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Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer
Abstract
Scaling up clean-energy applications necessitates the development of platinum group metal (PGM)-free fuel cell electrocatalysts with high activity, stability, and low cost. Here, X-ray absorption (XAS) at the Fe K-edge and Fe Kβ X-ray emission (XES) spectroscopies were used to study the electronic structure of Fe centers in highly active Fe–N–C oxygen reduction catalysts with significant commercial potential. X-ray absorption near-edge structure (XANES) analysis has shown that the majority (>95%) of Fe centers are in the Fe3+ oxidation state, while extended X-ray absorption fine structure (EXAFS) detected a mixture of single site Fe–N4 centers (>95%) and centers with short (~2.5 Å) Fe–Fe interactions of Fe metal and/or Fe-carbide nanoparticles (<5%) featuring the Feo oxidation state. Surprisingly, addition of Nafion, the most widely used ionomer, resulted in pronounced changes in the XAS spectra, consistent with a strong catalyst–ionomer interaction where long Fe–Fe interactions at ~3.1 Å were shown to be a feature of Fe3+ ions bound with the Nafion. We conclude that exposure to Nafion during the device formulation has a different effect from the aggressive acid leaching typically used in the preparation of Fe–N–C catalysts. Furthermore, it was hypothesized that the polymer interacts with single sites’ Fe3+ centers, as wellmore »
- Authors:
-
[1];
[1];
[2];
[3];
[1]
- Purdue University, West Lafayette, IN (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); National Science Foundation (NSF)
- OSTI Identifier:
- 2282945
- Alternate Identifier(s):
- OSTI ID: 2310278
- Report Number(s):
- BNL-225307-2024-JAAM
Journal ID: ISSN 2574-0962
- Grant/Contract Number:
- AC05-00OR22725; SC0012704; AC02-06CH11357; CHE-2155060
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Energy Materials
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 2574-0962
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Fe-N-C catalyst; Earth-abundant fuel cell catalyst; Oxygen reduction reaction; X-ray emission spectroscopy; X-ray Absorption spectroscopy; 36 MATERIALS SCIENCE
Citation Formats
Ezhov, Roman, Maximova, Olga, Lyu, Xiang, Leshchev, Denis, Stavitski, Eli, Serov, Alexey, and Pushkar, Yulia. Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer. United States: N. p., 2023.
Web. doi:10.1021/acsaem.3c02522.
Ezhov, Roman, Maximova, Olga, Lyu, Xiang, Leshchev, Denis, Stavitski, Eli, Serov, Alexey, & Pushkar, Yulia. Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer. United States. https://doi.org/10.1021/acsaem.3c02522
Ezhov, Roman, Maximova, Olga, Lyu, Xiang, Leshchev, Denis, Stavitski, Eli, Serov, Alexey, and Pushkar, Yulia. Thu .
"Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer". United States. https://doi.org/10.1021/acsaem.3c02522.
@article{osti_2282945,
title = {Spectroscopic Characterization of Highly Active Fe–N–C Oxygen Reduction Catalysts and Discovery of Strong Interaction with Nafion Ionomer},
author = {Ezhov, Roman and Maximova, Olga and Lyu, Xiang and Leshchev, Denis and Stavitski, Eli and Serov, Alexey and Pushkar, Yulia},
abstractNote = {Scaling up clean-energy applications necessitates the development of platinum group metal (PGM)-free fuel cell electrocatalysts with high activity, stability, and low cost. Here, X-ray absorption (XAS) at the Fe K-edge and Fe Kβ X-ray emission (XES) spectroscopies were used to study the electronic structure of Fe centers in highly active Fe–N–C oxygen reduction catalysts with significant commercial potential. X-ray absorption near-edge structure (XANES) analysis has shown that the majority (>95%) of Fe centers are in the Fe3+ oxidation state, while extended X-ray absorption fine structure (EXAFS) detected a mixture of single site Fe–N4 centers (>95%) and centers with short (~2.5 Å) Fe–Fe interactions of Fe metal and/or Fe-carbide nanoparticles (<5%) featuring the Feo oxidation state. Surprisingly, addition of Nafion, the most widely used ionomer, resulted in pronounced changes in the XAS spectra, consistent with a strong catalyst–ionomer interaction where long Fe–Fe interactions at ~3.1 Å were shown to be a feature of Fe3+ ions bound with the Nafion. We conclude that exposure to Nafion during the device formulation has a different effect from the aggressive acid leaching typically used in the preparation of Fe–N–C catalysts. Furthermore, it was hypothesized that the polymer interacts with single sites’ Fe3+ centers, as well as with graphene layers protecting the Feo nanoparticles, and extracts some Fe ions into the Nafion matrix.},
doi = {10.1021/acsaem.3c02522},
journal = {ACS Applied Energy Materials},
number = 2,
volume = 7,
place = {United States},
year = {Thu Dec 28 00:00:00 EST 2023},
month = {Thu Dec 28 00:00:00 EST 2023}
}
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