Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization

Autores
Piqueras, Cristian Martin; Costilla, Ignacio Oscar; Belelli, Patricia Gabriela; Castellani, Norberto Jorge; Damiani, Daniel Eduardo
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A set of Pd-γAl2O3 catalysts of different metallic particle sizes and modified with 2-chloro-butane was used for triglyceride hydrogenation. The experiments were carried out in single-phase conditions using propane as a supercritical solvent. A generalized criterion was used to determine the absence of mass-transfer limitations for both reactants inside the pore structure of the catalyst. FTIR spectra of CO on diverse catalysts showed different absorption bands and significant shifts to higher wavelengths of the CO species corresponding to on-top and bridge configurations. In order to test these results, theoretical studies using the density functional theory (DFT) were carried out for the FTIR of CO adsorption on two Pd ensembles, with or without charge deficiency and with Cl adsorbed on them. The results showed similar displacements of the band frequencies to those obtained experimentally, and demonstrate an enhancement of the CO adsorption energy of the on-top, isolated bridge and three-fold bridge CO species on electron deficient ensembles. Enhancement of the adsorption bond strength could promote the direct hydrogenation of the diunsaturated compound to complete saturated fatty acid chains. The decrease of the specific reaction rate (TOF) and the increase of the saturated fatty acids production, as well as a decrease of the monounsaturated and isomers content observed is in line with a possible modification of the electronic properties of the Pd particles. The influence of some planes of Pd clusters intervening on the direct hydrogenation is discussed. © 2008 Elsevier B.V. All rights reserved.
Fil: Piqueras, Cristian Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Costilla, Ignacio Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Damiani, Daniel Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Materia
Ftir
Hydrogenation
Palladium
Supercritical Propane
Triglyceride
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/62675
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/62675
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network_name_str CONICET Digital (CONICET)
spelling Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterizationPiqueras, Cristian MartinCostilla, Ignacio OscarBelelli, Patricia GabrielaCastellani, Norberto JorgeDamiani, Daniel EduardoFtirHydrogenationPalladiumSupercritical PropaneTriglyceridehttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2A set of Pd-γAl2O3 catalysts of different metallic particle sizes and modified with 2-chloro-butane was used for triglyceride hydrogenation. The experiments were carried out in single-phase conditions using propane as a supercritical solvent. A generalized criterion was used to determine the absence of mass-transfer limitations for both reactants inside the pore structure of the catalyst. FTIR spectra of CO on diverse catalysts showed different absorption bands and significant shifts to higher wavelengths of the CO species corresponding to on-top and bridge configurations. In order to test these results, theoretical studies using the density functional theory (DFT) were carried out for the FTIR of CO adsorption on two Pd ensembles, with or without charge deficiency and with Cl adsorbed on them. The results showed similar displacements of the band frequencies to those obtained experimentally, and demonstrate an enhancement of the CO adsorption energy of the on-top, isolated bridge and three-fold bridge CO species on electron deficient ensembles. Enhancement of the adsorption bond strength could promote the direct hydrogenation of the diunsaturated compound to complete saturated fatty acid chains. The decrease of the specific reaction rate (TOF) and the increase of the saturated fatty acids production, as well as a decrease of the monounsaturated and isomers content observed is in line with a possible modification of the electronic properties of the Pd particles. The influence of some planes of Pd clusters intervening on the direct hydrogenation is discussed. © 2008 Elsevier B.V. All rights reserved.Fil: Piqueras, Cristian Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Costilla, Ignacio Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Damiani, Daniel Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaElsevier Science2008-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/62675Piqueras, Cristian Martin; Costilla, Ignacio Oscar; Belelli, Patricia Gabriela; Castellani, Norberto Jorge; Damiani, Daniel Eduardo; Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization; Elsevier Science; Applied Catalysis A: General; 347; 1; 9-2008; 1-100926-860XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2008.05.029info:eu-repo/semantics/altIdentifier/url/https://linkinghub.elsevier.com/retrieve/pii/S0926860X0800344Xinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:25:11Zoai:ri.conicet.gov.ar:11336/62675instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-15 14:25:11.243CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
title Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
spellingShingle Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
Piqueras, Cristian Martin
Ftir
Hydrogenation
Palladium
Supercritical Propane
Triglyceride
title_short Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
title_full Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
title_fullStr Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
title_full_unstemmed Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
title_sort Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization
dc.creator.none.fl_str_mv Piqueras, Cristian Martin
Costilla, Ignacio Oscar
Belelli, Patricia Gabriela
Castellani, Norberto Jorge
Damiani, Daniel Eduardo
author Piqueras, Cristian Martin
author_facet Piqueras, Cristian Martin
Costilla, Ignacio Oscar
Belelli, Patricia Gabriela
Castellani, Norberto Jorge
Damiani, Daniel Eduardo
author_role author
author2 Costilla, Ignacio Oscar
Belelli, Patricia Gabriela
Castellani, Norberto Jorge
Damiani, Daniel Eduardo
author2_role author
author
author
author
dc.subject.none.fl_str_mv Ftir
Hydrogenation
Palladium
Supercritical Propane
Triglyceride
topic Ftir
Hydrogenation
Palladium
Supercritical Propane
Triglyceride
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv A set of Pd-γAl2O3 catalysts of different metallic particle sizes and modified with 2-chloro-butane was used for triglyceride hydrogenation. The experiments were carried out in single-phase conditions using propane as a supercritical solvent. A generalized criterion was used to determine the absence of mass-transfer limitations for both reactants inside the pore structure of the catalyst. FTIR spectra of CO on diverse catalysts showed different absorption bands and significant shifts to higher wavelengths of the CO species corresponding to on-top and bridge configurations. In order to test these results, theoretical studies using the density functional theory (DFT) were carried out for the FTIR of CO adsorption on two Pd ensembles, with or without charge deficiency and with Cl adsorbed on them. The results showed similar displacements of the band frequencies to those obtained experimentally, and demonstrate an enhancement of the CO adsorption energy of the on-top, isolated bridge and three-fold bridge CO species on electron deficient ensembles. Enhancement of the adsorption bond strength could promote the direct hydrogenation of the diunsaturated compound to complete saturated fatty acid chains. The decrease of the specific reaction rate (TOF) and the increase of the saturated fatty acids production, as well as a decrease of the monounsaturated and isomers content observed is in line with a possible modification of the electronic properties of the Pd particles. The influence of some planes of Pd clusters intervening on the direct hydrogenation is discussed. © 2008 Elsevier B.V. All rights reserved.
Fil: Piqueras, Cristian Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Costilla, Ignacio Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Castellani, Norberto Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Damiani, Daniel Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina
description A set of Pd-γAl2O3 catalysts of different metallic particle sizes and modified with 2-chloro-butane was used for triglyceride hydrogenation. The experiments were carried out in single-phase conditions using propane as a supercritical solvent. A generalized criterion was used to determine the absence of mass-transfer limitations for both reactants inside the pore structure of the catalyst. FTIR spectra of CO on diverse catalysts showed different absorption bands and significant shifts to higher wavelengths of the CO species corresponding to on-top and bridge configurations. In order to test these results, theoretical studies using the density functional theory (DFT) were carried out for the FTIR of CO adsorption on two Pd ensembles, with or without charge deficiency and with Cl adsorbed on them. The results showed similar displacements of the band frequencies to those obtained experimentally, and demonstrate an enhancement of the CO adsorption energy of the on-top, isolated bridge and three-fold bridge CO species on electron deficient ensembles. Enhancement of the adsorption bond strength could promote the direct hydrogenation of the diunsaturated compound to complete saturated fatty acid chains. The decrease of the specific reaction rate (TOF) and the increase of the saturated fatty acids production, as well as a decrease of the monounsaturated and isomers content observed is in line with a possible modification of the electronic properties of the Pd particles. The influence of some planes of Pd clusters intervening on the direct hydrogenation is discussed. © 2008 Elsevier B.V. All rights reserved.
publishDate 2008
dc.date.none.fl_str_mv 2008-09
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/62675
Piqueras, Cristian Martin; Costilla, Ignacio Oscar; Belelli, Patricia Gabriela; Castellani, Norberto Jorge; Damiani, Daniel Eduardo; Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization; Elsevier Science; Applied Catalysis A: General; 347; 1; 9-2008; 1-10
0926-860X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/62675
identifier_str_mv Piqueras, Cristian Martin; Costilla, Ignacio Oscar; Belelli, Patricia Gabriela; Castellani, Norberto Jorge; Damiani, Daniel Eduardo; Pd-γAl2O3 applied to triglycerides hydrogenation with supercritical propane. Experimental and theoretical catalysts characterization; Elsevier Science; Applied Catalysis A: General; 347; 1; 9-2008; 1-10
0926-860X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2008.05.029
info:eu-repo/semantics/altIdentifier/url/https://linkinghub.elsevier.com/retrieve/pii/S0926860X0800344X
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.891075

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