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Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites

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Summary:Friedel-Crafts acylation was studied under mild conditions using hierarchical MCM-22 zeolites prepared by desilication and by desilication + acid treatment, using furan, pyrrole and anisole as substrates, and acetic anhydride as acylating agent. Enhanced catalysis was observed for furan and anisole, especially at short reaction times. Kinetic results modelling using non-linear regressions applied to a simplified Langmuir-Hinshelwood equation showed that desilication treatment followed by acid treatment improved kinetics (higher k and TOF). A QSPR methodology using nine substrate and zeolite descriptors was applied to model kinetics and adsorption. For both processes, the best QSPR model equations lead to the same descriptors, namely, Bronsted acidity, as zeolite's feature, and both van der Waals volume and Dimroth-Reichardt E-T(N) parameter (related to dipolarity and Lewis acidity) as substrates' characteristics. Normalization of descriptors allowed quantification of each descriptor's relative importance leading to a better understanding of the catalytic and adsorption processes.
Main Authors:Aleixo, Rodrigo
Other Authors:Elvas Leitao, Ruben; Martins, Filomena; Carvalho, Ana; Brigas, Amadeu; Martins, Angela; Nunes, Nelson
Subject:Hierarchical MCM-22 Friedel-Crafts acylation reactions Kinetic modelling Non-linear regressions QSPR methodology
Year:2017
Country:Portugal
Document type:article
Access type:restricted access
Associated institution:Instituto Politécnico de Lisboa
Language:English
Origin:Repositório Científico do Instituto Politécnico de Lisboa
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author Aleixo, Rodrigo
author2 Elvas Leitao, Ruben
Martins, Filomena
Carvalho, Ana
Brigas, Amadeu
Martins, Angela
Nunes, Nelson
author2_role author
author
author
author
author
author
author_facet Aleixo, Rodrigo
Elvas Leitao, Ruben
Martins, Filomena
Carvalho, Ana
Brigas, Amadeu
Martins, Angela
Nunes, Nelson
author_role author
contributor_name_str_mv RCIPL
country_str PT
creators_json_txt [{\"Person.name\":\"Aleixo, Rodrigo\"},{\"Person.name\":\"Elvas Leitao, Ruben\",\"Person.identifier.orcid\":\"0000-0002-2196-412X\"},{\"Person.name\":\"Martins, Filomena\",\"Person.identifier.orcid\":\"0000-0003-4189-1228\"},{\"Person.name\":\"Carvalho, Ana\",\"Person.identifier.orcid\":\"0000-0002-3144-2800\"},{\"Person.name\":\"Brigas, Amadeu\"},{\"Person.name\":\"Martins, Angela\",\"Person.identifier.orcid\":\"0000-0003-1637-478X\"},{\"Person.name\":\"Nunes, Nelson\",\"Person.identifier.orcid\":\"0000-0003-4499-0379\"}]
datacite.contributors.contributor.contributorName.fl_str_mv RCIPL
datacite.creators.creator.creatorName.fl_str_mv Aleixo, Rodrigo
Elvas Leitao, Ruben
Martins, Filomena
Carvalho, Ana
Brigas, Amadeu
Martins, Angela
Nunes, Nelson
datacite.date.Accepted.fl_str_mv 2017-06-01T00:00:00Z
datacite.date.available.fl_str_mv 2017-11-29T10:28:51Z
datacite.date.embargoed.fl_str_mv 2017-11-29T10:28:51Z
datacite.rights.fl_str_mv http://purl.org/coar/access_right/c_16ec
datacite.subjects.subject.fl_str_mv Hierarchical MCM-22
Friedel-Crafts acylation reactions
Kinetic modelling
Non-linear regressions
QSPR methodology
datacite.titles.title.fl_str_mv Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
dc.contributor.none.fl_str_mv RCIPL
dc.creator.none.fl_str_mv Aleixo, Rodrigo
Elvas Leitao, Ruben
Martins, Filomena
Carvalho, Ana
Brigas, Amadeu
Martins, Angela
Nunes, Nelson
dc.date.Accepted.fl_str_mv 2017-06-01T00:00:00Z
dc.date.available.fl_str_mv 2017-11-29T10:28:51Z
dc.date.embargoed.fl_str_mv 2017-11-29T10:28:51Z
dc.format.none.fl_str_mv application/pdf
dc.identifier.none.fl_str_mv http://hdl.handle.net/10400.21/7611
dc.language.none.fl_str_mv eng
dc.publisher.none.fl_str_mv Elsevier Science
dc.rights.none.fl_str_mv http://purl.org/coar/access_right/c_16ec
dc.subject.none.fl_str_mv Hierarchical MCM-22
Friedel-Crafts acylation reactions
Kinetic modelling
Non-linear regressions
QSPR methodology
dc.title.fl_str_mv Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
dc.type.none.fl_str_mv http://purl.org/coar/resource_type/c_6501
description Friedel-Crafts acylation was studied under mild conditions using hierarchical MCM-22 zeolites prepared by desilication and by desilication + acid treatment, using furan, pyrrole and anisole as substrates, and acetic anhydride as acylating agent. Enhanced catalysis was observed for furan and anisole, especially at short reaction times. Kinetic results modelling using non-linear regressions applied to a simplified Langmuir-Hinshelwood equation showed that desilication treatment followed by acid treatment improved kinetics (higher k and TOF). A QSPR methodology using nine substrate and zeolite descriptors was applied to model kinetics and adsorption. For both processes, the best QSPR model equations lead to the same descriptors, namely, Bronsted acidity, as zeolite's feature, and both van der Waals volume and Dimroth-Reichardt E-T(N) parameter (related to dipolarity and Lewis acidity) as substrates' characteristics. Normalization of descriptors allowed quantification of each descriptor's relative importance leading to a better understanding of the catalytic and adsorption processes.
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eu_rights_str_mv restrictedAccess
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fulltext.url.fl_str_mv https://repositorio.ipl.pt/bitstreams/59e3a23b-fa17-446d-afb4-8879afeab604/download
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identifier.url.fl_str_mv http://hdl.handle.net/10400.21/7611
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organization_str_mv urn:organizationAcronym:ipl
person_str_mv Aleixo, Rodrigo
Elvas Leitao, Ruben
Elvas Leitao, Ruben
https://www.ciencia-id.pt/F41B-8A26-88D4
F41B-8A26-88D4
http://orcid.org/0000-0002-2196-412X
0000-0002-2196-412X
Martins, Filomena
Martins, Filomena
https://www.ciencia-id.pt/7F12-A33A-EBAB
7F12-A33A-EBAB
http://orcid.org/0000-0003-4189-1228
0000-0003-4189-1228
Carvalho, Ana
Carvalho, Ana
https://www.ciencia-id.pt/8011-6264-7957
8011-6264-7957
http://orcid.org/0000-0002-3144-2800
0000-0002-3144-2800
Brigas, Amadeu
Martins, Angela
Martins, Angela
https://www.ciencia-id.pt/781F-79D3-9070
781F-79D3-9070
http://orcid.org/0000-0003-1637-478X
0000-0003-1637-478X
Nunes, Nelson
Nunes, Nelson
https://www.ciencia-id.pt/1B16-7872-5A09
1B16-7872-5A09
http://orcid.org/0000-0003-4499-0379
0000-0003-4499-0379
publishDate 2017
publisher.none.fl_str_mv Elsevier Science
reponame_str Repositório Científico do Instituto Politécnico de Lisboa
repository_id_str urn:repositoryAcronym:ripl
service_str_mv urn:repositoryAcronym:ripl
spelling engElsevier Sciencept_PTFriedel-Crafts acylation was studied under mild conditions using hierarchical MCM-22 zeolites prepared by desilication and by desilication + acid treatment, using furan, pyrrole and anisole as substrates, and acetic anhydride as acylating agent. Enhanced catalysis was observed for furan and anisole, especially at short reaction times. Kinetic results modelling using non-linear regressions applied to a simplified Langmuir-Hinshelwood equation showed that desilication treatment followed by acid treatment improved kinetics (higher k and TOF). A QSPR methodology using nine substrate and zeolite descriptors was applied to model kinetics and adsorption. For both processes, the best QSPR model equations lead to the same descriptors, namely, Bronsted acidity, as zeolite's feature, and both van der Waals volume and Dimroth-Reichardt E-T(N) parameter (related to dipolarity and Lewis acidity) as substrates' characteristics. Normalization of descriptors allowed quantification of each descriptor's relative importance leading to a better understanding of the catalytic and adsorption processes.application/pdfpt_PTKinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolitesAleixo, RodrigoPersonalElvas Leitao, RubenDSpacehttp://dspace.org/items/440b7129-d4d9-4225-a936-ca694c0984b6DSpacehttp://dspace.org/items/440b7129-d4d9-4225-a936-ca694c0984b6Elvas LeitaoRubenCiência IDhttps://www.ciencia-id.ptF41B-8A26-88D4ORCIDhttp://orcid.org0000-0002-2196-412XResearcher IDhttps://www.researcherid.comD-2452-2009Scopus Author IDhttps://www.scopus.com55667178200PersonalMartins, FilomenaDSpacehttp://dspace.org/items/a2fde0f8-54f8-445d-9015-315e0e4ba68bDSpacehttp://dspace.org/items/a2fde0f8-54f8-445d-9015-315e0e4ba68bmartinsfilomenaCiência IDhttps://www.ciencia-id.pt7F12-A33A-EBABORCIDhttp://orcid.org0000-0003-4189-1228Researcher IDhttps://www.researcherid.comE-6287-2012Scopus Author IDhttps://www.scopus.com17342433200PersonalCarvalho, AnaDSpacehttp://dspace.org/items/5d0d14e6-8215-4437-9957-ca9185c04b66DSpacehttp://dspace.org/items/5d0d14e6-8215-4437-9957-ca9185c04b66CarvalhoAnaCiência IDhttps://www.ciencia-id.pt8011-6264-7957ORCIDhttp://orcid.org0000-0002-3144-2800Scopus Author IDhttps://www.scopus.com55611516400Brigas, AmadeuPersonalMartins, AngelaDSpacehttp://dspace.org/items/61c012c2-e555-4d7e-8fad-27b1facc34caDSpacehttp://dspace.org/items/61c012c2-e555-4d7e-8fad-27b1facc34caMartinsAngelaCiência IDhttps://www.ciencia-id.pt781F-79D3-9070ORCIDhttp://orcid.org0000-0003-1637-478XResearcher IDhttps://www.researcherid.comB-1775-2012Scopus Author IDhttps://www.scopus.com7203013509PersonalNunes, NelsonDSpacehttp://dspace.org/items/3541747c-0373-4a73-b1f3-77095e675385DSpacehttp://dspace.org/items/3541747c-0373-4a73-b1f3-77095e675385NunesNelsonCiência IDhttps://www.ciencia-id.pt1B16-7872-5A09ORCIDhttp://orcid.org0000-0003-4499-0379Researcher IDhttps://www.researcherid.comA-8516-2012Scopus Author IDhttps://www.scopus.com11540776800HostingInstitutionOrganizationalRCIPLe-mailmailto:rcaap@sp.ipl.ptrcaap@sp.ipl.ptISSNIsPartOf2468-8231DOIIsPartOf10.1016/j.mcat.2017.03.0072017-11-29T10:28:51Z2017-062017-06-01T00:00:00ZHandlehttp://hdl.handle.net/10400.21/7611http://purl.org/coar/access_right/c_16ecrestricted accessHierarchical MCM-22Friedel-Crafts acylation reactionsKinetic modellingNon-linear regressionsQSPR methodology1049825 bytesliteraturehttp://purl.org/coar/resource_type/c_6501journal articlehttp://purl.org/coar/access_right/c_16ecapplication/pdffulltexthttps://repositorio.ipl.pt/bitstreams/59e3a23b-fa17-446d-afb4-8879afeab604/downloadJournal of Molecular Catalysis A: Chemical434183175
spellingShingle Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
Aleixo, Rodrigo
Hierarchical MCM-22
Friedel-Crafts acylation reactions
Kinetic modelling
Non-linear regressions
QSPR methodology
status SINGLETON
subject.fl_str_mv Hierarchical MCM-22
Friedel-Crafts acylation reactions
Kinetic modelling
Non-linear regressions
QSPR methodology
title Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
title_full Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
title_fullStr Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
title_full_unstemmed Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
title_short Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
title_sort Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolites
topic Hierarchical MCM-22
Friedel-Crafts acylation reactions
Kinetic modelling
Non-linear regressions
QSPR methodology
topic_facet Hierarchical MCM-22
Friedel-Crafts acylation reactions
Kinetic modelling
Non-linear regressions
QSPR methodology
url http://hdl.handle.net/10400.21/7611
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