Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor

Autores
Rojas, Mariana Isabel; Andreussi, Oliviero; Gomez, Cesar Gerardo; Avalle, Lucia Bernardita
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The kinetics and mechanism of the hydrogen peroxide reduction reaction (HPRR) on a recently proposed carbon-based electrode is studied by means of experiments and simulations. The electrode is highly oriented pyrolytic graphite (HOPG) modified by the deposition of a graphite carbon nitride (g-C3N4) film. Current transients obtained from chronoamperometry measurements allow us to propose a kinetic model for the HPRR on the surface. The model produces excellent fits of current transients, providing sensible rate constants for each electrocatalytic step. The rate constants obtained are consistent with low energy barriers for each step, suggesting outstanding electrocatalytic activity of the g-C3N4/HOPG electrode. Moreover, different trends are found for low and high analyte concentrations, evidencing a change in the reaction mechanism. To clarify the mechanisms involved in the reaction, first-principles atomistic simulations were performed. The different reaction steps were modeled at the substrate/water interface, including solvent environment through continuum embedding approaches. The simulated thermodynamics and kinetics of the different processes show that a significant role in the electrocatalytic activity of the system is associated with the geometrical rearrangements of the interface, with a critical role played by the corrugation/decorrugation processes of the outermost sheet of the electrode.
Fil: Rojas, Mariana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Andreussi, Oliviero. University of North Texas; Estados Unidos
Fil: Gomez, Cesar Gerardo. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina
Fil: Avalle, Lucia Bernardita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Materia
ELECTROCATALYTIC ACTIVITY
KINETICS AND MECHANISM
EXPERIMENTS
ATOMISTIC SIMULATIONS
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:11336/125646
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/125646
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensorRojas, Mariana IsabelAndreussi, OlivieroGomez, Cesar GerardoAvalle, Lucia BernarditaELECTROCATALYTIC ACTIVITYKINETICS AND MECHANISMEXPERIMENTSATOMISTIC SIMULATIONShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The kinetics and mechanism of the hydrogen peroxide reduction reaction (HPRR) on a recently proposed carbon-based electrode is studied by means of experiments and simulations. The electrode is highly oriented pyrolytic graphite (HOPG) modified by the deposition of a graphite carbon nitride (g-C3N4) film. Current transients obtained from chronoamperometry measurements allow us to propose a kinetic model for the HPRR on the surface. The model produces excellent fits of current transients, providing sensible rate constants for each electrocatalytic step. The rate constants obtained are consistent with low energy barriers for each step, suggesting outstanding electrocatalytic activity of the g-C3N4/HOPG electrode. Moreover, different trends are found for low and high analyte concentrations, evidencing a change in the reaction mechanism. To clarify the mechanisms involved in the reaction, first-principles atomistic simulations were performed. The different reaction steps were modeled at the substrate/water interface, including solvent environment through continuum embedding approaches. The simulated thermodynamics and kinetics of the different processes show that a significant role in the electrocatalytic activity of the system is associated with the geometrical rearrangements of the interface, with a critical role played by the corrugation/decorrugation processes of the outermost sheet of the electrode.Fil: Rojas, Mariana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Andreussi, Oliviero. University of North Texas; Estados UnidosFil: Gomez, Cesar Gerardo. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; ArgentinaFil: Avalle, Lucia Bernardita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaAmerican Chemical Society2019-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/125646Rojas, Mariana Isabel; Andreussi, Oliviero; Gomez, Cesar Gerardo; Avalle, Lucia Bernardita; Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor; American Chemical Society; Journal of Physical Chemistry C; 124; 1; 12-2019; 336-3461932-74471932-7455CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.9b07315info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.9b07315info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-06-10T09:50:18Zoai:ri.conicet.gov.ar:11336/125646instacron: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:34982026-06-10 09:50:19.031CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
title Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
spellingShingle Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
Rojas, Mariana Isabel
ELECTROCATALYTIC ACTIVITY
KINETICS AND MECHANISM
EXPERIMENTS
ATOMISTIC SIMULATIONS
title_short Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
title_full Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
title_fullStr Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
title_full_unstemmed Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
title_sort Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor
dc.creator.none.fl_str_mv Rojas, Mariana Isabel
Andreussi, Oliviero
Gomez, Cesar Gerardo
Avalle, Lucia Bernardita
author Rojas, Mariana Isabel
author_facet Rojas, Mariana Isabel
Andreussi, Oliviero
Gomez, Cesar Gerardo
Avalle, Lucia Bernardita
author_role author
author2 Andreussi, Oliviero
Gomez, Cesar Gerardo
Avalle, Lucia Bernardita
author2_role author
author
author
dc.subject.none.fl_str_mv ELECTROCATALYTIC ACTIVITY
KINETICS AND MECHANISM
EXPERIMENTS
ATOMISTIC SIMULATIONS
topic ELECTROCATALYTIC ACTIVITY
KINETICS AND MECHANISM
EXPERIMENTS
ATOMISTIC SIMULATIONS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The kinetics and mechanism of the hydrogen peroxide reduction reaction (HPRR) on a recently proposed carbon-based electrode is studied by means of experiments and simulations. The electrode is highly oriented pyrolytic graphite (HOPG) modified by the deposition of a graphite carbon nitride (g-C3N4) film. Current transients obtained from chronoamperometry measurements allow us to propose a kinetic model for the HPRR on the surface. The model produces excellent fits of current transients, providing sensible rate constants for each electrocatalytic step. The rate constants obtained are consistent with low energy barriers for each step, suggesting outstanding electrocatalytic activity of the g-C3N4/HOPG electrode. Moreover, different trends are found for low and high analyte concentrations, evidencing a change in the reaction mechanism. To clarify the mechanisms involved in the reaction, first-principles atomistic simulations were performed. The different reaction steps were modeled at the substrate/water interface, including solvent environment through continuum embedding approaches. The simulated thermodynamics and kinetics of the different processes show that a significant role in the electrocatalytic activity of the system is associated with the geometrical rearrangements of the interface, with a critical role played by the corrugation/decorrugation processes of the outermost sheet of the electrode.
Fil: Rojas, Mariana Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Andreussi, Oliviero. University of North Texas; Estados Unidos
Fil: Gomez, Cesar Gerardo. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina
Fil: Avalle, Lucia Bernardita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
description The kinetics and mechanism of the hydrogen peroxide reduction reaction (HPRR) on a recently proposed carbon-based electrode is studied by means of experiments and simulations. The electrode is highly oriented pyrolytic graphite (HOPG) modified by the deposition of a graphite carbon nitride (g-C3N4) film. Current transients obtained from chronoamperometry measurements allow us to propose a kinetic model for the HPRR on the surface. The model produces excellent fits of current transients, providing sensible rate constants for each electrocatalytic step. The rate constants obtained are consistent with low energy barriers for each step, suggesting outstanding electrocatalytic activity of the g-C3N4/HOPG electrode. Moreover, different trends are found for low and high analyte concentrations, evidencing a change in the reaction mechanism. To clarify the mechanisms involved in the reaction, first-principles atomistic simulations were performed. The different reaction steps were modeled at the substrate/water interface, including solvent environment through continuum embedding approaches. The simulated thermodynamics and kinetics of the different processes show that a significant role in the electrocatalytic activity of the system is associated with the geometrical rearrangements of the interface, with a critical role played by the corrugation/decorrugation processes of the outermost sheet of the electrode.
publishDate 2019
dc.date.none.fl_str_mv 2019-12
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/11336/125646
Rojas, Mariana Isabel; Andreussi, Oliviero; Gomez, Cesar Gerardo; Avalle, Lucia Bernardita; Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor; American Chemical Society; Journal of Physical Chemistry C; 124; 1; 12-2019; 336-346
1932-7447
1932-7455
CONICET Digital
CONICET
url http://hdl.handle.net/11336/125646
identifier_str_mv Rojas, Mariana Isabel; Andreussi, Oliviero; Gomez, Cesar Gerardo; Avalle, Lucia Bernardita; Kinetics and mechanism of the hydrogen peroxide reduction reaction on a graphite carbon ntride sensor; American Chemical Society; Journal of Physical Chemistry C; 124; 1; 12-2019; 336-346
1932-7447
1932-7455
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.9b07315
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.9b07315
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 12.9928255

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