Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Tipo de documento: | Dissertação |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10362/110680 |
Resumo: | The continuous strong growth of CO2 emissions and the intensification of environmental impacts caused by this gas have aroused an increasing interest in the development of strategies to transform CO2. Formate dehydrogenases (FDH) are enzymes that perform the reversible interconversion of formate to CO2, hence these biocatalysts can transform CO2 into a compound that can be used either as a biofuel or as chemical precursor for sustainable chemical synthesis. Reports on direct electrochemical approaches, avoiding kinetic limitations of the mediating molecules and additional steps of cofactors regeneration, have been scarce until recently. In this Thesis, the electrochemical characterisation of the molybdenum-containing FDH from Desulfovibrio desulfuricans (DdFDH) was accomplished through non-mediated methods, in the absence of added substrates (non-turnover conditions), for the enzyme physically adsorbed onto a pyrolytic graphite electrode, at pH 6.5. A redox process with formal potential of -124 ± 11 mV vs NHE was assigned to the redox pair Mo (VI/IV) of the active centre. The heterogeneous electron transfer rate constant increased with the scan rate, which is indicative of a good communication between the enzyme and the electrode. The DdFDH catalytic response towards CO2 reduction was attained without mediators as well, upon the addition of saturated CO2 solution and sodium carbonate solution for the DdFDH adsorbed onto a stationary pyrolytic graphite electrode. The electrocatalysis towards CO2 reduction was also attained for DdFDH physically adsorbed on glassy carbon and graphite, under the hydrodynamic regime, and for the DdFDH encapsulated on felt carbon, a gas diffusion electrode. |
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Electrocatalysis of Formate Dehydrogenase Towards CO2 ReductionCO2 valorisationElectrocatalysisFormate dehydrogenaseProtein electrochemistryDomínio/Área Científica::Engenharia e Tecnologia::Outras Engenharias e TecnologiasThe continuous strong growth of CO2 emissions and the intensification of environmental impacts caused by this gas have aroused an increasing interest in the development of strategies to transform CO2. Formate dehydrogenases (FDH) are enzymes that perform the reversible interconversion of formate to CO2, hence these biocatalysts can transform CO2 into a compound that can be used either as a biofuel or as chemical precursor for sustainable chemical synthesis. Reports on direct electrochemical approaches, avoiding kinetic limitations of the mediating molecules and additional steps of cofactors regeneration, have been scarce until recently. In this Thesis, the electrochemical characterisation of the molybdenum-containing FDH from Desulfovibrio desulfuricans (DdFDH) was accomplished through non-mediated methods, in the absence of added substrates (non-turnover conditions), for the enzyme physically adsorbed onto a pyrolytic graphite electrode, at pH 6.5. A redox process with formal potential of -124 ± 11 mV vs NHE was assigned to the redox pair Mo (VI/IV) of the active centre. The heterogeneous electron transfer rate constant increased with the scan rate, which is indicative of a good communication between the enzyme and the electrode. The DdFDH catalytic response towards CO2 reduction was attained without mediators as well, upon the addition of saturated CO2 solution and sodium carbonate solution for the DdFDH adsorbed onto a stationary pyrolytic graphite electrode. The electrocatalysis towards CO2 reduction was also attained for DdFDH physically adsorbed on glassy carbon and graphite, under the hydrodynamic regime, and for the DdFDH encapsulated on felt carbon, a gas diffusion electrode.Cordas, CristinaMaia, LuísaRUNBaptista, Rita Helena Duarte2022-10-01T00:31:12Z2021-01-1420212021-01-14T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfhttp://hdl.handle.net/10362/110680enginfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-03-11T04:54:30Zoai:run.unl.pt:10362/110680Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T03:41:41.291820Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction |
title |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction |
spellingShingle |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction Baptista, Rita Helena Duarte CO2 valorisation Electrocatalysis Formate dehydrogenase Protein electrochemistry Domínio/Área Científica::Engenharia e Tecnologia::Outras Engenharias e Tecnologias |
title_short |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction |
title_full |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction |
title_fullStr |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction |
title_full_unstemmed |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction |
title_sort |
Electrocatalysis of Formate Dehydrogenase Towards CO2 Reduction |
author |
Baptista, Rita Helena Duarte |
author_facet |
Baptista, Rita Helena Duarte |
author_role |
author |
dc.contributor.none.fl_str_mv |
Cordas, Cristina Maia, Luísa RUN |
dc.contributor.author.fl_str_mv |
Baptista, Rita Helena Duarte |
dc.subject.por.fl_str_mv |
CO2 valorisation Electrocatalysis Formate dehydrogenase Protein electrochemistry Domínio/Área Científica::Engenharia e Tecnologia::Outras Engenharias e Tecnologias |
topic |
CO2 valorisation Electrocatalysis Formate dehydrogenase Protein electrochemistry Domínio/Área Científica::Engenharia e Tecnologia::Outras Engenharias e Tecnologias |
description |
The continuous strong growth of CO2 emissions and the intensification of environmental impacts caused by this gas have aroused an increasing interest in the development of strategies to transform CO2. Formate dehydrogenases (FDH) are enzymes that perform the reversible interconversion of formate to CO2, hence these biocatalysts can transform CO2 into a compound that can be used either as a biofuel or as chemical precursor for sustainable chemical synthesis. Reports on direct electrochemical approaches, avoiding kinetic limitations of the mediating molecules and additional steps of cofactors regeneration, have been scarce until recently. In this Thesis, the electrochemical characterisation of the molybdenum-containing FDH from Desulfovibrio desulfuricans (DdFDH) was accomplished through non-mediated methods, in the absence of added substrates (non-turnover conditions), for the enzyme physically adsorbed onto a pyrolytic graphite electrode, at pH 6.5. A redox process with formal potential of -124 ± 11 mV vs NHE was assigned to the redox pair Mo (VI/IV) of the active centre. The heterogeneous electron transfer rate constant increased with the scan rate, which is indicative of a good communication between the enzyme and the electrode. The DdFDH catalytic response towards CO2 reduction was attained without mediators as well, upon the addition of saturated CO2 solution and sodium carbonate solution for the DdFDH adsorbed onto a stationary pyrolytic graphite electrode. The electrocatalysis towards CO2 reduction was also attained for DdFDH physically adsorbed on glassy carbon and graphite, under the hydrodynamic regime, and for the DdFDH encapsulated on felt carbon, a gas diffusion electrode. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-01-14 2021 2021-01-14T00:00:00Z 2022-10-01T00:31:12Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10362/110680 |
url |
http://hdl.handle.net/10362/110680 |
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eng |
language |
eng |
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info:eu-repo/semantics/openAccess |
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openAccess |
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application/pdf |
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reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799138029656342528 |