6 research outputs found

    N-Doped graphene as a metal-free catalyst for glucose oxidation to succinic acid

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    [EN] N-Containing graphenes obtained either by simultaneous amination and reduction of graphene oxide or by pyrolysis of chitosan under an inert atmosphere have been found to act as catalysts for the selective wet oxidation of glucose to succinic acid. Selectivity values over 60% at complete glucose conversion have been achieved by performing the reaction at 160 degrees C and 18 atm O-2 pressure for 20 h. This activity has been attributed to graphenic-type N atoms on graphene. The active N-containing graphene catalysts were used four times without observing a decrease in conversion and selectivity of the process. A mechanism having tartaric and fumaric acids as key intermediates is proposed.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, Grapas and CTQ2015-69153-CO2-R1) and Generalitat Valenciana (Prometeo 2013-014) is gratefully acknowledged. Prof. Simona M. Coman kindly acknowledges UEFISCDI for financial support (project PN-II-PT-PCCA-2013-4-1090, Nr. 44/2014). Cristina Bucur acknowledges Core Programme, Project PN-480103/2016.Rizescu, C.; Podolean, I.; Albero-Sancho, J.; Parvulescu, VI.; Coman, SM.; Bucur, C.; Puche Panadero, M.... (2017). N-Doped graphene as a metal-free catalyst for glucose oxidation to succinic acid. Green Chemistry. 19(8):1999-2005. https://doi.org/10.1039/C7GC00473GS19992005198Alonso, D. M., Wettstein, S. G., & Dumesic, J. A. (2012). Bimetallic catalysts for upgrading of biomass to fuels and chemicals. Chemical Society Reviews, 41(24), 8075. doi:10.1039/c2cs35188aCherubini, F. (2010). The biorefinery concept: Using biomass instead of oil for producing energy and chemicals. Energy Conversion and Management, 51(7), 1412-1421. doi:10.1016/j.enconman.2010.01.015Christensen, C. H., Rass-Hansen, J., Marsden, C. C., Taarning, E., & Egeblad, K. (2008). The Renewable Chemicals Industry. 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Chemical Reviews, 110(6), 3552-3599. doi:10.1021/cr900354uPodolean, I., Rizescu, C., Bala, C., Rotariu, L., Parvulescu, V. I., Coman, S. M., & Garcia, H. (2016). Unprecedented Catalytic Wet Oxidation of Glucose to Succinic Acid Induced by the Addition ofn-Butylamine to a RuIIICatalyst. ChemSusChem, 9(17), 2307-2311. doi:10.1002/cssc.201600474Huang, C., Li, C., & Shi, G. (2012). Graphene based catalysts. Energy & Environmental Science, 5(10), 8848. doi:10.1039/c2ee22238hNavalon, S., Dhakshinamoorthy, A., Alvaro, M., & Garcia, H. (2014). Carbocatalysis by Graphene-Based Materials. Chemical Reviews, 114(12), 6179-6212. doi:10.1021/cr4007347Su, D. S., Perathoner, S., & Centi, G. (2013). Nanocarbons for the Development of Advanced Catalysts. Chemical Reviews, 113(8), 5782-5816. doi:10.1021/cr300367dDhakshinamoorthy, A., Primo, A., Concepcion, P., Alvaro, M., & Garcia, H. (2013). 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Chemical Communications, 49(85), 9914. doi:10.1039/c3cc43401jYang, J.-H., Sun, G., Gao, Y., Zhao, H., Tang, P., Tan, J., … Ma, D. (2013). Direct catalytic oxidation of benzene to phenol over metal-free graphene-based catalyst. Energy & Environmental Science, 6(3), 793. doi:10.1039/c3ee23623dRocha, R. P., Gonçalves, A. G., Pastrana-Martínez, L. M., Bordoni, B. C., Soares, O. S. G. P., Órfão, J. J. M., … Pereira, M. F. R. (2015). Nitrogen-doped graphene-based materials for advanced oxidation processes. Catalysis Today, 249, 192-198. doi:10.1016/j.cattod.2014.10.046Wang, Y., Xie, Y., Sun, H., Xiao, J., Cao, H., & Wang, S. (2016). Efficient Catalytic Ozonation over Reduced Graphene Oxide for p-Hydroxylbenzoic Acid (PHBA) Destruction: Active Site and Mechanism. ACS Applied Materials & Interfaces, 8(15), 9710-9720. doi:10.1021/acsami.6b01175Duan, X., Su, C., Zhou, L., Sun, H., Suvorova, A., Odedairo, T., … Wang, S. (2016). 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The Journal of Physical Chemistry Letters, 8(1), 264-278. doi:10.1021/acs.jpclett.6b0199

    Engineering active sites on reduced graphene oxide by hydrogen plasma irradiation: mimicking bifunctional metal/supported catalysts in hydrogenation reactions

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    [EN] H2 plasma has been used to generate carbon vacancies on reduced graphene oxide to increase its catalytic activity as a hydrogenation catalyst. A relationship between the power of the plasma treatment and the exposure time with the activity of the material was observed for CvC double bond hydrogenation. The activity data in the case of 1-octene, showing skeletal isomerization besides hydrogenation, indicate that H2 plasma treatment can introduce hydrogenating and acid sites rendering a bifunctional catalyst that is reminiscent of the activity of noble metals supported on acid supports.Financial support from the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, CTQ2015-69563-CO2-R1 and Grapas) is gratefully acknowledged. AP thanks the Ministry for a Ramon y Cajal research associate contract. AFG thanks the Center of Supercomputing of Galicia (CESGA) for the computational facilities. MM acknowledges financial support from the PN 16 47 01 04 project. VIP kindly acknowledges UEFISCDI for financial support (project PN-III-P4-ID-PCE-2016-0146, No. 121/2017).Primo Arnau, AM.; Franconetti, A.; Magureanu, M.; Mandache, NB.; Bucur, C.; Rizescu, C.; Cojocaru, B.... (2018). Engineering active sites on reduced graphene oxide by hydrogen plasma irradiation: mimicking bifunctional metal/supported catalysts in hydrogenation reactions. Green Chemistry. 20(11):2611-2623. https://doi.org/10.1039/c7gc03397dS261126232011Grondal, C., Jeanty, M., & Enders, D. (2010). Organocatalytic cascade reactions as a new tool in total synthesis. Nature Chemistry, 2(3), 167-178. doi:10.1038/nchem.539Stephan, D. W., & Erker, G. (2009). Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More. Angewandte Chemie International Edition, 49(1), 46-76. doi:10.1002/anie.200903708Thomas, A., Fischer, A., Goettmann, F., Antonietti, M., Müller, J.-O., Schlögl, R., & Carlsson, J. M. (2008). 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    Catalytic Properties of 3D Graphene-Like Microporous Carbons Synthesized in a Zeolite Template

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    [EN] The inherent properties of a single atomic carbon layer in graphene offer opportunities for the creation of catalytically active centers tailored on a molecular level on a support with high thermal stability and very high specific surface area. We demonstrate that organization of the two-dimensional system of the carbon layer into three-dimensional (3D) graphene-like catalytic materials with the connectivity of a pore network providing good accessibility to the active centers allows the preparation of catalytic materials that exploit the properties of graphene. In this study, 3D graphene-like microporous carbons, denoted as)6 beta-carbon and Y-carbon, were synthesized by nanocasting of beta (*BEA) and faujasite (FAU) zeolite templates. Structural analyses show that the materials are characterized by 3D-assembled and highly stable single-atom graphene an open porous system resembling the regular channel system of the zeolites with a specific surface area comparable to the surface area of graphene. The materials effectively catalyze the hydrogenation of alkenes, alkynes, and cycloalkenes into the corresponding alkanes and cycloalkanes. The materials facilitate catalytic intramolecular rearrangements, including the selective isomerization of double bonds and branching of linear chains, as well as stereoselective isomerization of unsaturated hydrocarbons. layers that formThis work was supported by the Grant Agency of the Czech Republic under project No. 15-12113S. The authors acknowledge the assistance provided by the Research Infrastructures NanoEnviCz (Project No. LM2015073) and Pro-NanoEnviCz (Project No. CZ.02.1.01/0.0/0.0/16_013/0001821), supported by the Ministry of Education, Youth and Sports of the Czech Republic.Sazama, P.; Pastvova, J.; Rizescu, C.; Tirsoaga, A.; Parvulescu, VI.; GarcĂ­a GĂłmez, H.; Kobera, L.... (2018). Catalytic Properties of 3D Graphene-Like Microporous Carbons Synthesized in a Zeolite Template. ACS Catalysis. 8(3):1779-1789. https://doi.org/10.1021/acscatal.7b04086S177917898

    Engineering hydrogenation active sites on graphene oxide and N-doped graphene by plasma treatment

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    [EN] Graphene oxide (GO) and N-doped graphene [(N)G] graphenes were submitted to H-2 glow discharge under different discharge regimes, in both the negative glow and positive column plasma regions. The resulted catalysts were fully characterized using several techniques such as Raman, DRIFT and XPS spectroscopy, powder X-ray diffraction, H-2 pulse chemisorption and H-2-, CO2- and NH3-TPD experiments. Density functional theory calculations were performed taking a slab model of graphene sheet with an optimized C-C bond length (1.426 angstrom) and a 16 angstrom vacuum layer between sheets. An overview of these characterizations showed that the O/C atomic ratio of GO is influenced by the plasma regime, indicating the occurrence of O removal, as also predicted by DFT calculations. In the case of (N)G, the plasma treatment also removes pyridinic N with an increase of the C/N ratio. The efficiency of the plasma modification has been checked through catalytic tests in hydroisomerization of 1-octene and hydrogenation of alpha-methyl-styrene. Contrarily to classical thermal activation requiring high temperatures, the generation of the defects by treating with plasma occurs at voltages in the range of 2 5 kV. In consequence, the hydrogenation and isomerization of alkenes resulted with high yields and good selectivities. Graphene prepared from sodium alginate from brown algae was considered as reference in these investigations.This work was supported by the Romanian Ministry of Education and Research UEFISCDI (projects PN-III-P4-ID-PCE-2016-0146, nr. 121/2017, PN-III-P1-1.1-TE-2016-2191, nr. 89/2018 and 16N/2019) and by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-89237-CO2-R1). MM thanks Dr. F. Gherendi for the calibration of the OES system.Magureanu, M.; Mandache, NB.; Rizescu, C.; Bucur, C.; Cojocaru, B.; Man, IC.; Primo Arnau, AM.... (2021). Engineering hydrogenation active sites on graphene oxide and N-doped graphene by plasma treatment. Applied Catalysis B Environmental. 287:1-11. https://doi.org/10.1016/j.apcatb.2021.119962S11128

    Nanometer-thick films of antimony oxide nanoparticles grafted on defective graphenes as heterogeneous base catalysts for coupling reactions

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    [EN] Films of few-layers defective N-doped or undoped graphene (10-15 nm) containing antimony oxide nanoparticles (15-30 nm) have been prepared on quartz by pyrolysis of alginate or chitosan adsorbing Sb(OAc)(3). XPS shows that the prevalent Sb oxidation state is +III, while thermoprogrammed CO2 desorption shows that these films exhibit basic sites. These thin films have used as basic catalysts to promote the Michael addition of active methylene compounds and the Henry condensation. These results have been rationalized by DFT calculations that have shown that undercoordinated or two-fold coordinated oxygen atoms on SbOx clusters can act as basic sites, providing a wide range of basic strength. (c) 2020 Elsevier Inc. All rights reserved.This work was supported by UEFISCDI (PN-III-P4-ID-PCE-2016-0146, nr. 121/2017 and project number PN-III-P1-1.1-TE-2016-2191, nr. 89/2018) and by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-890237-CO2-1).Simion, A.; Candu, N.; Cojocaru, B.; Coman, SM.; Bucur, C.; Forneli Rubio, MA.; Primo Arnau, AM.... (2020). Nanometer-thick films of antimony oxide nanoparticles grafted on defective graphenes as heterogeneous base catalysts for coupling reactions. Journal of Catalysis. 390:135-149. https://doi.org/10.1016/j.jcat.2020.07.033S135149390Navalon, S., Dhakshinamoorthy, A., Alvaro, M., & Garcia, H. (2016). Metal nanoparticles supported on two-dimensional graphenes as heterogeneous catalysts. Coordination Chemistry Reviews, 312, 99-148. doi:10.1016/j.ccr.2015.12.005Blanita, G., & Lazar, M. D. (2013). Review of Graphene-Supported Metal Nanoparticles as New and Efficient Heterogeneous Catalysts. 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