Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation

Autores
Luna, Maria Alejandra; Moyano, Fernando; Sereno, Leonides Edmundo; D'eramo, Fabiana
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report herein the catalytic oxidation of water to molecular oxygen with water-soluble 5,10,15,20-tetra(N-methylpyridyl) porphyrinato manganese (III) chloride, [PMn(III)]Cl5. The homogeneous chemical and electrochemical oxidation of [PMn(III)]Cl5 was studied in aqueous buffer solution by UV-vis and cyclic voltammetry techniques. Firstly, [PMn(III)]Cl5 was characterized by spectroscopy in pH 7 and 10, measuring the changes produced by oxidation with a chemical agent. These studies showed that intermediates with higher oxidation states, [PMn(IV) = O]Cl4 and [PMn(V) = O]Cl5, are formed under these conditions and they are more stable at pH 10 at room temperature. The same result was obtained by electrochemical oxidation. The electrochemical studies showed that [PMn(III)]Cl5 is adsorbed on glassy carbon electrode surface. However, this does not help explain the high oxidation current obtained in both pHs at high anodic potentials. We demonstrated that these currents, in the cyclic voltammperogram of the [PMn(III)]Cl5, are due mainly to the water catalytic oxidation by the [PMn(V) = O]+5 intermediate. Besides, we show that chloride ion present in the porphyrin structure can also be oxidized by the same mechanism.
Fil: Luna, Maria Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Moyano, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Sereno, Leonides Edmundo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: D'eramo, Fabiana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Materia
Manganese Porphyrin
Electrocatalysis
Electrochemistry
Water Oxidation
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/34076
Acceder
id CONICETDig_758e92d3ec1ae0154090230285ad83f0
oai_identifier_str oai:ri.conicet.gov.ar:11336/34076
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidationLuna, Maria AlejandraMoyano, FernandoSereno, Leonides EdmundoD'eramo, FabianaManganese PorphyrinElectrocatalysisElectrochemistryWater Oxidationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report herein the catalytic oxidation of water to molecular oxygen with water-soluble 5,10,15,20-tetra(N-methylpyridyl) porphyrinato manganese (III) chloride, [PMn(III)]Cl5. The homogeneous chemical and electrochemical oxidation of [PMn(III)]Cl5 was studied in aqueous buffer solution by UV-vis and cyclic voltammetry techniques. Firstly, [PMn(III)]Cl5 was characterized by spectroscopy in pH 7 and 10, measuring the changes produced by oxidation with a chemical agent. These studies showed that intermediates with higher oxidation states, [PMn(IV) = O]Cl4 and [PMn(V) = O]Cl5, are formed under these conditions and they are more stable at pH 10 at room temperature. The same result was obtained by electrochemical oxidation. The electrochemical studies showed that [PMn(III)]Cl5 is adsorbed on glassy carbon electrode surface. However, this does not help explain the high oxidation current obtained in both pHs at high anodic potentials. We demonstrated that these currents, in the cyclic voltammperogram of the [PMn(III)]Cl5, are due mainly to the water catalytic oxidation by the [PMn(V) = O]+5 intermediate. Besides, we show that chloride ion present in the porphyrin structure can also be oxidized by the same mechanism.Fil: Luna, Maria Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Moyano, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Sereno, Leonides Edmundo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: D'eramo, Fabiana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaPergamon-Elsevier Science Ltd.2014-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/34076Luna, Maria Alejandra; Moyano, Fernando; Sereno, Leonides Edmundo; D'eramo, Fabiana; Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation; Pergamon-Elsevier Science Ltd.; Electrochimica Acta; 135; 5-2014; 301-3100013-4686CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.electacta.2014.04.157info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0013468614009372info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:19:09Zoai:ri.conicet.gov.ar:11336/34076instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:19:09.298CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
title Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
spellingShingle Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
Luna, Maria Alejandra
Manganese Porphyrin
Electrocatalysis
Electrochemistry
Water Oxidation
title_short Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
title_full Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
title_fullStr Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
title_full_unstemmed Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
title_sort Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation
dc.creator.none.fl_str_mv Luna, Maria Alejandra
Moyano, Fernando
Sereno, Leonides Edmundo
D'eramo, Fabiana
author Luna, Maria Alejandra
author_facet Luna, Maria Alejandra
Moyano, Fernando
Sereno, Leonides Edmundo
D'eramo, Fabiana
author_role author
author2 Moyano, Fernando
Sereno, Leonides Edmundo
D'eramo, Fabiana
author2_role author
author
author
dc.subject.none.fl_str_mv Manganese Porphyrin
Electrocatalysis
Electrochemistry
Water Oxidation
topic Manganese Porphyrin
Electrocatalysis
Electrochemistry
Water Oxidation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report herein the catalytic oxidation of water to molecular oxygen with water-soluble 5,10,15,20-tetra(N-methylpyridyl) porphyrinato manganese (III) chloride, [PMn(III)]Cl5. The homogeneous chemical and electrochemical oxidation of [PMn(III)]Cl5 was studied in aqueous buffer solution by UV-vis and cyclic voltammetry techniques. Firstly, [PMn(III)]Cl5 was characterized by spectroscopy in pH 7 and 10, measuring the changes produced by oxidation with a chemical agent. These studies showed that intermediates with higher oxidation states, [PMn(IV) = O]Cl4 and [PMn(V) = O]Cl5, are formed under these conditions and they are more stable at pH 10 at room temperature. The same result was obtained by electrochemical oxidation. The electrochemical studies showed that [PMn(III)]Cl5 is adsorbed on glassy carbon electrode surface. However, this does not help explain the high oxidation current obtained in both pHs at high anodic potentials. We demonstrated that these currents, in the cyclic voltammperogram of the [PMn(III)]Cl5, are due mainly to the water catalytic oxidation by the [PMn(V) = O]+5 intermediate. Besides, we show that chloride ion present in the porphyrin structure can also be oxidized by the same mechanism.
Fil: Luna, Maria Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Moyano, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Sereno, Leonides Edmundo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: D'eramo, Fabiana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
description We report herein the catalytic oxidation of water to molecular oxygen with water-soluble 5,10,15,20-tetra(N-methylpyridyl) porphyrinato manganese (III) chloride, [PMn(III)]Cl5. The homogeneous chemical and electrochemical oxidation of [PMn(III)]Cl5 was studied in aqueous buffer solution by UV-vis and cyclic voltammetry techniques. Firstly, [PMn(III)]Cl5 was characterized by spectroscopy in pH 7 and 10, measuring the changes produced by oxidation with a chemical agent. These studies showed that intermediates with higher oxidation states, [PMn(IV) = O]Cl4 and [PMn(V) = O]Cl5, are formed under these conditions and they are more stable at pH 10 at room temperature. The same result was obtained by electrochemical oxidation. The electrochemical studies showed that [PMn(III)]Cl5 is adsorbed on glassy carbon electrode surface. However, this does not help explain the high oxidation current obtained in both pHs at high anodic potentials. We demonstrated that these currents, in the cyclic voltammperogram of the [PMn(III)]Cl5, are due mainly to the water catalytic oxidation by the [PMn(V) = O]+5 intermediate. Besides, we show that chloride ion present in the porphyrin structure can also be oxidized by the same mechanism.
publishDate 2014
dc.date.none.fl_str_mv 2014-05
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/34076
Luna, Maria Alejandra; Moyano, Fernando; Sereno, Leonides Edmundo; D'eramo, Fabiana; Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation; Pergamon-Elsevier Science Ltd.; Electrochimica Acta; 135; 5-2014; 301-310
0013-4686
CONICET Digital
CONICET
url http://hdl.handle.net/11336/34076
identifier_str_mv Luna, Maria Alejandra; Moyano, Fernando; Sereno, Leonides Edmundo; D'eramo, Fabiana; Spectroscopic and electrochemical studies of high-valent water soluble manganese porphyrine. Electrocatalytic water oxidation; Pergamon-Elsevier Science Ltd.; Electrochimica Acta; 135; 5-2014; 301-310
0013-4686
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.electacta.2014.04.157
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0013468614009372
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd.
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd.
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1844614160387670016
score 13.070432

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