Cu and Fe modified derivatives of 2D MWW-type zeolites (MCM-22, ITQ-2 and MCM-36) as new catalysts for DeNOx process

Zeolites with MWW topology (MCM-22, ITQ-2, and MCM-36) exchanged with copper and iron were studied as catalysts for selective catalytic reduction of NO with ammonia. It was shown that delamination and pillaring of layered MCM-22 zeolite resulted in the formation of ITQ-2 and MCM-36, respectively. Both these materials were characterized by MWW topology and significant contribution of mesopores. In a series of the zeolite based catalyst the most promising results in a process of selective catalytic reduction of NO with ammonia were obtained for the copper doped samples (Cu-MCM-22 and Cu-ITQ-2), however catalytic performance of the studied catalytic systems strongly depends on type, content and form of deposited transition metal species. Moreover, both these catalysts were found to be catalytically stable in the DeNOx process after hydrothermal treatment.U.D. and A.E.P. thank for the financial support to Spanish Government by Consolider-Ingenio MULTICAT CSD2009-00050, MAT2011-29020-0O2-01 and Severo Ochoa Excellence Program SEV-2012-0267.Rutkowska, M.; Díaz Morales, UM.; Palomares Gimeno, AE.; Chmielarz, L. (2015). Cu and Fe modified derivatives of 2D MWW-type zeolites (MCM-22, ITQ-2 and MCM-36) as new catalysts for DeNOx process. Applied Catalysis B: Environmental. 168:531-539. https://doi.org/10.1016/j.apcatb.2015.01.016S53153916

Ferrierite and Its Delaminated and Silica-Intercalated Forms Modified with Copper as Effective Catalysts for NH3-SCR Process

[EN] The main goal of the study was the development of effective catalysts for the low-temperature selective catalytic reduction of NO with ammonia (NH3-SCR), based on ferrierite (FER) and its delaminated (ITQ-6) and silica-intercalated (ITQ-36) forms modified with copper. The copper exchange zeolitic samples, with the intended framework Si/Al ratio of 30 and 50, were synthetized and characterized with respect to their chemical composition (ICP-OES), structure (XRD), texture (low-temperature N(2)adsorption), form and aggregation of deposited copper species (UV-vis-DRS), surface acidity (NH3-TPD) and reducibility (H-2-TPR). The samples of the Cu-ITQ-6 and Cu-ITQ-36 series were found to be significantly more active NH3-SCR catalysts compared to Cu-FER. The activity of these catalysts in low-temperature NH3-SCR was assigned to the significant contribution of highly dispersed copper species (monomeric cations and small oligomeric species) catalytically active in the oxidation of NO to NO(2,)which is necessary for fast-SCR. The zeolitic catalysts, with the higher framework alumina content, were more effective in high-temperature NH3-SCR due to their limited catalytic activity in the side reaction of ammonia oxidation.This work was supported by the National Science Centre-Poland [2016/21/B/ST5/00242].Swies, A.; Kowalczyk, A.; Rutkowska, M.; Díaz Morales, UM.; Palomares Gimeno, AE.; Chmielarz, L. (2020). Ferrierite and Its Delaminated and Silica-Intercalated Forms Modified with Copper as Effective Catalysts for NH3-SCR Process. Catalysts. 10(7):1-21. https://doi.org/10.3390/catal10070734S121107Kowalczyk, A., Święs, A., Gil, B., Rutkowska, M., Piwowarska, Z., Borcuch, A., … Chmielarz, L. (2018). Effective catalysts for the low-temperature NH3-SCR process based on MCM-41 modified with copper by template ion-exchange (TIE) method. Applied Catalysis B: Environmental, 237, 927-937. doi:10.1016/j.apcatb.2018.06.052Busca, G., Lietti, L., Ramis, G., & Berti, F. (1998). Chemical and mechanistic aspects of the selective catalytic reduction of NO by ammonia over oxide catalysts: A review. Applied Catalysis B: Environmental, 18(1-2), 1-36. doi:10.1016/s0926-3373(98)00040-xKompio, P. G. W. A., Brückner, A., Hipler, F., Auer, G., Löffler, E., & Grünert, W. (2012). A new view on the relations between tungsten and vanadium in V2O5WO3/TiO2 catalysts for the selective reduction of NO with NH3. Journal of Catalysis, 286, 237-247. doi:10.1016/j.jcat.2011.11.008Moon Lee, S., Su Kim, S., & Chang Hong, S. (2012). Systematic mechanism study of the high temperature SCR of NO by NH3 over a W/TiO2 catalyst. Chemical Engineering Science, 79, 177-185. doi:10.1016/j.ces.2012.05.032Mladenović, M., Paprika, M., & Marinković, A. (2018). Denitrification techniques for biomass combustion. Renewable and Sustainable Energy Reviews, 82, 3350-3364. doi:10.1016/j.rser.2017.10.054Rutkowska, M., Pacia, I., Basąg, S., Kowalczyk, A., Piwowarska, Z., Duda, M., … Chmielarz, L. (2017). Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH 3 -SCR and NH 3 -SCO processes. Microporous and Mesoporous Materials, 246, 193-206. doi:10.1016/j.micromeso.2017.03.017Rutkowska, M., Díaz, U., Palomares, A. E., & Chmielarz, L. (2015). Cu and Fe modified derivatives of 2D MWW-type zeolites (MCM-22, ITQ-2 and MCM-36) as new catalysts for DeNO x process. Applied Catalysis B: Environmental, 168-169, 531-539. doi:10.1016/j.apcatb.2015.01.016Jodłowski, P. J., Kuterasiński, Ł., Jędrzejczyk, R. J., Chlebda, D., Gancarczyk, A., Basąg, S., & Chmielarz, L. (2017). DeNOx Abatement Modelling over Sonically Prepared Copper USY and ZSM5 Structured Catalysts. Catalysts, 7(7), 205. doi:10.3390/catal7070205Boroń, P., Chmielarz, L., & Dzwigaj, S. (2015). Influence of Cu on the catalytic activity of FeBEA zeolites in SCR of NO with NH 3. Applied Catalysis B: Environmental, 168-169, 377-384. doi:10.1016/j.apcatb.2014.12.052Martín, N., Boruntea, C. R., Moliner, M., & Corma, A. (2015). Efficient synthesis of the Cu-SSZ-39 catalyst for DeNOx applications. Chemical Communications, 51(55), 11030-11033. doi:10.1039/c5cc03200hShan, Y., Sun, Y., Du, J., Zhang, Y., Shi, X., Yu, Y., … He, H. (2020). Hydrothermal aging alleviates the inhibition effects of NO2 on Cu-SSZ-13 for NH3-SCR. Applied Catalysis B: Environmental, 275, 119105. doi:10.1016/j.apcatb.2020.119105Clark, A. H., Nuguid, R. J. G., Steiger, P., Marberger, A., Petrov, A. W., Ferri, D., … Kröcher, O. (2020). Selective Catalytic Reduction of NO with NH 3 on Cu−SSZ‐13: Deciphering the Low and High‐temperature Rate‐limiting Steps by Transient XAS Experiments. ChemCatChem, 12(5), 1429-1435. doi:10.1002/cctc.201901916Shan, Y., Du, J., Yu, Y., Shan, W., Shi, X., & He, H. (2020). Precise control of post-treatment significantly increases hydrothermal stability of in-situ synthesized cu-zeolites for NH3-SCR reaction. Applied Catalysis B: Environmental, 266, 118655. doi:10.1016/j.apcatb.2020.118655Marosz, M., Samojeden, B., Kowalczyk, A., Rutkowska, M., Motak, M., Díaz, U., … Chmielarz, L. (2020). MCM-22, MCM-36, and ITQ-2 Zeolites with Different Si/Al Molar Ratios as Effective Catalysts of Methanol and Ethanol Dehydration. Materials, 13(10), 2399. doi:10.3390/ma13102399Chmielarz, L., & Jabłońska, M. (2015). Advances in selective catalytic oxidation of ammonia to dinitrogen: a review. RSC Advances, 5(54), 43408-43431. doi:10.1039/c5ra03218kDe Pietre, M. K., Bonk, F. A., Rettori, C., Garcia, F. A., & Pastore, H. O. (2011). [V,Al]-ITQ-6: Novel porous material and the effect of delamination conditions on V sites and their distribution. Microporous and Mesoporous Materials, 145(1-3), 108-117. doi:10.1016/j.micromeso.2011.04.031Radko, M., Rutkowska, M., Kowalczyk, A., Mikrut, P., Święs, A., Díaz, U., … Chmielarz, L. (2020). Catalytic oxidation of organic sulfides by H2O2 in the presence of titanosilicate zeolites. Microporous and Mesoporous Materials, 302, 110219. doi:10.1016/j.micromeso.2020.110219Schreyeck, L., Caullet, P., Mougenel, J. C., Guth, J. L., & Marler, B. (1996). PREFER: a new layered (alumino) silicate precursor of FER-type zeolite. Microporous Materials, 6(5-6), 259-271. doi:10.1016/0927-6513(96)00032-6Ishihara, A., Hashimoto, T., & Nasu, H. (2012). Large Mesopore Generation in an Amorphous Silica-Alumina by Controlling the Pore Size with the Gel Skeletal Reinforcement and Its Application to Catalytic Cracking. Catalysts, 2(3), 368-385. doi:10.3390/catal2030368Thommes, M. (2010). Physical Adsorption Characterization of Nanoporous Materials. Chemie Ingenieur Technik, 82(7), 1059-1073. doi:10.1002/cite.201000064Hu, H., Ke, M., Zhang, K., Liu, Q., Yu, P., Liu, Y., … Liu, W. (2017). Designing ferrierite-based catalysts with improved properties for skeletal isomerization of n-butene to isobutene. RSC Advances, 7(50), 31535-31543. doi:10.1039/c7ra04777kDomokos, L., Lefferts, L., Seshan, K., & Lercher, J. . (2000). The importance of acid site locations for n-butene skeletal isomerization on ferrierite. Journal of Molecular Catalysis A: Chemical, 162(1-2), 147-157. doi:10.1016/s1381-1169(00)00286-7Cañizares, P., & Carrero, A. (2003). Dealumination of ferrierite by ammonium hexafluorosilicate treatment: characterization and testing in the skeletal isomerization of n-butene. Applied Catalysis A: General, 248(1-2), 227-237. doi:10.1016/s0926-860x(03)00159-5Wichterlová, B., Tvarůžková, Z., Sobalı́k, Z., & Sarv, P. (1998). Determination and properties of acid sites in H-ferrierite. Microporous and Mesoporous Materials, 24(4-6), 223-233. doi:10.1016/s1387-1811(98)00167-xThibault-Starzyk, F., Stan, I., Abelló, S., Bonilla, A., Thomas, K., Fernandez, C., … Pérez-Ramírez, J. (2009). Quantification of enhanced acid site accessibility in hierarchical zeolites – The accessibility index. Journal of Catalysis, 264(1), 11-14. doi:10.1016/j.jcat.2009.03.006Macina, D., Piwowarska, Z., Tarach, K., Góra-Marek, K., Ryczkowski, J., & Chmielarz, L. (2016). Mesoporous silica materials modified with alumina polycations as catalysts for the synthesis of dimethyl ether from methanol. Materials Research Bulletin, 74, 425-435. doi:10.1016/j.materresbull.2015.11.018Huo, Q., Margolese, D. I., & Stucky, G. D. (1996). Surfactant Control of Phases in the Synthesis of Mesoporous Silica-Based Materials. Chemistry of Materials, 8(5), 1147-1160. doi:10.1021/cm960137hMartins, L., Peguin, R. P. S., Wallau, M., & Urquieta, G. A. (2004). Cu-, Co-, Cu/Ca- and Co/Ca-exchanged ZSM-5 zeolites: Activity in the reduction of NO with methane or propane. Recent Advances in the Science and Technology of Zeolites and Related Materials, Proceedings of the 14th International Zeolite Conference, 2475-2483. doi:10.1016/s0167-2991(04)80513-5Carniti, P., Gervasini, A., Modica, V. H., & Ravasio, N. (2000). Catalytic selective reduction of NO with ethylene over a series of copper catalysts on amorphous silicas. Applied Catalysis B: Environmental, 28(3-4), 175-185. doi:10.1016/s0926-3373(00)00172-7Minchev, C., Köhn, R., Tsoncheva, T., Dimitrov, M., & Fröba, M. (2001). 07-P-19-Preparation and characterization of copper oxide modified MCM-41 molecular sieves. Zeolites and Mesoporous Materials at the dawn of the 21st century, Proceedings of the 13th International Zeolite Conference,, 253. doi:10.1016/s0167-2991(01)81539-1Martins, L., Peguin, R. P. S., & Urquiet-González, E. A. (2006). Cu and Co exchanged ZSM-5 zeolites: activity towards no reduction and hydrocarbon oxidation. Química Nova, 29(2), 223-229. doi:10.1590/s0100-40422006000200009Sullivan, J. A., & Cunningham, J. (1998). Selective catalytic reduction of NO with C2H4 over Cu/ZSM-5: Influences of oxygen partial pressure and incorporated rhodia. Applied Catalysis B: Environmental, 15(3-4), 275-289. doi:10.1016/s0926-3373(97)00055-6Yang, X., Wang, X., Qiao, X., Jin, Y., & Fan, B. (2020). Effect of Hydrothermal Aging Treatment on Decomposition of NO by Cu-ZSM-5 and Modified Mechanism of Doping Ce against This Influence. Materials, 13(4), 888. doi:10.3390/ma1304088

Ferrierite and Its Delaminated Forms Modified with Copper as Effective Catalysts for NH3-SCO Process

[EN] Ferrierites and their delaminated forms (ITQ-6), containing aluminum or titanium in the zeolite framework, were synthetized and modified with copper by an ion-exchange method. The obtained samples were characterized with respect to their chemical composition (ICP-OES), structure (XRD, UV-Vis DRS), textural parameters (N-2-sorption), surface acidity (NH3-TPD), form and reducibility of deposited copper species (UV-Vis DRS and H-2-TPR). Ferrierites and delaminated ITQ-6 zeolites modified with copper were studied as catalysts for the selective catalytic oxidation of ammonia to dinitrogen (NH3-SCO). It was shown that aggregated copper oxide species, which were preferentially formed on Ti-zeolites, were catalytically active in direct low-temperature ammonia oxidation to NO, while copper introduced into Al-zeolites was present mainly in the form of monomeric copper cations catalytically active in selective reduction of NO by ammonia to dinitrogen. It was postulated that ammonia oxidation in the presence of the studied catalysts proceeds according to the internal-selective catalytic reduction mechanism (i-SCR) and therefore the suitable ratio between aggregated copper oxide species and monomeric copper cations is necessary to obtain active and selective catalysts for the NH3-SCO process. Cu/Al-ITQ-6 presented the best catalytic properties possibly due to the most optimal ratio of these copper species.The studies financed by National Science Centre-Poland [2016/21/B/ST5/00242]. A.. has been partly supported by the EU Project POWR.03.02.00-00-I004/16. U.D. acknowledges the Spanish Government for the funding [MAT2017-82288-C2-1-P]. Part of the research was done with equipment purchased in the frame of European Regional Development Fund (Polish Innovation Economy Operational Program (POIG.02.01.00-12-023/08)).Swies, A.; Rutkowska, M.; Kowalczyk, A.; Díaz Morales, UM.; Palomares Gimeno, AE.; Chmielarz, L. (2020). Ferrierite and Its Delaminated Forms Modified with Copper as Effective Catalysts for NH3-SCO Process. Materials. 13(21):1-18. https://doi.org/10.3390/ma13214885S118132

The Polish version of the Juvenile Arthritis Multidimensional Assessment Report (JAMAR)

The Juvenile Arthritis Multidimensional Assessment Report (JAMAR) is a new parent/patient-reported outcome measure that enables a thorough assessment of the disease status in children with juvenile idiopathic arthritis (JIA). We report the results of the cross-cultural adaptation and validation of the parent and patient versions of the JAMAR in the Polish language. The reading comprehension of the questionnaire was tested in 10 JIA parents and patients. Each participating centre was asked to collect demographic, clinical data and the JAMAR in 100 consecutive JIA patients or all consecutive patients seen in a 6-month period and to administer the JAMAR to 100 healthy children and their parents. The statistical validation phase explored descriptive statistics and the psychometric issues of the JAMAR: the 3 Likert assumptions, floor/ceiling effects, internal consistency, Cronbach\u2019s alpha, interscale correlations, test\u2013retest reliability, and construct validity (convergent and discriminant validity). A total of 154 JIA patients (10.4% systemic, 50.0% oligoarticular, 24.7% RF-negative polyarthritis, 14.9% other categories) and 91 healthy children, were enrolled in two centres. The JAMAR components discriminated well healthy subjects from JIA patients. All JAMAR components revealed good psychometric performances. In conclusion, the Polish version of the JAMAR is a valid tool for the assessment of children with JIA and is suitable for use both in routine clinical practice and clinical research

orchaRd 2.0 : an R package for visualising meta-analyses with orchard plots

1. Although meta-analysis has become an essential tool in ecology and evolution, reporting of meta-analytic results can still be much improved. To aid this, we have introduced the orchard plot, which presents not only overall estimates and their confidence intervals, but also shows corresponding heterogeneity (as prediction intervals) and individual effect sizes. 2. Here, we have added significant enhancements by integrating many new functionalities into orchaRd 2.0. This updated version allows the visualisation of heteroscedasticity (different variances across levels of a categorical moderator), marginal estimates (e.g. marginalising out effects other than the one visualised), conditional estimates (i.e. estimates of different groups conditioned upon specific values of a continuous variable) and visualisations of all types of interactions between two categorical/continuous moderators. 3. orchaRd 2.0 has additional functions which calculate key statistics from multilevel meta-analytic models such as $I^{2}$ and $R^{2}$. Importantly, orchaRd 2.0 contributes to better reporting by complying with PRISMA-EcoEvo (preferred reporting items for systematic reviews and meta-analyses in ecology and evolution). Taken together, orchaRd 2.0 can improve the presentation of meta-analytic results and facilitate the exploration of previously neglected patterns. 4. In addition, as a part of a literature survey, we found that graphical packages are rarely cited (~3%). We plea that researchers credit developers and maintainers of graphical packages, for example, by citations in a figure legend, acknowledging the use of relevant packages

MCM-22, MCM-36, and ITQ-2 Zeolites with Different Si/Al Molar Ratios as Effective Catalysts of Methanol and Ethanol Dehydration

[EN] MCM-22, MCM-36, and ITQ-2 zeolites with the intended Si/Al molar ratios of 15, 25, and 50 were synthetized and tested as catalysts for dehydration of methanol to dimethyl ether and dehydration of ethanol to diethyl ether and ethylene. The surface concentration of acid sites was regulated by the synthesis of zeolite precursors with different aluminum content in the zeolite framework, while the influence of porous structure on the overall efficiency of alcohol conversion was analyzed by application of zeolitic materials with different types of porosity-microporous MCM-22 as well as microporous-mesoporous MCM-36 and ITQ-2. The zeolitic samples were characterized with respect to their: chemical composition (ICP-OES), structure (XRD, FT-IR), texture (N-2 sorption), and surface acidity (NH3-TPD). Comparison of the catalytic activity of the studied zeolitic catalysts with other reported catalytic systems, including zeolites with the similar Si/Al ratio as well as gamma-Al2O3 (one of the commercial catalysts for methanol dehydration), shows a great potential of MCM-22, MCM-36, and ITQ-2 in the reactions of alcohols dehydration.This research was funded by National Science Centre-Poland grant number 2016/21/B/ST5/00242. U.D. acknowledges to the Spanish Government grant number MAT2017-82288-C2-1-P. The research was partially done using the equipment purchased from the funds of European Regional Development Fund, Polish Innovation Economy Operational Program, grant numberPOIG.02.01.00-12-023/08.Marosz, M.; Samojeden, B.; Kowalczyk, A.; Rutkowska, M.; Motak, M.; Díaz Morales, UM.; Palomares Gimeno, AE.... (2020). MCM-22, MCM-36, and ITQ-2 Zeolites with Different Si/Al Molar Ratios as Effective Catalysts of Methanol and Ethanol Dehydration. Materials. 13(10):1-17. https://doi.org/10.3390/ma13102399S1171310Clausen, L. R., Houbak, N., & Elmegaard, B. (2010). Technoeconomic analysis of a methanol plant based on gasification of biomass and electrolysis of water. Energy, 35(5), 2338-2347. doi:10.1016/j.energy.2010.02.034Huisman, G. H., Van Rens, G. L. M. A., De Lathouder, H., & Cornelissen, R. L. (2011). Cost estimation of biomass-to-fuel plants producing methanol, dimethylether or hydrogen. Biomass and Bioenergy, 35, S155-S166. doi:10.1016/j.biombioe.2011.04.038Sarkar, S., Kumar, A., & Sultana, A. (2011). Biofuels and biochemicals production from forest biomass in Western Canada. Energy, 36(10), 6251-6262. doi:10.1016/j.energy.2011.07.024Gavahian, M., Munekata, P. E. S., Eş, I., Lorenzo, J. M., Mousavi Khaneghah, A., & Barba, F. J. (2019). Emerging techniques in bioethanol production: from distillation to waste valorization. Green Chemistry, 21(6), 1171-1185. doi:10.1039/c8gc02698jBarbarossa, V., Viscardi, R., Maestri, G., Maggi, R., Mirabile Gattia, D., & Paris, E. (2019). Sulfonated catalysts for methanol dehydration to dimethyl ether (DME). Materials Research Bulletin, 113, 64-69. doi:10.1016/j.materresbull.2019.01.018Marchionna, M., Patrini, R., Sanfilippo, D., & Migliavacca, G. (2008). Fundamental investigations on di-methyl ether (DME) as LPG substitute or make-up for domestic uses. Fuel Processing Technology, 89(12), 1255-1261. doi:10.1016/j.fuproc.2008.07.013Rownaghi, A. A., Rezaei, F., Stante, M., & Hedlund, J. (2012). Selective dehydration of methanol to dimethyl ether on ZSM-5 nanocrystals. Applied Catalysis B: Environmental, 119-120, 56-61. doi:10.1016/j.apcatb.2012.02.017Stiefel, M., Ahmad, R., Arnold, U., & Döring, M. (2011). Direct synthesis of dimethyl ether from carbon-monoxide-rich synthesis gas: Influence of dehydration catalysts and operating conditions. Fuel Processing Technology, 92(8), 1466-1474. doi:10.1016/j.fuproc.2011.03.007Tokay, K. C., Dogu, T., & Dogu, G. (2012). Dimethyl ether synthesis over alumina based catalysts. Chemical Engineering Journal, 184, 278-285. doi:10.1016/j.cej.2011.12.034Semelsberger, T. A., Borup, R. L., & Greene, H. L. (2006). Dimethyl ether (DME) as an alternative fuel. Journal of Power Sources, 156(2), 497-511. doi:10.1016/j.jpowsour.2005.05.082Arcoumanis, C., Bae, C., Crookes, R., & Kinoshita, E. (2008). The potential of di-methyl ether (DME) as an alternative fuel for compression-ignition engines: A review. Fuel, 87(7), 1014-1030. doi:10.1016/j.fuel.2007.06.007Takahara, I., Saito, M., Inaba, M., & Murata, K. (2005). Dehydration of Ethanol into Ethylene over Solid Acid Catalysts. Catalysis Letters, 105(3-4), 249-252. doi:10.1007/s10562-005-8698-1Kito-Borsa, T., Pacas, D. A., Selim, S., & Cowley, S. W. (1998). Properties of an Ethanol−Diethyl Ether−Water Fuel Mixture for Cold-Start Assistance of an Ethanol-Fueled Vehicle. Industrial & Engineering Chemistry Research, 37(8), 3366-3374. doi:10.1021/ie970171lCiftci, A., Varisli, D., Cem Tokay, K., Aslı Sezgi, N., & Dogu, T. (2012). Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous catalysts. Chemical Engineering Journal, 207-208, 85-93. doi:10.1016/j.cej.2012.04.016Xu, M., Lunsford, J. H., Goodman, D. W., & Bhattacharyya, A. (1997). Synthesis of dimethyl ether (DME) from methanol over solid-acid catalysts. Applied Catalysis A: General, 149(2), 289-301. doi:10.1016/s0926-860x(96)00275-xYaripour, F., Baghaei, F., Schmidt, I., & Perregaard, J. (2005). Catalytic dehydration of methanol to dimethyl ether (DME) over solid-acid catalysts. Catalysis Communications, 6(2), 147-152. doi:10.1016/j.catcom.2004.11.012Abu-Dahrieh, J., Rooney, D., Goguet, A., & Saih, Y. (2012). Activity and deactivation studies for direct dimethyl ether synthesis using CuO–ZnO–Al2O3 with NH4ZSM-5, HZSM-5 or γ-Al2O3. Chemical Engineering Journal, 203, 201-211. doi:10.1016/j.cej.2012.07.011De Oliveira, T. K. R., Rosset, M., & Perez-Lopez, O. W. (2018). Ethanol dehydration to diethyl ether over Cu-Fe/ZSM-5 catalysts. Catalysis Communications, 104, 32-36. doi:10.1016/j.catcom.2017.10.013Chmielarz, L., Kowalczyk, A., Skoczek, M., Rutkowska, M., Gil, B., Natkański, P., … Ryczkowski, J. (2018). Porous clay heterostructures intercalated with multicomponent pillars as catalysts for dehydration of alcohols. Applied Clay Science, 160, 116-125. doi:10.1016/j.clay.2017.12.015Marosz, M., Kowalczyk, A., & Chmielarz, L. (2020). Modified vermiculites as effective catalysts for dehydration of methanol and ethanol. Catalysis Today, 355, 466-475. doi:10.1016/j.cattod.2019.07.003Marosz, M., Kowalczyk, A., Gil, B., & Chmielarz, L. (2020). Acid-treated Clay Minerals as Catalysts for Dehydration of Methanol and Ethanol. Clays and Clay Minerals, 68(1), 23-37. doi:10.1007/s42860-019-00051-yCorma, A., Corell, C., & Pérez-Pariente, J. (1995). Synthesis and characterization of the MCM-22 zeolite. Zeolites, 15(1), 2-8. doi:10.1016/0144-2449(94)00013-iDíaz, U., Fornés, V., & Corma, A. (2006). On the mechanism of zeolite growing: Crystallization by seeding with delayered zeolites. Microporous and Mesoporous Materials, 90(1-3), 73-80. doi:10.1016/j.micromeso.2005.09.025Rutkowska, M., Díaz, U., Palomares, A. E., & Chmielarz, L. (2015). Cu and Fe modified derivatives of 2D MWW-type zeolites (MCM-22, ITQ-2 and MCM-36) as new catalysts for DeNO x process. Applied Catalysis B: Environmental, 168-169, 531-539. doi:10.1016/j.apcatb.2015.01.016Jun, J. W., Ahmed, I., Kim, C.-U., Jeong, K.-E., Jeong, S.-Y., & Jhung, S. H. (2014). Synthesis of ZSM-5 zeolites using hexamethylene imine as a template: Effect of microwave aging. Catalysis Today, 232, 108-113. doi:10.1016/j.cattod.2013.08.017Mansouri, N., Rikhtegar, N., Panahi, H. A., Atabi, F., & Shahraki, B. K. (2013). Porosity, characteriza-tion and structural properties of natural zeolite – clinoptilolite – as a sorbent. Environment Protection Engineering, 39(1). doi:10.37190/epe130111Juybar, M., Khanmohammadi Khorrami, M., Bagheri Garmarudi, A., & Zandbaaf, S. (2020). Determination of acidity in metal incorporated zeolites by infrared spectrometry using artificial neural network as chemometric approach. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 228, 117539. doi:10.1016/j.saa.2019.117539Carriço, C. S., Cruz, F. T., Santos, M. B., Pastore, H. O., Andrade, H. M. C., & Mascarenhas, A. J. S. (2013). Efficiency of zeolite MCM-22 with different SiO2/Al2O3 molar ratios in gas phase glycerol dehydration to acrolein. Microporous and Mesoporous Materials, 181, 74-82. doi:10.1016/j.micromeso.2013.07.020Chmielarz, L., Kuśtrowski, P., Dziembaj, R., Cool, P., & Vansant, E. F. (2010). SBA-15 mesoporous silica modified with metal oxides by MDD method in the role of DeNOx catalysts. Microporous and Mesoporous Materials, 127(1-2), 133-141. doi:10.1016/j.micromeso.2009.07.003Baran, R., Millot, Y., Onfroy, T., Krafft, J.-M., & Dzwigaj, S. (2012). Influence of the nitric acid treatment on Al removal, framework composition and acidity of BEA zeolite investigated by XRD, FTIR and NMR. Microporous and Mesoporous Materials, 163, 122-130. doi:10.1016/j.micromeso.2012.06.055Frontera, P., Testa, F., Aiello, R., Candamano, S., & Nagy, J. B. (2007). Transformation of MCM-22(P) into ITQ-2: The role of framework aluminium. Microporous and Mesoporous Materials, 106(1-3), 107-114. doi:10.1016/j.micromeso.2007.02.031Yang, S.-T., Kim, J.-Y., Kim, J., & Ahn, W.-S. (2012). CO2 capture over amine-functionalized MCM-22, MCM-36 and ITQ-2. Fuel, 97, 435-442. doi:10.1016/j.fuel.2012.03.034Diep, B. T., & Wainwright, M. S. (1987). Thermodynamic equilibrium constants for the methanol-dimethyl ether-water system. Journal of Chemical & Engineering Data, 32(3), 330-333. doi:10.1021/je00049a015Barthos, R., Széchenyi, A., & Solymosi, F. (2006). Decomposition and Aromatization of Ethanol on ZSM-Based Catalysts. The Journal of Physical Chemistry B, 110(43), 21816-21825. doi:10.1021/jp063522vKondo, J. N., Ito, K., Yoda, E., Wakabayashi, F., & Domen, K. (2005). An Ethoxy Intermediate in Ethanol Dehydration on Brønsted Acid Sites in Zeolite. The Journal of Physical Chemistry B, 109(21), 10969-10972. doi:10.1021/jp050721qMacina, D., Piwowarska, Z., Tarach, K., Góra-Marek, K., Ryczkowski, J., & Chmielarz, L. (2016). Mesoporous silica materials modified with alumina polycations as catalysts for the synthesis of dimethyl ether from methanol. Materials Research Bulletin, 74, 425-435. doi:10.1016/j.materresbull.2015.11.018Rutkowska, M., Macina, D., Mirocha-Kubień, N., Piwowarska, Z., & Chmielarz, L. (2015). Hierarchically structured ZSM-5 obtained by desilication as new catalyst for DME synthesis from methanol. Applied Catalysis B: Environmental, 174-175, 336-343. doi:10.1016/j.apcatb.2015.03.00

Catalytic oxidation of organic sulfides by H2O2 in the presence of titanosilicate zeolites

[EN] Titanosilicate ferrierite zeolite (FER) and its delaminated form (ITQ-6), with various Si/Ti molar ratios, were synthetized and tested as catalysts for diphenyl sulfide (Ph2S) and dimethyl sulfide (DMS) oxidation with H2O2. The zeolites were characterized with respect to their chemical composition (ICP-OES), structure (XRD, UV-vis DRS) and texture (low-temperature N-2 adsorption-desorption). Titanium in the FER and ITQ-6 samples was present mainly in the zeolite framework with a significant contribution of titanium in the extraframework positions. Titanosilicate zeolites of FER and ITQ-6 series were found to be active catalysts of diphenyl and dimethyl sulfides oxidation by H2O2 to sulfoxides (Ph2SO/DMSO) and sulfones (Ph2SO2/DMSO2). The efficiency of these reactions depends on the porous structure of the zeolite catalysts - conversion of larger molecules of diphenyl sulfide was significantly higher in the presence of delaminated zeolite Ti-ITQ-6 due to the possibility of the interlayer mesopores penetration by reactants. On the other side diphenyl sulfide molecules are too large to be accommodated into micropores of FER zeolite. The efficiency of dimethyl sulfide conversion, due to relatively small size of this molecule, was similar in the presence of Ti-FER and Ti-ITQ-6 zeolites. For all catalysts, the organic sulfide conversion was significantly intensified under UV irradiation. It was suggested that Ti cations in the zeolite framework, as well as in the extraframework, species play a role of the single site photocatalysts active in the formation of hydroxyl radicals, which are known to be effective oxidants of the organic sulfides.The studies were carried out in the frame of project 2016/21/B/ST5/00242 from the National Science Centre (Poland). Part of the research was done with equipment purchased in the frame of European Regional Development Fund (Polish Innovation Economy Operational Program -contract no. POIG.02.01.00-12-023/08). U.D. acknowledges to the Spanish Government by the funding (MAT2017-82288-C2-1-P). The work was partially supported by the Foundation for Polish Science (FNP) within the TEAM project (POIR.04.04.00-00-3D74/16).Radko, M.; Rutkowska, M.; Kowalczyk, A.; Mikrut, P.; Swies, A.; Díaz Morales, UM.; Palomares Gimeno, AE.... (2020). Catalytic oxidation of organic sulfides by H2O2 in the presence of titanosilicate zeolites. Microporous and Mesoporous Materials. 302:1-9. https://doi.org/10.1016/j.micromeso.2020.110219S19302Weitkamp, J. (2000). Zeolites and catalysis. Solid State Ionics, 131(1-2), 175-188. doi:10.1016/s0167-2738(00)00632-9Schreyeck, L., Caullet, P., Mougenel, J.-C., Guth, J.-L., & Marler, B. (1995). A layered microporous aluminosilicate precursor of FER-type zeolite. Journal of the Chemical Society, Chemical Communications, (21), 2187. doi:10.1039/c39950002187Solsona, B., Lopez Nieto, J. M., & Díaz, U. (2006). Siliceous ITQ-6: A new support for vanadia in the oxidative dehydrogenation of propane. Microporous and Mesoporous Materials, 94(1-3), 339-347. doi:10.1016/j.micromeso.2006.04.007Corma, A., Diaz, U., Domine, M. E., & Fornés, V. (2000). AlITQ-6 and TiITQ-6: Synthesis, Characterization, and Catalytic Activity. Angewandte Chemie International Edition, 39(8), 1499-1501. doi:10.1002/(sici)1521-3773(20000417)39:83.0.co;2-0Corma, A., Diaz, U., Domine, M. E., & Fornés, V. (2000). New Aluminosilicate and Titanosilicate Delaminated Materials Active for Acid Catalysis, and Oxidation Reactions Using H2O2. Journal of the American Chemical Society, 122(12), 2804-2809. doi:10.1021/ja9938130Shevade, S., Ahedi, R. K., & Kotasthane, A. N. (1997). Catalysis Letters, 49(1/2), 69-75. doi:10.1023/a:1019092918937Anand, R., Shevade, S. S., Ahedi, R. K., Mirajkar, S. P., & Rao, B. S. (1999). Catalysis Letters, 62(2/4), 209-213. doi:10.1023/a:1019099006237Corma, A., Diaz, U., Domine, M. E., & Fornés, V. (2000). Ti-ferrierite and TiITQ-6: synthesis and catalytic activity for the epoxidation of olefins with H2O2. Chemical Communications, (2), 137-138. doi:10.1039/a908748fMartausová, I., Spustová, D., Cvejn, D., Martaus, A., Lacný, Z., & Přech, J. (2019). Catalytic activity of advanced titanosilicate zeolites in hydrogen peroxide S-oxidation of methyl(phenyl)sulfide. Catalysis Today, 324, 144-153. doi:10.1016/j.cattod.2018.07.003Kon, Y., Yokoi, T., Yoshioka, M., Uesaka, Y., Kujira, H., Sato, K., & Tatsumi, T. (2013). Selective oxidation of bulky sulfides to sulfoxides over titanosilicates having an MWW structure in the presence of H2O2 under organic solvent-free conditions. Tetrahedron Letters, 54(36), 4918-4921. doi:10.1016/j.tetlet.2013.07.006Přech, J. (2017). Catalytic performance of advanced titanosilicate selective oxidation catalysts – a review. Catalysis Reviews, 60(1), 71-131. doi:10.1080/01614940.2017.1389111Sato, K., Hyodo, M., Aoki, M., Zheng, X.-Q., & Noyori, R. (2001). Oxidation of sulfides to sulfoxides and sulfones with 30% hydrogen peroxide under organic solvent- and halogen-free conditions. Tetrahedron, 57(13), 2469-2476. doi:10.1016/s0040-4020(01)00068-0Radko, M., Kowalczyk, A., Bidzińska, E., Witkowski, S., Górecka, S., Wierzbicki, D., … Chmielarz, L. (2018). Titanium dioxide doped with vanadium as effective catalyst for selective oxidation of diphenyl sulfide to diphenyl sulfonate. Journal of Thermal Analysis and Calorimetry, 132(3), 1471-1480. doi:10.1007/s10973-018-7119-9Xia, Q.-H., & Tatsumi, T. (2005). Crystallization kinetics of nanosized Tiβ zeolites with high oxidation activity by a dry-gel conversion technique. Materials Chemistry and Physics, 89(1), 89-98. doi:10.1016/j.matchemphys.2004.08.034Corma, A., Fornés, V., & Díaz, U. (2001). Chemical Communications, (24), 2642-2643. doi:10.1039/b108777kChica, A., Diaz, U., Fornés, V., & Corma, A. (2009). Changing the hydroisomerization to hydrocracking ratio of long chain alkanes by varying the level of delamination in zeolitic (ITQ-6) materials. Catalysis Today, 147(3-4), 179-185. doi:10.1016/j.cattod.2008.10.046Hu, H., Ke, M., Zhang, K., Liu, Q., Yu, P., Liu, Y., … Liu, W. (2017). Designing ferrierite-based catalysts with improved properties for skeletal isomerization of n-butene to isobutene. RSC Advances, 7(50), 31535-31543. doi:10.1039/c7ra04777kThommes, M., Kaneko, K., Neimark, A. V., Olivier, J. P., Rodriguez-Reinoso, F., Rouquerol, J., & Sing, K. S. W. (2015). Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure and Applied Chemistry, 87(9-10), 1051-1069. doi:10.1515/pac-2014-1117Corma, A., Fornes, V., & Rey, F. (2002). Delaminated Zeolites: An Efficient Support for Enzymes. Advanced Materials, 14(1), 71-74. doi:10.1002/1521-4095(20020104)14:13.0.co;2-wZukal, A., Dominguez, I., Mayerová, J., & Čejka, J. (2009). Functionalization of Delaminated Zeolite ITQ-6 for the Adsorption of Carbon Dioxide. Langmuir, 25(17), 10314-10321. doi:10.1021/la901156zSegura, Y., Chmielarz, L., Kustrowski, P., Cool, P., Dziembaj, R., & Vansant, E. F. (2005). Characterisation and reactivity of vanadia–titania supported SBA-15 in the SCR of NO with ammonia. Applied Catalysis B: Environmental, 61(1-2), 69-78. doi:10.1016/j.apcatb.2005.04.011Corma, A. (1997). From Microporous to Mesoporous Molecular Sieve Materials and Their Use in Catalysis. Chemical Reviews, 97(6), 2373-2420. doi:10.1021/cr960406nBlasco, T., Corma, A., Navarro, M. T., & Pariente, J. P. (1995). Synthesis, Characterization, and Catalytic Activity of Ti-MCM-41 Structures. Journal of Catalysis, 156(1), 65-74. doi:10.1006/jcat.1995.1232Yang, B.-T., & Wu, P. (2014). Post-synthesis and catalytic performance of FER type sub-zeolite Ti-ECNU-8. Chinese Chemical Letters, 25(12), 1511-1514. doi:10.1016/j.cclet.2014.09.003Chmielarz, L., Piwowarska, Z., Kuśtrowski, P., Gil, B., Adamski, A., Dudek, B., & Michalik, M. (2009). Porous clay heterostructures (PCHs) intercalated with silica-titania pillars and modified with transition metals as catalysts for the DeNOx process. Applied Catalysis B: Environmental, 91(1-2), 449-459. doi:10.1016/j.apcatb.2009.06.014Radko, M., Kowalczyk, A., Mikrut, P., Witkowski, S., Mozgawa, W., Macyk, W., & Chmielarz, L. (2020). Catalytic and photocatalytic oxidation of diphenyl sulphide to diphenyl sulfoxide over titanium dioxide doped with vanadium, zinc, and tin. RSC Advances, 10(7), 4023-4031. doi:10.1039/c9ra09903dBordiga, S., Bonino, F., Damin, A., & Lamberti, C. (2007). Reactivity of Ti(iv) species hosted in TS-1 towards H2O2–H2O solutions investigated by ab initio cluster and periodic approaches combined with experimental XANES and EXAFS data: a review and new highlights. Physical Chemistry Chemical Physics, 9(35), 4854. doi:10.1039/b706637fTozzola, G., Mantegazza, M. A., Ranghino, G., Petrini, G., Bordiga, S., Ricchiardi, G., … Zecchina, A. (1998). On the Structure of the Active Site of Ti-Silicalite in Reactions with Hydrogen Peroxide: A Vibrational and Computational Study. Journal of Catalysis, 179(1), 64-71. doi:10.1006/jcat.1998.2205Novara, C., Alfayate, A., Berlier, G., Maurelli, S., & Chiesa, M. (2013). The interaction of H2O2 with TiAlPO-5 molecular sieves: probing the catalytic potential of framework substituted Ti ions. Physical Chemistry Chemical Physics, 15(26), 11099. doi:10.1039/c3cp51214bChen, L. ., Jaenicke, S., Chuah, G. ., & Ang, H. . (1996). UV absorption study of solid catalysts. Journal of Electron Spectroscopy and Related Phenomena, 82(3), 203-208. doi:10.1016/s0368-2048(96)03072-1Karlsen, E., & Schöffel, K. (1996). Titanium-silicalite catalyzed epoxidation of ethylene with hydrogen peroxide. A theoretical study. Catalysis Today, 32(1-4), 107-114. doi:10.1016/s0920-5861(96)00176-9Juan, Z., Dishun, Z., Liyan, Y., & Yongbo, L. (2010). Photocatalytic oxidation dibenzothiophene using TS-1. Chemical Engineering Journal, 156(3), 528-531. doi:10.1016/j.cej.2009.04.032Lee, G. D., Jung, S. K., Jeong, Y. J., Park, J. H., Lim, K. T., Ahn, B. H., & Hong, S. S. (2003). Photocatalytic decomposition of 4-nitrophenol over titanium silicalite (TS-1) catalysts. Applied Catalysis A: General, 239(1-2), 197-208. doi:10.1016/s0926-860x(02)00389-7Howe, R. F., & Krisnandi, Y. K. (2001). Photoreactivity of ETS-10. Chemical Communications, (17), 1588-1589. doi:10.1039/b104870

Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH3-SCR and NH3-SCO processes

[EN] In the presented manuscript an influence of the mesoporosity generation in commercial ZSM-5 zeolite on its catalytic performance in two environmental processes, such as NO reduction with ammonia (NH3SCR, Selective Catalytic Reduction of NO with NH3) and NH3 oxidation (NH3-SCO, Selective Catalytic Oxidation of NH3) was examined. Micro-mesoporous catalysts with the properties of ZSM-5 zeolite were obtained by desilication with NaOH and NaOH/TPAOH (tetrapropylammonium hydroxide) mixture with different ratios (TPA+/OH- = 0.2, 0.4, 0.6, 0.8 and infinity) and for different durations (1, 2, 4 and 6 h). The results of the catalytic studies (over the Cu-exchanged samples) showed higher activity of this novel mesostructured group of zeolitic materials. Enhanced catalytic performance was related to the generated mesoporosity (improved Hierarchy Factor (HF) of the samples), that was observed especially with the use of Pore Directing Agent (PDA) additive, TPAOH. Applied desilication conditions did not influence significantly the crystallinity of the samples (X-ray diffraction analysis (XRD)), despite the treatment for 6 h in NaOH solution, which was found to be too severe to preserve the zeolitic properties of the samples. The modified porous structure and accessibility of acid sites (increased surface acidity determined by temperature programmed desorption of ammonia (NH3-TPD)) influenced the red-ox properties of copper species introduced by ion-exchange method (temperature programmed reduction with hydrogen (H-2-TPR). Increased acidity of the micro-mesoporous samples, as well as the content of easily reducible copper species resulted in a significant improvement of Cu-ZSM-5 catalytic efficiency in the NH3-SCR and NH3-SCO processes. (C) 2017 Elsevier Inc. All rights reserved.This work was supported by the National Science Center under grant no. 2011/03/N/ST5/04820. Part of the research was carried out with the equipment purchased thanks to the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (contract no. POIG.02.01.00-12-023/08). U. D. acknowledges to Spanish Government by the funding (MAT2014-52085-C2-1-P).Rutkowska, M.; Pacia, I.; Basag, S.; Kowalczyk, A.; Piwowarska, Z.; Duda, M.; Tarach, K.... (2017). Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH3-SCR and NH3-SCO processes. Microporous and Mesoporous Materials. 246:193-206. https://doi.org/10.1016/j.micromeso.2017.03.017S19320624

Adipokines and Insulin Resistance in Young Adult Survivors of Childhood Cancer

We examined the association between adipokines (leptin, adiponectin, and resistin), radiotherapy, measurement of body fat, and insulin resistance among young adult survivors of childhood cancer (CCS). Materials and Methods. Seventy-six survivors were included (mean age 24.1±3.5 years). Insulin resistance (IR) was calculated using the homeostasis model assessment (HOMA-IR). The serum levels of adipokines were assayed by immunoassays. Fat mass was evaluated by DXA. Results. Mean adiponectin level and mean body FAT were higher in the examined females than in males (10009±6367 ng/mL versus 6433±4136 ng/mL, p<0.01; 35.98±9.61% versus 22.7±7.46%, p<0.001). Among CCS, one of 75 patients met the criteria of insulin resistance, and in 14 patients there was impaired fasting glucose. The multiple regression model for females showed that leptin/adiponectin ratio (LA ratio) significantly affected HOMA-IR (increase of 0.024 per each unit of LA ratio; p<0.05). Radiotherapy had no effect on serum adipokines and IR. Conclusion. The observed results support the hypothesis that adiponectin might be associated with insulin resistance and it can not be ruled out that changes in the mean level of adiponectin per FAT mass or leptin/adiponectin ratio may precede the occurrence of insulin resistance in the future