Spectroscopic Evidence and Density Functional Theory (DFT) Analysis of Low-Temperature Oxidation of Cu+ to Cu2+NOx in Cu-CHA Catalysts: Implications for the SCR-NOx Reaction Mechanism

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, 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/acscatal.8b04717."[EN] Despite the intense investigation on the NH3-SCR-NOx reaction mechanism catalyzed by small pore Cu-CHA zeolites, neither the rate-determining step of the process nor the exact nature of the active sites under reaction conditions are clearly established. In this work, in situ EPR and IR techniques combined with DFT calculations are applied to the study of the oxidation half-cycle of the NH3-SCR-NOx reaction on Cu-SSZ-13 and Cu-SAPO-34 catalysts. EPR and IR spectroscopies unambiguously show that Cu+ is oxidized to Cu2+ at room temperature in the presence of the reaction mixture (NO, O-2, and NH3) or NO and O-2, producing adsorbed NO2, nitrites, and nitrates. Several pathways are proposed from DFT calculations to oxidize Cu+ cations placed in the plane of the 6R ring units of SSZ-13 and SAPO-34 to Cu2+, either by NO2 alone or by a mixture of NO and O-2, with activation energy barriers lower than 70 kJ mol(-1). The results reported here demonstrate that a reaction mechanism invoking the formation of nitrate/nitrite intermediates on copper cations attached to the zeolite framework can be operational in the low-temperature region (T < 350 degrees C). Moreover, different intermediates, nitrites versus nitrates, are preferentially stabilized, depending on the catalyst composition, silicoaluminophosphate vs aluminosilicate.This work was supported by the Spanish Government through "Severo Ochoa Program" (Nos. SEV 2012-0267; SEV-2016-0683), No. MAT2015-71261-R, and No. CTQ2015-68951-C3-1-R, and by the European Union through No. ERC-AdG-2014-671093 (SynCatMatch). Red Espanola de Supercomputacion (RES) and Centre de Calcul de la Universitat de Valencia are gratefully acknowledged for computational resources and technical support. R.M. acknowledges "La Caixa-Severo Ochoa" International PhD Fellowships (call 2015).Moreno-González, M.; Millán-Cabrera, R.; Concepción Heydorn, P.; Blasco Lanzuela, T.; Boronat Zaragoza, M. (2019). Spectroscopic Evidence and Density Functional Theory (DFT) Analysis of Low-Temperature Oxidation of Cu+ to Cu2+NOx in Cu-CHA Catalysts: Implications for the SCR-NOx Reaction Mechanism. ACS Catalysis. 9(4):2725-2738. https://doi.org/10.1021/acscatal.8b04717S272527389

Study of propane oxidation on Cu-zeolite catalysts by in-situ EPR and IR spectroscopies

Three Cu-zeolites with different structure, Cu-TNU-9, Cu-ITQ-2 and Cu Y have been tested as catalysts for propane oxidation reaction. The activity follows the trend: Cu-TNU-9 > Cu-ITQ-2 > Cu Y, and in situ electron paramagnetic resonance (EPR) and infrared (IR) spectroscopies have been used to ascertain the origin of their different behavior. The IR spectra show bands ascribed to the formation of COO&#8722; and CHO adsorbed on the Cu-zeolites as reaction intermediates in the oxidation of propane with an intensity that follows the same tendency that their oxidation activity. The EPR spectra of the three Cu-zeolites show that about 40 50% of total copper is present as isolated Cu2+ species, and heating under propane or propane oxygen mixture at 350 °C provokes the reduction of Cu2+ to Cu+ following the same trend that the oxidation activity, i.e., Cu-TNU-9 > Cu-ITQ-2 > Cu Y. Further analysis of the EPR spectra suggests that the reducibility of exchanged Cu2+ cations in the Cu-zeolites is determined by their accessibility to the propane molecules.The authors acknowledge the financial support from the Spanish Ministry of Economy and Competitiveness through the Severo Ochoa program (SEV-2012-0267) as well as operating grants Consolider Ingenio Multicat (CSD-2009-00050) and MAT-20123856-0O2-01.Moreno González, M.; Blasco Lanzuela, T.; Góra-Marek, K.; Palomares Gimeno, AE.; Corma Canós, A. (2014). Study of propane oxidation on Cu-zeolite catalysts by in-situ EPR and IR spectroscopies. Catalysis Today. 227:123-129. https://doi.org/10.1016/j.cattod.2013.10.055S12312922

AgY zeolite as catalyst for the selective catalytic oxidation of NH3

[EN] Ag-exchanged Y zeolites (Si/Al = 2.5; Ag/Al = 0.30-0.95) have been tested in the NH3-SCO reaction, the most promising method for the elimination of ammonia emissions, and deeply characterized before and after reaction by using a variety of techniques (XRD, TEM, UV-Vis, Ag-109 NMR, XAS spectroscopies). The most active centres for the NH3-SCO reaction are Ag-0 nanoparticles (NPs) formed under reduction conditions and both activity and selectivity to N-2 increase with the silver loading. The Ag-0 NPs are dramatically modified under reaction conditions, being most of them dispersed resulting in small clusters and even atomically Ag+ cations, the latter accounting for around half silver atoms. The presence of water into the reaction feed promotes the dispersion and oxidation of silver nanoparticles, but the catalyst performance is only slightly affected. The results are fully consistent with the previously proposed i-SCR mechanism for NH3-SCO reaction on silver catalysts.Financial support by the Ministerio de Ciencia e Innovacion (MICINN) of Spain through the Severo Ochoa (SEV-2016-0683) , RTI2018-101784-B-I00, RTI2018-09639-A-I00 and InnovaXN-26-2019 projects is gratefully acknowledged. The authors also thank the Microscopy Service of the Universitat Politecnica de Valencia for its assistance in microscopy characterization (TEM and FESEM equipment preparation) . C. W. Lopes (Science without Borders Process no. 13191/13-6) thanks CAPES for a predoctoral fellowship and J. Martinez-Ortigosa (SEV-2012-0267-02) is grateful to Severo Ochoa Program for a predoctoral fellowship. The authors also want to thank the ALBA synchrotron and CL AE SS beamline staff for providing beamtime (proposal 2017092477) and for setting the beamline up to perform these studies.Martinez-Ortigosa, J.; Lopes, CW.; Agostini, G.; Palomares Gimeno, AE.; Blasco Lanzuela, T.; Rey Garcia, F. (2021). AgY zeolite as catalyst for the selective catalytic oxidation of NH3. Microporous and Mesoporous Materials. 323:1-14. https://doi.org/10.1016/j.micromeso.2021.111230S11432

Modeling of EPR Parameters for Cu(II): Application to the Selective Reduction of NOx Catalyzed by Cu-Zeolites

[EN] We present a combined theoretical-experimental study aiming to provide information about the location and coordination environment of the Cu2+ species involved in the selective reduction of NOx with NH3 catalyzed by Cu-zeolites. From the experimental side, we show and discuss the EPR spectra of the three molecular sieves most widely used as catalysts for the NH3-SCR-NOx reaction, namely Cu-SSZ-13, Cu-SAPO-34 and Cu-ZSM-5 both in their hydrated state and after dehydration. Then, we investigate the EPR spectra of Cu-SSZ-13 and Cu-SAPO-34 under the following conditions: (i) after NH3 adsorption, (ii) after NO addition, and (iii) in the presence of a NO/O-2 mixture. As regards the theoretical part, an exhaustive computational study has been performed that includes geometry optimization and calculation of the EPR parameters of all the relevant systems involved in the NH3-SCR-NOx reaction. The influence of local geometry and Al/Si distribution in the zeolite framework on the EPR parameters and the most probable location of Cu2+ in each material are analyzed, and assignations of the EPR signals obtained under different reaction conditions are discussed.This work has been supported by the Spanish Government through Severo Ochoa Program (SEV 2012-0267), MAT2015-71261-R and CTQ2015-68951-C3-1-R, and by the European Union through ERC-AdG-2014-671093 (SynCatMatch). Red Española de Supercomputación (RES) and Centre de Càlcul de la Universitat de Valencia are gratefully acknowledged for computational resources and technical support. E.F.V. thanks MINECO for her fellowship SVP-2013-068146.Fernández-Villanueva, E.; Moreno González, M.; Moliner Marin, M.; Blasco Lanzuela, T.; Boronat Zaragoza, M.; Corma Canós, A. (2018). Modeling of EPR Parameters for Cu(II): Application to the Selective Reduction of NOx Catalyzed by Cu-Zeolites. 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The role of promoters on the catalytic performance of MxV2O5 bronzes for the selective partial oxidation of H2S

[EN] Metal-containing vanadium oxide bronzes (MxV2O5; M= Cu, Ag and Ca) have been prepared, characterized (before and after reaction) by various physicochemical techniques, and tested in the partial oxidation of H2S. The catalysts were prepared hydrothermally at 175 ¿C (from gels containing M/V molar ratios of 0.17 or 0.33) and heat-treated at 500 ¿C/2 h in N2. The most effective catalysts, showing a sulfur selectivity greater than 95 % for a H2S conversion beyond 90 %, were those presenting vanadium oxide bronze (ß-Cu0.261V2O5 or Ag0.333V2O5) as the main crystalline phase. Cu- and Ag-containing vanadium oxide bronzes were stable under reaction conditions. For calcium containing materials (mainly presenting the Ca0.17V2O5 bronze phase), the formation of CaSO4 has been observed during the reaction, which resulted in a negative effect on both activity and selectivity. The nature of active and selective sites in this type of catalysts, as well as the role of promoters, are also discussed.The authors would like to acknowledge the Ministerio de Ciencia e Innovacion of Spain (TED2021-130756B-C31, TED2021-130756B-C32 and MAT2017-84118-C2-1-R projects) . Authors from ITQ also thank Project SEV-2016-0683 for supporting this research. A.A. acknowledges Severo Ochoa Excellence Program for his fellowship (BES-2017-080329) and Dr. Ferran Sabate from ITQ for his assistance with the EPR data treatment.Ruiz-Rodríguez, L.; De Arriba-Mateos, A.; Vidal Moya, JA.; Blasco Lanzuela, T.; Rodríguez-Castellón, E.; López Nieto, JM. (2022). The role of promoters on the catalytic performance of MxV2O5 bronzes for the selective partial oxidation of H2S. Applied Catalysis A General. 647:1-11. https://doi.org/10.1016/j.apcata.2022.11890011164

Host-Guest and Guest-Guest Interactions of P- and N-Containing Structure Directing Agents Entrapped inside MFI-Type Zeolite by Multinuclear NMR Spectroscopy

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpcc.9b05689".[EN] Highly crystalline pure silica MFI zeolites have been synthesized using tetraethylammonium (TEA), tetraethylphosphonium (TEP), or a mixture of both cations in different proportions as organic structure directing agents (OSDAs). The zeolites have been deeply characterized in order to get insight about the guest guest interactions involving the OSDAs and the guest host interactions involving the OSDAs and the inorganic framework, as well as the main features of the resulting materials. The results show that the average size of the MFI crystals decreases when TEP is present within the zeolite and that this cation is homogeneously distributed throughout the crystallites. The multinuclear NMR investigation (H-1, C-13, N-14, F-19, Si-29, P-31) indicates that TEP interacts with the zeolite host creating higher heterogeneity of the SiO4 crystallographic sites and a diminution on the mobility of fluorine atoms incorporated into the zeolite. Moreover, the presence of TEP influences the dynamics of the nitrogen atoms of the TEA molecules, and 2D heteronuclear correlation experiments give evidence on the spatial proximity of the TEA and TEP molecules in the MFI zeolites. Then, it is concluded that TEA and TEP are intimately mixed within the zeolite voids of the pure silica MFI samples synthesized by the dual template route.Financial support by the MINECO of Spain through the Severo Ochoa (SEV-2016-0683) and RTI2018-101784-B-I00 projects is gratefully acknowledged. The authors also thank the Microscopy Service of the Universitat Politecnica de Valencia for its assistance in microscopy characterization (FESEM equipment preparation). J.M.-O. (SEV-2012-0267-02) is grateful to the Severo Ochoa Program for a predoctoral fellowship.Martinez-Ortigosa, J.; Simancas-Coloma, J.; Vidal Moya, JA.; Gaveau, P.; Rey Garcia, F.; Alonso, B.; Blasco Lanzuela, T. (2019). Host-Guest and Guest-Guest Interactions of P- and N-Containing Structure Directing Agents Entrapped inside MFI-Type Zeolite by Multinuclear NMR Spectroscopy. The Journal of Physical Chemistry C. 123(36):22324-22334. https://doi.org/10.1021/acs.jpcc.9b05689S223242233412336Davis, M. E., & Lobo, R. F. (1992). Zeolite and molecular sieve synthesis. Chemistry of Materials, 4(4), 756-768. doi:10.1021/cm00022a005Cundy, C. S., & Cox, P. A. (2003). The Hydrothermal Synthesis of Zeolites:  History and Development from the Earliest Days to the Present Time. 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Partial oxidation of hydrogen sulphide to sulphur over vanadium oxides bronzes

[EN] Me-containing V2O5 materials (Me =Ag, Cu, Ca and Na) were prepared hydrothermally (from aqueous gels containing V2O5/H2O2/MeClx mixtures, with Me/V ratios of 0.17). The samples were finally heattreated in air or in N2 atmosphere. The heat-treated samples have been characterized by several physicochemical techniques and tested in the partial oxidation of hydrogen sulfide. According to XRD, electron paramagnetic resonance and 51V NMR results, Ag0.35V2O5 and Na0.33V2O5 (or NaV6O15) bronzes with a minority presence of V2O5 were mainly obtained in the case of Ag- and Na-containing materials in samples both heat-treated in air or in N2 atmosphere. In the case of Cu- and Ca-containing samples, V2O5 was mainly observed in samples calcined in air. However, Cu0.26V2O5 and Ca0.17V2O5 bronzes, with the minority presence of V2O5, have been observed in Cu- and Ca-containing samples heat-treated in N2. On the other hand, the catalytic behavior strongly depends on the metal promoter. Thus catalysts presenting vanadium oxide bronzes, i.e. samples presenting Ag0.35V2O5, NaV6O15, Cu0.26V2O5 or Ca0.17V2O5 shows a catalytic activity during the partial oxidation of H2S to sulfur higher than that observed over pure V2O5 or over promoted catalysts presenting mainly V2O5 (i.e. Cu- or Ca-containing samples calcined in air). Moreover, some differences in the selectivity to sulfur were observed. A higher formation of SO2 at high reaction temperature has been favored over Ag0.35V2O5-containing catalyst. This different behavior between samples could be explained by the presence of metallic Ag on the surface of Ag0.35V2O5, which was detected by XRD. Also, higher formation of SO2 is favored in the case of catalyst heat-treated in N2, in which the presence of VO2, as minority, could have a role in combustion of sulfur. Accordingly, this work should be considered as a first approach to relate catalytic activity of the Me-containing vanadium oxide bronze (containing Ag, Cu, Ca and Na) for the selective oxidation of hydrogen sulfide.The authors would like to thank the DGICYT in Spain (Projects CTQ2012-37925-0O3-01 and CTQ2012-37925-0O3-03) for financial support.Soriano Rodríguez, MD.; Vidal Moya, JA.; Rodriguez Castellon, E.; Melo Faus, FV.; Blasco Lanzuela, T.; López Nieto, JM. (2015). Partial oxidation of hydrogen sulphide to sulphur over vanadium oxides bronzes. Catalysis Today. 259:237-244. https://doi.org/10.1016/j.cattod.2015.08.009S23724425

Catalytic VOCs elimination over copper and cerium oxide modified mesoporous SBA-15 silica

[EN] Copper and cerium oxide bi-component materials with different Cu/Ce ratio were prepared using ordered SBA-15 silica as a support and compared with their bulk analogs. The samples were characterized by nitrogen physisorption, XRD, UV-Vis, FTIR, XPS, Raman spectroscopy and TPR with hydrogen. Cyclohexanol conversion was used as a catalytic test to obtain more information for the surface properties of the supported materials. The catalytic properties of the samples were studied in VOCs oxidation using toluene and ethyl acetate as probe molecules. A strong effect of mesoporous silica support and samples composition on the formation of catalytic sites was established. (C) 2012 Elsevier B.V. All rights reserved.Financial support of Bulgarian Academy of Science and National Scientific Fond of Ministry of Education Projects DTK 02/64 and ДНTC/Киtай 01/8, financial support from DGICYT in Spain (Project CTQ-2009-14495) and bilateral project Bulgarian-Spain Inter-academic Exchange Agreement (Project 2009BG0002) are acknowledged.Tsoncheva, T.; Issa, G.; Blasco Lanzuela, T.; Dimitrov, M.; Popova, M.; Hernández Morejudo, S.; Kovacheva, D.... (2013). Catalytic VOCs elimination over copper and cerium oxide modified mesoporous SBA-15 silica. Applied Catalysis A General. 453:1-12. https://doi.org/10.1016/j.apcata.2012.12.007S11245

Al2O3-Supported W-V-O bronzes catalysts for oxidative dehydrogenation of ethane

[EN] Supported vanadium-containing hexagonal tungsten bronzes (HTBs) were prepared for the first time using a combination of a new soft synthetic procedure and fine-tuned heat treatments. The characterization of heat-treated samples indicates that both unsupported and Al2O3-supported materials present mainly vanadium-containing crystals with HTB structure smaller in the supported materials. Raman, diffuse reflectance UV-visible and EPR spectroscopic results suggest the presence of different V species depending on the V loading and catalyst composition. When used as catalysts for ethane oxidative dehydrogenation (ODH), selected supported vanadium-HTBs show selectivity to ethylene as high as 80% at ethane conversion of around 18%. These values position these new materials among the most active and selective catalysts so far reported in the literature for ethane ODH over supported vanadium oxide catalysts.The authors acknowledge the DGICYT in Spain (projects RTI2018-099668-B-C21 and SEV-2016-0683) for financial support. The research group of Prof. Fabrizio Cavani (University of Bologna, Italy) and Consorzio INSTM (Firenze) are gratefully acknowledged for a PhD grant to A. C. The authors also thank the Electron Microscopy Service of Universitat Politecnica de Valencia for its support.Benomar, S.; Chieregato, A.; Masso, A.; Soriano Rodríguez, MD.; Vidal Moya, JA.; Blasco Lanzuela, T.; Issaadi, R.... (2020). Al2O3-Supported W-V-O bronzes catalysts for oxidative dehydrogenation of ethane. Catalysis Science & Technology. 10(23):8064-8076. https://doi.org/10.1039/d0cy01220cS806480761023GUO, J.-D., & WHITTINGHAM, M. S. (1993). TUNGSTEN OXIDES AND BRONZES: SYNTHESIS, DIFFUSION AND REACTIVITY. 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Use of Alkylarsonium Directing Agents for the Synthesis and Study of Zeolites

This is the peer reviewed version of the following article: Chem. Eur. J. 2019, 25, 16390 16396 , which has been published in final form at https://doi.org/10.1002/chem.201904043. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Expanding the previously known family of -onium (ammonium, phosphonium, and sulfonium) organic structure-directing agents (OSDAs) for the synthesis of zeolite MFI, a new member, the arsonium cation, is used for the first time. The new group of tetraalkylarsonium cations has allowed the synthesis of the zeolite ZSM-5 with several different chemical compositions, opening a route for the synthesis of zeolites with a new series of OSDA. Moreover, the use of As replacing N in the OSDA allows the introduction of probe atoms that facilitate the study of these molecules by powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (MAS NMR), and X-ray absorption spectroscopy (XAS). Finally, the influence of trivalent elements such as B, Al, or Ga isomorphically replacing Si atoms in the framework structure and its interaction with the As species has been studied. The suitability of the tetraalkylarsonium cation for carrying out the crystallization of zeolites is demonstrated along with the benefit of the presence of As atoms in the occluded OSDA, which allows its advanced characterization as well as the study of its evolution during OSDA removal by thermal treatments.Program Severo Ochoa SEV-2016-0683 and Maria de Maeztu MDM-2015-0538 are gratefully acknowledged. S.S-F. thanks MEC for his Severo Ochoa Grant SPV-2013-067884, P.O.-B. and G.M.E. thank MEC for his Ramon y Cajal contracts (RYC-2014-16620 and RYC-2013-14386). The authors thank the financial support by the Spanish Government (RTI2018-096399-A-I00, RTI2018-101784-B-I00 and CTQ2017-89528-P) and the Generalitat Valeciana (PROMETEO/2017/066). The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization. We gratefully acknowledge ESRF synchrotron for allocating beamtime (proposal CH-5193), the Italian CRG beam-line at ESRF (LISA-BM08), and Alessandro Puri for the help and technical support during our experiment. C.W.L. (Science without Frontiers-Process no. 13191/13-6) thanks CAPES for a predoctoral fellowship.Saez-Ferre, S.; Lopes, CW.; Simancas-Coloma, J.; Vidal Moya, JA.; Blasco Lanzuela, T.; Agostini, G.; Mínguez Espallargas, G.... (2019). Use of Alkylarsonium Directing Agents for the Synthesis and Study of Zeolites. Chemistry - A European Journal. 25(71):16390-16396. https://doi.org/10.1002/chem.201904043S16390163962571Sun, J., Bonneau, C., Cantín, Á., Corma, A., Díaz-Cabañas, M. J., Moliner, M., … Zou, X. (2009). The ITQ-37 mesoporous chiral zeolite. Nature, 458(7242), 1154-1157. doi:10.1038/nature07957Jiang, J., Yu, J., & Corma, A. (2010). 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