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Title: Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells

Abstract

We report that while Fe–N–C materials are a promising alternative to platinum for catalysing the oxygen reduction reaction in acidic polymer fuel cells, limited understanding of their operando degradation restricts rational approaches towards improved durability. Here we show that Fe–N–C catalysts initially comprising two distinct FeNx sites (S1 and S2) degrade via the transformation of S1 into iron oxides while the structure and number of S2 were unmodified. Structure–activity correlations drawn from end-of-test 57Fe Mössbauer spectroscopy reveal that both sites initially contribute to the oxygen reduction reaction activity but only S2 substantially contributes after 50 h of operation. From in situ 57Fe Mössbauer spectroscopy in inert gas coupled to calculations of the Mössbauer signature of FeNx moieties in different electronic states, we identify S1 to be a high-spin FeN4C12 moiety and S2 a low- or intermediate-spin FeN4C10 moiety. These insights lay the groundwork for rational approaches towards Fe–N–C cathodes with improved durability in acidic fuel cells.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4];  [5];  [6];  [6]; ORCiD logo [6];  [7]; ORCiD logo [1]
  1. Montpellier Univ. 2 (France)
  2. Synchrotron SOLEIL, Gif-sur-Yvette (France)
  3. University of New Mexico, Albuquerque, NM (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. University of California, Irvine, CA (United States)
  5. University of Camerino (Italy)
  6. University of Savoie Mont Blanc, Grenoble (France)
  7. National Institute of Chemistry, Ljubljana (Slovenia)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC); French National Research Agency; FCH Joint Undertaking; Centre of Excellence of Multifunctional Architectured Materials (CEMAM); Grand équipement national de calcul intensif; Slovenian Research Agency
OSTI Identifier:
1876785
Report Number(s):
LA-UR-19-31453
Journal ID: ISSN 2520-1158
Grant/Contract Number:  
89233218CNA000001; ANR-16-CE05-0007; 779366; ANR-10-LABX-44-01; AC02-06CH11357; AC02-05CH11231; 2019-A0050807369; P2-0393
Resource Type:
Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electrocatalysis; energy; fuel cells; heterogeneous catalysis

Citation Formats

Li, Jingkun, Sougrati, Moulay Tahar, Zitolo, Andrea, Ablett, James M., Oğuz, Ismail Can, Mineva, Tzonka, Matanovic, Ivana, Atanassov, Plamen, Huang, Ying, Zenyuk, Iryna, Di Cicco, Andrea, Kumar, Kavita, Dubau, Laetitia, Maillard, Frédéric, Dražić, Goran, and Jaouen, Frédéric. Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells. United States: N. p., 2020. Web. doi:10.1038/s41929-020-00545-2.
Li, Jingkun, Sougrati, Moulay Tahar, Zitolo, Andrea, Ablett, James M., Oğuz, Ismail Can, Mineva, Tzonka, Matanovic, Ivana, Atanassov, Plamen, Huang, Ying, Zenyuk, Iryna, Di Cicco, Andrea, Kumar, Kavita, Dubau, Laetitia, Maillard, Frédéric, Dražić, Goran, & Jaouen, Frédéric. Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells. United States. https://doi.org/10.1038/s41929-020-00545-2
Li, Jingkun, Sougrati, Moulay Tahar, Zitolo, Andrea, Ablett, James M., Oğuz, Ismail Can, Mineva, Tzonka, Matanovic, Ivana, Atanassov, Plamen, Huang, Ying, Zenyuk, Iryna, Di Cicco, Andrea, Kumar, Kavita, Dubau, Laetitia, Maillard, Frédéric, Dražić, Goran, and Jaouen, Frédéric. Mon . "Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells". United States. https://doi.org/10.1038/s41929-020-00545-2. https://www.osti.gov/servlets/purl/1876785.
@article{osti_1876785,
title = {Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells},
author = {Li, Jingkun and Sougrati, Moulay Tahar and Zitolo, Andrea and Ablett, James M. and Oğuz, Ismail Can and Mineva, Tzonka and Matanovic, Ivana and Atanassov, Plamen and Huang, Ying and Zenyuk, Iryna and Di Cicco, Andrea and Kumar, Kavita and Dubau, Laetitia and Maillard, Frédéric and Dražić, Goran and Jaouen, Frédéric},
abstractNote = {We report that while Fe–N–C materials are a promising alternative to platinum for catalysing the oxygen reduction reaction in acidic polymer fuel cells, limited understanding of their operando degradation restricts rational approaches towards improved durability. Here we show that Fe–N–C catalysts initially comprising two distinct FeNx sites (S1 and S2) degrade via the transformation of S1 into iron oxides while the structure and number of S2 were unmodified. Structure–activity correlations drawn from end-of-test 57Fe Mössbauer spectroscopy reveal that both sites initially contribute to the oxygen reduction reaction activity but only S2 substantially contributes after 50 h of operation. From in situ 57Fe Mössbauer spectroscopy in inert gas coupled to calculations of the Mössbauer signature of FeNx moieties in different electronic states, we identify S1 to be a high-spin FeN4C12 moiety and S2 a low- or intermediate-spin FeN4C10 moiety. These insights lay the groundwork for rational approaches towards Fe–N–C cathodes with improved durability in acidic fuel cells.},
doi = {10.1038/s41929-020-00545-2},
journal = {Nature Catalysis},
number = 1,
volume = 4,
place = {United States},
year = {2020},
month = {12}
}

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