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Ketonic decarboxylation reaction mechanism: A combined experimental and DFT study

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Ketonic decarboxylation reaction mechanism: A combined experimental and DFT study

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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
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