MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes

[EN] A series of MIL-101(Cr)-X functionalized with electron withdrawing (NO2, SO3H or Cl) or electron donor (NH2 or CH3) groups has been tested for the solvent-free oxidative coupling of thiophenol to disulfides. No byproducts were observed. A relationship between the catalytic activity of these MOF...

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Autores: Vallés-García, Cristina, Santiago-Portillo, Andrea, Alvaro Rodríguez, Maria Mercedes|||0000-0001-5070-4207, Navalón Oltra, Sergio|||0000-0001-8423-0759, García Gómez, Hermenegildo|||0000-0002-9664-493X
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/164221
Acceso en línea:https://riunet.upv.es/handle/10251/164221
Access Level:acceso abierto
Palabra clave:Heterogeneous catalysis
MIL-101(Cr)-NO(2)as catalyst
Aerobic oxidations
Thiophenol coupling
Fuel
Desulfurization
QUIMICA ORGANICA
QUIMICA ANALITICA
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repository_id_str
spelling MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenesVallés-García, CristinaSantiago-Portillo, AndreaAlvaro Rodríguez, Maria Mercedes|||0000-0001-5070-4207Navalón Oltra, Sergio|||0000-0001-8423-0759García Gómez, Hermenegildo|||0000-0002-9664-493XHeterogeneous catalysisMIL-101(Cr)-NO(2)as catalystAerobic oxidationsThiophenol couplingFuelDesulfurizationQUIMICA ORGANICAQUIMICA ANALITICA[EN] A series of MIL-101(Cr)-X functionalized with electron withdrawing (NO2, SO3H or Cl) or electron donor (NH2 or CH3) groups has been tested for the solvent-free oxidative coupling of thiophenol to disulfides. No byproducts were observed. A relationship between the catalytic activity of these MOFs with the substituent meta Hammet constant on the terephthalate ligand and with their redox potential was found, MIL-101(Cr)-NO2 being the most active catalyst. NO2-substituted MIL-101 is also more efficient than the parent MIL-101(Cr) to promote the aerobic desulfurization of dibenzothiophenes in n-dodecane or commercial Diesel as solvent. No byproduct formation was observed. Mechanistic studies reveal that MIL-101(Cr)-NO2 is acting as heterogeneous catalyst in thiophenol oxidation and as radical initiator for the aerobic desulfurization. For both reactions, the catalyst can be reused without deactivation, maintaining its crystallinity and with negligible metal leaching.Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. S.N. thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovacion y Universidades CTQ-2018 RTI2018-099482-A-I00 project and Generalitat Valenciana grupos de investigacion consolidables 2019 (AICO2019/214 project).ElsevierInstituto Universitario Mixto de Tecnología QuímicaDepartamento de QuímicaEscuela Técnica Superior de Ingeniería IndustrialGrupo de Fotoquímica Heterogénea y MedioambientalGeneralitat ValencianaFundación Ramón ArecesAgencia Estatal de InvestigaciónRepositorio Institucional de la Universitat Politècnica de València Riunet20202020-01-25journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfapplication/pdfhttps://riunet.upv.es/handle/10251/164221reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengGeneralitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2017%2F083Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 RTI2018-098237-B-C21 HETEROUNIONES DE GRAFENO CON CONFIGURACION CONTROLADA. SINTESIS Y APLICACIONES COMO SOPORTE EN CATALISIS Y EN ELECTRODOSAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 RTI2018-099482-A-I00 DESCOMPOSICION FOTOCATALITICA DEL AGUA ASISTIDA POR LUZ VISIBLE EMPLEANDO MATERIALES NOVEDOSOS Y MULTIFUNCIONALES UIO-66%2F67Generalitat Valenciana https://doi.org/10.13039/501100003359 AICO%2F2019%2F214open 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:10251/1642212026-06-13T07:49:27Z
dc.title.none.fl_str_mv MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
title MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
spellingShingle MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
Vallés-García, Cristina
Heterogeneous catalysis
MIL-101(Cr)-NO(2)as catalyst
Aerobic oxidations
Thiophenol coupling
Fuel
Desulfurization
QUIMICA ORGANICA
QUIMICA ANALITICA
title_short MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
title_full MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
title_fullStr MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
title_full_unstemmed MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
title_sort MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
dc.creator.none.fl_str_mv Vallés-García, Cristina
Santiago-Portillo, Andrea
Alvaro Rodríguez, Maria Mercedes|||0000-0001-5070-4207
Navalón Oltra, Sergio|||0000-0001-8423-0759
García Gómez, Hermenegildo|||0000-0002-9664-493X
author Vallés-García, Cristina
author_facet Vallés-García, Cristina
Santiago-Portillo, Andrea
Alvaro Rodríguez, Maria Mercedes|||0000-0001-5070-4207
Navalón Oltra, Sergio|||0000-0001-8423-0759
García Gómez, Hermenegildo|||0000-0002-9664-493X
author_role author
author2 Santiago-Portillo, Andrea
Alvaro Rodríguez, Maria Mercedes|||0000-0001-5070-4207
Navalón Oltra, Sergio|||0000-0001-8423-0759
García Gómez, Hermenegildo|||0000-0002-9664-493X
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Instituto Universitario Mixto de Tecnología Química
Departamento de Química
Escuela Técnica Superior de Ingeniería Industrial
Grupo de Fotoquímica Heterogénea y Medioambiental
Generalitat Valenciana
Fundación Ramón Areces
Agencia Estatal de Investigación
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Heterogeneous catalysis
MIL-101(Cr)-NO(2)as catalyst
Aerobic oxidations
Thiophenol coupling
Fuel
Desulfurization
QUIMICA ORGANICA
QUIMICA ANALITICA
topic Heterogeneous catalysis
MIL-101(Cr)-NO(2)as catalyst
Aerobic oxidations
Thiophenol coupling
Fuel
Desulfurization
QUIMICA ORGANICA
QUIMICA ANALITICA
description [EN] A series of MIL-101(Cr)-X functionalized with electron withdrawing (NO2, SO3H or Cl) or electron donor (NH2 or CH3) groups has been tested for the solvent-free oxidative coupling of thiophenol to disulfides. No byproducts were observed. A relationship between the catalytic activity of these MOFs with the substituent meta Hammet constant on the terephthalate ligand and with their redox potential was found, MIL-101(Cr)-NO2 being the most active catalyst. NO2-substituted MIL-101 is also more efficient than the parent MIL-101(Cr) to promote the aerobic desulfurization of dibenzothiophenes in n-dodecane or commercial Diesel as solvent. No byproduct formation was observed. Mechanistic studies reveal that MIL-101(Cr)-NO2 is acting as heterogeneous catalyst in thiophenol oxidation and as radical initiator for the aerobic desulfurization. For both reactions, the catalyst can be reused without deactivation, maintaining its crystallinity and with negligible metal leaching.
publishDate 2020
dc.date.none.fl_str_mv 2020
2020-01-25
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/10251/164221
url https://riunet.upv.es/handle/10251/164221
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Generalitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2017%2F083
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 RTI2018-098237-B-C21 HETEROUNIONES DE GRAFENO CON CONFIGURACION CONTROLADA. SINTESIS Y APLICACIONES COMO SOPORTE EN CATALISIS Y EN ELECTRODOS
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 RTI2018-099482-A-I00 DESCOMPOSICION FOTOCATALITICA DEL AGUA ASISTIDA POR LUZ VISIBLE EMPLEANDO MATERIALES NOVEDOSOS Y MULTIFUNCIONALES UIO-66%2F67
Generalitat Valenciana https://doi.org/10.13039/501100003359 AICO%2F2019%2F214
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
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 15,301603

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