Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts

Autores
Roncaroli, Federico; Dal Molin, Emiliano S.; Viva, Federico Andrés; Bruno, Mariano Martín; Halac, Emilia Beatriz
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Cobalt and Iron based catalysts for the Oxygen Reduction Reaction (ORR) are a promising alternative to the use of Pt in Polymer Electrolyte Fuel Cells (PEMFC). A systematic study on the influence of the nitrogenated ligand in the precursor complex on the ORR activity was performed. Several Fe and Co complexes were prepared with different N-heterocyclic ligands, namely: meso-tetra-(4-carboxyphenyl)-porphyrin (TCPP), N-methylimidazole (N-Me-Im), 3-amino-1,2,4-triazole-5-carboxylic acid (ATZC), 2,2′-bis(4,5-dimethylimidazole) (bis-Me-Im), phenanthroline (phen), 2-pyrazinecarboxylic acid (CO2-Pz), 3,6-di-2-pyridyl-1,2,4,5-tetrazine (DPTZ) and 2,4,6-tri(2-pyridyl)-s-triazine (TPTZ), adsorbed on a carbon substrate and submitted to thermal treatment. These ligands comprise five and six membered rings with one to four N-atoms. Key parameters such as the pyrolysis temperature, the complex load and the metal: ligand ratio were studied, in order to optimize the efficiency of the catalysts. The synthesized catalysts were characterized by several physical bulk and surface techniques, namely XRD, TGA, Raman spectroscopy, XPS, EDX and electron microscopies (SEM and TEM). The best catalyst was obtained from a Cobalt-phenanthroline precursor, adsorbed on a mesoporous carbon material, and pyrolyzed at 700 °C. The equilibrium potential was 0.90 V vs NHE (1.0 V for Pt), exchange current density 25 μA cm−2, Tafel slope was 90 mV dec−1, and 4.0 exchanged electrons, less than 9 % in H2O2 yield, and half wave potential only 80 mV lower than that of Platinum (10%). This catalyst exhibited the highest N content as determined by XPS. The electrochemical data of the prepared catalysts were analyzed in the context of the TGA, XRD and XPS information. A correlation between ORR activity and the N content (XPS) was found. This result strongly supports the model that proposes N atoms as the active sites, and provides a rational tool for designing new catalysts.
Fil: Roncaroli, Federico. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Dal Molin, Emiliano S.. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Viva, Federico Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Bruno, Mariano Martín. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Halac, Emilia Beatriz. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina
Materia
Non-Noble Catalyst
Orr
Platinum-Free
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
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oai:ri.conicet.gov.ar:11336/41777
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction CatalystsRoncaroli, FedericoDal Molin, Emiliano S.Viva, Federico AndrésBruno, Mariano MartínHalac, Emilia BeatrizNon-Noble CatalystOrrPlatinum-Freehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Cobalt and Iron based catalysts for the Oxygen Reduction Reaction (ORR) are a promising alternative to the use of Pt in Polymer Electrolyte Fuel Cells (PEMFC). A systematic study on the influence of the nitrogenated ligand in the precursor complex on the ORR activity was performed. Several Fe and Co complexes were prepared with different N-heterocyclic ligands, namely: meso-tetra-(4-carboxyphenyl)-porphyrin (TCPP), N-methylimidazole (N-Me-Im), 3-amino-1,2,4-triazole-5-carboxylic acid (ATZC), 2,2′-bis(4,5-dimethylimidazole) (bis-Me-Im), phenanthroline (phen), 2-pyrazinecarboxylic acid (CO2-Pz), 3,6-di-2-pyridyl-1,2,4,5-tetrazine (DPTZ) and 2,4,6-tri(2-pyridyl)-s-triazine (TPTZ), adsorbed on a carbon substrate and submitted to thermal treatment. These ligands comprise five and six membered rings with one to four N-atoms. Key parameters such as the pyrolysis temperature, the complex load and the metal: ligand ratio were studied, in order to optimize the efficiency of the catalysts. The synthesized catalysts were characterized by several physical bulk and surface techniques, namely XRD, TGA, Raman spectroscopy, XPS, EDX and electron microscopies (SEM and TEM). The best catalyst was obtained from a Cobalt-phenanthroline precursor, adsorbed on a mesoporous carbon material, and pyrolyzed at 700 °C. The equilibrium potential was 0.90 V vs NHE (1.0 V for Pt), exchange current density 25 μA cm−2, Tafel slope was 90 mV dec−1, and 4.0 exchanged electrons, less than 9 % in H2O2 yield, and half wave potential only 80 mV lower than that of Platinum (10%). This catalyst exhibited the highest N content as determined by XPS. The electrochemical data of the prepared catalysts were analyzed in the context of the TGA, XRD and XPS information. A correlation between ORR activity and the N content (XPS) was found. This result strongly supports the model that proposes N atoms as the active sites, and provides a rational tool for designing new catalysts.Fil: Roncaroli, Federico. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Dal Molin, Emiliano S.. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Viva, Federico Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Bruno, Mariano Martín. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Halac, Emilia Beatriz. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; ArgentinaPergamon-Elsevier Science Ltd2015-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/41777Roncaroli, Federico; Dal Molin, Emiliano S.; Viva, Federico Andrés; Bruno, Mariano Martín; Halac, Emilia Beatriz; Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts; Pergamon-Elsevier Science Ltd; Electrochimica Acta; 174; 8-2015; 66-770013-4686CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.electacta.2015.05.136info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0013468615012992info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:35:34Zoai:ri.conicet.gov.ar:11336/41777instacron: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 09:35:35.039CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
title Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
spellingShingle Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
Roncaroli, Federico
Non-Noble Catalyst
Orr
Platinum-Free
title_short Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
title_full Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
title_fullStr Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
title_full_unstemmed Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
title_sort Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts
dc.creator.none.fl_str_mv Roncaroli, Federico
Dal Molin, Emiliano S.
Viva, Federico Andrés
Bruno, Mariano Martín
Halac, Emilia Beatriz
author Roncaroli, Federico
author_facet Roncaroli, Federico
Dal Molin, Emiliano S.
Viva, Federico Andrés
Bruno, Mariano Martín
Halac, Emilia Beatriz
author_role author
author2 Dal Molin, Emiliano S.
Viva, Federico Andrés
Bruno, Mariano Martín
Halac, Emilia Beatriz
author2_role author
author
author
author
dc.subject.none.fl_str_mv Non-Noble Catalyst
Orr
Platinum-Free
topic Non-Noble Catalyst
Orr
Platinum-Free
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Cobalt and Iron based catalysts for the Oxygen Reduction Reaction (ORR) are a promising alternative to the use of Pt in Polymer Electrolyte Fuel Cells (PEMFC). A systematic study on the influence of the nitrogenated ligand in the precursor complex on the ORR activity was performed. Several Fe and Co complexes were prepared with different N-heterocyclic ligands, namely: meso-tetra-(4-carboxyphenyl)-porphyrin (TCPP), N-methylimidazole (N-Me-Im), 3-amino-1,2,4-triazole-5-carboxylic acid (ATZC), 2,2′-bis(4,5-dimethylimidazole) (bis-Me-Im), phenanthroline (phen), 2-pyrazinecarboxylic acid (CO2-Pz), 3,6-di-2-pyridyl-1,2,4,5-tetrazine (DPTZ) and 2,4,6-tri(2-pyridyl)-s-triazine (TPTZ), adsorbed on a carbon substrate and submitted to thermal treatment. These ligands comprise five and six membered rings with one to four N-atoms. Key parameters such as the pyrolysis temperature, the complex load and the metal: ligand ratio were studied, in order to optimize the efficiency of the catalysts. The synthesized catalysts were characterized by several physical bulk and surface techniques, namely XRD, TGA, Raman spectroscopy, XPS, EDX and electron microscopies (SEM and TEM). The best catalyst was obtained from a Cobalt-phenanthroline precursor, adsorbed on a mesoporous carbon material, and pyrolyzed at 700 °C. The equilibrium potential was 0.90 V vs NHE (1.0 V for Pt), exchange current density 25 μA cm−2, Tafel slope was 90 mV dec−1, and 4.0 exchanged electrons, less than 9 % in H2O2 yield, and half wave potential only 80 mV lower than that of Platinum (10%). This catalyst exhibited the highest N content as determined by XPS. The electrochemical data of the prepared catalysts were analyzed in the context of the TGA, XRD and XPS information. A correlation between ORR activity and the N content (XPS) was found. This result strongly supports the model that proposes N atoms as the active sites, and provides a rational tool for designing new catalysts.
Fil: Roncaroli, Federico. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Dal Molin, Emiliano S.. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Viva, Federico Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Bruno, Mariano Martín. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Halac, Emilia Beatriz. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina
description Cobalt and Iron based catalysts for the Oxygen Reduction Reaction (ORR) are a promising alternative to the use of Pt in Polymer Electrolyte Fuel Cells (PEMFC). A systematic study on the influence of the nitrogenated ligand in the precursor complex on the ORR activity was performed. Several Fe and Co complexes were prepared with different N-heterocyclic ligands, namely: meso-tetra-(4-carboxyphenyl)-porphyrin (TCPP), N-methylimidazole (N-Me-Im), 3-amino-1,2,4-triazole-5-carboxylic acid (ATZC), 2,2′-bis(4,5-dimethylimidazole) (bis-Me-Im), phenanthroline (phen), 2-pyrazinecarboxylic acid (CO2-Pz), 3,6-di-2-pyridyl-1,2,4,5-tetrazine (DPTZ) and 2,4,6-tri(2-pyridyl)-s-triazine (TPTZ), adsorbed on a carbon substrate and submitted to thermal treatment. These ligands comprise five and six membered rings with one to four N-atoms. Key parameters such as the pyrolysis temperature, the complex load and the metal: ligand ratio were studied, in order to optimize the efficiency of the catalysts. The synthesized catalysts were characterized by several physical bulk and surface techniques, namely XRD, TGA, Raman spectroscopy, XPS, EDX and electron microscopies (SEM and TEM). The best catalyst was obtained from a Cobalt-phenanthroline precursor, adsorbed on a mesoporous carbon material, and pyrolyzed at 700 °C. The equilibrium potential was 0.90 V vs NHE (1.0 V for Pt), exchange current density 25 μA cm−2, Tafel slope was 90 mV dec−1, and 4.0 exchanged electrons, less than 9 % in H2O2 yield, and half wave potential only 80 mV lower than that of Platinum (10%). This catalyst exhibited the highest N content as determined by XPS. The electrochemical data of the prepared catalysts were analyzed in the context of the TGA, XRD and XPS information. A correlation between ORR activity and the N content (XPS) was found. This result strongly supports the model that proposes N atoms as the active sites, and provides a rational tool for designing new catalysts.
publishDate 2015
dc.date.none.fl_str_mv 2015-08
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/11336/41777
Roncaroli, Federico; Dal Molin, Emiliano S.; Viva, Federico Andrés; Bruno, Mariano Martín; Halac, Emilia Beatriz; Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts; Pergamon-Elsevier Science Ltd; Electrochimica Acta; 174; 8-2015; 66-77
0013-4686
CONICET Digital
CONICET
url http://hdl.handle.net/11336/41777
identifier_str_mv Roncaroli, Federico; Dal Molin, Emiliano S.; Viva, Federico Andrés; Bruno, Mariano Martín; Halac, Emilia Beatriz; Cobalt and Iron Complexes with N-heterocyclic Ligands as Pyrolysis Precursors for Oxygen Reduction Catalysts; Pergamon-Elsevier Science Ltd; Electrochimica Acta; 174; 8-2015; 66-77
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.2015.05.136
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0013468615012992
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
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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
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score 13.070432

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