Mostrar el registro sencillo del ítem
dc.contributor.author | Pulido Junquera, Maria Angeles | es_ES |
dc.contributor.author | Oliver Tomás, Borja | es_ES |
dc.contributor.author | Renz, Michael | es_ES |
dc.contributor.author | Boronat Zaragoza, Mercedes | es_ES |
dc.contributor.author | Corma Canós, Avelino | es_ES |
dc.date.accessioned | 2016-03-07T13:24:33Z | |
dc.date.issued | 2013 | |
dc.identifier.issn | 1864-5631 | |
dc.identifier.uri | http://hdl.handle.net/10251/61529 | |
dc.description.abstract | The ketonic decarboxylation of carboxylic acids has been carried out experimentally and studied theoretically by DFT calculations. In the experiments, monoclinic zirconia was identified as a good catalyst, giving high activity and high selectivity when compared with other potential catalysts, such as silica, alumina, or ceria. It was also shown that it could be used for a wide range of substrates, namely, for carboxylic acids with two to eighteen carbon atoms. The reaction mechanism for the ketonic decarboxylation of acetic acid over monoclinic zirconia was investigated by using a periodic DFT slab model. A reaction pathway with the formation of a β-keto acid intermediate was considered, as well as a concerted mechanism, involving simultaneous carbon-carbon bond formation and carbon dioxide elimination. DFT results showed that the mechanism with the β-keto acid was the kinetically favored one and this was further supported by an experiment employing a mixture of isomeric (linear and branched) pentanoic acids. This way or that? Monoclinic zirconia has great potential as a catalyst for ketonic decarboxylation of carboxylic acids (see picture). A combined experimental and DFT study shows a route involving a β-keto acid intermediate as the kinetically preferred reaction pathway. | es_ES |
dc.description.sponsorship | We thank MINECO (MAT2011-28009, Consolider Ingenio 2010-MULTICAT, CSD2009-00050 and CTQ2011-27550) and the Spanish National Research Council (CSIC, Es 2010RU0108) for funding. Red Espanola de Supercomputacion (RES) and Centre de Calcul de la Universitat de Valencia are acknowledged for computational facilities and technical assistance. A. P. and B.O.-T. thank MINECO (Juan de la Cierva Programme) and CSIC (JAE Programme), respectively, for their fellowships. | en_EN |
dc.language | Inglés | es_ES |
dc.publisher | Wiley-VCH Verlag | es_ES |
dc.relation.ispartof | ChemSusChem | es_ES |
dc.rights | Reserva de todos los derechos | es_ES |
dc.subject | ab initio calculations | es_ES |
dc.subject | biomass | es_ES |
dc.subject | carboxylic acids | es_ES |
dc.subject | heterogeneous catalysis | es_ES |
dc.subject | ketones | es_ES |
dc.subject.classification | QUIMICA INORGANICA | es_ES |
dc.subject.classification | QUIMICA ORGANICA | es_ES |
dc.title | Ketonic decarboxylation reaction mechanism: A combined experimental and DFT study | es_ES |
dc.type | Artículo | es_ES |
dc.embargo.lift | 10000-01-01 | |
dc.embargo.terms | forever | es_ES |
dc.identifier.doi | 10.1002/cssc.201200419 | |
dc.relation.projectID | info:eu-repo/grantAgreement/MICINN//CSD2009-00050/ES/Desarrollo de catalizadores más eficientes para el diseño de procesos químicos sostenibles y produccion limpia de energia/ / | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/CSIC//2010RU0108/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MICINN//CTQ2011-27550/ES/TRANSFORMACION CATALITICA DE BIOMASA EN DIESEL Y EN PRODUCTOS QUIMICOS/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MINECO//MAT2011-28009/ES/CATALIZADORES MONO- Y MULTIFUNCIONALES BASADOS EN NANOPARTICULAS METALICAS DIRIGIDOS A TRANSFORMACIONES SECUENCIALES O REACCIONES EN CASCADA/ | es_ES |
dc.rights.accessRights | Cerrado | es_ES |
dc.contributor.affiliation | Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química | es_ES |
dc.contributor.affiliation | Universitat Politècnica de València. Departamento de Química - Departament de Química | es_ES |
dc.description.bibliographicCitation | Pulido Junquera, MA.; Oliver Tomás, B.; Renz, M.; Boronat Zaragoza, M.; Corma Canós, A. (2013). Ketonic decarboxylation reaction mechanism: A combined experimental and DFT study. ChemSusChem. 6(1):141-151. https://doi.org/10.1002/cssc.201200419 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | http://dx.doi.org/10.1002/cssc.201200419 | es_ES |
dc.description.upvformatpinicio | 141 | es_ES |
dc.description.upvformatpfin | 151 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 6 | es_ES |
dc.description.issue | 1 | es_ES |
dc.relation.senia | 257996 | es_ES |
dc.identifier.eissn | 1864-564X | |
dc.contributor.funder | Consejo Superior de Investigaciones Científicas | es_ES |
dc.contributor.funder | Ministerio de Economía y Competitividad | es_ES |
dc.description.references | Huber, G. W., Iborra, S., & Corma, A. (2006). Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering. Chemical Reviews, 106(9), 4044-4098. doi:10.1021/cr068360d | es_ES |
dc.description.references | Corma, A., Renz, M., & Schaverien, C. (2008). Coupling Fatty Acids by Ketonic Decarboxylation Using Solid Catalysts for the Direct Production of Diesel, Lubricants, and Chemicals. ChemSusChem, 1(8-9), 739-741. doi:10.1002/cssc.200800103 | es_ES |
dc.description.references | Alonso, D. M., Bond, J. Q., & Dumesic, J. A. (2010). Catalytic conversion of biomass to biofuels. Green Chemistry, 12(9), 1493. doi:10.1039/c004654j | es_ES |
dc.description.references | S. L. Malhotra R. W. Wong M. P. Breton Xerox Corporation 2002 | es_ES |
dc.description.references | A. D. Tomlinson Unilever PLC 2001 | es_ES |
dc.description.references | W. Seipel H. Hensen N. Boyxen Cognis Deutschland GmbH 2001 | es_ES |
dc.description.references | Friedel, C. (1858). Ueber s. g. gemischte Acetone. Annalen der Chemie und Pharmacie, 108(1), 122-125. doi:10.1002/jlac.18581080124 | es_ES |
dc.description.references | H. Froehlich M. Schneider W. Himmele M. Strohmeyer G. Sandrock K. Baer 1979 | es_ES |
dc.description.references | Neunhoeffer, O., & Paschke, P. (1939). Über den Mechanismus der Ketonbildung aus Carbonsäuren. Berichte der deutschen chemischen Gesellschaft (A and B Series), 72(4), 919-929. doi:10.1002/cber.19390720442 | es_ES |
dc.description.references | Bayer & Co 1911 | es_ES |
dc.description.references | C. A. Smith L. F. Theiling Jr. 1979 | es_ES |
dc.description.references | Rand, L., Wagner, W., Warner, P. O., & Kovac, L. R. (1962). Reactions Catalyzed by Potassium Fluoride. II. The Conversion of Adipic Acid to Cyclopentanone. The Journal of Organic Chemistry, 27(3), 1034-1035. doi:10.1021/jo01050a504 | es_ES |
dc.description.references | V. I. Yakerson A. M. Rubinshtein L. A. Gorskaya 1970 | es_ES |
dc.description.references | Renz, M. (2005). Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope. European Journal of Organic Chemistry, 2005(6), 979-988. doi:10.1002/ejoc.200400546 | es_ES |
dc.description.references | H. Lermer W. Hoelderich M. Schwarzmann 1986 | es_ES |
dc.description.references | Serrano-Ruiz, J. C., Wang, D., & Dumesic, J. A. (2010). Catalytic upgrading of levulinic acid to 5-nonanone. Green Chemistry, 12(4), 574. doi:10.1039/b923907c | es_ES |
dc.description.references | W. A. Beavers 2007 | es_ES |
dc.description.references | Gliński, M., Kijeński, J., & Jakubowski, A. (1995). Ketones from monocarboxylic acids: Catalytic ketonization over oxide systems. Applied Catalysis A: General, 128(2), 209-217. doi:10.1016/0926-860x(95)00082-8 | es_ES |
dc.description.references | A. Westfechtel C. Breucker B. Gutsche L. Jeromin H. Eierdanz H. Baumann K. H. Schmid W. Nonnenkamp 1993 | es_ES |
dc.description.references | Martinez, R. (2004). Ketonization of acetic acid on titania-functionalized silica monoliths. Journal of Catalysis, 222(2), 404-409. doi:10.1016/j.jcat.2003.12.002 | es_ES |
dc.description.references | Parida, K., & Mishra, H. K. (1999). Catalytic ketonisation of acetic acid over modified zirconia. Journal of Molecular Catalysis A: Chemical, 139(1), 73-80. doi:10.1016/s1381-1169(98)00184-8 | es_ES |
dc.description.references | Ignatchenko, A. V., & Kozliak, E. I. (2012). Distinguishing Enolic and Carbonyl Components in the Mechanism of Carboxylic Acid Ketonization on Monoclinic Zirconia. ACS Catalysis, 2(8), 1555-1562. doi:10.1021/cs3002989 | es_ES |
dc.description.references | Miller, A. L., Cook, N. C., & Whitmore, F. C. (1950). The Ketonic Decarboxylation Reaction1: The Ketonic Decarboxylation of Trimethylacetic Acid2and Isobutyric Acid. Journal of the American Chemical Society, 72(6), 2732-2735. doi:10.1021/ja01162a107 | es_ES |
dc.description.references | Sugiyama, S., Sato, K., Yamasaki, S., Kawashiro, K., & Hayashi, H. (1992). Ketones from carboxylic acids over supported magnesium oxide and related catalysts. Catalysis Letters, 14(1), 127-133. doi:10.1007/bf00764227 | es_ES |
dc.description.references | Pestman, R., Koster, R. M., van Duijne, A., Pieterse, J. A. Z., & Ponec, V. (1997). Reactions of Carboxylic Acids on Oxides. Journal of Catalysis, 168(2), 265-272. doi:10.1006/jcat.1997.1624 | es_ES |
dc.description.references | Cowan, D. M., Jeffery, G. H., & Vogel, A. I. (1940). 31. Physical properties and chemical constitution. Part V. Alkyl ketones. Journal of the Chemical Society (Resumed), 171. doi:10.1039/jr9400000171 | es_ES |
dc.description.references | G. P. Hussmann 1988 | es_ES |
dc.description.references | Müller-Erlwein, E., & Rosenberger, F. B. (1990). Heterogen katalysierte Ketonisierung von Laurin- und Stearinsäure in der Gasphase. Chemie Ingenieur Technik, 62(6), 512-513. doi:10.1002/cite.330620621 | es_ES |
dc.description.references | F. Wattimena 1983 | es_ES |
dc.description.references | Rajadurai, S. (1994). Pathways for Carboxylic Acid Decomposition on Transition Metal Oxides. Catalysis Reviews, 36(3), 385-403. doi:10.1080/01614949408009466 | es_ES |
dc.description.references | Cressely, J., Farkhani, D., Deluzarche, A., & Kiennemann, A. (1984). Evolution des especes carboxylates dans le cadre des syntheses CO-H2. Reduction de l’acide acetique sur systeme Co, Cu, Fe. Materials Chemistry and Physics, 11(5), 413-431. doi:10.1016/0254-0584(84)90065-8 | es_ES |
dc.description.references | KURIACOSE, J. (1977). Studies on the surface interaction of acetic acid on iron oxide. Journal of Catalysis, 50(2), 330-341. doi:10.1016/0021-9517(77)90042-2 | es_ES |
dc.description.references | LORENZELLI, V. (1980). Infrared study of the surface reactivity of hematite. Journal of Catalysis, 66(1), 28-35. doi:10.1016/0021-9517(80)90004-4 | es_ES |
dc.description.references | Müller-Erlwein, E. (1990). Heterogen katalysierte Ketonisierung von Laurin- und Stearinsäure in Flüssigphase. Chemie Ingenieur Technik, 62(5), 416-417. doi:10.1002/cite.330620518 | es_ES |
dc.description.references | Gooßen, L. J., Mamone, P., & Oppel, C. (2010). Catalytic Decarboxylative Cross-Ketonisation of Aryl- and Alkylcarboxylic Acids using Magnetite Nanoparticles. Advanced Synthesis & Catalysis, 353(1), 57-63. doi:10.1002/adsc.201000429 | es_ES |
dc.description.references | Hites, R. A., & Biemann, K. (1972). Mechanism of ketonic decarboxylation. Pyrolysis of calcium decanoate. Journal of the American Chemical Society, 94(16), 5772-5777. doi:10.1021/ja00771a039 | es_ES |
dc.description.references | Ignatchenko, A., Nealon, D. G., Dushane, R., & Humphries, K. (2006). Interaction of water with titania and zirconia surfaces. Journal of Molecular Catalysis A: Chemical, 256(1-2), 57-74. doi:10.1016/j.molcata.2006.04.031 | es_ES |
dc.description.references | Ignatchenko, A. V. (2011). Density Functional Theory Study of Carboxylic Acids Adsorption and Enolization on Monoclinic Zirconia Surfaces. The Journal of Physical Chemistry C, 115(32), 16012-16018. doi:10.1021/jp203381h | es_ES |
dc.description.references | Korhonen, S. T., Calatayud, M., & Krause, A. O. I. (2008). Stability of Hydroxylated (1̄11) and (1̄01) Surfaces of Monoclinic Zirconia: A Combined Study by DFT and Infrared Spectroscopy. The Journal of Physical Chemistry C, 112(16), 6469-6476. doi:10.1021/jp8008546 | es_ES |
dc.description.references | SERRANORUIZ, J., LUETTICH, J., SEPULVEDAESCRIBANO, A., & RODRIGUEZREINOSO, F. (2006). Effect of the support composition on the vapor-phase hydrogenation of crotonaldehyde over Pt/CexZr1−xO2 catalysts. Journal of Catalysis, 241(1), 45-55. doi:10.1016/j.jcat.2006.04.006 | es_ES |
dc.description.references | Murnaghan, F. D. (1944). The Compressibility of Media under Extreme Pressures. Proceedings of the National Academy of Sciences, 30(9), 244-247. doi:10.1073/pnas.30.9.244 | es_ES |
dc.description.references | Birch, F. (1947). Finite Elastic Strain of Cubic Crystals. Physical Review, 71(11), 809-824. doi:10.1103/physrev.71.809 | es_ES |
dc.description.references | Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set. Physical Review B, 54(16), 11169-11186. doi:10.1103/physrevb.54.11169 | es_ES |
dc.description.references | Perdew, J. P., & Wang, Y. (1992). Accurate and simple analytic representation of the electron-gas correlation energy. Physical Review B, 45(23), 13244-13249. doi:10.1103/physrevb.45.13244 | es_ES |
dc.description.references | Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J., & Fiolhais, C. (1992). Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Physical Review B, 46(11), 6671-6687. doi:10.1103/physrevb.46.6671 | es_ES |
dc.description.references | Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24), 17953-17979. doi:10.1103/physrevb.50.17953 | es_ES |
dc.description.references | Kresse, G., & Joubert, D. (1999). From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 59(3), 1758-1775. doi:10.1103/physrevb.59.1758 | es_ES |
dc.description.references | Christensen, A., & Carter, E. A. (1998). First-principles study of the surfaces of zirconia. Physical Review B, 58(12), 8050-8064. doi:10.1103/physrevb.58.8050 | es_ES |
dc.description.references | Henkelman, G., & Jónsson, H. (1999). A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. The Journal of Chemical Physics, 111(15), 7010-7022. doi:10.1063/1.480097 | es_ES |
dc.description.references | Henkelman, G., & Jónsson, H. (2000). Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. The Journal of Chemical Physics, 113(22), 9978-9985. doi:10.1063/1.1323224 | es_ES |
dc.description.references | Grimme, S., Antony, J., Ehrlich, S., & Krieg, H. (2010). A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. The Journal of Chemical Physics, 132(15), 154104. doi:10.1063/1.3382344 | es_ES |
dc.description.references | http://toc.uni-muenster.de/DFTD3/ | es_ES |
dc.description.references | Barteau, M. A. (1996). Organic Reactions at Well-Defined Oxide Surfaces. Chemical Reviews, 96(4), 1413-1430. doi:10.1021/cr950222t | es_ES |