Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores

Detalhes bibliográficos
Autor(a) principal: Castro, Isabela Alves de
Data de Publicação: 2015
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFSCAR
Texto Completo: https://repositorio.ufscar.br/handle/ufscar/7292
Resumo: The use of semiconductors for environmental applications and solar photoconversion has been widely explored recently. Due the intensive researches on renewable energy such as the photoelectrochemical H2 evolution from water splitting reaction, the design of new catalysts has been investigated. In this context, tungsten oxide – WO3 – is a promising catalyst for such application, however its conduction band is located at a more positive potential than the potential of water reduction, as a result WO3 does not have the ability to reduce H+ to H2. In the first part, this work deal with the synthesis of WO3 by the oxidant peroxide method, as a promising catalyst for this reaction. Tuning of the band-edge levels for the different synthesized catalysts was verified from Mott Schottky plot, and it represents the effective photoelectrocatalytic water splitting.In the second part, the study of heterostructuring TiO2 with WO3was investigated because of the possibility to mitigate the recombination of electron–hole pairs and therefore obtain more active systems for photocatalytic applications. The synthesis of WO3/TiO2 heterostructures was evaluated by hydrothermal method using three different routes: (I) precursors used as peroxo-complexes; (II) tungsten peroxo-complex and TiO2 pre-formed oxide; (III) pre-formed oxides as building blocks. The results showed by electrochemical characterization demonstrated how the electronic parameters (band edge positions, Fermi level energy and charge migration) affect the photocatalytic activity of heterostructures obtained by the distinct synthetic routes. The as-synthesized materials was investigated toward the photodegradation of organic dye (Rhodamine-B) under visible and UV illumination. The growth mechanism was observed to play a significant role in governing surface and interfacial properties, which has a direct influence on xvi materials photoactivity. The band edge positions for the materials was determined from Mott Schottky plot and the experimentally determined energy diagram is consistent with the formation of a type II heterostructure for WO3/TiO2 and it is well correlated to recent reports in literature. As a result, the photogenerated electrons and holes can be spatially distributed in two different crystalline phases in contact and the charge recombination is inhibited, which is efficient for photocatalytic reactions.Additionally, regarding the energy diagram obtained for the heterostrucutres, it is possible from the thermodynamic aspect the use of those structures as promising candidates for the photoelectrocatalytic water splitting, since the band positions are sufficiently large to overcome the character of this reaction.
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spelling Castro, Isabela Alves deOliveira, Cauê Ribeiro dehttp://lattes.cnpq.br/5321313558714462http://lattes.cnpq.br/60657945853462312ac28eec-681e-4052-b73e-1474047126f22016-09-20T18:15:04Z2016-09-20T18:15:04Z2015-12-08CASTRO, Isabela Alves de. Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores. 2015. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/ufscar/7292.https://repositorio.ufscar.br/handle/ufscar/7292The use of semiconductors for environmental applications and solar photoconversion has been widely explored recently. Due the intensive researches on renewable energy such as the photoelectrochemical H2 evolution from water splitting reaction, the design of new catalysts has been investigated. In this context, tungsten oxide – WO3 – is a promising catalyst for such application, however its conduction band is located at a more positive potential than the potential of water reduction, as a result WO3 does not have the ability to reduce H+ to H2. In the first part, this work deal with the synthesis of WO3 by the oxidant peroxide method, as a promising catalyst for this reaction. Tuning of the band-edge levels for the different synthesized catalysts was verified from Mott Schottky plot, and it represents the effective photoelectrocatalytic water splitting.In the second part, the study of heterostructuring TiO2 with WO3was investigated because of the possibility to mitigate the recombination of electron–hole pairs and therefore obtain more active systems for photocatalytic applications. The synthesis of WO3/TiO2 heterostructures was evaluated by hydrothermal method using three different routes: (I) precursors used as peroxo-complexes; (II) tungsten peroxo-complex and TiO2 pre-formed oxide; (III) pre-formed oxides as building blocks. The results showed by electrochemical characterization demonstrated how the electronic parameters (band edge positions, Fermi level energy and charge migration) affect the photocatalytic activity of heterostructures obtained by the distinct synthetic routes. The as-synthesized materials was investigated toward the photodegradation of organic dye (Rhodamine-B) under visible and UV illumination. The growth mechanism was observed to play a significant role in governing surface and interfacial properties, which has a direct influence on xvi materials photoactivity. The band edge positions for the materials was determined from Mott Schottky plot and the experimentally determined energy diagram is consistent with the formation of a type II heterostructure for WO3/TiO2 and it is well correlated to recent reports in literature. As a result, the photogenerated electrons and holes can be spatially distributed in two different crystalline phases in contact and the charge recombination is inhibited, which is efficient for photocatalytic reactions.Additionally, regarding the energy diagram obtained for the heterostrucutres, it is possible from the thermodynamic aspect the use of those structures as promising candidates for the photoelectrocatalytic water splitting, since the band positions are sufficiently large to overcome the character of this reaction.O uso de semicondutores para aplicações ambientais e na fotoconversão solar tem sido amplamente explorado recentemente. Devido a pesquisas intensivas sobre energias renováveis como a reação de produção fotoeletroquímica de H2 a partir da água, o desenvolvimento de novos catalisadores tem sido investigado. O óxido de tungstênio – WO3– é um material promissor para tais aplicações, entretanto, a posição da sua banda de condução possui valores mais positivos que o potencial de redução da água, e desta forma este material não tem a habilidade de reduzir diretamente o H+ para H2. Na primeira parte, este trabalho aborda a síntese de WO3 pelo método dos peróxidos oxidantes (OPM), como um catalisador promissor para esta reação. Foi observado deslocamento nas bandas de energia para o filme de WO3 obtido pela rota OPM em relação ao óxido obtido pela rota convencional, determinado pela da relação de Mott Schottky e estes resultados caracterizam a efetiva reação water splitting. Na segunda parte, foi investigado a formação de heteroestruturas de TiO2 com WO3, no acoplamento entre as estruturas eletronicas dos óxidos semicondutores para obtenção de sistemas mais ativos em processos fotocatalíticos. A síntese de heteroestruturas WO3/TiO2 foi avaliada pelo método hidrotérmico utilizando três rotas distintas: (I) precursores na forma de peroxo-complexos estáveis; (II) peroxo-complexo de tungstênio e óxido pré-formado de TiO2 e (III) óxidos pré-formados como “blocos de construção”. De acordo com os resultados obtidos por caracterização eletroquímica, os parâmetros eletrônicos (posições de banda de energia, nível de Fermi e migração de cargas) influenciaram na atividade fotocatalítica de heteroestruturas obtidas por rotas sintéticas distintas. Os materiais foram investigados na reação defotodegradação do corante orgânico (Rodamina-B) sob xiv iluminação visível e UV. Observou-se que o mecanismo de crescimento das estruturas desempenha um papel significativo nas propriedades finais dos catalisadores produzidos, e uma influência direta sobre a fotoatividade destes. As posições do nível de Fermi para os materiais foi determinada a partir da caracterização eletroquímica pela relação de Mott Schottky e o diagrama de energia determinado experimentalmente é consistente com a formação de uma heteroestrutura tipo II para WO3/TiO2 e está de acordo com relatos recentes na literatura. Como consequência, os elétrons e buracos fotogerados podem estar espacialmente distribuídos nas fases cristalinas em contato e a taxa de recombinação é inibida, o que é eficaz para reações catalíticas. Além disso, em relação ao diagrama de energia obtida para as heteroestruturas, é possível do ponto de vista termodinâmico, a utilização como candidatos promissores para a reação fotoeletrocatalítica de water splitting, uma vez que os potenciais são energeticamente favoráveis para esta reação.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESP: 2011/07484-8CAPES: 8218-13-7porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarFotodegradaçãoSemicondutorHeteroestruturaWater splittingFotocatalisadorCIENCIAS EXATAS E DA TERRASíntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadoresWO3 and WO3/TiO2 heterostructures synthesized trhough oxidant peroxid method and their potential use as phototacalystsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnline60060019447b82-be97-4aec-a6e8-de69229cbfdeinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTeseIAC.pdfTeseIAC.pdfapplication/pdf3635782https://repositorio.ufscar.br/bitstream/ufscar/7292/1/TeseIAC.pdfaf0cdbb8c8caf2d9a90377d533f6b0caMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstream/ufscar/7292/2/license.txtae0398b6f8b235e40ad82cba6c50031dMD52TEXTTeseIAC.pdf.txtTeseIAC.pdf.txtExtracted texttext/plain270073https://repositorio.ufscar.br/bitstream/ufscar/7292/3/TeseIAC.pdf.txtcdd659035a07dbd1d86e089a08bafba1MD53THUMBNAILTeseIAC.pdf.jpgTeseIAC.pdf.jpgIM Thumbnailimage/jpeg10771https://repositorio.ufscar.br/bitstream/ufscar/7292/4/TeseIAC.pdf.jpg8dfe2e0aa277cfdc0ea3609c9797944fMD54ufscar/72922023-09-18 18:31:23.231oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:23Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false
dc.title.por.fl_str_mv Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
dc.title.alternative.eng.fl_str_mv WO3 and WO3/TiO2 heterostructures synthesized trhough oxidant peroxid method and their potential use as phototacalysts
title Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
spellingShingle Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
Castro, Isabela Alves de
Fotodegradação
Semicondutor
Heteroestrutura
Water splitting
Fotocatalisador
CIENCIAS EXATAS E DA TERRA
title_short Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
title_full Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
title_fullStr Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
title_full_unstemmed Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
title_sort Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores
author Castro, Isabela Alves de
author_facet Castro, Isabela Alves de
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/6065794585346231
dc.contributor.author.fl_str_mv Castro, Isabela Alves de
dc.contributor.advisor1.fl_str_mv Oliveira, Cauê Ribeiro de
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/5321313558714462
dc.contributor.authorID.fl_str_mv 2ac28eec-681e-4052-b73e-1474047126f2
contributor_str_mv Oliveira, Cauê Ribeiro de
dc.subject.por.fl_str_mv Fotodegradação
Semicondutor
Heteroestrutura
Water splitting
Fotocatalisador
topic Fotodegradação
Semicondutor
Heteroestrutura
Water splitting
Fotocatalisador
CIENCIAS EXATAS E DA TERRA
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA
description The use of semiconductors for environmental applications and solar photoconversion has been widely explored recently. Due the intensive researches on renewable energy such as the photoelectrochemical H2 evolution from water splitting reaction, the design of new catalysts has been investigated. In this context, tungsten oxide – WO3 – is a promising catalyst for such application, however its conduction band is located at a more positive potential than the potential of water reduction, as a result WO3 does not have the ability to reduce H+ to H2. In the first part, this work deal with the synthesis of WO3 by the oxidant peroxide method, as a promising catalyst for this reaction. Tuning of the band-edge levels for the different synthesized catalysts was verified from Mott Schottky plot, and it represents the effective photoelectrocatalytic water splitting.In the second part, the study of heterostructuring TiO2 with WO3was investigated because of the possibility to mitigate the recombination of electron–hole pairs and therefore obtain more active systems for photocatalytic applications. The synthesis of WO3/TiO2 heterostructures was evaluated by hydrothermal method using three different routes: (I) precursors used as peroxo-complexes; (II) tungsten peroxo-complex and TiO2 pre-formed oxide; (III) pre-formed oxides as building blocks. The results showed by electrochemical characterization demonstrated how the electronic parameters (band edge positions, Fermi level energy and charge migration) affect the photocatalytic activity of heterostructures obtained by the distinct synthetic routes. The as-synthesized materials was investigated toward the photodegradation of organic dye (Rhodamine-B) under visible and UV illumination. The growth mechanism was observed to play a significant role in governing surface and interfacial properties, which has a direct influence on xvi materials photoactivity. The band edge positions for the materials was determined from Mott Schottky plot and the experimentally determined energy diagram is consistent with the formation of a type II heterostructure for WO3/TiO2 and it is well correlated to recent reports in literature. As a result, the photogenerated electrons and holes can be spatially distributed in two different crystalline phases in contact and the charge recombination is inhibited, which is efficient for photocatalytic reactions.Additionally, regarding the energy diagram obtained for the heterostrucutres, it is possible from the thermodynamic aspect the use of those structures as promising candidates for the photoelectrocatalytic water splitting, since the band positions are sufficiently large to overcome the character of this reaction.
publishDate 2015
dc.date.issued.fl_str_mv 2015-12-08
dc.date.accessioned.fl_str_mv 2016-09-20T18:15:04Z
dc.date.available.fl_str_mv 2016-09-20T18:15:04Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.citation.fl_str_mv CASTRO, Isabela Alves de. Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores. 2015. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/ufscar/7292.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/ufscar/7292
identifier_str_mv CASTRO, Isabela Alves de. Síntese de WO3 e de heteroestruturas WO3/TiO2 pelo método de oxidação por peróxido e avaliação do potencial como fotocatalisadores. 2015. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/ufscar/7292.
url https://repositorio.ufscar.br/handle/ufscar/7292
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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 Química - PPGQ
dc.publisher.initials.fl_str_mv UFSCar
publisher.none.fl_str_mv Universidade Federal de São Carlos
Câmpus São Carlos
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