Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction

Seeking alternatives to noble metals-based electrocatalysts for oxygen reduction reaction (ORR), hollow carbon spheres (CSs) were finely tuned with stable single-atom Fe–N species through a synthesis methodology requiring only earth-abundant metal precursors. CSs with different sizes were synthesize...

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Autores: Ribeiro, Rui S., Vieira, Ana Luísa S., Biernacki, Krzysztof, Magalhães, Alexandre L., Delgado, Juan J., Morais, Rafael G., Rocha, Raquel P., Pereira, M. Fernando R.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/349266
Acceso en línea:http://hdl.handle.net/10261/349266
https://api.elsevier.com/content/abstract/scopus_id/85161571523
Access Level:acceso abierto
Palabra clave:Single-atomic catalysts
Density-functional theory (DFT)
Electrocatalysis
Fuel cells
ORR
http://metadata.un.org/sdg/7
http://metadata.un.org/sdg/9
Ensure access to affordable, reliable, sustainable and modern energy for all
Build resilient infrastructure, promote inclusive and sustainable industrialization and foster innovation
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spelling Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reactionRibeiro, Rui S.Vieira, Ana Luísa S.Biernacki, KrzysztofMagalhães, Alexandre L.Delgado, Juan J.Morais, Rafael G.Rocha, Raquel P.Pereira, M. Fernando R.Single-atomic catalystsDensity-functional theory (DFT)ElectrocatalysisFuel cellsORRhttp://metadata.un.org/sdg/7http://metadata.un.org/sdg/9Ensure access to affordable, reliable, sustainable and modern energy for allBuild resilient infrastructure, promote inclusive and sustainable industrialization and foster innovationSeeking alternatives to noble metals-based electrocatalysts for oxygen reduction reaction (ORR), hollow carbon spheres (CSs) were finely tuned with stable single-atom Fe–N species through a synthesis methodology requiring only earth-abundant metal precursors. CSs with different sizes were synthesized by sol-gel polycondensation of resorcinol with formaldehyde over silica nanoparticles, followed by thermal annealing and silica etching. A catalyst screening revealed the positive impact of both the hollow core and structural defects of the CSs for ORR. Single-atom Fe–N active sites were introduced on the best performing CSs through simultaneous incorporation of iron and nitrogen precursors, and glucose. A significant enhancement in ORR activity was observed despite the small iron load introduced (0.12 wt%). ORR performance indicators, advanced characterization, and molecular simulation studies revealed nitrogen's crucial role in anchoring individual iron atoms and modulating the charge density nearby the active sites (increase of 80 mV in the half-wave potential). Adding glucose as a chelating agent enhances the metal-heteroatom coordination and subsequent dispersion of iron, accounting for an increase of 20 mV in the half-wave potential, an average of electrons transferred as high as 3.9 (at 0.4 V vs. RHE), and higher stability (99%) than that of a platinum-based (20 wt%) electrocatalyst (92%).This work was financially supported by Projects PTDC/EQU-EQU/1707/2020 (“BiCat4Energy”), LA/P/0045/2020 (ALiCE), UIDB/50020/2020 and UIDP/50020/2020 (LSRE-LCM), funded by national funds through FCT/MCTES (PIDDAC), and HyGreen&LowEmissions (NORTE-01-0145-FEDER-000077), supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund (ERDF). RSR acknowledges FCT funding under Stimulus of Scientific Employment, Individual Support Call (CEEC IND) 5th Edition (2022.04079.CEECIND). RGM acknowledges the research grant from FCT (2020.06422.BD). Technical assistance with SEM and XPS, and XRD analyses is gratefully acknowledged to CEMUP and UME-UTAD teams, respectively.Peer reviewedElsevierEuropean CommissionRey Raap, Natalia [0000-0002-5003-0035]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/349266https://api.elsevier.com/content/abstract/scopus_id/85161571523reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)InglésCarbonhttps://doi.org/10.1016/j.carbon.2023.118192Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3492662026-05-22T06:33:51Z
dc.title.none.fl_str_mv Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
title Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
spellingShingle Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
Ribeiro, Rui S.
Single-atomic catalysts
Density-functional theory (DFT)
Electrocatalysis
Fuel cells
ORR
http://metadata.un.org/sdg/7
http://metadata.un.org/sdg/9
Ensure access to affordable, reliable, sustainable and modern energy for all
Build resilient infrastructure, promote inclusive and sustainable industrialization and foster innovation
title_short Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
title_full Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
title_fullStr Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
title_full_unstemmed Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
title_sort Engineering single-atom Fe–N active sites on hollow carbon spheres for oxygen reduction reaction
dc.creator.none.fl_str_mv Ribeiro, Rui S.
Vieira, Ana Luísa S.
Biernacki, Krzysztof
Magalhães, Alexandre L.
Delgado, Juan J.
Morais, Rafael G.
Rocha, Raquel P.
Pereira, M. Fernando R.
author Ribeiro, Rui S.
author_facet Ribeiro, Rui S.
Vieira, Ana Luísa S.
Biernacki, Krzysztof
Magalhães, Alexandre L.
Delgado, Juan J.
Morais, Rafael G.
Rocha, Raquel P.
Pereira, M. Fernando R.
author_role author
author2 Vieira, Ana Luísa S.
Biernacki, Krzysztof
Magalhães, Alexandre L.
Delgado, Juan J.
Morais, Rafael G.
Rocha, Raquel P.
Pereira, M. Fernando R.
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
Rey Raap, Natalia [0000-0002-5003-0035]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Single-atomic catalysts
Density-functional theory (DFT)
Electrocatalysis
Fuel cells
ORR
http://metadata.un.org/sdg/7
http://metadata.un.org/sdg/9
Ensure access to affordable, reliable, sustainable and modern energy for all
Build resilient infrastructure, promote inclusive and sustainable industrialization and foster innovation
topic Single-atomic catalysts
Density-functional theory (DFT)
Electrocatalysis
Fuel cells
ORR
http://metadata.un.org/sdg/7
http://metadata.un.org/sdg/9
Ensure access to affordable, reliable, sustainable and modern energy for all
Build resilient infrastructure, promote inclusive and sustainable industrialization and foster innovation
description Seeking alternatives to noble metals-based electrocatalysts for oxygen reduction reaction (ORR), hollow carbon spheres (CSs) were finely tuned with stable single-atom Fe–N species through a synthesis methodology requiring only earth-abundant metal precursors. CSs with different sizes were synthesized by sol-gel polycondensation of resorcinol with formaldehyde over silica nanoparticles, followed by thermal annealing and silica etching. A catalyst screening revealed the positive impact of both the hollow core and structural defects of the CSs for ORR. Single-atom Fe–N active sites were introduced on the best performing CSs through simultaneous incorporation of iron and nitrogen precursors, and glucose. A significant enhancement in ORR activity was observed despite the small iron load introduced (0.12 wt%). ORR performance indicators, advanced characterization, and molecular simulation studies revealed nitrogen's crucial role in anchoring individual iron atoms and modulating the charge density nearby the active sites (increase of 80 mV in the half-wave potential). Adding glucose as a chelating agent enhances the metal-heteroatom coordination and subsequent dispersion of iron, accounting for an increase of 20 mV in the half-wave potential, an average of electrons transferred as high as 3.9 (at 0.4 V vs. RHE), and higher stability (99%) than that of a platinum-based (20 wt%) electrocatalyst (92%).
publishDate 2023
dc.date.none.fl_str_mv 2023
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/349266
https://api.elsevier.com/content/abstract/scopus_id/85161571523
url http://hdl.handle.net/10261/349266
https://api.elsevier.com/content/abstract/scopus_id/85161571523
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Carbon
https://doi.org/10.1016/j.carbon.2023.118192
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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