Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole

Mesoporous SBA-15 silica materials have been functionalized with perfluorosulfonic acidic Nafion resin using a post-synthetic impregnation method. The remarkable physicochemical properties of hexagonally ordered SBA-15 silicas (high surface area, large and narrow pore size distribution and thermal s...

ver descrição completa

Detalhes bibliográficos
Autores: Martínez, F., Morales, G., Martín, A., van Grieken, R.
Formato: artículo
Fecha de publicación:2008
País:España
Recursos:Universidad Rey Juan Carlos
Repositorio:BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
OAI Identifier:oai:burjcdigital.urjc.es:10115/3752
Acesso em linha:http://hdl.handle.net/10115/3752
Access Level:acceso abierto
Palavra-chave:Química
23 Química
id ES_6dce585a2a3eddf15b0e9cee0f2e39dc
oai_identifier_str oai:burjcdigital.urjc.es:10115/3752
network_acronym_str ES
network_name_str España
repository_id_str
spelling Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisoleMartínez, F.Morales, G.Martín, A.van Grieken, R.Química23 QuímicaMesoporous SBA-15 silica materials have been functionalized with perfluorosulfonic acidic Nafion resin using a post-synthetic impregnation method. The remarkable physicochemical properties of hexagonally ordered SBA-15 silicas (high surface area, large and narrow pore size distribution and thermal stability) make them particularly attractive for the immobilization of strongly acidic perfluorosulfonic sites. The loading of Nafion resin was varied between 10 and 20 wt%. The synthesized Nafion/SBA-15 hybrid materials were evaluated in the Friedel Crafts acylation of anisole. The optimum catalytic performance of Nafion/SBA-15 hybrid material with a resin loading around 13 wt% was compared with other perfluorosulfonic acid-based catalysts either commercially available or prepared following recipes reported in the literature. The influence of several variables on the acylation of anisole, such as the reaction temperature and the anisole/acylating agent ratio, has also been assessed by means of a factorial design of experiments. The catalytic activity of Nafion-modified SBA-15 materials is strongly affected by the reaction temperature, whereas a lesser effect was evidenced for the reaction mixture composition in the range under study. The optimal operation conditions in terms of anisole conversion were achieved at 150ºC and equimolar anisole/acetic anhydride mixture. The deposition of poly-acetylated by-products on the catalytic acid sites is mainly responsible for the catalyst deactivation, whereas the leaching of sulfonic groups and their contribution in the anisole acylation via homogeneous catalysis has been ruled out. Finally, the recovery of the catalytic activity by regeneration of the spent catalyst by refluxing in nitric acid solution was demonstrated. The characterization of the regenerated catalyst indicates that the regained activity is likely related to the displacement of the deactivating by-products out of the perflurorosulfonic acid sites during the nitric acid regeneration.Tecnología Química y AmbientalELSEVIER201020102008info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10115/3752reponame:BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlosinstname:Universidad Rey Juan CarlosInglésAtribución-NoComercial-SinDerivadas 3.0 Españahttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:burjcdigital.urjc.es:10115/37522026-06-24T12:48:17Z
dc.title.none.fl_str_mv Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
title Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
spellingShingle Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
Martínez, F.
Química
23 Química
title_short Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
title_full Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
title_fullStr Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
title_full_unstemmed Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
title_sort Perfluorinated nafion-modified SBA-15 materials for catalytic acylation of anisole
dc.creator.none.fl_str_mv Martínez, F.
Morales, G.
Martín, A.
van Grieken, R.
author Martínez, F.
author_facet Martínez, F.
Morales, G.
Martín, A.
van Grieken, R.
author_role author
author2 Morales, G.
Martín, A.
van Grieken, R.
author2_role author
author
author
dc.subject.none.fl_str_mv Química
23 Química
topic Química
23 Química
description Mesoporous SBA-15 silica materials have been functionalized with perfluorosulfonic acidic Nafion resin using a post-synthetic impregnation method. The remarkable physicochemical properties of hexagonally ordered SBA-15 silicas (high surface area, large and narrow pore size distribution and thermal stability) make them particularly attractive for the immobilization of strongly acidic perfluorosulfonic sites. The loading of Nafion resin was varied between 10 and 20 wt%. The synthesized Nafion/SBA-15 hybrid materials were evaluated in the Friedel Crafts acylation of anisole. The optimum catalytic performance of Nafion/SBA-15 hybrid material with a resin loading around 13 wt% was compared with other perfluorosulfonic acid-based catalysts either commercially available or prepared following recipes reported in the literature. The influence of several variables on the acylation of anisole, such as the reaction temperature and the anisole/acylating agent ratio, has also been assessed by means of a factorial design of experiments. The catalytic activity of Nafion-modified SBA-15 materials is strongly affected by the reaction temperature, whereas a lesser effect was evidenced for the reaction mixture composition in the range under study. The optimal operation conditions in terms of anisole conversion were achieved at 150ºC and equimolar anisole/acetic anhydride mixture. The deposition of poly-acetylated by-products on the catalytic acid sites is mainly responsible for the catalyst deactivation, whereas the leaching of sulfonic groups and their contribution in the anisole acylation via homogeneous catalysis has been ruled out. Finally, the recovery of the catalytic activity by regeneration of the spent catalyst by refluxing in nitric acid solution was demonstrated. The characterization of the regenerated catalyst indicates that the regained activity is likely related to the displacement of the deactivating by-products out of the perflurorosulfonic acid sites during the nitric acid regeneration.
publishDate 2008
dc.date.none.fl_str_mv 2008
2010
2010
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10115/3752
url http://hdl.handle.net/10115/3752
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
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:BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
instname:Universidad Rey Juan Carlos
instname_str Universidad Rey Juan Carlos
reponame_str BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
collection BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869410378867277824
score 15.812429

Registos relacionados