Selective ammonia oxidation over ZSM-5 zeolite: Impact of catalyst's support porosity and type of deposited iron species

[EN] In the presented studies an influence of different parameters, such as zeolite sample porosity, form of used iron source ([Fe-3(OAc)(6)O(H2O)(3)](+)oligocations or FeSO4 solutions) and method of iron species deposition (ion-exchange, impregnation), on the catalytic activity in the process of the selective catalytic oxidation of ammonia (NH3-SCO) was studied. Conventional and mesoporous ZSM-5 zeolites, obtained by desilication and modified with iron species, were analysed with respect to their textural, surface and crystalline properties (N-2-sorption, HRTEM, SEM, XRD) as well as the form of introduced Fe species (UV-vis-DRS). Ion-exchange with [Fe-3(OAc)(6)O (H2O)(3)](+) oligocations and impregnation with these oligocations and FeSO4 solutions were found as the most effective methods of the zeolite samples activation for NH3-SCO.This work was carried out in the frame of project No. 0670/IP3/2016/74 from the Polish Ministry of Science and Higher Education in the years 2016-2019. Part of the work was performed in the frame of project No. 2012/05/B/ST5/00269from the National Science Centre (Poland). U. D. acknowledges to the Spanish Government by the funding (MAT2017-82288-C2-1-P). The authors would like to acknowledge to Clariant Company for the providing of the HMFI zeolite material for the presented research.Borcuch, A.; Rutkowska, M.; Marzec, A.; Kowalczyk, A.; Michalik, M.; Moreno, J.; Díaz Morales, UM.... (2020). Selective ammonia oxidation over ZSM-5 zeolite: Impact of catalyst's support porosity and type of deposited iron species. Catalysis Today. 348:223-229. https://doi.org/10.1016/j.cattod.2019.08.054S223229348Weckhuysen, B. M., & Yu, J. (2015). Recent advances in zeolite chemistry and catalysis. Chemical Society Reviews, 44(20), 7022-7024. doi:10.1039/c5cs90100fVerboekend, D., & Pérez-Ramírez, J. (2011). Design of hierarchical zeolite catalysts by desilication. Catalysis Science & Technology, 1(6), 879. doi:10.1039/c1cy00150gRutkowska, 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.2017.03.017Góra-Marek, K., Brylewska, K., Tarach, K. A., Rutkowska, M., Jabłońska, M., Choi, M., & Chmielarz, L. (2015). IR studies of Fe modified ZSM-5 zeolites of diverse mesopore topologies in the terms of their catalytic performance in NH3-SCR and NH3-SCO processes. Applied Catalysis B: Environmental, 179, 589-598. doi:10.1016/j.apcatb.2015.05.053Macina, D., Piwowarska, Z., Góra-Marek, K., Tarach, K., Rutkowska, M., Girman, V., … Chmielarz, L. (2016). SBA-15 loaded with iron by various methods as catalyst for DeNOx process. Materials Research Bulletin, 78, 72-82. doi:10.1016/j.materresbull.2016.02.026Rutkowska, M., Duda, M., Macina, D., Górecka, S., Dębek, R., Moreno, J. M., … Chmielarz, L. (2019). Mesoporous Beta zeolite functionalisation with FexCry oligocations; catalytic activity in the NH3SCO process. Microporous and Mesoporous Materials, 278, 1-13. doi:10.1016/j.micromeso.2018.11.003Miller, J. T., Glusker, E., Peddi, R., Zheng, T., & Regalbuto, J. R. (1998). Catalysis Letters, 51(1/2), 15-22. doi:10.1023/a:1019072631175Kowalczyk, A., Borcuch, A., Michalik, M., Rutkowska, M., Gil, B., Sojka, Z., … Chmielarz, L. (2017). MCM-41 modified with transition metals by template ion-exchange method as catalysts for selective catalytic oxidation of ammonia to dinitrogen. Microporous and Mesoporous Materials, 240, 9-21. doi:10.1016/j.micromeso.2016.11.002Chmielarz, L., & Jabłońska, M. (2015). Advances in selective catalytic oxidation of ammonia to dinitrogen: a review. RSC Advances, 5(54), 43408-43431. doi:10.1039/c5ra03218kThommes, 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-2014-1117Qi, G., & Yang, R. T. (2005). Selective catalytic oxidation (SCO) of ammonia to nitrogen over Fe/ZSM-5 catalysts. Applied Catalysis A: General, 287(1), 25-33. doi:10.1016/j.apcata.2005.03.00

Influence of iron aggregation on the catalytic performance of desilicated MFI in the DeNO(x) process

[EN] In the present study, an influence of the iron aggregation in conventional and micro-mesoporous MFI on their catalytic activity in the NO reduction with ammonia (DeNO(x) process) was studied. Modification of MFI zeolite properties was done by the desilication in the presence of NaOH and TPAOH (tertapropylammonium hydroxide). In the next step, the samples were modified with iron by ion-exchange with the use of a conventional solution of Fe cations (FeSO4) and a solution of iron triple-metallic aggregates (oligocations) ([Fe-3(OAc)(6)O(H2O)(3)](+)). Both of the applied modification techniques (desilication and modification with Fe-3 oligocations) increased the catalytic activity of the MFI zeolite in the DeNO(x) process. This increased catalytic activity was connected with changes in sample porosity, Si/Al ratio, topology, as well as aggregation and dispersion of iron species on the catalyst surface, which was investigated by N-2-sorption, XRD, ICP, NMR, HRTEM and UV-vis-DRS techniques.This work was carried out in the frame of project No. 0670/IP3/2016/74 from the Polish Ministry of Science and Higher Education in the years 2016-2019 and in the frame of project No. 2012/05/B/ST5/00269 from the National Science Centre (Poland). U. D. acknowledges to the Spanish Government by the funding (MAT2017-82288-C2-1-P).Rutkowska, M.; Borcuch, A.; Marzec, A.; Kowalczyk, A.; Samojeden, B.; Moreno, J.; Díaz Morales, UM.... (2020). Influence of iron aggregation on the catalytic performance of desilicated MFI in the DeNO(x) process. Microporous and Mesoporous Materials. 304:1-8. https://doi.org/10.1016/j.micromeso.2018.09.015S1830

Dicer and microRNAs protect adult dopamine neurons

MicroRNAs (miRs) are important post-transcriptional regulators of gene expression implicated in neuronal development, differentiation, aging and neurodegenerative diseases, including Parkinson's disease (PD). Several miRs have been linked to PD-associated genes, apoptosis and stress response pathways, suggesting that deregulation of miRs may contribute to the development of the neurodegenerative phenotype. Here, we investigate the cell-autonomous role of miR processing RNAse Dicer in the functional maintenance of adult dopamine (DA) neurons. We demonstrate a reduction of Dicer in the ventral midbrain and altered miR expression profiles in laser-microdissected DA neurons of aged mice. Using a mouse line expressing tamoxifen-inducible CreERT2 recombinase under control of the DA transporter promoter, we show that a tissue-specific conditional ablation of Dicer in DA neurons of adult mice led to decreased levels of striatal DA and its metabolites without a reduction in neuronal body numbers in hemizygous mice (Dicer(HET)) and to progressive loss of DA neurons with severe locomotor deficits in nullizygous mice (Dicer(CKO)). Moreover, we show that pharmacological stimulation of miR biosynthesis promoted survival of cultured DA neurons and reduced their vulnerability to thapsigargin-induced endoplasmic reticulum stress. Our data demonstrate that Dicer is crucial for maintenance of adult DA neurons, whereas a stimulation of miR production can promote neuronal survival, which may have direct implications for PD treatment.Peer reviewe

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

Thermal transformations of Cu–Mg (Zn)–Al(Fe) hydrotalcite-like materials into metal oxide systems and their catalytic activity in selective oxidation of ammonia to dinitrogen

Layered double hydroxides (LDHs) containing $Mg^{2+}$, $Cu^{2+}$ or $Zn^{2+}$ cations in the $Me^{II}$ positions and $Al^{3+}$ and $Fe^{3+}$ in the $Me^{III}$ positions were synthesized by co- precipitation method. Detailed studies of thermal trans- formation of obtained LDHs into metal oxide systems were performed using high temperature X-ray diffraction in oxidising and reducing atmosphere, thermogravimetry coupled with mass spectrometry and temperature-pro- grammed reduction. The LDH samples calcined at 600 and 900 $^{o}\textrm{C}$ were tested in the role of catalysts for selective oxidation of ammonia into nitrogen and water vapour. It was shown that all copper congaing samples presented high catalytic activity and additionally, for the Cu–Mg–Al and Cu–Mg–Fe hydrotalcite samples calcined at 600 $^{o}\textrm{C}$ rela- tively high stability and selectivity to dinitrogen was obtained. An increase in calcination temperature to 900 $^{o}\textrm{C}$ resulted in a decrease of their catalytic activity, possibly due to formation of well-crystallised metal oxide phase which are less catalytically active in the process of selective oxidation of ammonia

Vanadium oxide supported on porous clay heterostructure for the partial oxidation of hydrogen sulphide to sulfur

Vanadium oxide supported on porous clay heterostructures (PCH) catalysts have been synthesized, characterized and evaluated in the selective oxidation of H2S to elemental sulfur. The catalysts were characterized by XRD, adsorption-desorption of N-2 at -196 degrees C, diffuse reflectance UV-vis, H-2-TPR, Raman spectroscopy and XPS. The catalysts with higher vanadium content are more active and selective, exhibiting a H2S conversion close to 70% after 360h on stream with a high selectivity toward elemental sulfur and a low formation of undesired SO2. The catalysts with V2O5 crystallites have shown a higher activity and resistance to the deactivation. The analysis of the spent catalyst has revealed the formation of V4O9 crystals during the catalytic test, which has been reported as the active phase in the selective oxidation of the H2S. (C) 2015 Elsevier B.V. All rights reserved.The authors would like to thank the DGICYT in Spain (Projects CTQ2012-37925-C03-01, CTQ2012-37925-C03-03 and FEDER funds, and MAT2010-19837-C06-05) and project of Excellence of Junta de Andalucia (project P12-RNM-1565) for financial support. A. Natoli thanks to SECAT (Spain) for a grant.Soriano Rodríguez, MD.; Cecilia, JA.; Natoli, A.; Jimenez-Jimenez, J.; López Nieto, JM.; Rodriguez Castellon, E. (2015). Vanadium oxide supported on porous clay heterostructure for the partial oxidation of hydrogen sulphide to sulfur. Catalysis Today. 254:36-42. https://doi.org/10.1016/j.cattod.2014.12.022S364225