Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO

Detalhes bibliográficos
Autor(a) principal: Maciel, Cristhiane Guimarães
Data de Publicação: 2010
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFSCAR
Texto Completo: https://repositorio.ufscar.br/handle/ufscar/3892
Resumo: The CO preferential oxidation reaction (PROX-CO) has been widely studied in last few years. Aiming H2 purification for proton-exchange membrane cells (PEMFC) use, the main role of the PROX-CO reaction should be reduce the CO contained in reformed gas to an acceptable level of CO concentration that do not provoke deactivation of Pt electrocatalyst. The search for substitutes for noble metals like Pt and Au, the first catalysts tested in PROX reaction, has been the subject of several studies. Among the proposed new solid, the Cu-O-Ce have received considerable attention. These catalysts have been shown be active and selective for PROX-CO in a temperature range that is appropriate for application in PEMFC cells and are materials of low cost. The metal-support interface of Cu-O-Ce system favors the CO oxidation reaction and some properties as metallic dispersion, particle size and morphology are determinants for the better performance of these catalysts. Therefore, in this present work, xCuO/CeO2 and xCuO/CeO2-Al2O3 catalyst (where x is the copper loading) were synthesized, characterized and tested in the CO preferential oxidation reaction. The effects of metal content, support composition, support preparation method and catalysts preparation method were evaluated. Experimental results showed that the metallic content influences the catalytic performance and the catalyst with 1% of copper content was the most active and selective for the PROX-CO. That catalyst also showed the best performance at lower temperature reaction. The study of the effect of support nature in the PROX-CO reaction showed that the strong interaction copper-ceria is a determining factor for the good performance of the catalysts. With alumina or ceria/alumina supports, the metal-support interaction is weaker and, in consequence, the catalysts were less active and selective. The preparation method study of ceria support showed that morphologic characteristics from its synthesis lead to different results of catalytic activity. The catalyst preparation method was important to catalytic activity results. The solids prepared by impregnation and citrate method were more active and selective than others. Although the catalysts synthesized by the deposition-precipitation and co-precipitation methods have also been active for the PROX-CO.
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spelling Maciel, Cristhiane GuimarãesAssaf, José Mansurhttp://lattes.cnpq.br/9563312407691130http://lattes.cnpq.br/1792781373802286c6a39a5b-8451-4baf-87b6-257c41e54ad22016-06-02T19:55:28Z2010-12-092016-06-02T19:55:28Z2010-06-30MACIEL, Cristhiane Guimarães. Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO. 2010. 184 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010.https://repositorio.ufscar.br/handle/ufscar/3892The CO preferential oxidation reaction (PROX-CO) has been widely studied in last few years. Aiming H2 purification for proton-exchange membrane cells (PEMFC) use, the main role of the PROX-CO reaction should be reduce the CO contained in reformed gas to an acceptable level of CO concentration that do not provoke deactivation of Pt electrocatalyst. The search for substitutes for noble metals like Pt and Au, the first catalysts tested in PROX reaction, has been the subject of several studies. Among the proposed new solid, the Cu-O-Ce have received considerable attention. These catalysts have been shown be active and selective for PROX-CO in a temperature range that is appropriate for application in PEMFC cells and are materials of low cost. The metal-support interface of Cu-O-Ce system favors the CO oxidation reaction and some properties as metallic dispersion, particle size and morphology are determinants for the better performance of these catalysts. Therefore, in this present work, xCuO/CeO2 and xCuO/CeO2-Al2O3 catalyst (where x is the copper loading) were synthesized, characterized and tested in the CO preferential oxidation reaction. The effects of metal content, support composition, support preparation method and catalysts preparation method were evaluated. Experimental results showed that the metallic content influences the catalytic performance and the catalyst with 1% of copper content was the most active and selective for the PROX-CO. That catalyst also showed the best performance at lower temperature reaction. The study of the effect of support nature in the PROX-CO reaction showed that the strong interaction copper-ceria is a determining factor for the good performance of the catalysts. With alumina or ceria/alumina supports, the metal-support interaction is weaker and, in consequence, the catalysts were less active and selective. The preparation method study of ceria support showed that morphologic characteristics from its synthesis lead to different results of catalytic activity. The catalyst preparation method was important to catalytic activity results. The solids prepared by impregnation and citrate method were more active and selective than others. Although the catalysts synthesized by the deposition-precipitation and co-precipitation methods have also been active for the PROX-CO.A reação de oxidação preferencial do CO (PROX-CO) tem sido extensivamente estudada nos últimos anos. Com o objetivo de purificar o H2 para o uso nas células a combustível do tipo membrana polimérica (PEMFC), esta reação reduz os níveis de CO que saem do gás reformado para valores tolerados pelo eletrocatalisador de platina. A busca por substituintes de metais nobres como Pt e Au, os primeiros catalisadores utilizados na reação de PROX-CO, tem sido o objetivo de vários estudos. Entre os sólidos propostos para este objetivo, o sistema Cu-O-Ce tem atraído considerável atenção. Estes catalisadores mostram-se ativos e seletivos para em temperaturas apropriadas para aplicação nas células PEMFC, além de apresentarem custo baixo. A interface metal-suporte do sistema Cu-O-Ce favorece a reação de oxidação do CO e algumas de suas propriedades como dispersão metálica, tamanho de partícula e morfologia são determinantes para o bom desempenho destes catalisadores. Neste presente trabalho, catalisadores do tipo xCuO/CeO2 e xCuO/CeO2-Al2O3 (onde x é o teor de cobre) foram sintetizados, caracterizados e testados na reação de oxidação preferencial do CO. Os efeitos do teor metálico, composição do suporte, método de preparação do suporte e dos catalisadores foram estudados. Os resultados experimentais mostraram que o teor metálico influencia na atividade catalítica e que o sólido com 1% de cobre foi o mais ativo e seletivo para a PROX-CO, uma vez que a dispersão do metal na superfície do suporte, mostrada pelas técnicas de caracterização, favorece a reação de PROX-CO. Este catalisador também mostrou melhor desempenho em baixas temperaturas. O estudo do efeito do suporte na reação de PROX-CO mostrou que a forte interação cobre-céria é um fator determinante para o bom desempennho catalítico. Com os suportes alumina pura ou céria/alumina, a interação metalsuporte é mais fraca e, como conseqüência, os catalisadores são menos ativos e seletivos, seja a altas temperaturas de reação, seja a baixas temperaturas reacionais. O método de preparação da céria mostrou que as características morfológicas de cada síntese levam a diferentes resultados catalíticos. E pelas análises de MEV e MET, mostrou-se que no método de preparação hidrotérmico, o cobre está mais disperso na superfície. O método de preparação dos catalisadores foi importante nos resultados de atividade catalítica. Os sólidos preparados por impregnação e pelo método do citrato apresentaram-se mais ativos e seletivos que os preparados pelos outros métodos, embora os preparados por deposiçãoprecipitação e co-precipitação também tenham sido ativos para a PROX-CO.Financiadora de Estudos e Projetosapplication/pdfporUniversidade Federal de São CarlosPrograma de Pós-Graduação em Engenharia Química - PPGEQUFSCarBRCatáliseProx-COCobreCériaAluminaENGENHARIAS::ENGENHARIA QUIMICAEstudo de catalisadores de cobre suportados para a reação de oxidação preferencial do COinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis-1-1d348d7f1-5523-40f0-9d08-b82dac73a6d8info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINAL3347.pdfapplication/pdf3138949https://repositorio.ufscar.br/bitstream/ufscar/3892/1/3347.pdf3d15697c0ec72d64e00515ac7bb7f7bbMD51THUMBNAIL3347.pdf.jpg3347.pdf.jpgIM Thumbnailimage/jpeg6921https://repositorio.ufscar.br/bitstream/ufscar/3892/2/3347.pdf.jpga981b56f8d9ab2ca04d62209e315d88aMD52ufscar/38922023-09-18 18:30:58.308oai:repositorio.ufscar.br:ufscar/3892Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:30:58Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false
dc.title.por.fl_str_mv Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
title Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
spellingShingle Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
Maciel, Cristhiane Guimarães
Catálise
Prox-CO
Cobre
Céria
Alumina
ENGENHARIAS::ENGENHARIA QUIMICA
title_short Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
title_full Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
title_fullStr Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
title_full_unstemmed Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
title_sort Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO
author Maciel, Cristhiane Guimarães
author_facet Maciel, Cristhiane Guimarães
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/1792781373802286
dc.contributor.author.fl_str_mv Maciel, Cristhiane Guimarães
dc.contributor.advisor1.fl_str_mv Assaf, José Mansur
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/9563312407691130
dc.contributor.authorID.fl_str_mv c6a39a5b-8451-4baf-87b6-257c41e54ad2
contributor_str_mv Assaf, José Mansur
dc.subject.por.fl_str_mv Catálise
Prox-CO
Cobre
Céria
Alumina
topic Catálise
Prox-CO
Cobre
Céria
Alumina
ENGENHARIAS::ENGENHARIA QUIMICA
dc.subject.cnpq.fl_str_mv ENGENHARIAS::ENGENHARIA QUIMICA
description The CO preferential oxidation reaction (PROX-CO) has been widely studied in last few years. Aiming H2 purification for proton-exchange membrane cells (PEMFC) use, the main role of the PROX-CO reaction should be reduce the CO contained in reformed gas to an acceptable level of CO concentration that do not provoke deactivation of Pt electrocatalyst. The search for substitutes for noble metals like Pt and Au, the first catalysts tested in PROX reaction, has been the subject of several studies. Among the proposed new solid, the Cu-O-Ce have received considerable attention. These catalysts have been shown be active and selective for PROX-CO in a temperature range that is appropriate for application in PEMFC cells and are materials of low cost. The metal-support interface of Cu-O-Ce system favors the CO oxidation reaction and some properties as metallic dispersion, particle size and morphology are determinants for the better performance of these catalysts. Therefore, in this present work, xCuO/CeO2 and xCuO/CeO2-Al2O3 catalyst (where x is the copper loading) were synthesized, characterized and tested in the CO preferential oxidation reaction. The effects of metal content, support composition, support preparation method and catalysts preparation method were evaluated. Experimental results showed that the metallic content influences the catalytic performance and the catalyst with 1% of copper content was the most active and selective for the PROX-CO. That catalyst also showed the best performance at lower temperature reaction. The study of the effect of support nature in the PROX-CO reaction showed that the strong interaction copper-ceria is a determining factor for the good performance of the catalysts. With alumina or ceria/alumina supports, the metal-support interaction is weaker and, in consequence, the catalysts were less active and selective. The preparation method study of ceria support showed that morphologic characteristics from its synthesis lead to different results of catalytic activity. The catalyst preparation method was important to catalytic activity results. The solids prepared by impregnation and citrate method were more active and selective than others. Although the catalysts synthesized by the deposition-precipitation and co-precipitation methods have also been active for the PROX-CO.
publishDate 2010
dc.date.available.fl_str_mv 2010-12-09
2016-06-02T19:55:28Z
dc.date.issued.fl_str_mv 2010-06-30
dc.date.accessioned.fl_str_mv 2016-06-02T19:55:28Z
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dc.identifier.citation.fl_str_mv MACIEL, Cristhiane Guimarães. Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO. 2010. 184 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/ufscar/3892
identifier_str_mv MACIEL, Cristhiane Guimarães. Estudo de catalisadores de cobre suportados para a reação de oxidação preferencial do CO. 2010. 184 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010.
url https://repositorio.ufscar.br/handle/ufscar/3892
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