Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato

Detalhes bibliográficos
Autor(a) principal: Farinos, Rosimeire Martins
Data de Publicação: 2016
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFSCAR
Texto Completo: https://repositorio.ufscar.br/handle/ufscar/8027
Resumo: Electrodeposition of a PbO2 film was performed onto reticulated vitreous carbon (RVC) substrates with porosities of 45, 60, and 80 ppi, at 65 ºC in a flow reactor, starting with a solution containing Pb(NO3)2, surfactant, and HNO3. Investigation was made of the effects of current density and electrodeposition time on the coverage and uniformity of the PbO2 film formed. The electrodes were characterized using scanning electron microscopy, X-ray diffractometry, and linear potential scanning. The use of high currents resulted in the formation of thick films in regions close to the counter-electrode, which compromised film adhesion, while the application of lower currents ensured a uniform and adherent PbO2 coating. In tests of the decoloration of AR 19 dye using the best electrodes produced, better performance was achieved using RVC/PbO2, compared to VC/PbO2, due to the greater specific surface area and increased hydrodynamic turbulence caused by the tridimensional substrate, which increased the mass transport coefficient and therefore enhanced the degradation process. The optimum conditions for use of the RVC/PbO2 electrode were 3.5 mA cm-2 and 30 minutes of electrosynthesis. Electrochemical degradation of the herbicide was performed using the 60 ppi RVC/PbO2 electrode in a flow reactor. Box-Behnken design was used to study the effects of current density, flow, and temperature on the kinetics of degradation (COD) and mineralization (TOC), current efficiency (ε), and energy consumption (η). The best degradation and mineralization kinetics values were obtained with the upper limits of the variables studied (30 mA cm-2, 150 mL min-1, and 50 oC). Increasing the flow rate from 150 to 1500 mL min-1 increased εG from 18% to 65%, and decreased ηG from 72 to 33 kWh kg-1, reflecting a higher mass transport coefficient. In comparative tests, using degradation of the herbicide and phenol, the performance of the RVC/PbO2 electrode was slightly lower than that of a boron-doped diamond (BDD) electrode. Considering that the RVC/PbO2 device is less expensive than DDB electrodes, it can be concluded that this tridimensional electrode is promising for use in the degradation of organic pollutants.
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spelling Farinos, Rosimeire MartinsRuotolo, Luís Augusto Martinshttp://lattes.cnpq.br/6167735734348703http://lattes.cnpq.br/85502479622425980ed5d105-9887-4199-87a5-670ad628ced62016-10-20T18:56:08Z2016-10-20T18:56:08Z2016-05-06FARINOS, Rosimeire Martins. Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato. 2016. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8027.https://repositorio.ufscar.br/handle/ufscar/8027Electrodeposition of a PbO2 film was performed onto reticulated vitreous carbon (RVC) substrates with porosities of 45, 60, and 80 ppi, at 65 ºC in a flow reactor, starting with a solution containing Pb(NO3)2, surfactant, and HNO3. Investigation was made of the effects of current density and electrodeposition time on the coverage and uniformity of the PbO2 film formed. The electrodes were characterized using scanning electron microscopy, X-ray diffractometry, and linear potential scanning. The use of high currents resulted in the formation of thick films in regions close to the counter-electrode, which compromised film adhesion, while the application of lower currents ensured a uniform and adherent PbO2 coating. In tests of the decoloration of AR 19 dye using the best electrodes produced, better performance was achieved using RVC/PbO2, compared to VC/PbO2, due to the greater specific surface area and increased hydrodynamic turbulence caused by the tridimensional substrate, which increased the mass transport coefficient and therefore enhanced the degradation process. The optimum conditions for use of the RVC/PbO2 electrode were 3.5 mA cm-2 and 30 minutes of electrosynthesis. Electrochemical degradation of the herbicide was performed using the 60 ppi RVC/PbO2 electrode in a flow reactor. Box-Behnken design was used to study the effects of current density, flow, and temperature on the kinetics of degradation (COD) and mineralization (TOC), current efficiency (ε), and energy consumption (η). The best degradation and mineralization kinetics values were obtained with the upper limits of the variables studied (30 mA cm-2, 150 mL min-1, and 50 oC). Increasing the flow rate from 150 to 1500 mL min-1 increased εG from 18% to 65%, and decreased ηG from 72 to 33 kWh kg-1, reflecting a higher mass transport coefficient. In comparative tests, using degradation of the herbicide and phenol, the performance of the RVC/PbO2 electrode was slightly lower than that of a boron-doped diamond (BDD) electrode. Considering that the RVC/PbO2 device is less expensive than DDB electrodes, it can be concluded that this tridimensional electrode is promising for use in the degradation of organic pollutants.Realizou-se a técnica de eletrodeposição do filme de PbO2 sobre o substrato de carbono vítreo reticulado (CVR) com porosidades de 45, 60 e 80 ppi, partindo-se da solução contendo Pb(NO3)2, surfactante e HNO3, a 65ºC, em reator de fluxo, investigando-se o efeito da densidade de corrente e do tempo de eletrodeposição sobre a cobertura e uniformidade do filme de PbO2 formado. Os eletrodos foram caracterizados por microscopia eletrônica de varredura, difratometria de raios X e varredura linear de potencial. A aplicação de correntes elevadas levou à formação de filmes espessos nas regiões próximas ao contra-eletrodo, comprometendo a aderência do filme, porém, a aplicação de correntes mais baixas garantiram um recobrimento de PbO2 uniforme e aderente. Os resultados da descoloração do corante AR 19 usando os melhores eletrodos produzidos revelaram um desempenho superior do CVR/PbO2 em relação ao CV/PbO2, devido à maior área superficial específica e o aumento da turbulência hidrodinâmica proporcionadas pelo substrato tridimensional, causando um aumento do coeficiente de transporte de massa e, consequentemente, uma melhoria do processo de degradação. A condição ótima do CVR/PbO2 foi obtida utilizando o eletrodo de 60 ppi, sintetizado a 3,5 mA cm-2 e 30 minutos, resultando um aumento na cinética de descoloração do corante AR 19 de 70%. Realizou-se a degradação eletroquímica do herbicida glifosato em um reator de fluxo e aplicando-se o planejamento Box-Behnken; estudou-se a densidade de corrente, vazão e temperatura sobre as cinéticas de degradação (DQO) e mineralização (COT), eficiência de corrente (ε) e consumo energético (η). Os melhores valores de cinética de degradação e mineralização ocorreram para os limites superiores das variáveis estudadas (30 mA cm-2, 150 mL min-1 e 50 oC). Aumentando-se a vazão de 150 para 1500 mL min-1 houve aumento da eficiência de corrente global (18% para 65%) e diminuição do consumo energético global (72 para 33 kWh kg-1) evidenciando a importância do aumento do coeficiente de transporte de massa. Comparando-se o CVR/PbO2 com o diamante dopado com boro (DDB) na degradação do glifosato e do fenol, concluiu-se que o CVR/PbO2 apresentou resultados semelhantes à degradação com DDB, e, considerando que o CVR/PbO2 possui um custo inferior ao DDB, conclui-se que o eletrodo tridimensional mostra-se promissor para a utilização em degradação de poluente orgânicos.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Engenharia Química - PPGEQUFSCarComposto orgânicoDegradaçãoChumboTridimensionalReatoresENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICAPreparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosatoPreparation, characterization and application of threedimensional reticulated vitreous carbon electrodes coated with Pbo2 films for degradation of effluents containing dye reactive AR19 e glyphosateinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnline600600cf9213f8-9cfd-427b-96e9-08a34508a5b6info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTeseRMF.pdfTeseRMF.pdfapplication/pdf8360686https://repositorio.ufscar.br/bitstream/ufscar/8027/1/TeseRMF.pdf559580b48a0212e963c85a31a6c3eb25MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstream/ufscar/8027/2/license.txtae0398b6f8b235e40ad82cba6c50031dMD52TEXTTeseRMF.pdf.txtTeseRMF.pdf.txtExtracted texttext/plain329373https://repositorio.ufscar.br/bitstream/ufscar/8027/3/TeseRMF.pdf.txte752c4aa6c7a70a38b632eabb10edc32MD53THUMBNAILTeseRMF.pdf.jpgTeseRMF.pdf.jpgIM Thumbnailimage/jpeg7917https://repositorio.ufscar.br/bitstream/ufscar/8027/4/TeseRMF.pdf.jpg1316cf82468dad72e0cb31e25c7ab5a7MD54ufscar/80272023-09-18 18:31:48.773oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:48Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false
dc.title.por.fl_str_mv Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
dc.title.alternative.eng.fl_str_mv Preparation, characterization and application of threedimensional reticulated vitreous carbon electrodes coated with Pbo2 films for degradation of effluents containing dye reactive AR19 e glyphosate
title Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
spellingShingle Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
Farinos, Rosimeire Martins
Composto orgânico
Degradação
Chumbo
Tridimensional
Reatores
ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA
title_short Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
title_full Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
title_fullStr Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
title_full_unstemmed Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
title_sort Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato
author Farinos, Rosimeire Martins
author_facet Farinos, Rosimeire Martins
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/8550247962242598
dc.contributor.author.fl_str_mv Farinos, Rosimeire Martins
dc.contributor.advisor1.fl_str_mv Ruotolo, Luís Augusto Martins
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/6167735734348703
dc.contributor.authorID.fl_str_mv 0ed5d105-9887-4199-87a5-670ad628ced6
contributor_str_mv Ruotolo, Luís Augusto Martins
dc.subject.por.fl_str_mv Composto orgânico
Degradação
Chumbo
Tridimensional
Reatores
topic Composto orgânico
Degradação
Chumbo
Tridimensional
Reatores
ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA
dc.subject.cnpq.fl_str_mv ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA
description Electrodeposition of a PbO2 film was performed onto reticulated vitreous carbon (RVC) substrates with porosities of 45, 60, and 80 ppi, at 65 ºC in a flow reactor, starting with a solution containing Pb(NO3)2, surfactant, and HNO3. Investigation was made of the effects of current density and electrodeposition time on the coverage and uniformity of the PbO2 film formed. The electrodes were characterized using scanning electron microscopy, X-ray diffractometry, and linear potential scanning. The use of high currents resulted in the formation of thick films in regions close to the counter-electrode, which compromised film adhesion, while the application of lower currents ensured a uniform and adherent PbO2 coating. In tests of the decoloration of AR 19 dye using the best electrodes produced, better performance was achieved using RVC/PbO2, compared to VC/PbO2, due to the greater specific surface area and increased hydrodynamic turbulence caused by the tridimensional substrate, which increased the mass transport coefficient and therefore enhanced the degradation process. The optimum conditions for use of the RVC/PbO2 electrode were 3.5 mA cm-2 and 30 minutes of electrosynthesis. Electrochemical degradation of the herbicide was performed using the 60 ppi RVC/PbO2 electrode in a flow reactor. Box-Behnken design was used to study the effects of current density, flow, and temperature on the kinetics of degradation (COD) and mineralization (TOC), current efficiency (ε), and energy consumption (η). The best degradation and mineralization kinetics values were obtained with the upper limits of the variables studied (30 mA cm-2, 150 mL min-1, and 50 oC). Increasing the flow rate from 150 to 1500 mL min-1 increased εG from 18% to 65%, and decreased ηG from 72 to 33 kWh kg-1, reflecting a higher mass transport coefficient. In comparative tests, using degradation of the herbicide and phenol, the performance of the RVC/PbO2 electrode was slightly lower than that of a boron-doped diamond (BDD) electrode. Considering that the RVC/PbO2 device is less expensive than DDB electrodes, it can be concluded that this tridimensional electrode is promising for use in the degradation of organic pollutants.
publishDate 2016
dc.date.accessioned.fl_str_mv 2016-10-20T18:56:08Z
dc.date.available.fl_str_mv 2016-10-20T18:56:08Z
dc.date.issued.fl_str_mv 2016-05-06
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/doctoralThesis
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status_str publishedVersion
dc.identifier.citation.fl_str_mv FARINOS, Rosimeire Martins. Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato. 2016. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8027.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/ufscar/8027
identifier_str_mv FARINOS, Rosimeire Martins. Preparação, caracterização e aplicação de eletrodos tridimensionais de carbono vítreo reticulado recobertos com filmes de PbO2 para a degradação do corante reativo AR 19 e glifosato. 2016. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2016. Disponível em: https://repositorio.ufscar.br/handle/ufscar/8027.
url https://repositorio.ufscar.br/handle/ufscar/8027
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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 Engenharia Química - PPGEQ
dc.publisher.initials.fl_str_mv UFSCar
publisher.none.fl_str_mv Universidade Federal de São Carlos
Câmpus São Carlos
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