Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity

Autores
Belelli, Patricia Gabriela; Ferretti, Cristián Alejandro; Apesteguia, Carlos Rodolfo; Ferullo, Ricardo; Di Cosimo, Juana Isabel
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The liquid-phase MgO-promoted glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), to give acylglycerol products was studied both, experimentally and by density functional theory (DFT). Catalytic results showed that strongly basic low coordination O2− surface sites participate in kinetically relevant steps of the glycerolysis reaction. Changes in the selectivity toward the different mono- and diglyceride isomers were investigated by varying the reaction conditions. The main product was always α-glyceryl monooleate (α-MG), a monoglyceride with the ester fragment at one of the terminal positions of the glycerol molecule; the β-MG isomer, with the ester substituted at position 2 was obtained in much lower amounts. The molecular modeling of glycerol (Gly) and FAME adsorptions as well as of the glycerolysis reaction was carried out using periodic DFT calculations and a model of stepped MgO surface. Results indicated that FAME was more weakly adsorbed than Gly; the latter adsorbs on a coordinatively unsaturated surface O2− site with Osingle bondH bond breaking at position 2 of the Gly molecule, giving therefore a surface β-glyceroxide species. Calculations explained the apparent contradiction between the preferential formation of the α-MG isomer and the energetically favored dissociation of the secondary OH group of Gly that leads to the β-glyceroxide species. They predict that the β-glyceroxide species participates in the pathways conducting to both, α- and β-MG isomers. Synthesis of α-MG occurs by Csingle bondO coupling of β-glyceroxide with FAME at one of the two primary OH groups of the β-glyceroxide species. Two transition states (TS) and a tetrahedral intermediate (TI) are involved in both, α-MG and β-MG isomer formation. However, the pathway toward β-MG is limited by the large sterical effects associated to the TI formation. Contrarily, the TI leading to α-MG is relatively easy to form.
Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Física del Sur; Argentina
Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
Materia
Mgo
Fatty Acid
Glycerolysis
Dft
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/6534
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/6534
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivityBelelli, Patricia GabrielaFerretti, Cristián AlejandroApesteguia, Carlos RodolfoFerullo, RicardoDi Cosimo, Juana IsabelMgoFatty AcidGlycerolysisDfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The liquid-phase MgO-promoted glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), to give acylglycerol products was studied both, experimentally and by density functional theory (DFT). Catalytic results showed that strongly basic low coordination O2− surface sites participate in kinetically relevant steps of the glycerolysis reaction. Changes in the selectivity toward the different mono- and diglyceride isomers were investigated by varying the reaction conditions. The main product was always α-glyceryl monooleate (α-MG), a monoglyceride with the ester fragment at one of the terminal positions of the glycerol molecule; the β-MG isomer, with the ester substituted at position 2 was obtained in much lower amounts. The molecular modeling of glycerol (Gly) and FAME adsorptions as well as of the glycerolysis reaction was carried out using periodic DFT calculations and a model of stepped MgO surface. Results indicated that FAME was more weakly adsorbed than Gly; the latter adsorbs on a coordinatively unsaturated surface O2− site with Osingle bondH bond breaking at position 2 of the Gly molecule, giving therefore a surface β-glyceroxide species. Calculations explained the apparent contradiction between the preferential formation of the α-MG isomer and the energetically favored dissociation of the secondary OH group of Gly that leads to the β-glyceroxide species. They predict that the β-glyceroxide species participates in the pathways conducting to both, α- and β-MG isomers. Synthesis of α-MG occurs by Csingle bondO coupling of β-glyceroxide with FAME at one of the two primary OH groups of the β-glyceroxide species. Two transition states (TS) and a tetrahedral intermediate (TI) are involved in both, α-MG and β-MG isomer formation. However, the pathway toward β-MG is limited by the large sterical effects associated to the TI formation. Contrarily, the TI leading to α-MG is relatively easy to form.Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Física del Sur; ArgentinaFil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; ArgentinaFil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; ArgentinaFil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; ArgentinaFil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; ArgentinaElsevier2015-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/6534Belelli, Patricia Gabriela; Ferretti, Cristián Alejandro; Apesteguia, Carlos Rodolfo; Ferullo, Ricardo; Di Cosimo, Juana Isabel; Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity; Elsevier; Journal of Catalysis; 323; 1-2015; 132-1440021-9517enginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0021951715000032info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2015.01.001info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:57:14Zoai:ri.conicet.gov.ar:11336/6534instacron: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:34982025-09-29 09:57:14.45CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
title Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
spellingShingle Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
Belelli, Patricia Gabriela
Mgo
Fatty Acid
Glycerolysis
Dft
title_short Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
title_full Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
title_fullStr Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
title_full_unstemmed Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
title_sort Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity
dc.creator.none.fl_str_mv Belelli, Patricia Gabriela
Ferretti, Cristián Alejandro
Apesteguia, Carlos Rodolfo
Ferullo, Ricardo
Di Cosimo, Juana Isabel
author Belelli, Patricia Gabriela
author_facet Belelli, Patricia Gabriela
Ferretti, Cristián Alejandro
Apesteguia, Carlos Rodolfo
Ferullo, Ricardo
Di Cosimo, Juana Isabel
author_role author
author2 Ferretti, Cristián Alejandro
Apesteguia, Carlos Rodolfo
Ferullo, Ricardo
Di Cosimo, Juana Isabel
author2_role author
author
author
author
dc.subject.none.fl_str_mv Mgo
Fatty Acid
Glycerolysis
Dft
topic Mgo
Fatty Acid
Glycerolysis
Dft
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The liquid-phase MgO-promoted glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), to give acylglycerol products was studied both, experimentally and by density functional theory (DFT). Catalytic results showed that strongly basic low coordination O2− surface sites participate in kinetically relevant steps of the glycerolysis reaction. Changes in the selectivity toward the different mono- and diglyceride isomers were investigated by varying the reaction conditions. The main product was always α-glyceryl monooleate (α-MG), a monoglyceride with the ester fragment at one of the terminal positions of the glycerol molecule; the β-MG isomer, with the ester substituted at position 2 was obtained in much lower amounts. The molecular modeling of glycerol (Gly) and FAME adsorptions as well as of the glycerolysis reaction was carried out using periodic DFT calculations and a model of stepped MgO surface. Results indicated that FAME was more weakly adsorbed than Gly; the latter adsorbs on a coordinatively unsaturated surface O2− site with Osingle bondH bond breaking at position 2 of the Gly molecule, giving therefore a surface β-glyceroxide species. Calculations explained the apparent contradiction between the preferential formation of the α-MG isomer and the energetically favored dissociation of the secondary OH group of Gly that leads to the β-glyceroxide species. They predict that the β-glyceroxide species participates in the pathways conducting to both, α- and β-MG isomers. Synthesis of α-MG occurs by Csingle bondO coupling of β-glyceroxide with FAME at one of the two primary OH groups of the β-glyceroxide species. Two transition states (TS) and a tetrahedral intermediate (TI) are involved in both, α-MG and β-MG isomer formation. However, the pathway toward β-MG is limited by the large sterical effects associated to the TI formation. Contrarily, the TI leading to α-MG is relatively easy to form.
Fil: Belelli, Patricia Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Física del Sur; Argentina
Fil: Ferretti, Cristián Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
Fil: Apesteguia, Carlos Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
Fil: Ferullo, Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina
Fil: Di Cosimo, Juana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica; Argentina
description The liquid-phase MgO-promoted glycerolysis of methyl oleate, a fatty acid methyl ester (FAME), to give acylglycerol products was studied both, experimentally and by density functional theory (DFT). Catalytic results showed that strongly basic low coordination O2− surface sites participate in kinetically relevant steps of the glycerolysis reaction. Changes in the selectivity toward the different mono- and diglyceride isomers were investigated by varying the reaction conditions. The main product was always α-glyceryl monooleate (α-MG), a monoglyceride with the ester fragment at one of the terminal positions of the glycerol molecule; the β-MG isomer, with the ester substituted at position 2 was obtained in much lower amounts. The molecular modeling of glycerol (Gly) and FAME adsorptions as well as of the glycerolysis reaction was carried out using periodic DFT calculations and a model of stepped MgO surface. Results indicated that FAME was more weakly adsorbed than Gly; the latter adsorbs on a coordinatively unsaturated surface O2− site with Osingle bondH bond breaking at position 2 of the Gly molecule, giving therefore a surface β-glyceroxide species. Calculations explained the apparent contradiction between the preferential formation of the α-MG isomer and the energetically favored dissociation of the secondary OH group of Gly that leads to the β-glyceroxide species. They predict that the β-glyceroxide species participates in the pathways conducting to both, α- and β-MG isomers. Synthesis of α-MG occurs by Csingle bondO coupling of β-glyceroxide with FAME at one of the two primary OH groups of the β-glyceroxide species. Two transition states (TS) and a tetrahedral intermediate (TI) are involved in both, α-MG and β-MG isomer formation. However, the pathway toward β-MG is limited by the large sterical effects associated to the TI formation. Contrarily, the TI leading to α-MG is relatively easy to form.
publishDate 2015
dc.date.none.fl_str_mv 2015-01
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/11336/6534
Belelli, Patricia Gabriela; Ferretti, Cristián Alejandro; Apesteguia, Carlos Rodolfo; Ferullo, Ricardo; Di Cosimo, Juana Isabel; Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity; Elsevier; Journal of Catalysis; 323; 1-2015; 132-144
0021-9517
url http://hdl.handle.net/11336/6534
identifier_str_mv Belelli, Patricia Gabriela; Ferretti, Cristián Alejandro; Apesteguia, Carlos Rodolfo; Ferullo, Ricardo; Di Cosimo, Juana Isabel; Glycerolysis of methyl oleate on MgO: experimental and theoretical study of the reaction selectivity; Elsevier; Journal of Catalysis; 323; 1-2015; 132-144
0021-9517
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/S0021951715000032
info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jcat.2015.01.001
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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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