An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study

Autores
Senthilnathan, Dhurairajan; Giunta, Pablo Daniel; Vetere, Valentina; Kachmar, Ali; Maldivi, Pascale; Franco, Alejandro A.
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this paper we report a theoretical and a multiscale simulation study of the hydrogen evolution reaction (HER) on the [Ni(PH 2N H 2)2]2+ catalyst in acidic media (2H+ + 2e- → H2). First, at the DFT calculations level, a cyclic pathway for the HER is proposed highlighting the shuttling of electrons with protons on the conformationally flexible catalyst. The theoretical calculation gives a better understanding of the efficient cyclic pathway of [Ni(PH 2NH 2) 2]2+, and the effect of solvent on the mechanism has been discussed. The σ-donating and π-accepting nature of H2-Ni bond has been identified in the H2 complex. The oxidation state of the Ni centre and geometrical changes of the catalyst in the reaction coordinate are also identified. Then a mean-field kinetic model incorporating the calculated DFT data has been developed. This model allows us to simulate the behaviour of these catalysts in electrochemical conditions representative of polymer electrolyte membrane water electrolyzers operation. Calculated results include experimental observables such as polarization curves showing good agreement with available experimental data. Competitive phenomena between the different electrochemical mechanisms, the protons and H2 transport, and their relative impact on the overall cell performance are particularly discussed.
Fil: Senthilnathan, Dhurairajan. Laboratoire de Reconnaissance Ionique et Chimie de Coordination; Francia
Fil: Giunta, Pablo Daniel. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Vetere, Valentina. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia
Fil: Kachmar, Ali. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia
Fil: Maldivi, Pascale. Laboratoire de Reconnaissance Ionique et Chimie de Coordination; Francia
Fil: Franco, Alejandro A.. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia
Materia
HYDROGEN
MULTISCALE
SIMULATION
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:11336/85279
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/85279
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation studySenthilnathan, DhurairajanGiunta, Pablo DanielVetere, ValentinaKachmar, AliMaldivi, PascaleFranco, Alejandro A.HYDROGENMULTISCALESIMULATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In this paper we report a theoretical and a multiscale simulation study of the hydrogen evolution reaction (HER) on the [Ni(PH 2N H 2)2]2+ catalyst in acidic media (2H+ + 2e- → H2). First, at the DFT calculations level, a cyclic pathway for the HER is proposed highlighting the shuttling of electrons with protons on the conformationally flexible catalyst. The theoretical calculation gives a better understanding of the efficient cyclic pathway of [Ni(PH 2NH 2) 2]2+, and the effect of solvent on the mechanism has been discussed. The σ-donating and π-accepting nature of H2-Ni bond has been identified in the H2 complex. The oxidation state of the Ni centre and geometrical changes of the catalyst in the reaction coordinate are also identified. Then a mean-field kinetic model incorporating the calculated DFT data has been developed. This model allows us to simulate the behaviour of these catalysts in electrochemical conditions representative of polymer electrolyte membrane water electrolyzers operation. Calculated results include experimental observables such as polarization curves showing good agreement with available experimental data. Competitive phenomena between the different electrochemical mechanisms, the protons and H2 transport, and their relative impact on the overall cell performance are particularly discussed.Fil: Senthilnathan, Dhurairajan. Laboratoire de Reconnaissance Ionique et Chimie de Coordination; FranciaFil: Giunta, Pablo Daniel. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Vetere, Valentina. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; FranciaFil: Kachmar, Ali. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; FranciaFil: Maldivi, Pascale. Laboratoire de Reconnaissance Ionique et Chimie de Coordination; FranciaFil: Franco, Alejandro A.. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; FranciaRoyal Society of Chemistry2014-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/85279Senthilnathan, Dhurairajan; Giunta, Pablo Daniel; Vetere, Valentina; Kachmar, Ali; Maldivi, Pascale; et al.; An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study; Royal Society of Chemistry; RSC Advances; 4; 10; 10-2014; 5177-51872046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C3RA44896Ginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2014/RA/c3ra44896ginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:49:39Zoai:ri.conicet.gov.ar:11336/85279instacron: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:34982025-09-03 09:49:39.999CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
title An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
spellingShingle An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
Senthilnathan, Dhurairajan
HYDROGEN
MULTISCALE
SIMULATION
title_short An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
title_full An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
title_fullStr An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
title_full_unstemmed An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
title_sort An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study
dc.creator.none.fl_str_mv Senthilnathan, Dhurairajan
Giunta, Pablo Daniel
Vetere, Valentina
Kachmar, Ali
Maldivi, Pascale
Franco, Alejandro A.
author Senthilnathan, Dhurairajan
author_facet Senthilnathan, Dhurairajan
Giunta, Pablo Daniel
Vetere, Valentina
Kachmar, Ali
Maldivi, Pascale
Franco, Alejandro A.
author_role author
author2 Giunta, Pablo Daniel
Vetere, Valentina
Kachmar, Ali
Maldivi, Pascale
Franco, Alejandro A.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv HYDROGEN
MULTISCALE
SIMULATION
topic HYDROGEN
MULTISCALE
SIMULATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this paper we report a theoretical and a multiscale simulation study of the hydrogen evolution reaction (HER) on the [Ni(PH 2N H 2)2]2+ catalyst in acidic media (2H+ + 2e- → H2). First, at the DFT calculations level, a cyclic pathway for the HER is proposed highlighting the shuttling of electrons with protons on the conformationally flexible catalyst. The theoretical calculation gives a better understanding of the efficient cyclic pathway of [Ni(PH 2NH 2) 2]2+, and the effect of solvent on the mechanism has been discussed. The σ-donating and π-accepting nature of H2-Ni bond has been identified in the H2 complex. The oxidation state of the Ni centre and geometrical changes of the catalyst in the reaction coordinate are also identified. Then a mean-field kinetic model incorporating the calculated DFT data has been developed. This model allows us to simulate the behaviour of these catalysts in electrochemical conditions representative of polymer electrolyte membrane water electrolyzers operation. Calculated results include experimental observables such as polarization curves showing good agreement with available experimental data. Competitive phenomena between the different electrochemical mechanisms, the protons and H2 transport, and their relative impact on the overall cell performance are particularly discussed.
Fil: Senthilnathan, Dhurairajan. Laboratoire de Reconnaissance Ionique et Chimie de Coordination; Francia
Fil: Giunta, Pablo Daniel. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Vetere, Valentina. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia
Fil: Kachmar, Ali. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia
Fil: Maldivi, Pascale. Laboratoire de Reconnaissance Ionique et Chimie de Coordination; Francia
Fil: Franco, Alejandro A.. Laboratoire des Composants pour Piles à combustible, Electrolyseurs, et de Modélisation; Francia
description In this paper we report a theoretical and a multiscale simulation study of the hydrogen evolution reaction (HER) on the [Ni(PH 2N H 2)2]2+ catalyst in acidic media (2H+ + 2e- → H2). First, at the DFT calculations level, a cyclic pathway for the HER is proposed highlighting the shuttling of electrons with protons on the conformationally flexible catalyst. The theoretical calculation gives a better understanding of the efficient cyclic pathway of [Ni(PH 2NH 2) 2]2+, and the effect of solvent on the mechanism has been discussed. The σ-donating and π-accepting nature of H2-Ni bond has been identified in the H2 complex. The oxidation state of the Ni centre and geometrical changes of the catalyst in the reaction coordinate are also identified. Then a mean-field kinetic model incorporating the calculated DFT data has been developed. This model allows us to simulate the behaviour of these catalysts in electrochemical conditions representative of polymer electrolyte membrane water electrolyzers operation. Calculated results include experimental observables such as polarization curves showing good agreement with available experimental data. Competitive phenomena between the different electrochemical mechanisms, the protons and H2 transport, and their relative impact on the overall cell performance are particularly discussed.
publishDate 2014
dc.date.none.fl_str_mv 2014-10
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/11336/85279
Senthilnathan, Dhurairajan; Giunta, Pablo Daniel; Vetere, Valentina; Kachmar, Ali; Maldivi, Pascale; et al.; An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study; Royal Society of Chemistry; RSC Advances; 4; 10; 10-2014; 5177-5187
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/85279
identifier_str_mv Senthilnathan, Dhurairajan; Giunta, Pablo Daniel; Vetere, Valentina; Kachmar, Ali; Maldivi, Pascale; et al.; An efficient and cyclic hydrogen evolution reaction mechanism on [Ni(P H 2NH 2)2]2+ catalysts: A theoretical and multiscale simulation study; Royal Society of Chemistry; RSC Advances; 4; 10; 10-2014; 5177-5187
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C3RA44896G
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2014/RA/c3ra44896g
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.13397

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