Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites

[EN] Zr-containing UiO-66 and MOF-808 are evaluated for converting levulinic acid (LA) into gamma-valerolactone (GVL) through various routes: (i) Step-wise esterification of LA to n-butyl levulinate (nBuL) and Meerwein-PonndorfVerley (MPV) reduction to GVL; (ii) One-pot two-steps esterification with...

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Autores: Guarinos, J.M., Cirujano, F.G., Rapeyko, Anastasia|||0000-0002-8309-3702, Llabrés i Xamena, Francesc Xavier|||0000-0002-4238-5784
Tipo de documento: artigo
Data de publicação:2021
País:España
Recursos:Universitat Politècnica de València (UPV)
Repositório:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglês
OAI Identifier:oai:riunet.upv.es:10251/188316
Acesso em linha:https://riunet.upv.es/handle/10251/188316
Access Level:Acceso aberto
Palavra-chave:Zirconium MOFs
MOF-808
UiO-66
Levulinic acid
Gamma-valerolactone
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repository_id_str
spelling Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sitesGuarinos, J.M.Cirujano, F.G.Rapeyko, Anastasia|||0000-0002-8309-3702Llabrés i Xamena, Francesc Xavier|||0000-0002-4238-5784Zirconium MOFsMOF-808UiO-66Levulinic acidGamma-valerolactone[EN] Zr-containing UiO-66 and MOF-808 are evaluated for converting levulinic acid (LA) into gamma-valerolactone (GVL) through various routes: (i) Step-wise esterification of LA to n-butyl levulinate (nBuL) and Meerwein-PonndorfVerley (MPV) reduction to GVL; (ii) One-pot two-steps esterification with n-butanol followed by MPV reduction with sec-butanol; and (iii) direct conversion of LA into GVL through a tandem reaction. Selection of this multistep complex reaction evidences the participation of the different acid sites (Lewis or Bronsted) of the material in each individual step: Bronsted-induced acid sites catalyze esterification reaction efficiently, while Lewis acid sites are the preferred sites for the MPV step. Sulfation of MOF-808 is used to enhance the Bronsted acidity of MOF-808, which improves the performance for esterification. However, the sulfate groups introduced are detrimental for the MPV step, since they reduce the intra-pore space available to form the required bulky transition state. These results evidence the need to find the best equilibrium between Bronsted and Lewis acid sites to optimize the outcome of this multistep reaction.Financial support by the Spanish Government is acknowledged through projects MAT2017-82288-C2-1-P and the Severo Ochoa program (SEV-2016-0683). Aula-CEMEX is also acknowledged for a fellowship to JMG.ElsevierInstituto Universitario Mixto de Tecnología QuímicaMinisterio de Economía y CompetitividadMinisterio Ciencia, Innovación y UniversidadesRepositorio Institucional de la Universitat Politècnica de València Riunet20212021-10-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/188316reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016 MAT2017-82288-C2-1-P MATERIALES HIBRIDOS MULTIFUNCIONALES BASADOS EN NANO-UNIDADES ESTRUCTURALES ACTIVASMinisterio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 SEV-2016-0683 Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelenciaopen accesshttp://purl.org/coar/access_right/c_abf2Reconocimiento - No comercial - Sin obra derivada (by-nc-nd) http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/1883162026-06-13T07:49:27Z
dc.title.none.fl_str_mv Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
title Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
spellingShingle Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
Guarinos, J.M.
Zirconium MOFs
MOF-808
UiO-66
Levulinic acid
Gamma-valerolactone
title_short Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
title_full Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
title_fullStr Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
title_full_unstemmed Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
title_sort Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites
dc.creator.none.fl_str_mv Guarinos, J.M.
Cirujano, F.G.
Rapeyko, Anastasia|||0000-0002-8309-3702
Llabrés i Xamena, Francesc Xavier|||0000-0002-4238-5784
author Guarinos, J.M.
author_facet Guarinos, J.M.
Cirujano, F.G.
Rapeyko, Anastasia|||0000-0002-8309-3702
Llabrés i Xamena, Francesc Xavier|||0000-0002-4238-5784
author_role author
author2 Cirujano, F.G.
Rapeyko, Anastasia|||0000-0002-8309-3702
Llabrés i Xamena, Francesc Xavier|||0000-0002-4238-5784
author2_role author
author
author
dc.contributor.none.fl_str_mv Instituto Universitario Mixto de Tecnología Química
Ministerio de Economía y Competitividad
Ministerio Ciencia, Innovación y Universidades
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Zirconium MOFs
MOF-808
UiO-66
Levulinic acid
Gamma-valerolactone
topic Zirconium MOFs
MOF-808
UiO-66
Levulinic acid
Gamma-valerolactone
description [EN] Zr-containing UiO-66 and MOF-808 are evaluated for converting levulinic acid (LA) into gamma-valerolactone (GVL) through various routes: (i) Step-wise esterification of LA to n-butyl levulinate (nBuL) and Meerwein-PonndorfVerley (MPV) reduction to GVL; (ii) One-pot two-steps esterification with n-butanol followed by MPV reduction with sec-butanol; and (iii) direct conversion of LA into GVL through a tandem reaction. Selection of this multistep complex reaction evidences the participation of the different acid sites (Lewis or Bronsted) of the material in each individual step: Bronsted-induced acid sites catalyze esterification reaction efficiently, while Lewis acid sites are the preferred sites for the MPV step. Sulfation of MOF-808 is used to enhance the Bronsted acidity of MOF-808, which improves the performance for esterification. However, the sulfate groups introduced are detrimental for the MPV step, since they reduce the intra-pore space available to form the required bulky transition state. These results evidence the need to find the best equilibrium between Bronsted and Lewis acid sites to optimize the outcome of this multistep reaction.
publishDate 2021
dc.date.none.fl_str_mv 2021
2021-10-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/188316
url https://riunet.upv.es/handle/10251/188316
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016 MAT2017-82288-C2-1-P MATERIALES HIBRIDOS MULTIFUNCIONALES BASADOS EN NANO-UNIDADES ESTRUCTURALES ACTIVAS
Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 SEV-2016-0683 Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelencia
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento - No comercial - Sin obra derivada (by-nc-nd)
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reconocimiento - No comercial - Sin obra derivada (by-nc-nd)
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.198674

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