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

Journal Article · · Nature Catalysis
 [1];  [1];  [2];  [2];  [1];  [1];  [3];  [4];  [4];  [4];  [5];  [6];  [6];  [6];  [7];  [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)
+ Show Author Affiliations
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.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
Centre of Excellence of Multifunctional Architectured Materials (CEMAM); FCH Joint Undertaking; French National Research Agency; Grand équipement national de calcul intensif; Slovenian Research Agency; USDOE Office of Science (SC)
Grant/Contract Number:
89233218CNA000001; AC02-05CH11231; AC02-06CH11357
OSTI ID:
1876785
Report Number(s):
LA-UR-19-31453
Journal Information:
Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 1 Vol. 4; ISSN 2520-1158
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

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