Influence of co-catalysts on the photocatalytic activity of MIL-125(Ti)-NH2 in the overall water splitting

[EN] Titanium containing aminoterephthalate metal organic framework promotes the photocatalytic overall water splitting into H-2 and O-2 at a rate that depends on the presence of Pt, RuOx and CoOx co-catalyst. The best values of have been obtained for the MIL-125-NH2 material that contains Pt and RuOx, reaching a production of 218 and 85 mu mol/g (-1)(photocataly)(st) at 24 h for H-2 and O-2, respectively.Financial support by the Spanish Ministry of Economy and Competitiveness [Severo Ochoa and CTQ2015-69163-CO2-R1] and Generalitat Valenciana [Prometeo 2017-083] is gratefully acknowledged. S.R.-B. also thanks the Research Executive Agency (REA) and the European Commission, for the funding received under the Marie Sklodowska-Curie actions [H2020-MSCA-IF-2015/ Grant agreement number 709023/ ZESMO]. S.N. thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016). The authors also wish to acknowledge the support provided by the Electron Microscopy Service facility at Universitat Politecnica de Valencia.Remiro-Buenamañana, S.; Cabrero-Antonino, M.; Martínez-Guanter, M.; Alvaro Rodríguez, MM.; Navalón Oltra, S.; García Gómez, H. (2019). Influence of co-catalysts on the photocatalytic activity of MIL-125(Ti)-NH2 in the overall water splitting. Applied Catalysis B Environmental. 254:677-684. https://doi.org/10.1016/j.apcatb.2019.05.027S67768425

Subphthalocyanine encapsulated within MIL-101(Cr)-NH2 as a solar light photoredox catalyst for dehalogenation of alpha-haloacetophenones

[EN] Subphthalocyanine has been incorporated into a robust metal-organic framework having amino groups as binding sites. The resulting SubPc@MIL-101(Cr)-NH2 composite has a loading of 2 wt%. Adsorption of subphthalocyanine does not deteriorate host crystallinity, but decreases the surface area and porosity of MIL-101(Cr)-NH2. The resulting SubPc@MIL-101(Cr)-NH2 composite exhibits a 575 nm absorption band responsible for the observed photoredox catalytic activity under simulated sunlight irradiation for hydrogenative dehalogenation of alpha-haloacetophenones and for the coupling of alpha-bromoacetophenone and styrene. The material undergoes a slight deactivation upon reuse. In comparison to the case of phthalocyanines the present study is one of the few cases showing the use of subphthalocyanine as a photoredox catalyst, with its activity derived from site isolation within the MOF cavities.Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and RTI2018-098237-B-C21) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged. S. N. is thankful for the financial support from the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), the Ministerio de Ciencia, Innovacion y Universidades RTI 2018-099482-A-I00 project and the Generalitat Valenciana grupos de investigacion consolidables 2019 (ref: AICO/2019/214) project. S. R.-B. also thanks the Research Executive Agency (REA) and the European Commission for the funding received under the Marie Sklodowska Curie actions (H2020-MSCA-IF-2015/Grant agreement number 709023/ZESMO).Santiago-Portillo, A.; Remiro-Buenamañana, S.; Navalón Oltra, S.; García Gómez, H. (2019). Subphthalocyanine encapsulated within MIL-101(Cr)-NH2 as a solar light photoredox catalyst for dehalogenation of alpha-haloacetophenones. Dalton Transactions. 48(48):17735-17740. https://doi.org/10.1039/c9dt04004hS17735177404848Deng, X., Li, Z., & García, H. (2017). Visible Light Induced Organic Transformations Using Metal-Organic-Frameworks (MOFs). Chemistry - A European Journal, 23(47), 11189-11209. doi:10.1002/chem.201701460Dhakshinamoorthy, A., Asiri, A. M., & García, H. (2016). Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production. Angewandte Chemie International Edition, 55(18), 5414-5445. doi:10.1002/anie.201505581Shen, L., Liang, R., & Wu, L. (2015). Strategies for engineering metal-organic frameworks as efficient photocatalysts. Chinese Journal of Catalysis, 36(12), 2071-2088. doi:10.1016/s1872-2067(15)60984-6Shi, Y., Yang, A.-F., Cao, C.-S., & Zhao, B. (2019). Applications of MOFs: Recent advances in photocatalytic hydrogen production from water. Coordination Chemistry Reviews, 390, 50-75. doi:10.1016/j.ccr.2019.03.012Wang, S., & Wang, X. (2015). Multifunctional Metal-Organic Frameworks for Photocatalysis. Small, 11(26), 3097-3112. doi:10.1002/smll.201500084Wen, M., Mori, K., Kuwahara, Y., An, T., & Yamashita, H. (2018). Design of Single-Site Photocatalysts by Using Metal-Organic Frameworks as a Matrix. Chemistry - An Asian Journal, 13(14), 1767-1779. doi:10.1002/asia.201800444Das, S., & Wan Daud, W. M. A. (2014). RETRACTED: Photocatalytic CO2 transformation into fuel: A review on advances in photocatalyst and photoreactor. Renewable and Sustainable Energy Reviews, 39, 765-805. doi:10.1016/j.rser.2014.07.046Claessens, C. G., González-Rodríguez, D., & Torres, T. (2002). Subphthalocyanines:  Singular Nonplanar Aromatic CompoundsSynthesis, Reactivity, and Physical Properties. Chemical Reviews, 102(3), 835-854. doi:10.1021/cr0101454N. Kobayashi , in The Porphyrin Handbook , ed. K. M. Kadish , K. M. Smith and R. Guilard , Academic Press , Amsterdam , 2003 , pp. 161–262Santiago-Portillo, A., Baldoví, H. G., Carbonell, E., Navalón, S., Álvaro, M., García, H., & Ferrer, B. (2018). Ruthenium(II) Tris(2,2′-bipyridyl) Complex Incorporated in UiO-67 as Photoredox Catalyst. The Journal of Physical Chemistry C, 122(51), 29190-29199. doi:10.1021/acs.jpcc.8b07204Ferey, G. (2005). A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. Science, 309(5743), 2040-2042. doi:10.1126/science.1116275Santiago-Portillo, A., Blandez, J. F., Navalón, S., Álvaro, M., & García, H. (2017). Influence of the organic linker substituent on the catalytic activity of MIL-101(Cr) for the oxidative coupling of benzylamines to imines. Catalysis Science & Technology, 7(6), 1351-1362. doi:10.1039/c6cy02577cSantiago-Portillo, A., Navalón, S., Concepción, P., Álvaro, M., & García, H. (2017). Influence of Terephthalic Acid Substituents on the Catalytic Activity of MIL-101(Cr) in Three Lewis Acid Catalyzed Reactions. ChemCatChem, 9(13), 2506-2511. doi:10.1002/cctc.201700236Claessens, C. G., González-Rodríguez, D., Rodríguez-Morgade, M. S., Medina, A., & Torres, T. (2013). Subphthalocyanines, Subporphyrazines, and Subporphyrins: Singular Nonplanar Aromatic Systems. Chemical Reviews, 114(4), 2192-2277. doi:10.1021/cr400088wGuilleme, J., Martínez-Fernández, L., González-Rodríguez, D., Corral, I., Yáñez, M., & Torres, T. (2014). An Insight into the Mechanism of the Axial Ligand Exchange Reaction in Boron Subphthalocyanine Macrocycles. Journal of the American Chemical Society, 136(40), 14289-14298. doi:10.1021/ja508181bManaga, M., Mack, J., Gonzalez-Lucas, D., Remiro-Buenamañana, S., Tshangana, C., Cammidge, A. N., & Nyokong, T. (2016). Photophysical properties of tetraphenylporphyrinsubphthalocyanine conjugates. Journal of Porphyrins and Phthalocyanines, 20(01n04), 1-20. doi:10.1142/s1088424615500959Bressan, G., Cammidge, A. N., Jones, G. A., Heisler, I. A., Gonzalez-Lucas, D., Remiro-Buenamañana, S., & Meech, S. R. (2019). Electronic Energy Transfer in a Subphthalocyanine–Zn Porphyrin Dimer Studied by Linear and Nonlinear Ultrafast Spectroscopy. The Journal of Physical Chemistry A, 123(27), 5724-5733. doi:10.1021/acs.jpca.9b04398Morse, G. E., & Bender, T. P. (2012). Boron Subphthalocyanines as Organic Electronic Materials. ACS Applied Materials & Interfaces, 4(10), 5055-5068. doi:10.1021/am3015197Sampson, K. 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Single-step hydrogen production from NH3, CH4, and biogas in stacked proton ceramic reactors

Proton ceramic reactors offer efficient extraction of hydrogen from ammonia, methane, and biogas by coupling endothermic reforming reactions with heat from electrochemical gas separation and compression. Preserving this efficiency in scale-up from cell to stack level poses challenges to the distribution of heat and gas flows and electric current throughout a robust functional design. Here, we demonstrate a 36-cell well-balanced reactor stack enabled by a new interconnect that achieves complete conversion of methane with more than 99% recovery to pressurized hydrogen, leaving a concentrated stream of carbon dioxide. Comparable cell performance was also achieved with ammonia, and the operation was confirmed at pressures exceeding 140 bars. The stacking of proton ceramic reactors into practical thermo-electrochemical devices demonstrates their potential in efficient hydrogen production.This work was supported by Norway’s Ministry of Petroleum and Energy through the Gassnova project CLIMIT grant 618191 in partnership with Engie SA, Equinor, ExxonMobil, Saudi Aramco, Shell, and TotalEnergies and the Research Council of Norway NANO2021 project DynaPro grant 296548

A π-Extended Donor-Acceptor-Donor Triphenylene Twin linked via a Pyrazine-bridge

Beta-amino triphenylenes can be accessed via palladium catalyzed amination of the corresponding triflate using benzophe-none imine. Transformation of amine 6 to benzoyl amide 18 is also straightforward and its wide mesophase range demon-strates that the new linkage supports columnar liquid crystal formation. Amine 6 also undergoes clean aerobic oxidation to give a new twinned structure linked through an electron-poor pyrazine ring. The new discotic liquid crystal motif contains donor and acceptor fragments, and is more oval in shape rather than disk-like. It forms a wide range columnar mesophase. Absorption spectra are strong and broad; emission is also broad and occurs with a Stokes shift of ca. 0.7 eV, indicative of charge-transfer characte

Design of cost-efficient and photocatalytically active Zn-based MOFs decorated with Cu2O nanoparticles for CO2 methanation

Here we show for the first time a MOF that is photocatalytically active for light-assisted CO2 methanation under mild conditions (215 °C) without the inclusion of metallic nanoparticles or any sacrificial agent. The presence of Cu2O nanoparticles causes a 50% increase in the photocatalytic activity. This result paves the way for developing efficient and cost-effective materials for CO2 elimination

Expanding the photoresponse of multidimensional hybrid lead bromide perovskites into the visible region by incorporation of subphthalocyanine

This work explores a new methodology to adsorb a subphthalocyanine molecule (SubPc) on a hybrid lead bromide perovskite crystal structure with the aim of extending its photoresponse into the visible region. This process consists in the preparation of multidimensional 2D-3D perovskites. The use of large organic cations allows the possibility to insert guest molecules in the crystal structure of the perovskite. In this work, layered and 3D materials are obtained modifying the ratio of the organic cations (A/R) in the perovskite structure (RNH3)2An-1BnX3n+1. The present results show that incorporation of metal-free subphthalocyanine in the interlayer space provided by the 2D phase is a valid procedure to enhance the photoresponse of the perovskite solar cells.We thank the microscopy service at Universitat Politècnica de València (UPV) for the support. S. R.-B. also thanks the Research Executive Agency (REA) and the European Commission for the funding received under the Marie Skłodowska Curie actions (H2020-MSCA-IF-2015/grant agreement number 709023/ZESMO). R. G. A. acknowledges the FPI scholarship from MINECO MAT2015-69669-P. P. A. acknowledges the financial support from the Spanish Government through ‘Severo Ochoa” (SEV-2016-0683, MINECO) and PGC2018-099744-B-I00 (MCIU/AEI/FEDER).Peer reviewe

Intensification of catalytic CO2 methanation mediated by in-situ water removal through a high-temperature polymeric thin-film composite membrane

Catalytic CO methanation technology can be improved by process intensification, i.e. enabling higher energy efficiency and process sustainability. Here, thin-film composite membranes (TFCM) were developed for in-situ water removal in a catalytic membrane reactor (CMR) for the Sabatier process. The selective separation layer (1.4 μm-thick) of the composite membrane is made of the polyimide 6FDA-6FpDA, a glassy polyimide, which exhibits high permeability and selectivity together with stable function at unprecedented high temperatures (>200 °C), compared to polyimides reported until now (90 °C), thus matching the temperature range of Sabatier reactors. Remarkably, TFCM developed in this work, allow to extract an outstanding amount of water up to 1 m/(m·h·bar) at 260 °C. TFCM was implemented for the water removal from the methanation reaction in a CMR operated at 260 °C and using Ni-Todorokite as catalyst. The TFCM-mediated water-extraction enabled to raise both catalytic stability and activity during CMR operation. CO conversion stability was greatly improved exhibiting a conversion value of 72 % during the course of the reaction (21 % increase in CO conversion), with a water removal of 12.5 % and specific flux of ∼100 g·h m.This work was financially supported by the Spanish Government (SVP-2014-068356, SVP-2014-068713, RTI2018-102161 and IJCI-2016-28330 grants) and Generalitat Valenciana (PROMETEO/2018/006 grant).Peer reviewe

Design of Cost-Efficient and Photocatalytically Active Zn-Based MOFs Decorated with Cu2O Nanoparticles for CO2 Methanation

Here we show for the first time a MOF that is photocatalyticallyactive for the light-assisted CO2 methanation at mild conditions(215 °C) without the inclusion of metallic nanoparticles or anysacrificial agent. The presence of Cu2O nanoparticles causes a 50 % increase in the photocatalytic activity. These results pave the way to developping efficient and cost-effective materials for CO2 elimination.</div