd–Sn centers in order to obtain an active catalyst. The authors thank the Spanish Government(projects MAT2009-14528-C02-01 and CONSOLIDER INGENIO 2010) and the European Union (European Community's Seventh Framework Programme FP7/2007-2013 under Grant Agreement No. 226347 Project)for the financial support. Franch Martí, C.; Palomares Gimeno, AE.; Corma Canós, A. (2011). A study of different supports for the catalytic reduction of nitrates from natural water with a continuous reactor. Catalysis Today. 172(1):90-94. https://doi.org/10.1016/j.cattod.2011.05.015

[EN] The aim of this work is to study the activity for the nitrate catalytic reduction in natural water, using a continuous stirred tank reactor, of Pd/Cu and Pd/Sn catalysts supported on different materials. The studied supports are: -Al2O3 (commercial), active carbon, graphite, hydrotalcite and alumina synthesized in our laboratory with a high surface area. The activity and selectivity of the catalysts supported on these materials have been compared. The best results have been obtained with the Pd/Sn catalysts supported on alumina. These results show thatthe surface area ofthe supportis notthe only important characteristic for an active catalyst in this reaction, but also its acid–base properties, electrical conductivity and interaction with the metallic active sites are very significant. The adequate combination of these characteristics is necessary to obtain an active catalyst. The influence of the Pd/Sn content on the activity of the alumina supported catalysts was studied, observing that the best activity was obtained when the Pd/Sn ratio was higher than 1. This result clearly indicates that it is necessary to have both Pd and Pd–Sn centers in order to obtain an active catalyst. ; The authors thank the Spanish Government(projects MAT2009-14528-C02-01 and CONSOLIDER INGENIO 2010) and the European Union (European Community's Seventh Framework Programme FP7/2007-2013 under Grant Agreement No. 226347 Project)for the financial support. ; Franch Martí, C.; Palomares Gimeno, AE.; Corma Canós, A. (2011). A study of different supports for the catalytic reduction of nitrates from natural water with a continuous reactor. Catalysis Today. 172(1):90-94. https://doi.org/10.1016/j.cattod.2011.05.015 ; S ; 90 ; 94 ; 172 ; 1

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/cm070553+ ; [EN] Layered organic-inorganic hybrid materials were synthesized by pillaring with viologen and nitroaniline compounds which are intercalated between magadiite layers. The bridged silsesquioxanes, 4,4'-bis(trimethoxysilylpropyl)viologen and 4-nitro-N,N'-bis(3-trimethoxysilyl)propylaniline react with the surface silanol groups of the inorganic layers of silicate, bonding covalently with them. The preparation process was followed by DRX, and the pillarization was corroborated using chemical and thermogravimetrical analyses. The presence of viologen and nitroaniline organic linkers covalently bonded to inorganic layers was confirmed by C-13 and Si-29 NMR spectroscopy. UV-visible diffuse reflectance permitted to observe the high stabilization achieved by the intercalated organic fragments. Micro- and mesoporosity were also generated because of the existence of interlayer galleries conformed by homogenously distributed organic linkers into the interlayer space. The layered organic-inorganic hybrids exhibited a thermally stable network, and the organic spacers remained after elimination of the swelling agents by acid extraction. The resultant materials can be of interest as sensors and for nonlinear optics. ; Financial support by the Spanish Government (MAT-2006-14274-C02-01 and MAT2006-26599-E) and Universidad Polite´cnica de Valencia (PPI-06-05) is gratefully acknowledged. ; Díaz Morales, UM.; Cantin Sanz, A.; Corma Canós, A. (2007). Novel layered organic-inorganic hybrid materirals with bridged silsesquioxanes as Pillars. Chemistry of Materials. 19(15):3686-3693. https://doi.org/10.1021/cm070553+ ; S ; 3686 ; 3693 ; 19 ; 15

[EN] The encapsulation of subnanometric metal entities (isolated metal atoms and metal clusters with a few atoms) in porous materials such as zeolites can be an effective strategy for the stabilization of those metal species and therefore can be further used for a variety of catalytic reactions. However, owing to the complexity of zeolite structures and their low stability under the electron beam, it is challenging to obtain atomic-level structural information of the subnanometric metal species encapsulated in zeolite crystallites. In this protocol, we show the application of a scanning transmission electron microscopy (STEM) technique that records simultaneously the high-angle annular dark-field (HAADF) images and integrated differential phase-contrast (iDPC) images for structural characterization of subnanometric Pt and Sn species within MFI zeolite. The approach relies on the use of a computational model to simulate results obtained under different conditions where the metals are present in different positions within the zeolite. This imaging technique allows to obtain simultaneously the spatial information of heavy elements (Pt and Sn in this work) and the zeolite framework structure, enabling direct determination of the location of the subnanometric metal species. Moreover, we also present the combination of other spectroscopy techniques as complementary tools for the STEM-iDPC imaging technique to obtain global understanding and insights on the spatial distributions of subnanometric metal species in zeolite structure. These structural insights can provide guidelines for the rational design of uniform metal-zeolite materials for catalytic applications. Precise knowledge of the structure of metals supported and stabilized by zeolite frameworks informs improved design and synthesis of the catalysts. This tutorial describes scanning transmission electron microscopy approaches for their structural analysis. ; This work was supported by the European Union through the European Research Council (grant ...

[EN] The modulated hydrothermal (MHT) synthesis of an active and selective Hf-MOF-808 material for the N-alkylation reaction of aniline with benzyl alcohol under base-free mild reaction conditions is reported. Through kinetic experiments and isotopically labeled NMR spectroscopy studies, we have demonstrated that the reaction mechanism occurs via borrowing hydrogen (BH) pathway, in which the alcohol dehydrogenation is the limiting step. The high concentration of defective -OH groups generated on the metallic nodes through MHT synthesis enhances the alcohol activation, while the unsaturated Hf4+, which acts as a Lewis acid site, is able to borrow the hydrogen from the methylene position of benzyl alcohol. This fact makes this material at least 14 times more active for the N-alkylation reaction than the material obtained via solvothermal synthesis. The methodology described in this work could be applied to a wide range of aniline and benzyl alcohol derivates, showing in all cases high selectivity toward the corresponding N-benzylaniline product. Finally, Hf-MOF-808, which acts as a true heterogeneous catalyst, can be reused in at least four consecutive runs without any activity loss. ; This work has been supported by Spanish Government through "severo Ochoa" (SEV-2016-0683, MINECO) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE). The Electron Microscopy Service of the UPV is also acknowledged for their help in sample characterization. ; Bohigues, B.; Rojas-Buzo, S.; Moliner Marin, M.; Corma Canós, A. (2021). Coordinatively Unsaturated Hf-MOF-808 Prepared via Hydrothermal Synthesis as a Bifunctional Catalyst for the Tandem N-Alkylation of Amines with Benzyl Alcohol. ACS Sustainable Chemistry & Engineering. 9(47):15793-15806. https://doi.org/10.1021/acssuschemeng.1c04903 ; S ; 15793 ; 15806 ; 9 ; 47

This is the peer reviewed version of the following article: E. Subbotina, A. Velty, J. S. M. Samec, A. Corma, ChemSusChem 2020, 13, 4528, which has been published in final form at https://doi.org/10.1002/cssc.202000330. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. ; [EN] Organosolv pulping releases reactive monomers from both lignin and hemicellulose by the cleavage of weak C-O bonds. These monomers recombine to form undesired polymers through the formation of recalcitrant C-C bonds. Different strategies have been developed to prevent this process by stabilizing the reactive monomers (i.e., lignin-first approaches). To date, all reported approaches rely on the addition of capping agents or metal-catalyzed stabilization reactions, which usually require high pressures of hydrogen gas. Herein, a metal- and additive-free approach is reported that uses zeolites as acid catalysts to convert the reactive monomers into more stable derivatives under organosolv pulping conditions. Experiments with model lignin compounds showed that the recondensation of aldehydes and allylic alcohols produced by the cleavage of beta-O-4 ' bonds was efficiently inhibited by the use of protonic beta zeolite. By applying a zeolite with a preferred pore size, the bimolecular reactions of reactive monomers were effectively inhibited, resulting in stable and valuable monophenolics. The developed methodology was further extended to birch wood to yield monophenolic compounds and value-added products from carbohydrates. ; This work was supported by the Swedish Energy Agency, Stiftelsen Olle Engkvist Byggm~stare, and the European Union through ERC-AdG-2014-671093-SynCatMatch. ; Subbotina, E.; Velty, A.; Samec, JSM.; Corma Canós, A. (2020). Zeolite-Assisted Lignin-First Fractionation of Lignocellulose: Overcoming Lignin Recondensation through Shape-Selective Catalysis. ChemSusChem. 13(17):4528-4536. https://doi.org/10.1002/cssc.202000330 ; S ; 4528 ; 4536 ; 13 ; 17 ; Adler, E. ...

[EN] The preparation of continuous layers of highly hydrophobic pure silica ITQ-29 zeolite, potentially applicable as hydrophobic membranes for separation of molecules based on their polarity, has been investigated. Continuous layers of intergrown ITQ-29 zeolite crystals were successfully grown on porous alumina supports by optimization of the synthesis conditions, such as the appropriate selection of the seeds, the procedure for the gel preparation, and the calcination conditions. This resulted in the formation of all silica ITQ-29 zeolite layers without the presence of germanium required in previously reported ITQ-29 membranes, with the subsequent improvement in quality and stability, as verified by the absence of cracks after calcination. We have proved that the incorporation of aluminum from the support into the zeolite layer does not occur, neither during the secondary growth nor through migration of aluminum species during calcination. ; This research was funded by the European Research Council, grant ERC-AdG-2014-671093 (SynCatMatch) and the Spanish Government, through "Severo Ochoa" grant SEV-2016-0683 and RTI2018-101784-B-I00. ; Palomino Roca, M.; Ono, H.; Valencia Valencia, S.; Corma Canós, A. (2020). Preparation of Continuous Highly Hydrophobic Pure Silica ITQ-29 Zeolite Layers on Alumina Supports. Molecules. 25(18):1-13. https://doi.org/10.3390/molecules25184150 ; S ; 1 ; 13 ; 25 ; 18 ; Mascal, M. (2012). Chemicals from biobutanol: technologies and markets. Biofuels, Bioproducts and Biorefining, 6(4), 483-493. doi:10.1002/bbb.1328 ; Ndaba, B., Chiyanzu, I., & Marx, S. (2015). n-Butanol derived from biochemical and chemical routes: A review. Biotechnology Reports, 8, 1-9. doi:10.1016/j.btre.2015.08.001 ; Huang, H.-J., Ramaswamy, S., & Liu, Y. (2014). Separation and purification of biobutanol during bioconversion of biomass. Separation and Purification Technology, 132, 513-540. doi:10.1016/j.seppur.2014.06.013 ; Barton, W. E., & Daugulis, A. (1992). Evaluation of solvents for extractive ...

1 13 25 18 ; S ; [EN] The preparation of continuous layers of highly hydrophobic pure silica ITQ-29 zeolite, potentially applicable as hydrophobic membranes for separation of molecules based on their polarity, has been investigated. Continuous layers of intergrown ITQ-29 zeolite crystals were successfully grown on porous alumina supports by optimization of the synthesis conditions, such as the appropriate selection of the seeds, the procedure for the gel preparation, and the calcination conditions. This resulted in the formation of all silica ITQ-29 zeolite layers without the presence of germanium required in previously reported ITQ-29 membranes, with the subsequent improvement in quality and stability, as verified by the absence of cracks after calcination. We have proved that the incorporation of aluminum from the support into the zeolite layer does not occur, neither during the secondary growth nor through migration of aluminum species during calcination. This research was funded by the European Research Council, grant ERC-AdG-2014-671093 (SynCatMatch) and the Spanish Government, through "Severo Ochoa" grant SEV-2016-0683 and RTI2018-101784-B-I00. Palomino Roca, M.; Ono, H.; Valencia Valencia, S.; Corma Canós, A. (2020). Preparation of Continuous Highly Hydrophobic Pure Silica ITQ-29 Zeolite Layers on Alumina Supports. Molecules. 25(18):1-13. https://doi.org/10.3390/molecules25184150 Mascal, M. (2012). Chemicals from biobutanol: technologies and markets. Biofuels, Bioproducts and Biorefining, 6(4), 483-493. doi:10.1002/bbb.1328 Ndaba, B., Chiyanzu, I., & Marx, S. (2015). n-Butanol derived from biochemical and chemical routes: A review. Biotechnology Reports, 8, 1-9. doi:10.1016/j.btre.2015.08.001 Huang, H.-J., Ramaswamy, S., & Liu, Y. (2014). Separation and purification of biobutanol during bioconversion of biomass. Separation and Purification Technology, 132, 513-540. doi:10.1016/j.seppur.2014.06.013 Barton, W. E., & Daugulis, A. (1992). Evaluation of solvents for extractive butanol fermentation ...

By using a faujasite zeolite as the sole Si and Al source with simple ammonium cyclic cations, it has been possible to synthesize the SSZ-39 zeolite with high yields, and to prepare a catalyst for potential industrial applications in the 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. C. R. B. thanks the Danish Agency for Science Technology and Innovation for a PhD scholarship. The authors thank Isabel Millet for technical support. ; Martin, N.; Boruntea, C.; Moliner Marin, M.; Corma Canós, A. (2015). Efficient synthesis of the Cu-SSZ-39 catalyst for DeNOx applications. Chemical Communications. 51(55):11030-11033. doi:10.1039/c5cc03200h ; S ; 11030 ; 11033 ; 51 ; 55 ; Moliner, 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/cm4015095 ; Brandenberger, S., Kröcher, O., Tissler, A., & Althoff, R. (2008). The State of the Art in Selective Catalytic Reduction of NOxby Ammonia Using Metal‐Exchanged Zeolite Catalysts. Catalysis Reviews, 50(4), 492-531. doi:10.1080/01614940802480122 ; Fickel, 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.2010.12.022 ; Kwak, J. H., Tonkyn, R. G., Kim, D. H., Szanyi, J., & Peden, C. H. F. (2010). Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3. Journal of Catalysis, 275(2), 187-190. doi:10.1016/j.jcat.2010.07.031 ; Fickel, D. W., & Lobo, R. F. (2009). Copper Coordination in Cu-SSZ-13 and Cu-SSZ-16 Investigated by Variable-Temperature XRD. The Journal of Physical Chemistry C, 114(3), 1633-1640. doi:10.1021/jp9105025 ; Wagner, P., Nakagawa, ...

2677 2688 3 10 ; S ; [EN] Bifunctional mesoporous hybrid materials, containing both proton sponges and acid groups, have been prepared following different synthetic routes: co-condensation processes (sol-gel or micellar one-pot routes) or post-synthetic grafting of the organic functionalities. 1,8-Bis(dimethylamino)naphthalene (DMAN), a proton sponge with high pK(a), was used as an organic functional builder base and 3-mercaptopropyltriethoxysilane (MPTES) as a pendant precursor of sulfonic acids. The bifunctional hybrid materials were extensively characterized and were investigated as heterogeneous catalysts for various one-pot C-C bond-forming cascade reactions such as deacetalization-Knoevenagel condensation or deacetalization-nitroaldol (Henry) reaction. The authors thank the Spanish Government for financial support by Consolider-Ingenio MULTICAT CSD2009-00050, MAT2011-29020-C02-01 and Severo Ochoa Excellence Program SEV-2012-0267. EG thanks the Marie Curie Fellowship (FP7-PEOPLE-2009-IEF) for financial support. Gianotti, E.; Díaz Morales, UM.; Velty, A.; Corma Canós, A. (2013). Designing bifunctional acid-base mesoporous hybrid catalysts for cascade reactions. Catalysis Science and Technology. 3(10):2677-2688. https://doi.org/10.1039/c3cy00269a Shylesh, S., & Thiel, W. R. (2010). Bifunctional Acid-Base Cooperativity in Heterogeneous Catalytic Reactions: Advances in Silica Supported Organic Functional Groups. ChemCatChem, 3(2), 278-287. doi:10.1002/cctc.201000353 Sharma, K. K., Buckley, R. P., & Asefa, T. (2008). Optimizing Acid−Base Bifunctional Mesoporous Catalysts for the Henry Reaction: Effects of the Surface Density and Site Isolation of Functional Groups. Langmuir, 24(24), 14306-14320. doi:10.1021/la8030107 Bass, J. D., Solovyov, A., Pascall, A. J., & Katz, A. (2006). Acid−Base Bifunctional and Dielectric Outer-Sphere Effects in Heterogeneous Catalysis: A Comparative Investigation of Model Primary Amine Catalysts. Journal of the American Chemical Society, 128(11), 3737-3747. ...

[EN] Bifunctional mesoporous hybrid materials, containing both proton sponges and acid groups, have been prepared following different synthetic routes: co-condensation processes (sol-gel or micellar one-pot routes) or post-synthetic grafting of the organic functionalities. 1,8-Bis(dimethylamino)naphthalene (DMAN), a proton sponge with high pK(a), was used as an organic functional builder base and 3-mercaptopropyltriethoxysilane (MPTES) as a pendant precursor of sulfonic acids. The bifunctional hybrid materials were extensively characterized and were investigated as heterogeneous catalysts for various one-pot C-C bond-forming cascade reactions such as deacetalization-Knoevenagel condensation or deacetalization-nitroaldol (Henry) reaction. ; The authors thank the Spanish Government for financial support by Consolider-Ingenio MULTICAT CSD2009-00050, MAT2011-29020-C02-01 and Severo Ochoa Excellence Program SEV-2012-0267. EG thanks the Marie Curie Fellowship (FP7-PEOPLE-2009-IEF) for financial support. ; Gianotti, E.; Díaz Morales, UM.; Velty, A.; Corma Canós, A. (2013). Designing bifunctional acid-base mesoporous hybrid catalysts for cascade reactions. Catalysis Science and Technology. 3(10):2677-2688. https://doi.org/10.1039/c3cy00269a ; S ; 2677 ; 2688 ; 3 ; 10 ; Shylesh, S., & Thiel, W. R. (2010). Bifunctional Acid-Base Cooperativity in Heterogeneous Catalytic Reactions: Advances in Silica Supported Organic Functional Groups. ChemCatChem, 3(2), 278-287. doi:10.1002/cctc.201000353 ; Sharma, K. K., Buckley, R. P., & Asefa, T. (2008). Optimizing Acid−Base Bifunctional Mesoporous Catalysts for the Henry Reaction: Effects of the Surface Density and Site Isolation of Functional Groups. Langmuir, 24(24), 14306-14320. doi:10.1021/la8030107 ; Bass, J. D., Solovyov, A., Pascall, A. J., & Katz, A. (2006). Acid−Base Bifunctional and Dielectric Outer-Sphere Effects in Heterogeneous Catalysis: A Comparative Investigation of Model Primary Amine Catalysts. Journal of the American Chemical Society, 128(11), 3737-3747. ...

[EN] Non-ordered organic-inorganic mesoporous hybrid materials with basic sites have been synthesized following a fluoride-catalysed sol-gel process at neutral pH and low temperatures that avoids the use of structural directing agents (SDAs). Proton sponges have been used as the organic builder of the hybrids, while the inorganic part corresponds to silica tetrahedra. The proton sponges are diamines that exhibit very high basicity and, after functionalization, have been introduced as part of the walls of the mesoporous silica by one-pot synthesis. Several hybrids with different organic loadings have been synthesized and characterized by gas adsorption, thermogravimetric and elemental analysis, solid state MAS-NMR and FTIR spectroscopy. These hybrids show high activity as base catalysts and can be recycled. ; The authors thank financial support by Consolider-Ingenio (MULTICAT project) from Spanish Government. EG thanks Marie Curie Fellowship (FP7-PEOPLE-2009-IEF) for financial support. ; Gianotti, E.; Díaz Morales, UM.; Coluccia, S.; Corma Canós, A. (2011). Hybrid organic-inorganic catalytic mesoporous materials with proton sponges as building blocks. Physical Chemistry Chemical Physics. 13(24):11702-11709. https://doi.org/10.1039/c1cp20588a ; S ; 11702 ; 11709 ; 13 ; 24 ; Hoffmann, F., Cornelius, M., Morell, J., & Fröba, M. (2006). Silica-Based Mesoporous Organic–Inorganic Hybrid Materials. Angewandte Chemie International Edition, 45(20), 3216-3251. doi:10.1002/anie.200503075 ; Sanchez, C., Rozes, L., Ribot, F., Laberty-Robert, C., Grosso, D., Sassoye, C., … Nicole, L. (2010). «Chimie douce»: A land of opportunities for the designed construction of functional inorganic and hybrid organic-inorganic nanomaterials. Comptes Rendus Chimie, 13(1-2), 3-39. doi:10.1016/j.crci.2009.06.001 ; Sanchez, C., Julián, B., Belleville, P., & Popall, M. (2005). Applications of hybrid organic–inorganic nanocomposites. Journal of Materials Chemistry, 15(35-36), 3559. doi:10.1039/b509097k ; Wight, A. P., & Davis, M. E. ...

[EN] The hydrogenation activity and physico-chemical characterization of a series of NiMo catalyst supported on materials with different acid-base properties (Al2O3, layered double hydroxides-derived MgAl oxides and MgO) have been investigated. The results show a clear correlation between the electrodonor capacity of the support, the negative charge density of the supported NiMo oxides and the intrinsic hydrogenation rate of the sulfided phase. Spectroscopic characterization ruled out any possible contribution derived from differences in the NiMoS2 stack or slab size distributions, as determined by high-resolution transmission electron microscopy. The experimental results obtained suggest the occurrence of an electron transfer phenomena from the support to the supported NiMoS2 slabs, being this effect stronger for supports with higher electrodonor capacity. This work presents a specific electronic support effect that goes beyond the classical dispersing and stabilizing role. ; This work has been supported by ExxonMobil Research and Engi-neering and by the Spanish Government through RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE) . We thank the Electron Microscopy Service of the UPV for their help in sample characterization. ; López-Cruz, C.; Guzman, J.; Cao, G.; Martínez, C.; Corma Canós, A. (2021). Modifying the catalytic properties of hydrotreating NiMo-S phases by changing the electrodonor capacity of the support. Catalysis Today. 382:130-141. https://doi.org/10.1016/j.cattod.2021.08.002 ; S ; 130 ; 141 ; 382

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acssuschemeng.0c04398 ; [EN] The catalytic performance of two different MOFs, UiO-66 and MOF-808, containing Lewis acid active sites has been evaluated for the transformation of glucose in water and compared with that of analogous Lewis acid Zr-beta zeolite. While fructose is the main product obtained on Zr-beta, mannose production increases when using Zr-MOFs as catalysts. Kinetic studies reveal a lower activation energy barrier for glucose epimerization to mannose when using Zr-MOF catalysts (similar to 83-88 and similar to 100 kJ/mol for glucose epimerization and isomerization, respectively). A C-13 NMR study using (13)C1-labeled glucose allows confirming that on Zr-MOF catalysts, mannose is exclusively formed following the glucose epimerization route through a 1,2-intramolecular carbon shift, whereas the two-step glucose -> fructose -> mannose isomerization via 1,2-intramolecular proton shifts is the preferred pathway on Zr-beta. A computational study reveals a different mode of adsorption of deprotonated glucose on Zr-MOFs that allows decreasing the activation barrier for the 1,2-intramolecular carbon shift. The combination of spectroscopic, kinetic, and theoretical studies allows unraveling the nature of the metal sites in Zr-MOFs and Zr-beta catalysts and to propose a structure-activity relationship between the different Lewis acid sites and the glucose transformation reactions. The results presented here could permit new rationalized MOF catalyst designs with the specific active sites to facilitate particular reaction mechanisms. ; This work was supported by the Spanish Government through "Severo Ochoa"(SEV-2016-0683, MINECO), MAT2017-82288-C2-1-P (AEI/FEDER, UE), and RTI2018-101033-BI00 ...