Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site

Autores
Ferretti, Cristián Alejandro; Fuente, Silvia Andrea; Ferullo, Ricardo; Castellani, Norberto Jorge; Apesteguia, Carlos Rodolfo; Di Cosimo, Juana Isabel
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The synthesis of monoglycerides by glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), was efficiently promoted on strongly basic MgO. The chemical nature of the base sites responsible for the catalytic activity was investigated, both experimentally and by density functional theory (DFT). MgO catalysts stabilized at different temperatures were used to control the distribution of surface base sites. The nature, density and strength of the catalyst base sites were characterized by TPD and FTIR of CO2. Catalytic results suggested that the synthesis of monoglycerides was promoted mainly on strongly basic low coordination (O2−) surface sites. The molecular modeling of glycerol (Gly) and FAME adsorptions was carried out using terrace, edge and corner sites for representing the MgO surface. Results indicated that Gly was more strongly adsorbed than FAME. Dissociative chemisorption of Gly with O-H bond breaking was favored on low coordination (O2−) surface sites such as those on edges, in agreement with the experimental results. Thus, the proton abstraction from the OH groups of Gly, a necessary step in the reaction mechanism, would take place on unsaturated oxygen anions and the resulting glyceroxides would react with weakly adsorbed FAME molecules.
Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Fuente, Silvia Andrea. Universidad Nacional del Sur. Departamento de Física; Argentina. 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: Ferullo, Ricardo. Universidad Nacional del Sur. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química 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. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Materia
GLYCEROL
MONOGLYCERIDE
DFT
BASE CATALYSIS
GLYCEROLYSIS
FATTY ACID METHYL ESTER
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:11336/271730
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/271730
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active siteFerretti, Cristián AlejandroFuente, Silvia AndreaFerullo, RicardoCastellani, Norberto JorgeApesteguia, Carlos RodolfoDi Cosimo, Juana IsabelGLYCEROLMONOGLYCERIDEDFTBASE CATALYSISGLYCEROLYSISFATTY ACID METHYL ESTERhttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The synthesis of monoglycerides by glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), was efficiently promoted on strongly basic MgO. The chemical nature of the base sites responsible for the catalytic activity was investigated, both experimentally and by density functional theory (DFT). MgO catalysts stabilized at different temperatures were used to control the distribution of surface base sites. The nature, density and strength of the catalyst base sites were characterized by TPD and FTIR of CO2. Catalytic results suggested that the synthesis of monoglycerides was promoted mainly on strongly basic low coordination (O2−) surface sites. The molecular modeling of glycerol (Gly) and FAME adsorptions was carried out using terrace, edge and corner sites for representing the MgO surface. Results indicated that Gly was more strongly adsorbed than FAME. Dissociative chemisorption of Gly with O-H bond breaking was favored on low coordination (O2−) surface sites such as those on edges, in agreement with the experimental results. Thus, the proton abstraction from the OH groups of Gly, a necessary step in the reaction mechanism, would take place on unsaturated oxygen anions and the resulting glyceroxides would react with weakly adsorbed FAME molecules.Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Fuente, Silvia Andrea. Universidad Nacional del Sur. Departamento de Física; Argentina. 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: Ferullo, Ricardo. Universidad Nacional del Sur. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química 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; Argentina. Universidad Nacional del Sur. Departamento de Física; ArgentinaFil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaElsevier Science2012-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/271730Ferretti, Cristián Alejandro; Fuente, Silvia Andrea; Ferullo, Ricardo; Castellani, Norberto Jorge; Apesteguia, Carlos Rodolfo; et al.; Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site; Elsevier Science; Applied Catalysis A: General; 413-414; 1-2012; 322-3310926-860XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0926860X1100696Xinfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2011.11.025info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:06:03Zoai:ri.conicet.gov.ar:11336/271730instacron: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 15:06:03.954CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
title Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
spellingShingle Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
Ferretti, Cristián Alejandro
GLYCEROL
MONOGLYCERIDE
DFT
BASE CATALYSIS
GLYCEROLYSIS
FATTY ACID METHYL ESTER
title_short Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
title_full Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
title_fullStr Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
title_full_unstemmed Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
title_sort Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site
dc.creator.none.fl_str_mv Ferretti, Cristián Alejandro
Fuente, Silvia Andrea
Ferullo, Ricardo
Castellani, Norberto Jorge
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author Ferretti, Cristián Alejandro
author_facet Ferretti, Cristián Alejandro
Fuente, Silvia Andrea
Ferullo, Ricardo
Castellani, Norberto Jorge
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author_role author
author2 Fuente, Silvia Andrea
Ferullo, Ricardo
Castellani, Norberto Jorge
Apesteguia, Carlos Rodolfo
Di Cosimo, Juana Isabel
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv GLYCEROL
MONOGLYCERIDE
DFT
BASE CATALYSIS
GLYCEROLYSIS
FATTY ACID METHYL ESTER
topic GLYCEROL
MONOGLYCERIDE
DFT
BASE CATALYSIS
GLYCEROLYSIS
FATTY ACID METHYL ESTER
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The synthesis of monoglycerides by glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), was efficiently promoted on strongly basic MgO. The chemical nature of the base sites responsible for the catalytic activity was investigated, both experimentally and by density functional theory (DFT). MgO catalysts stabilized at different temperatures were used to control the distribution of surface base sites. The nature, density and strength of the catalyst base sites were characterized by TPD and FTIR of CO2. Catalytic results suggested that the synthesis of monoglycerides was promoted mainly on strongly basic low coordination (O2−) surface sites. The molecular modeling of glycerol (Gly) and FAME adsorptions was carried out using terrace, edge and corner sites for representing the MgO surface. Results indicated that Gly was more strongly adsorbed than FAME. Dissociative chemisorption of Gly with O-H bond breaking was favored on low coordination (O2−) surface sites such as those on edges, in agreement with the experimental results. Thus, the proton abstraction from the OH groups of Gly, a necessary step in the reaction mechanism, would take place on unsaturated oxygen anions and the resulting glyceroxides would react with weakly adsorbed FAME molecules.
Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Fuente, Silvia Andrea. Universidad Nacional del Sur. Departamento de Física; Argentina. 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: Ferullo, Ricardo. Universidad Nacional del Sur. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química 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. Universidad Nacional del Sur. Departamento de Física; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina
description The synthesis of monoglycerides by glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), was efficiently promoted on strongly basic MgO. The chemical nature of the base sites responsible for the catalytic activity was investigated, both experimentally and by density functional theory (DFT). MgO catalysts stabilized at different temperatures were used to control the distribution of surface base sites. The nature, density and strength of the catalyst base sites were characterized by TPD and FTIR of CO2. Catalytic results suggested that the synthesis of monoglycerides was promoted mainly on strongly basic low coordination (O2−) surface sites. The molecular modeling of glycerol (Gly) and FAME adsorptions was carried out using terrace, edge and corner sites for representing the MgO surface. Results indicated that Gly was more strongly adsorbed than FAME. Dissociative chemisorption of Gly with O-H bond breaking was favored on low coordination (O2−) surface sites such as those on edges, in agreement with the experimental results. Thus, the proton abstraction from the OH groups of Gly, a necessary step in the reaction mechanism, would take place on unsaturated oxygen anions and the resulting glyceroxides would react with weakly adsorbed FAME molecules.
publishDate 2012
dc.date.none.fl_str_mv 2012-01
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/11336/271730
Ferretti, Cristián Alejandro; Fuente, Silvia Andrea; Ferullo, Ricardo; Castellani, Norberto Jorge; Apesteguia, Carlos Rodolfo; et al.; Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site; Elsevier Science; Applied Catalysis A: General; 413-414; 1-2012; 322-331
0926-860X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/271730
identifier_str_mv Ferretti, Cristián Alejandro; Fuente, Silvia Andrea; Ferullo, Ricardo; Castellani, Norberto Jorge; Apesteguia, Carlos Rodolfo; et al.; Monoglyceride synthesis by glycerolysis of methyl oleate on MgO: Catalytic and DFT study of the active site; Elsevier Science; Applied Catalysis A: General; 413-414; 1-2012; 322-331
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/url/http://www.sciencedirect.com/science/article/pii/S0926860X1100696X
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.apcata.2011.11.025
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
application/pdf
application/pdf
application/pdf
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 13.22299

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