The influence of ethanol-assisted washes to obtain swollen and pillared MWW-type zeolite with high degree ordering of lamellar structure

[EN] We studied the influence of the ethanol used as a washing solvent for obtaining swollen and pillared MWW topology zeolites with long-range ordering of lamellar structure. The diffractogram results showed that the increased number of washes increases the degree of order of the lamellar structure. Thermogravimetric results showed a considerable removal of the weakly interacting surfactant molecules after the third wash. The washes with ethanol did not remove the surfactant that strongly interacted with the MWW structure. The pillared material after the third wash showed a long-range ordering of the lamellar structure with the surface area of 728 m(2) g(-1), mesopore sizes of 2-4 nm and morphology characteristic of pillared MWW-type zeolites.Anderson Joel Schwanke is grateful the CAPES Foundation and PDSE program (process number 99999.004779/2014-02). Urbano Diaz acknowledges to the Spanish Government (MAT2014-52085-C2-1-P and MAT2017-82288-C2-1-P).Schwanke, AJ.; Díaz Morales, UM.; Corma Canós, A.; Pergher, S. (2019). The influence of ethanol-assisted washes to obtain swollen and pillared MWW-type zeolite with high degree ordering of lamellar structure. Microporous and Mesoporous Materials. 275:26-30. https://doi.org/10.1016/j.micromeso.2018.08.010S263027

The influence of swelling agents molecular dimensions on lamellar morphology of MWW-type zeolites active for fructose conversion

[EN] A new route to obtain pillared, disordered or desilicated MWW-type zeolites was developed assisted by quaternary ammonium surfactants with different hydrocarbon tail size acting as swelling agents (C(12)TA(+), C(I6)TA(+), C(18)TA(+)) and TPA(+) both exchanged to their hydroxide forms instead of only one swelling agent (C(n)TA(+) or TPA(+)) in hydroxide form. Effect of surfactant concentration and swelling conditions were determinant to obtain MWW-type zeolites with different lamellar organization and spatial distribution of individual zeolitic layers. Specifically, soft swelling at 25 degrees C with C(12)TA(+) preserved layer structure reaching a final disordered/pillared structure while pillared structures are obtained in the case of materials swollen with C(16)TA(+) and C(18)TA(+). Aggressive swelling processes at 80 degrees C favored desilication, damaging the layers structure in case of C(12)TA(+) while pillared materials are obtained after swollen with C(16)TA(+) and C(18)TA(+) surfactants. It was proved that both swelling agents in hydroxide forms combining with swelling and pillaring procedure influenced on physico-chemical and morphological nature of MWW-type materials due to the particular conditions used. The obtained derivative MWW zeolites with different morphology, order and accessibility levels were firstly evaluated by catalytic dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) showing superior activity compared to beta zeolites reported in literature.Anderson Joel Schwanke is grateful to CAPES Foundation and PDSE program (process number 99999.004779/2014-02) from Ministry of Education of Brazil. U.D and A.C acknowledge to the Spanish Government (Severo Ochoa program SEV-2012-0267 and MAT2014-52085-C2-1-P) and to the Generalitat Valenciana (Prometeo 11/2013-011) by the funding. The European Union is also acknowledged by ERC-AdG-2014-671093 - SynCatMatch.Schwanke, AJ.; Pergher, S.; Díaz Morales, UM.; Corma Canós, A. (2017). The influence of swelling agents molecular dimensions on lamellar morphology of MWW-type zeolites active for fructose conversion. Microporous and Mesoporous Materials. 254:17-27. https://doi.org/10.1016/j.micromeso.2016.11.007S172725

A Lamellar MWW Zeolite With Silicon and Niobium Oxide Pillars: A Catalyst for the Oxidation of Volatile Organic Compounds

This is the peer reviewed version of the following article: A. J. Schwanke, R. Balzer, C. Wittee Lopes, D. Motta Meira, U. Díaz, A. Corma, S. Pergher, Chem. Eur. J. 2020, 26, 10459, which has been published in final form at https://doi.org/10.1002/chem.202000862. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] In this work, an MWW-type zeolite with pillars containing silicon and niobium oxide was synthesized to obtain a hierarchical zeolite. The effect of niobium insertion in the pillaring process was determined by combining a controllable acidity and accessibility in the final material. All pillared materials had niobium occupying framework positions in pillars and extra-framework positions. The pillared material, Pil-Nb-4.5 with 4.5 wt % niobium, did not compromise the mesoporosity formed by pillaring, while the increase of niobium in the structure gradually decreased the mesoporosity and ordering of lamellar stacking. The morphology of the pillared zeolites and the niobium content were found to directly affect the catalytic activity. Specifically, we report on the activity of the MWW-type zeolites with niobium catalyzing the gas-phase oxidation of volatile organic compounds (VOCs), which is an important reaction for clean environmental. All produced MWW-type zeolites with niobium were catalytically active, even at low temperatures and low niobium loading, and provided excellent conversion efficiencies.A.J.S. thanks the CordenacAo de Aperfeicoamento de Pessoal de Nivel Superior-Brasil (CAPES)-Finance Code 001, the PDSE program (process number 99999.004779/2014-02) and the prof. Claudio Radtke from the PPGQ-UFRGS for the XPS analyses. C.W.L. is grateful to INOMAT/CAPES for a postdoctoral fellowship. U.D. thanks the funding by the Spanish Government (MAT2017-82288-C2-1-P).Schwanke, AJ.; Balzer, R.; Lopes, CW.; Meira, DM.; Díaz Morales, UM.; Corma Canós, A.; Pergher, S. (2020). A Lamellar MWW Zeolite With Silicon and Niobium Oxide Pillars: A Catalyst for the Oxidation of Volatile Organic Compounds. Chemistry - A European Journal. 26(46):1-12. https://doi.org/10.1002/chem.202000862S1122646Zhang, X., Guo, J., Guan, P., Liu, C., Huang, H., Xue, F., … Chisholm, M. F. (2013). Catalytically active single-atom niobium in graphitic layers. Nature Communications, 4(1). doi:10.1038/ncomms2929Yan, W., Zhang, G., Yan, H., Liu, Y., Chen, X., Feng, X., … Yang, C. (2018). Liquid-Phase Epoxidation of Light Olefins over W and Nb Nanocatalysts. ACS Sustainable Chemistry & Engineering, 6(4), 4423-4452. doi:10.1021/acssuschemeng.7b03101Ziolek, M., & Sobczak, I. (2017). The role of niobium component in heterogeneous catalysts. 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Modelling human choices: MADeM and decision‑making

Research supported by FAPESP 2015/50122-0 and DFG-GRTK 1740/2. RP and AR are also part of the Research, Innovation and Dissemination Center for Neuromathematics FAPESP grant (2013/07699-0). RP is supported by a FAPESP scholarship (2013/25667-8). ACR is partially supported by a CNPq fellowship (grant 306251/2014-0)

Hierarchical MWW-type zeolites by soft and hard templates - Niobium insertion and catalytic activity

A síntese das zeólitas hierárquicas de estrutura MWW foram realizadas empregando estratégias de soft e hard templates. Os materiais foram caracterizados por diversas técnicas como DRX, TG, ICP, Isotermas de adsorção de N2, MEV, MET e, UV-Vis e FTIR com piridina adsorvida. A estratégia por soft template foi realizada empregando surfactantes com diferentes tamanhos de cadeia em diferentes tratamentos (suave e agressivo). Foi observado que o tamanho do surfactante em sinergia de tratamento (suave ou agressivo) influencia na arquitetura final gerando materiais pilarizados, desorganizados e desilicados. De uma forma geral, foi observado que o tratamento agressivo danifica a estrutura, porém cria regiões de acessibilidade devido à quebra de algumas lâminas MWW, resultando em uma atividade catalítica para conversão de frutose a 5-hidroximetilfurfural (5-HMF) semelhante aos materiais com tratamento suave. Para as zeólitas com pilares mistos de Si/Nb, a inserção do metal aumenta a acidez de Lewis devido a incorporação de nióbio. O nióbio se encontra como espécies mononucleares tetraédricamente coordenado com o silício nos pilares e o seu aumento gradual da quantidade de nióbio nos pilares acaba por diminuir a mesoporosidade interlamelar. O uso de partículas de carbono tipo BP 2000 como hard templates em zeólitas tipo MCM-22 foi efetivo e no controle de morfologia microesférica. Isto se deve ao procedimento de síntese utilizado, em modo dinâmico, e particularmente, a forma tortuosa das dos aglomerados de partículas primárias do carbono BP 2000 que interage com os núcleos zeolíticos. O crescimento dos cristais se dá em orientações aleatórias, na forma de castelo de cartas com regiões de meso e macroporos acessíveis em toda a microesfera as quais possuem tamanhos entre 6-10 µm. O controle da morfologia na forma de microesferas não afeta a atividade catalítica comparado à síntese tradicional da MCM-22. As microesferas na forma acidificadas foram impregnadas com nióbio e demonstraram sinergia entre a acidez da zeólita e o metal apresentando atividade catalítica superior para a conversão de frutose a 5-HMF à sua forma acidificada nos primeiros 45 minutos de reação. Foi demonstrado que as estratégias por soft e hard template são atrativas e potencias para a criação de porosidade hierárquica em zeólitas de estrutura MWW.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)A síntese das zeólitas hierárquicas de estrutura MWW foram realizadas empregando estratégias de soft e hard templates. Os materiais foram caracterizados por diversas técnicas como DRX, TG, ICP, Isotermas de adsorção de N2, MEV, MET e, UV-Vis e FTIR com piridina adsorvida. A estratégia por soft template foi realizada empregando surfactantes com diferentes tamanhos de cadeia em diferentes tratamentos (suave e agressivo). Foi observado que o tamanho do surfactante em sinergia de tratamento (suave ou agressivo) influencia na arquitetura final gerando materiais pilarizados, desorganizados e desilicados. De uma forma geral, foi observado que o tratamento agressivo danifica a estrutura, porém cria regiões de acessibilidade devido à quebra de algumas lâminas MWW, resultando em uma atividade catalítica para conversão de frutose a 5-hidroximetilfurfural (5-HMF) semelhante aos materiais com tratamento suave. Para as zeólitas com pilares mistos de Si/Nb, a inserção do metal aumenta a acidez de Lewis devido a incorporação de nióbio. O nióbio se encontra como espécies mononucleares tetraédricamente coordenado com o silício nos pilares e o seu aumento gradual da quantidade de nióbio nos pilares acaba por diminuir a mesoporosidade interlamelar. O uso de partículas de carbono tipo BP 2000 como hard templates em zeólitas tipo MCM-22 foi efetivo e no controle de morfologia microesférica. Isto se deve ao procedimento de síntese utilizado, em modo dinâmico, e particularmente, a forma tortuosa das dos aglomerados de partículas primárias do carbono BP 2000 que interage com os núcleos zeolíticos. O crescimento dos cristais se dá em orientações aleatórias, na forma de castelo de cartas com regiões de meso e macroporos acessíveis em toda a microesfera as quais possuem tamanhos entre 6-10 µm. O controle da morfologia na forma de microesferas não afeta a atividade catalítica comparado à síntese tradicional da MCM-22. As microesferas na forma acidificadas foram impregnadas com nióbio e demonstraram sinergia entre a acidez da zeólita e o metal apresentando atividade catalítica superior para a conversão de frutose a 5-HMF à sua forma acidificada nos primeiros 45 minutos de reação. Foi demonstrado que as estratégias por soft e hard template são atrativas e potencias para a criação de porosidade hierárquica em zeólitas de estrutura MWW

Recyclable swelling solutions for friendly preparation of pillared MWW-type zeolites

[EN] We studied the recycling of swelling solution of MWW-type lamellar zeolitic precursor with a Si/Al = 25. Swollen materials were obtained up to a third reuse without any compensation of reactants, pH or decrease of lamellar ordering degree. The pillared material showed a surface area of 777 m(2) g(-1) and mesopores sizes of 2-4 nm characteristic of pillared MWW materials obtained by traditional approaches.Anderson Joel Schwanke thanks the CAPES Foundation and PDSE program (process number 99999.004779/2014-02). Urbano Diaz acknowledges to the Spanish Government (MAT2014-52085C2-1-P).Schwanke, AJ.; Díaz Morales, UM.; Corma Canós, A.; Pergher, S. (2017). Recyclable swelling solutions for friendly preparation of pillared MWW-type zeolites. Microporous and Mesoporous Materials. 253:91-95. https://doi.org/10.1016/j.micromeso.2017.06.045S919525