Evidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reduction

Abstract While Fe–N–C materials have shown promising initial oxygen reduction reaction (ORR) activity, they lack durability in acidic medium. Key degradation mechanisms include FeN4 site demetallation and deactivation by reactive oxygen species. Here we show for mainstream Fe–N–Cs that adding 1 wt.%...

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Main Authors: Nicolas A. Ishiki, Keyla Teixeira Santos, Nicolas Bibent, Kavita Kumar, Ina Reichmann, Yu-Ping Ku, Tristan Asset, Laetitia Dubau, Michel Mermoux, Hongxin Ge, Sandrine Berthon-Fabry, Viktoriia A. Saveleva, Vinod K. Paidi, Pieter Glatzel, Andrea Zitolo, Tzonka Mineva, Hazar Guesmi, Serhiy Cherevko, Edson A. Ticianelli, Frédéric Maillard, Frédéric Jaouen
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-61806-x
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author Nicolas A. Ishiki
Keyla Teixeira Santos
Nicolas Bibent
Kavita Kumar
Ina Reichmann
Yu-Ping Ku
Tristan Asset
Laetitia Dubau
Michel Mermoux
Hongxin Ge
Sandrine Berthon-Fabry
Viktoriia A. Saveleva
Vinod K. Paidi
Pieter Glatzel
Andrea Zitolo
Tzonka Mineva
Hazar Guesmi
Serhiy Cherevko
Edson A. Ticianelli
Frédéric Maillard
Frédéric Jaouen
author_facet Nicolas A. Ishiki
Keyla Teixeira Santos
Nicolas Bibent
Kavita Kumar
Ina Reichmann
Yu-Ping Ku
Tristan Asset
Laetitia Dubau
Michel Mermoux
Hongxin Ge
Sandrine Berthon-Fabry
Viktoriia A. Saveleva
Vinod K. Paidi
Pieter Glatzel
Andrea Zitolo
Tzonka Mineva
Hazar Guesmi
Serhiy Cherevko
Edson A. Ticianelli
Frédéric Maillard
Frédéric Jaouen
author_sort Nicolas A. Ishiki
collection DOAJ
description Abstract While Fe–N–C materials have shown promising initial oxygen reduction reaction (ORR) activity, they lack durability in acidic medium. Key degradation mechanisms include FeN4 site demetallation and deactivation by reactive oxygen species. Here we show for mainstream Fe–N–Cs that adding 1 wt.% Pt nanoparticles via a soft polyol method results in well-defined and stable Pt/Fe–N–C hybrids. The Pt addition strongly reduces the H2O2 production and Fe leaching rate during ORR, while post mortem Mössbauer spectroscopy reveals that the highly active but unstable Fe(III)N4 site is partially stabilized. The similar H2O2 electroreduction activity of Pt/Fe–N–C and Fe–N–C and other analyses point toward a long-distance electronic effect of Pt nanoparticles in stabilizing FeN4 sites. Computational chemistry reveals that spin polarization of distant Pt atoms mitigates the structural changes of FeN4 sites upon adsorption of oxygenated species atop Fe, especially in high-spin state.
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spelling doaj-art-2a8e99edc4954a918c8202709fb04b602025-08-20T04:02:57ZengNature PortfolioNature Communications2041-17232025-07-0116111510.1038/s41467-025-61806-xEvidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reductionNicolas A. Ishiki0Keyla Teixeira Santos1Nicolas Bibent2Kavita Kumar3Ina Reichmann4Yu-Ping Ku5Tristan Asset6Laetitia Dubau7Michel Mermoux8Hongxin Ge9Sandrine Berthon-Fabry10Viktoriia A. Saveleva11Vinod K. Paidi12Pieter Glatzel13Andrea Zitolo14Tzonka Mineva15Hazar Guesmi16Serhiy Cherevko17Edson A. Ticianelli18Frédéric Maillard19Frédéric Jaouen20Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMIUniv. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMIICGM, Univ. Montpellier, CNRS, ENSCM, 1919 route de MendeUniv. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMIForschungszentrum Jülich GmbH, Helmholtz-Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Cauerstraße 1Forschungszentrum Jülich GmbH, Helmholtz-Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Cauerstraße 1ICGM, Univ. Montpellier, CNRS, ENSCM, 1919 route de MendeUniv. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMIUniv. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMIMINES Paris, PSL University PERSEE - Centre procédés, énergies renouvelables et systèmes énergétiques, CS 10207 rue Claude DaunesseMINES Paris, PSL University PERSEE - Centre procédés, énergies renouvelables et systèmes énergétiques, CS 10207 rue Claude DaunesseESRF, The European Synchrotron, 71 Avenue des MartyrsESRF, The European Synchrotron, 71 Avenue des MartyrsESRF, The European Synchrotron, 71 Avenue des MartyrsSynchrotron SOLEIL, L’Orme des Merisiers, BP 48 Saint AubinICGM, Univ. Montpellier, CNRS, ENSCM, 1919 route de MendeICGM, Univ. Montpellier, CNRS, ENSCM, 1919 route de MendeForschungszentrum Jülich GmbH, Helmholtz-Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Cauerstraße 1Instituto de Química de São Carlos (IQSC), Universidade de São Paulo, Av. Trabalhador São-Carlense, 400, CP 780Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMIICGM, Univ. Montpellier, CNRS, ENSCM, 1919 route de MendeAbstract While Fe–N–C materials have shown promising initial oxygen reduction reaction (ORR) activity, they lack durability in acidic medium. Key degradation mechanisms include FeN4 site demetallation and deactivation by reactive oxygen species. Here we show for mainstream Fe–N–Cs that adding 1 wt.% Pt nanoparticles via a soft polyol method results in well-defined and stable Pt/Fe–N–C hybrids. The Pt addition strongly reduces the H2O2 production and Fe leaching rate during ORR, while post mortem Mössbauer spectroscopy reveals that the highly active but unstable Fe(III)N4 site is partially stabilized. The similar H2O2 electroreduction activity of Pt/Fe–N–C and Fe–N–C and other analyses point toward a long-distance electronic effect of Pt nanoparticles in stabilizing FeN4 sites. Computational chemistry reveals that spin polarization of distant Pt atoms mitigates the structural changes of FeN4 sites upon adsorption of oxygenated species atop Fe, especially in high-spin state.https://doi.org/10.1038/s41467-025-61806-x
spellingShingle Nicolas A. Ishiki
Keyla Teixeira Santos
Nicolas Bibent
Kavita Kumar
Ina Reichmann
Yu-Ping Ku
Tristan Asset
Laetitia Dubau
Michel Mermoux
Hongxin Ge
Sandrine Berthon-Fabry
Viktoriia A. Saveleva
Vinod K. Paidi
Pieter Glatzel
Andrea Zitolo
Tzonka Mineva
Hazar Guesmi
Serhiy Cherevko
Edson A. Ticianelli
Frédéric Maillard
Frédéric Jaouen
Evidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reduction
Nature Communications
title Evidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reduction
title_full Evidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reduction
title_fullStr Evidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reduction
title_full_unstemmed Evidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reduction
title_short Evidence for the stabilization of FeN4 sites by Pt particles during acidic oxygen reduction
title_sort evidence for the stabilization of fen4 sites by pt particles during acidic oxygen reduction
url https://doi.org/10.1038/s41467-025-61806-x
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