Nanoestructured catalysts for organic reactions: design, synthesis and applications
Ano de defesa: | 2016 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | eng |
Instituição de defesa: |
Universidade Federal de São Carlos
Câmpus São Carlos |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química - PPGQ
|
Departamento: |
Não Informado pela instituição
|
País: |
Não Informado pela instituição
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | https://repositorio.ufscar.br/handle/ufscar/10395 |
Resumo: | The development of more efficient and selective catalysts actively contributes for the design of safer, cleaner and less energy-demanding processes, and, therefore, catalysis is one of the cornerstones of green chemistry. In this sense, supported-heterogeneous catalysts represent a great advance in this field, especially because they overcome the difficulty in catalyst separation associated to homogeneous catalysts. In this context, this thesis is focused on the development of nanostructured materials for application in Organic Synthesis. In Chapter 1, a brief introduction regarding fundamental concepts in catalysis is presented, focusing on the synthesis and application of magnetically recoverable catalysts. Chapter 2 described the design, preparation and characterization of a new magnetically recoverable niobium nanocatalyst for application in the synthesis of 3,4-dihydropyrimidinones via Biginelli reaction. The catalyst (Fe3O4@Nb2O5) was prepared by coating magnetite nanoparticles with niobium oxide by using a simple wet impregnation method. The developed protocol was applicable to a wide range of aliphatic and aromatic substrates, and structurally diverse products were obtained in excellent yields. Additionally, the nanocatalyst could be easily separated from the reaction mixture with the aid of a magnetic field and reused several times without any losses in its catalytic activity. Moreover, experimental observations provided an insight into the reaction pathway. Chapter 3 describes the synthesis and characterization of a magnetic ZSM-5 zeolite with core-shell type structure for application on the valorization of bio-derived furfuryl alcohol. The magnetic HZSM-5 zeolite catalyst was prepared by the encapsulation of magnetite particles in the zeolite grains using a cationic polymer followed by calcination and next, an ion exchange to obtain the zeolite in its acid form. Remarkably, the catalytic system displayed a tunable selectivity to γ- valerolactone, alkyl levulinates and even levulinic acid by simply changing the reaction conditions. Furthermore, the catalyst could be easily recovered and reused for several reaction cycles without significant losses in its catalytic activity. |
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Lima, Carolina Guimarães de SouzaPaixão, Márcio Weberhttp://lattes.cnpq.br/3773908504964104http://lattes.cnpq.br/80508100291103352018-08-22T12:27:10Z2018-08-22T12:27:10Z2016-07-29LIMA, Carolina Guimarães de Souza. Nanoestructured catalysts for organic reactions: design, synthesis and applications. 2016. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10395.https://repositorio.ufscar.br/handle/ufscar/10395The development of more efficient and selective catalysts actively contributes for the design of safer, cleaner and less energy-demanding processes, and, therefore, catalysis is one of the cornerstones of green chemistry. In this sense, supported-heterogeneous catalysts represent a great advance in this field, especially because they overcome the difficulty in catalyst separation associated to homogeneous catalysts. In this context, this thesis is focused on the development of nanostructured materials for application in Organic Synthesis. In Chapter 1, a brief introduction regarding fundamental concepts in catalysis is presented, focusing on the synthesis and application of magnetically recoverable catalysts. Chapter 2 described the design, preparation and characterization of a new magnetically recoverable niobium nanocatalyst for application in the synthesis of 3,4-dihydropyrimidinones via Biginelli reaction. The catalyst (Fe3O4@Nb2O5) was prepared by coating magnetite nanoparticles with niobium oxide by using a simple wet impregnation method. The developed protocol was applicable to a wide range of aliphatic and aromatic substrates, and structurally diverse products were obtained in excellent yields. Additionally, the nanocatalyst could be easily separated from the reaction mixture with the aid of a magnetic field and reused several times without any losses in its catalytic activity. Moreover, experimental observations provided an insight into the reaction pathway. Chapter 3 describes the synthesis and characterization of a magnetic ZSM-5 zeolite with core-shell type structure for application on the valorization of bio-derived furfuryl alcohol. The magnetic HZSM-5 zeolite catalyst was prepared by the encapsulation of magnetite particles in the zeolite grains using a cationic polymer followed by calcination and next, an ion exchange to obtain the zeolite in its acid form. Remarkably, the catalytic system displayed a tunable selectivity to γ- valerolactone, alkyl levulinates and even levulinic acid by simply changing the reaction conditions. Furthermore, the catalyst could be easily recovered and reused for several reaction cycles without significant losses in its catalytic activity.O desenvolvimento de catalisadores mais eficientes e seletivos contribui para o design de processos mais seguros, mais limpos e mais energeticamente viáveis, e, portanto, a catálise é um dos pilares da Química Verde. Neste sentido, catalisadores heterogêneos suportados representam um grande avanço nesta área, principalmente porque superam as dificuldades de separação dos catalisadores homogêneos. Neste contexto, esta tese é focada no desenvolvimento de materiais nanoestruturados para aplicação em Síntese Orgânica. No Capítulo 1 é apresentada uma breve introdução envolvendo conceitos fundamentais em catálise, com foco na síntese e aplicação de catalisadores magneticamente recuperáveis. O Capítulo 2 descreve o design, preparação e caracterização de um novo catalisador de nióbio magneticamente recuperável e sua aplicação na síntese de 1,4-dihidropirimidinonas via reação de Biginelli. O catalisador foi preparado a partir do recobrimento de nanopartículas de magnetita com óxido de nióbio utilizando um simples método de impregnação úmida. O método desenvolvido pôde ser aplicado para uma grande quantidade de substratos alifáticos e aromáticos, e produtos com grande diversidade estrutural foram obtidos com rendimentos excelentes. Além disso, o nanocatalisador pode ser facilmente separado do meio reacional usando um campo magnético e reutilizado várias vezes sem nenhuma perda significativa de sua atividade catalítica. Adicionalmente, observações experimentais forneceram informações sobre o mecanismo da reação. O Capítulo 3 descreve a síntese e caracterização de uma zeólita magneticamente recuperável do tipo HZSM-5 e sua aplicação na valorização do álcool furfurílico. O catalisador constituído pela zeólita magnética foi preparado através do encapsulamento de partículas de magnetita nos grãos da zeólita utilizando um polímero catiônico seguido de calcinação e de uma etapa de troca iônica para a obtenção da zeólita em sua forma ácida. Interessantemente, a atividade catalítica deste sistema mostrou possuir uma seletividade ajustável para γ-valerolactona, levulinatos de alquila e até mesmo ácido levulínico através da simples mudança das condições reacionais. Além disso, o catalisador pôde ser facilmente recuperado e reutilizado em vários ciclos reacionais sem perdas significativas em sua atividade catalítica.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)engUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarCatálise heterogêneaReações multicomponenteQuímica verdeBiomassaSíntese orgânicaHeterogeneous catalystReaction mixtureGreen chemistryBiomassOrganic synthesisCIENCIAS EXATAS E DA TERRA::QUIMICACIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA::CINETICA QUIMICA E CATALISECIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICANanoestructured catalysts for organic reactions: design, synthesis and applicationsCatalisadores nanoestruturados para reações orgânicas: design, síntese e aplicaçõesCatalisadores nanoestruturados para reações orgânicas: design, síntese e aplicaçõesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnlineinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARLICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10395/4/license.txtae0398b6f8b235e40ad82cba6c50031dMD54ORIGINALLIMA_Carolina_2018.pdfLIMA_Carolina_2018.pdfapplication/pdf16715552https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10395/5/LIMA_Carolina_2018.pdf663e8bac690f87738487c8a4e351a514MD55TEXTLIMA_Carolina_2018.pdf.txtLIMA_Carolina_2018.pdf.txtExtracted texttext/plain294489https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10395/6/LIMA_Carolina_2018.pdf.txt50c6024f741b0ed955a725a1d66434deMD56THUMBNAILLIMA_Carolina_2018.pdf.jpgLIMA_Carolina_2018.pdf.jpgIM Thumbnailimage/jpeg8392https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10395/7/LIMA_Carolina_2018.pdf.jpg493de6db3da2dde0bc5e149b18193d51MD57ufscar/103952019-09-11 03:20:25.051oai:repositorio.ufscar.br:ufscar/10395TElDRU7Dh0EgREUgRElTVFJJQlVJw4fDg08gTsODTy1FWENMVVNJVkEKCkNvbSBhIGFwcmVzZW50YcOnw6NvIGRlc3RhIGxpY2Vuw6dhLCB2b2PDqiAobyBhdXRvciAoZXMpIG91IG8gdGl0dWxhciBkb3MgZGlyZWl0b3MgZGUgYXV0b3IpIGNvbmNlZGUgw6AgVW5pdmVyc2lkYWRlCkZlZGVyYWwgZGUgU8OjbyBDYXJsb3MgbyBkaXJlaXRvIG7Do28tZXhjbHVzaXZvIGRlIHJlcHJvZHV6aXIsICB0cmFkdXppciAoY29uZm9ybWUgZGVmaW5pZG8gYWJhaXhvKSwgZS9vdQpkaXN0cmlidWlyIGEgc3VhIHRlc2Ugb3UgZGlzc2VydGHDp8OjbyAoaW5jbHVpbmRvIG8gcmVzdW1vKSBwb3IgdG9kbyBvIG11bmRvIG5vIGZvcm1hdG8gaW1wcmVzc28gZSBlbGV0csO0bmljbyBlCmVtIHF1YWxxdWVyIG1laW8sIGluY2x1aW5kbyBvcyBmb3JtYXRvcyDDoXVkaW8gb3UgdsOtZGVvLgoKVm9jw6ogY29uY29yZGEgcXVlIGEgVUZTQ2FyIHBvZGUsIHNlbSBhbHRlcmFyIG8gY29udGXDumRvLCB0cmFuc3BvciBhIHN1YSB0ZXNlIG91IGRpc3NlcnRhw6fDo28KcGFyYSBxdWFscXVlciBtZWlvIG91IGZvcm1hdG8gcGFyYSBmaW5zIGRlIHByZXNlcnZhw6fDo28uCgpWb2PDqiB0YW1iw6ltIGNvbmNvcmRhIHF1ZSBhIFVGU0NhciBwb2RlIG1hbnRlciBtYWlzIGRlIHVtYSBjw7NwaWEgYSBzdWEgdGVzZSBvdQpkaXNzZXJ0YcOnw6NvIHBhcmEgZmlucyBkZSBzZWd1cmFuw6dhLCBiYWNrLXVwIGUgcHJlc2VydmHDp8Ojby4KClZvY8OqIGRlY2xhcmEgcXVlIGEgc3VhIHRlc2Ugb3UgZGlzc2VydGHDp8OjbyDDqSBvcmlnaW5hbCBlIHF1ZSB2b2PDqiB0ZW0gbyBwb2RlciBkZSBjb25jZWRlciBvcyBkaXJlaXRvcyBjb250aWRvcwpuZXN0YSBsaWNlbsOnYS4gVm9jw6ogdGFtYsOpbSBkZWNsYXJhIHF1ZSBvIGRlcMOzc2l0byBkYSBzdWEgdGVzZSBvdSBkaXNzZXJ0YcOnw6NvIG7Do28sIHF1ZSBzZWphIGRlIHNldQpjb25oZWNpbWVudG8sIGluZnJpbmdlIGRpcmVpdG9zIGF1dG9yYWlzIGRlIG5pbmd1w6ltLgoKQ2FzbyBhIHN1YSB0ZXNlIG91IGRpc3NlcnRhw6fDo28gY29udGVuaGEgbWF0ZXJpYWwgcXVlIHZvY8OqIG7Do28gcG9zc3VpIGEgdGl0dWxhcmlkYWRlIGRvcyBkaXJlaXRvcyBhdXRvcmFpcywgdm9jw6oKZGVjbGFyYSBxdWUgb2J0ZXZlIGEgcGVybWlzc8OjbyBpcnJlc3RyaXRhIGRvIGRldGVudG9yIGRvcyBkaXJlaXRvcyBhdXRvcmFpcyBwYXJhIGNvbmNlZGVyIMOgIFVGU0NhcgpvcyBkaXJlaXRvcyBhcHJlc2VudGFkb3MgbmVzdGEgbGljZW7Dp2EsIGUgcXVlIGVzc2UgbWF0ZXJpYWwgZGUgcHJvcHJpZWRhZGUgZGUgdGVyY2Vpcm9zIGVzdMOhIGNsYXJhbWVudGUKaWRlbnRpZmljYWRvIGUgcmVjb25oZWNpZG8gbm8gdGV4dG8gb3Ugbm8gY29udGXDumRvIGRhIHRlc2Ugb3UgZGlzc2VydGHDp8OjbyBvcmEgZGVwb3NpdGFkYS4KCkNBU08gQSBURVNFIE9VIERJU1NFUlRBw4fDg08gT1JBIERFUE9TSVRBREEgVEVOSEEgU0lETyBSRVNVTFRBRE8gREUgVU0gUEFUUk9Dw41OSU8gT1UKQVBPSU8gREUgVU1BIEFHw4pOQ0lBIERFIEZPTUVOVE8gT1UgT1VUUk8gT1JHQU5JU01PIFFVRSBOw4NPIFNFSkEgQSBVRlNDYXIsClZPQ8OKIERFQ0xBUkEgUVVFIFJFU1BFSVRPVSBUT0RPUyBFIFFVQUlTUVVFUiBESVJFSVRPUyBERSBSRVZJU8ODTyBDT01PClRBTULDiU0gQVMgREVNQUlTIE9CUklHQcOHw5VFUyBFWElHSURBUyBQT1IgQ09OVFJBVE8gT1UgQUNPUkRPLgoKQSBVRlNDYXIgc2UgY29tcHJvbWV0ZSBhIGlkZW50aWZpY2FyIGNsYXJhbWVudGUgbyBzZXUgbm9tZSAocykgb3UgbyhzKSBub21lKHMpIGRvKHMpCmRldGVudG9yKGVzKSBkb3MgZGlyZWl0b3MgYXV0b3JhaXMgZGEgdGVzZSBvdSBkaXNzZXJ0YcOnw6NvLCBlIG7Do28gZmFyw6EgcXVhbHF1ZXIgYWx0ZXJhw6fDo28sIGFsw6ltIGRhcXVlbGFzCmNvbmNlZGlkYXMgcG9yIGVzdGEgbGljZW7Dp2EuCg==Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-05-25T12:55:09.248799Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.eng.fl_str_mv |
Nanoestructured catalysts for organic reactions: design, synthesis and applications |
dc.title.alternative.por.fl_str_mv |
Catalisadores nanoestruturados para reações orgânicas: design, síntese e aplicações Catalisadores nanoestruturados para reações orgânicas: design, síntese e aplicações |
title |
Nanoestructured catalysts for organic reactions: design, synthesis and applications |
spellingShingle |
Nanoestructured catalysts for organic reactions: design, synthesis and applications Lima, Carolina Guimarães de Souza Catálise heterogênea Reações multicomponente Química verde Biomassa Síntese orgânica Heterogeneous catalyst Reaction mixture Green chemistry Biomass Organic synthesis CIENCIAS EXATAS E DA TERRA::QUIMICA CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA::CINETICA QUIMICA E CATALISE CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
title_short |
Nanoestructured catalysts for organic reactions: design, synthesis and applications |
title_full |
Nanoestructured catalysts for organic reactions: design, synthesis and applications |
title_fullStr |
Nanoestructured catalysts for organic reactions: design, synthesis and applications |
title_full_unstemmed |
Nanoestructured catalysts for organic reactions: design, synthesis and applications |
title_sort |
Nanoestructured catalysts for organic reactions: design, synthesis and applications |
author |
Lima, Carolina Guimarães de Souza |
author_facet |
Lima, Carolina Guimarães de Souza |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8050810029110335 |
dc.contributor.author.fl_str_mv |
Lima, Carolina Guimarães de Souza |
dc.contributor.advisor1.fl_str_mv |
Paixão, Márcio Weber |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3773908504964104 |
contributor_str_mv |
Paixão, Márcio Weber |
dc.subject.por.fl_str_mv |
Catálise heterogênea Reações multicomponente Química verde Biomassa Síntese orgânica |
topic |
Catálise heterogênea Reações multicomponente Química verde Biomassa Síntese orgânica Heterogeneous catalyst Reaction mixture Green chemistry Biomass Organic synthesis CIENCIAS EXATAS E DA TERRA::QUIMICA CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA::CINETICA QUIMICA E CATALISE CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
dc.subject.eng.fl_str_mv |
Heterogeneous catalyst Reaction mixture Green chemistry Biomass Organic synthesis |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA::CINETICA QUIMICA E CATALISE CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA::SINTESE ORGANICA |
description |
The development of more efficient and selective catalysts actively contributes for the design of safer, cleaner and less energy-demanding processes, and, therefore, catalysis is one of the cornerstones of green chemistry. In this sense, supported-heterogeneous catalysts represent a great advance in this field, especially because they overcome the difficulty in catalyst separation associated to homogeneous catalysts. In this context, this thesis is focused on the development of nanostructured materials for application in Organic Synthesis. In Chapter 1, a brief introduction regarding fundamental concepts in catalysis is presented, focusing on the synthesis and application of magnetically recoverable catalysts. Chapter 2 described the design, preparation and characterization of a new magnetically recoverable niobium nanocatalyst for application in the synthesis of 3,4-dihydropyrimidinones via Biginelli reaction. The catalyst (Fe3O4@Nb2O5) was prepared by coating magnetite nanoparticles with niobium oxide by using a simple wet impregnation method. The developed protocol was applicable to a wide range of aliphatic and aromatic substrates, and structurally diverse products were obtained in excellent yields. Additionally, the nanocatalyst could be easily separated from the reaction mixture with the aid of a magnetic field and reused several times without any losses in its catalytic activity. Moreover, experimental observations provided an insight into the reaction pathway. Chapter 3 describes the synthesis and characterization of a magnetic ZSM-5 zeolite with core-shell type structure for application on the valorization of bio-derived furfuryl alcohol. The magnetic HZSM-5 zeolite catalyst was prepared by the encapsulation of magnetite particles in the zeolite grains using a cationic polymer followed by calcination and next, an ion exchange to obtain the zeolite in its acid form. Remarkably, the catalytic system displayed a tunable selectivity to γ- valerolactone, alkyl levulinates and even levulinic acid by simply changing the reaction conditions. Furthermore, the catalyst could be easily recovered and reused for several reaction cycles without significant losses in its catalytic activity. |
publishDate |
2016 |
dc.date.issued.fl_str_mv |
2016-07-29 |
dc.date.accessioned.fl_str_mv |
2018-08-22T12:27:10Z |
dc.date.available.fl_str_mv |
2018-08-22T12:27:10Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
LIMA, Carolina Guimarães de Souza. Nanoestructured catalysts for organic reactions: design, synthesis and applications. 2016. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10395. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/10395 |
identifier_str_mv |
LIMA, Carolina Guimarães de Souza. Nanoestructured catalysts for organic reactions: design, synthesis and applications. 2016. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10395. |
url |
https://repositorio.ufscar.br/handle/ufscar/10395 |
dc.language.iso.fl_str_mv |
eng |
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eng |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química - PPGQ |
dc.publisher.initials.fl_str_mv |
UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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