Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ
Autor(a) principal: | |
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Data de Publicação: | 2018 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/10808 |
Resumo: | The modification of platinum-based electrodes for the efficiency optimization of the fuel cells has generated a great scientific interest, due to the problems associated with the poisoning of the catalytic surface. In addition, the use of renewable fuels is an important advantage for these systems by associating the high performance of the electric motors with the low emission of pollutants. In this way, the scientific community has studied numerous materials such as alloys and multilayer metallic structures (MM), and fuels as small organic molecules. In this work, Ptpc/M/Pt metallic multilayers were developed, in which rhodium or ruthenium was used as an intermediate layer, and their catalytic activities were investigated for the methanol and ethanol electro-oxidation in acid medium. For this purpose, cyclic voltammetry (VC) and in situ infrared spectroscopy (in situ FTIR) were used. In addition, the behavior and catalytic activity of MM Ptpc/Rh/Pt for the methanol electro-oxidation in alkaline medium using VC was evaluated. In acid medium, the compositions Ptpc/Rh2,0/Pt1,0 and Ptpc/Ru5,0/Pt2,0 presented increases of 283% and 422%, respectively, in the peak current density compared to Ptpc for the methanol oxidation and 32% and 67%, respectively, for the ethanol electro-oxidation. Using FTIR in situ, the appearance of a band at ~ 2340 cm-1, attributed to CO2, which is the total oxidation product of the alcohols, was observed. In alkaline medium, Ptpc/Rh2,0/Pt1,0 had an increase in the current density of 70% compared to Ptpc. Therefore, the addition of rhodium and ruthenium as intermediate layers promoted an improvement in the catalytic activity compared to Ptpc, probably by altering the electronic configuration of the platinum or improving the bifunctional effect. |
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Silva, Camila Daiane Ferreira daSouza, Ernesto Chaves Pereira dehttp://lattes.cnpq.br/1505400360366643http://lattes.cnpq.br/86468219204628995c504a31-0451-48be-839c-0b2791e7e5fe2018-12-14T17:08:31Z2018-12-14T17:08:31Z2018-09-06SILVA, Camila Daiane Ferreira da. Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ. 2018. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10808.https://repositorio.ufscar.br/handle/ufscar/10808The modification of platinum-based electrodes for the efficiency optimization of the fuel cells has generated a great scientific interest, due to the problems associated with the poisoning of the catalytic surface. In addition, the use of renewable fuels is an important advantage for these systems by associating the high performance of the electric motors with the low emission of pollutants. In this way, the scientific community has studied numerous materials such as alloys and multilayer metallic structures (MM), and fuels as small organic molecules. In this work, Ptpc/M/Pt metallic multilayers were developed, in which rhodium or ruthenium was used as an intermediate layer, and their catalytic activities were investigated for the methanol and ethanol electro-oxidation in acid medium. For this purpose, cyclic voltammetry (VC) and in situ infrared spectroscopy (in situ FTIR) were used. In addition, the behavior and catalytic activity of MM Ptpc/Rh/Pt for the methanol electro-oxidation in alkaline medium using VC was evaluated. In acid medium, the compositions Ptpc/Rh2,0/Pt1,0 and Ptpc/Ru5,0/Pt2,0 presented increases of 283% and 422%, respectively, in the peak current density compared to Ptpc for the methanol oxidation and 32% and 67%, respectively, for the ethanol electro-oxidation. Using FTIR in situ, the appearance of a band at ~ 2340 cm-1, attributed to CO2, which is the total oxidation product of the alcohols, was observed. In alkaline medium, Ptpc/Rh2,0/Pt1,0 had an increase in the current density of 70% compared to Ptpc. Therefore, the addition of rhodium and ruthenium as intermediate layers promoted an improvement in the catalytic activity compared to Ptpc, probably by altering the electronic configuration of the platinum or improving the bifunctional effect.A modificação de eletrodos a base de platina para a otimização da eficiência das células a combustível direto vem gerando um grande interesse científico, devido aos problemas associados ao envenenamento da superfície catalítica. Além disso, a utilização de combustíveis renováveis é uma vantagem importante para estes sistemas por associarem o alto rendimento dos motores elétricos com a baixa emissão de poluentes. Desta maneira, inúmeros materiais, como ligas e estruturas multicamadas metálicas (MM), e combustíveis como moléculas orgânicas pequenas têm sido estudados pela comunidade científica. Neste trabalho, foram desenvolvidas multicamadas metálicas do tipo Ptpc/M/Pt, em que ródio ou rutênio foram usados como camada intermediária, e foram investigadas suas atividades catalíticas para a eletro-oxidação de metanol e etanol em meio ácido. Para tanto, a voltametria cíclica (VC) e a espectroscopia de infravermelho in situ (FTIR in situ) foram utilizadas. Além disso, foi avaliado o comportamento e atividade catalítica das MM Ptpc/Rh/Pt para a eletro-oxidação de metanol em meio alcalino utilizando VC. Em meio ácido, as composições Ptpc/Rh2,0/Pt1,0 e Ptpc/Ru5,0/Pt2,0 apresentaram aumentos na densidade de corrente de pico comparadas à Ptpc de 283% e 422%, respectivamente, para a oxidação do metanol e de 32% e 67%, respectivamente, para a eletro-oxidação de etanol. Utilizando o FTIR in situ, foi observado o aparecimento de uma banda em ~2340 cm-1 atribuída ao CO2, que é o produto de oxidação total dos álcoois. Em meio alcalino, Ptpc/Rh2,0/Pt1,0 apresentou 70% de aumento na densidade de corrente na oxidação de metanol em relação à Ptpc. Portanto, a adição de ródio e rutênio como camadas intermediárias promoveram uma melhora na atividade catalítica frente à Ptpc, provavelmente por alterar a configuração eletrônica da platina ou melhorar o efeito bifuncional.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CNPq: 143341/2014-6porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarEletrocatáliseMulticamadas metálicasFTIR in situCIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICAEstudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situStudy of the electro-oxidation of small organic molecules on metallic multilayers Ptpc/Rh/Pt and Ptpc/Ru/Pt by FTIR in situinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnline60060016229a12-027e-4f0e-96b0-518d49092280info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALtese_CamilaDFSilva_corrigida.pdftese_CamilaDFSilva_corrigida.pdfapplication/pdf2480183https://repositorio.ufscar.br/bitstream/ufscar/10808/1/tese_CamilaDFSilva_corrigida.pdf5782936c0295818c0fd394bf6fae18dcMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstream/ufscar/10808/4/license.txtae0398b6f8b235e40ad82cba6c50031dMD54TEXTtese_CamilaDFSilva_corrigida.pdf.txttese_CamilaDFSilva_corrigida.pdf.txtExtracted texttext/plain164109https://repositorio.ufscar.br/bitstream/ufscar/10808/5/tese_CamilaDFSilva_corrigida.pdf.txtf0c16991547806284c955f7997baa87eMD55THUMBNAILtese_CamilaDFSilva_corrigida.pdf.jpgtese_CamilaDFSilva_corrigida.pdf.jpgIM Thumbnailimage/jpeg10128https://repositorio.ufscar.br/bitstream/ufscar/10808/6/tese_CamilaDFSilva_corrigida.pdf.jpga9965b3bd6fff4e429c7801e49146a77MD56ufscar/108082023-09-18 18:31:18.777oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:18Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ |
dc.title.alternative.eng.fl_str_mv |
Study of the electro-oxidation of small organic molecules on metallic multilayers Ptpc/Rh/Pt and Ptpc/Ru/Pt by FTIR in situ |
title |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ |
spellingShingle |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ Silva, Camila Daiane Ferreira da Eletrocatálise Multicamadas metálicas FTIR in situ CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
title_short |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ |
title_full |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ |
title_fullStr |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ |
title_full_unstemmed |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ |
title_sort |
Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ |
author |
Silva, Camila Daiane Ferreira da |
author_facet |
Silva, Camila Daiane Ferreira da |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8646821920462899 |
dc.contributor.author.fl_str_mv |
Silva, Camila Daiane Ferreira da |
dc.contributor.advisor1.fl_str_mv |
Souza, Ernesto Chaves Pereira de |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/1505400360366643 |
dc.contributor.authorID.fl_str_mv |
5c504a31-0451-48be-839c-0b2791e7e5fe |
contributor_str_mv |
Souza, Ernesto Chaves Pereira de |
dc.subject.por.fl_str_mv |
Eletrocatálise Multicamadas metálicas FTIR in situ |
topic |
Eletrocatálise Multicamadas metálicas FTIR in situ CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA::FISICO-QUIMICA |
description |
The modification of platinum-based electrodes for the efficiency optimization of the fuel cells has generated a great scientific interest, due to the problems associated with the poisoning of the catalytic surface. In addition, the use of renewable fuels is an important advantage for these systems by associating the high performance of the electric motors with the low emission of pollutants. In this way, the scientific community has studied numerous materials such as alloys and multilayer metallic structures (MM), and fuels as small organic molecules. In this work, Ptpc/M/Pt metallic multilayers were developed, in which rhodium or ruthenium was used as an intermediate layer, and their catalytic activities were investigated for the methanol and ethanol electro-oxidation in acid medium. For this purpose, cyclic voltammetry (VC) and in situ infrared spectroscopy (in situ FTIR) were used. In addition, the behavior and catalytic activity of MM Ptpc/Rh/Pt for the methanol electro-oxidation in alkaline medium using VC was evaluated. In acid medium, the compositions Ptpc/Rh2,0/Pt1,0 and Ptpc/Ru5,0/Pt2,0 presented increases of 283% and 422%, respectively, in the peak current density compared to Ptpc for the methanol oxidation and 32% and 67%, respectively, for the ethanol electro-oxidation. Using FTIR in situ, the appearance of a band at ~ 2340 cm-1, attributed to CO2, which is the total oxidation product of the alcohols, was observed. In alkaline medium, Ptpc/Rh2,0/Pt1,0 had an increase in the current density of 70% compared to Ptpc. Therefore, the addition of rhodium and ruthenium as intermediate layers promoted an improvement in the catalytic activity compared to Ptpc, probably by altering the electronic configuration of the platinum or improving the bifunctional effect. |
publishDate |
2018 |
dc.date.accessioned.fl_str_mv |
2018-12-14T17:08:31Z |
dc.date.available.fl_str_mv |
2018-12-14T17:08:31Z |
dc.date.issued.fl_str_mv |
2018-09-06 |
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 |
SILVA, Camila Daiane Ferreira da. Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ. 2018. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10808. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/10808 |
identifier_str_mv |
SILVA, Camila Daiane Ferreira da. Estudo da eletro-oxidação de moléculas orgânicas pequenas sobre multicamadas metálicas Ptpc/Rh/Pt e Ptpc/Ru/Pt utilizando FTIR in situ. 2018. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2018. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10808. |
url |
https://repositorio.ufscar.br/handle/ufscar/10808 |
dc.language.iso.fl_str_mv |
por |
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por |
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600 600 |
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info:eu-repo/semantics/openAccess |
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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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