Unravelling the Stability Stressors of Atomically Dispersed Fe–N–C Oxygen Reduction Catalysts

Xiaohong Xie; Boyang Li; Pan Xu; Moulay Tahar Sougrati; Ricardo Garcia-Serres; David A. Cullen; A. Jeremy Kropf; Fan Xia; Miao Song; Sulay Saha; Yachao Zeng; Mark H. Engelhard; Mark E. Bowden; Hanguang Zhang; Litao Yan; Teresa Lemmon; Xiaohong S. Li; Ulises Martinez; Yingwen Cheng; Gang Wu; Piotr Zelenay; Vijay Ramani; Deborah J. Myers; Frédéric Jaouen; Lijun Yang; Guofeng Wang; Yuyan Shao

doi:10.1021/jacs.5c15451

Unravelling the Stability Stressors of Atomically Dispersed Fe–N–C Oxygen Reduction Catalysts

Xiaohong Xie
, Boyang Li
, Pan Xu
, Moulay Tahar Sougrati
, Ricardo Garcia-Serres
, David A. Cullen
, A. Jeremy Kropf
, Fan Xia
, Miao Song
, Sulay Saha
, Yachao Zeng
, Mark H. Engelhard
, Mark E. Bowden
, Hanguang Zhang
, Litao Yan
, Teresa Lemmon
, Xiaohong S. Li
, Ulises Martinez
, Yingwen Cheng
, Gang Wu

Piotr Zelenay, Vijay Ramani, Deborah J. Myers, Frédéric Jaouen, Lijun Yang, Guofeng Wang, Yuyan Shao

Department of Chemical and Biological Engineering

University at Buffalo

Pacific Northwest National Laboratory
University of Pittsburgh
Ballard Power Systems
ENSCM
Université Grenoble Alpes
Oak Ridge National Laboratory
Argonne National Laboratory
Northern Illinois University
Washington University St. Louis
SUNY Buffalo
Los Alamos National Laboratory

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

Enhancing the catalytic stability of Fe–N–C catalysts for cathodic oxygen reduction in proton-exchange membrane fuel cells (PEMFCs) necessitates an in-depth understanding of their degradation mechanisms. This study identifies key stressors affecting the stability of Fe–N–C catalysts, specifically acidic environment, oxygen (O₂), and reactive oxygen species (ROS). Through ex situ/operando experiments, we show that the oxidation of local carbon by acidic environment + O₂ + ROS, along with the demetalation of catalytic FeN_xC_y sites by O₂ or O₂ + ROS, is the primary factor responsible for the initial fast degradation of Fe–N–C catalysts. The demetalation of FeN_xC_y sites, influenced by O₂, in particular by O₂ + ROS, leads to the subsequent gradual degradation of Fe–N–C. Notably, FeN₄C₁₂-type active sites are more susceptible to demetalation than FeN₄C₁₀-type sites in O₂ or O₂ + ROS. Our findings indicate that, besides constructing more stable FeN_xC_y sites, preventing local carbon oxidation and scavenging of ROS are all critical for maintaining the stability of Fe–N–C catalysts.

Original language	English
Pages (from-to)	48117-48126
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	147
Issue number	52
DOIs	https://doi.org/10.1021/jacs.5c15451
State	Published - Dec 31 2025

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10.1021/jacs.5c15451

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Xie, X., Li, B., Xu, P., Sougrati, M. T., Garcia-Serres, R., Cullen, D. A., Kropf, A. J., Xia, F., Song, M., Saha, S., Zeng, Y., Engelhard, M. H., Bowden, M. E., Zhang, H., Yan, L., Lemmon, T., Li, X. S., Martinez, U., Cheng, Y., ... Shao, Y. (2025). Unravelling the Stability Stressors of Atomically Dispersed Fe–N–C Oxygen Reduction Catalysts. Journal of the American Chemical Society, 147(52), 48117-48126. https://doi.org/10.1021/jacs.5c15451

@article{c19215e4540f4a2cbb8b031b0958ece7,

title = "Unravelling the Stability Stressors of Atomically Dispersed Fe{\textendash}N{\textendash}C Oxygen Reduction Catalysts",

abstract = "Enhancing the catalytic stability of Fe{\textendash}N{\textendash}C catalysts for cathodic oxygen reduction in proton-exchange membrane fuel cells (PEMFCs) necessitates an in-depth understanding of their degradation mechanisms. This study identifies key stressors affecting the stability of Fe{\textendash}N{\textendash}C catalysts, specifically acidic environment, oxygen (O2), and reactive oxygen species (ROS). Through ex situ/operando experiments, we show that the oxidation of local carbon by acidic environment + O2 + ROS, along with the demetalation of catalytic FeNxCy sites by O2 or O2 + ROS, is the primary factor responsible for the initial fast degradation of Fe{\textendash}N{\textendash}C catalysts. The demetalation of FeNxCy sites, influenced by O2, in particular by O2 + ROS, leads to the subsequent gradual degradation of Fe{\textendash}N{\textendash}C. Notably, FeN4C12-type active sites are more susceptible to demetalation than FeN4C10-type sites in O2 or O2 + ROS. Our findings indicate that, besides constructing more stable FeNxCy sites, preventing local carbon oxidation and scavenging of ROS are all critical for maintaining the stability of Fe{\textendash}N{\textendash}C catalysts.",

author = "Xiaohong Xie and Boyang Li and Pan Xu and Sougrati, \{Moulay Tahar\} and Ricardo Garcia-Serres and Cullen, \{David A.\} and Kropf, \{A. Jeremy\} and Fan Xia and Miao Song and Sulay Saha and Yachao Zeng and Engelhard, \{Mark H.\} and Bowden, \{Mark E.\} and Hanguang Zhang and Litao Yan and Teresa Lemmon and Li, \{Xiaohong S.\} and Ulises Martinez and Yingwen Cheng and Gang Wu and Piotr Zelenay and Vijay Ramani and Myers, \{Deborah J.\} and Fr{\'e}d{\'e}ric Jaouen and Lijun Yang and Guofeng Wang and Yuyan Shao",

note = "Publisher Copyright: {\textcopyright} 2025 American Chemical Society",

year = "2025",

month = dec,

day = "31",

doi = "10.1021/jacs.5c15451",

language = "English",

volume = "147",

pages = "48117--48126",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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Xie, X, Li, B, Xu, P, Sougrati, MT, Garcia-Serres, R, Cullen, DA, Kropf, AJ, Xia, F, Song, M, Saha, S, Zeng, Y, Engelhard, MH, Bowden, ME, Zhang, H, Yan, L, Lemmon, T, Li, XS, Martinez, U, Cheng, Y, Wu, G, Zelenay, P, Ramani, V, Myers, DJ, Jaouen, F, Yang, L, Wang, G & Shao, Y 2025, 'Unravelling the Stability Stressors of Atomically Dispersed Fe–N–C Oxygen Reduction Catalysts', Journal of the American Chemical Society, vol. 147, no. 52, pp. 48117-48126. https://doi.org/10.1021/jacs.5c15451

TY - JOUR

T1 - Unravelling the Stability Stressors of Atomically Dispersed Fe–N–C Oxygen Reduction Catalysts

AU - Xie, Xiaohong

AU - Li, Boyang

AU - Xu, Pan

AU - Sougrati, Moulay Tahar

AU - Garcia-Serres, Ricardo

AU - Cullen, David A.

AU - Kropf, A. Jeremy

AU - Xia, Fan

AU - Song, Miao

AU - Saha, Sulay

AU - Zeng, Yachao

AU - Engelhard, Mark H.

AU - Bowden, Mark E.

AU - Zhang, Hanguang

AU - Yan, Litao

AU - Lemmon, Teresa

AU - Li, Xiaohong S.

AU - Martinez, Ulises

AU - Cheng, Yingwen

AU - Wu, Gang

AU - Zelenay, Piotr

AU - Ramani, Vijay

AU - Myers, Deborah J.

AU - Jaouen, Frédéric

AU - Yang, Lijun

AU - Wang, Guofeng

AU - Shao, Yuyan

PY - 2025/12/31

Y1 - 2025/12/31

N2 - Enhancing the catalytic stability of Fe–N–C catalysts for cathodic oxygen reduction in proton-exchange membrane fuel cells (PEMFCs) necessitates an in-depth understanding of their degradation mechanisms. This study identifies key stressors affecting the stability of Fe–N–C catalysts, specifically acidic environment, oxygen (O2), and reactive oxygen species (ROS). Through ex situ/operando experiments, we show that the oxidation of local carbon by acidic environment + O2 + ROS, along with the demetalation of catalytic FeNxCy sites by O2 or O2 + ROS, is the primary factor responsible for the initial fast degradation of Fe–N–C catalysts. The demetalation of FeNxCy sites, influenced by O2, in particular by O2 + ROS, leads to the subsequent gradual degradation of Fe–N–C. Notably, FeN4C12-type active sites are more susceptible to demetalation than FeN4C10-type sites in O2 or O2 + ROS. Our findings indicate that, besides constructing more stable FeNxCy sites, preventing local carbon oxidation and scavenging of ROS are all critical for maintaining the stability of Fe–N–C catalysts.

AB - Enhancing the catalytic stability of Fe–N–C catalysts for cathodic oxygen reduction in proton-exchange membrane fuel cells (PEMFCs) necessitates an in-depth understanding of their degradation mechanisms. This study identifies key stressors affecting the stability of Fe–N–C catalysts, specifically acidic environment, oxygen (O2), and reactive oxygen species (ROS). Through ex situ/operando experiments, we show that the oxidation of local carbon by acidic environment + O2 + ROS, along with the demetalation of catalytic FeNxCy sites by O2 or O2 + ROS, is the primary factor responsible for the initial fast degradation of Fe–N–C catalysts. The demetalation of FeNxCy sites, influenced by O2, in particular by O2 + ROS, leads to the subsequent gradual degradation of Fe–N–C. Notably, FeN4C12-type active sites are more susceptible to demetalation than FeN4C10-type sites in O2 or O2 + ROS. Our findings indicate that, besides constructing more stable FeNxCy sites, preventing local carbon oxidation and scavenging of ROS are all critical for maintaining the stability of Fe–N–C catalysts.

UR - https://www.scopus.com/pages/publications/105026454059

U2 - 10.1021/jacs.5c15451

DO - 10.1021/jacs.5c15451

M3 - Article

C2 - 41400425

SN - 0002-7863

VL - 147

SP - 48117

EP - 48126

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 52

ER -

Unravelling the Stability Stressors of Atomically Dispersed Fe–N–C Oxygen Reduction Catalysts

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