Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts

Yachao Zeng; Chenzhao Li; Boyang Li; Jiashun Liang; Michael J. Zachman; David A. Cullen; Raphael P. Hermann; E. Ercan Alp; Barbara Lavina; Stavros Karakalos; Marcos Lucero; Bingzhang Zhang; Maoyu Wang; Zhenxing Feng; Guofeng Wang; Jian Xie; Deborah J. Myers; Jean Pol Dodelet; Gang Wu

doi:10.1038/s41929-023-01062-8

Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts

Yachao Zeng, Chenzhao Li, Boyang Li, Jiashun Liang, Michael J. Zachman, David A. Cullen, Raphael P. Hermann, E. Ercan Alp, Barbara Lavina, Stavros Karakalos, Marcos Lucero, Bingzhang Zhang, Maoyu Wang, Zhenxing Feng, Guofeng Wang, Jian Xie, Deborah J. Myers, Jean Pol Dodelet, Gang Wu

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

117 Scopus citations

Abstract

Fe–N–C catalysts are the most promising platinum group metal-free oxygen-reduction catalysts, but they suffer from a low density of active metal sites and the so-called activity–stability trade-off. Here we report an Fe–N–C catalyst prepared by adding an optimal amount of H₂ to the traditional inert atmosphere during the thermal activation. The presence of H₂ significantly increases the total density of FeN₄ sites, suppressing the unstable pyrrolic-N-coordinated S1 sites and favouring the stable pyridinic-N-coordinated S2 sites with shortened Fe–N bond lengths. We propose that the intrinsically stable S2 sites are probably arranged in well-graphitized carbon layers, and the S1 sites exist in less-graphitized carbon. H₂ could remove unstable S1 sites and retain stable S2 sites during the pyrolysis to break the challenging activity–stability trade-off. The Fe–N–C catalyst in membrane electrode assemblies maintains a current density of 67 mA cm⁻² at 0.8 V (H₂–air) after 30,000 voltage cycles (0.60 to 0.95 V under H₂–air), achieving encouraging durability and performance simultaneously. [Figure not available: see fulltext.].

Original language	English
Pages (from-to)	1215-1227
Number of pages	13
Journal	Nature Catalysis
Volume	6
Issue number	12
DOIs	https://doi.org/10.1038/s41929-023-01062-8
State	Published - Dec 2023

Funding

We acknowledge support from the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office. Scanning transmission electron microscopy research was supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. This work was in part authored by Argonne National Laboratory, which is operated for the US DOE by the University of Chicago Argonne LLC under contract no. DE-AC02-06CH11357. G. Wu also thanks the New York State’s Center of Excellence in Materials Informatics (CMI) at the University at Buffalo, as well as the National Science Foundation (CBET-1604392, 1804326 and 2223467), for partial support.

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Zeng, Y., Li, C., Li, B., Liang, J., Zachman, M. J., Cullen, D. A., Hermann, R. P., Alp, E. E., Lavina, B., Karakalos, S., Lucero, M., Zhang, B., Wang, M., Feng, Z., Wang, G., Xie, J., Myers, D. J., Dodelet, J. P., & Wu, G. (2023). Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts. Nature Catalysis, 6(12), 1215-1227. https://doi.org/10.1038/s41929-023-01062-8

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title = "Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts",

abstract = "Fe–N–C catalysts are the most promising platinum group metal-free oxygen-reduction catalysts, but they suffer from a low density of active metal sites and the so-called activity–stability trade-off. Here we report an Fe–N–C catalyst prepared by adding an optimal amount of H2 to the traditional inert atmosphere during the thermal activation. The presence of H2 significantly increases the total density of FeN4 sites, suppressing the unstable pyrrolic-N-coordinated S1 sites and favouring the stable pyridinic-N-coordinated S2 sites with shortened Fe–N bond lengths. We propose that the intrinsically stable S2 sites are probably arranged in well-graphitized carbon layers, and the S1 sites exist in less-graphitized carbon. H2 could remove unstable S1 sites and retain stable S2 sites during the pyrolysis to break the challenging activity–stability trade-off. The Fe–N–C catalyst in membrane electrode assemblies maintains a current density of 67 mA cm−2 at 0.8 V (H2–air) after 30,000 voltage cycles (0.60 to 0.95 V under H2–air), achieving encouraging durability and performance simultaneously. [Figure not available: see fulltext.].",

author = "Yachao Zeng and Chenzhao Li and Boyang Li and Jiashun Liang and Zachman, {Michael J.} and Cullen, {David A.} and Hermann, {Raphael P.} and Alp, {E. Ercan} and Barbara Lavina and Stavros Karakalos and Marcos Lucero and Bingzhang Zhang and Maoyu Wang and Zhenxing Feng and Guofeng Wang and Jian Xie and Myers, {Deborah J.} and Dodelet, {Jean Pol} and Gang Wu",

note = "Publisher Copyright: {\textcopyright} 2023, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2023",

month = dec,

doi = "10.1038/s41929-023-01062-8",

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Zeng, Y, Li, C, Li, B, Liang, J, Zachman, MJ , Cullen, DA , Hermann, RP, Alp, EE, Lavina, B, Karakalos, S, Lucero, M, Zhang, B, Wang, M, Feng, Z, Wang, G, Xie, J, Myers, DJ, Dodelet, JP & Wu, G 2023, 'Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts', Nature Catalysis, vol. 6, no. 12, pp. 1215-1227. https://doi.org/10.1038/s41929-023-01062-8

TY - JOUR

T1 - Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts

AU - Zeng, Yachao

AU - Li, Chenzhao

AU - Li, Boyang

AU - Liang, Jiashun

AU - Zachman, Michael J.

AU - Cullen, David A.

AU - Hermann, Raphael P.

AU - Alp, E. Ercan

AU - Lavina, Barbara

AU - Karakalos, Stavros

AU - Lucero, Marcos

AU - Zhang, Bingzhang

AU - Wang, Maoyu

AU - Feng, Zhenxing

AU - Wang, Guofeng

AU - Xie, Jian

AU - Myers, Deborah J.

AU - Dodelet, Jean Pol

AU - Wu, Gang

PY - 2023/12

Y1 - 2023/12

N2 - Fe–N–C catalysts are the most promising platinum group metal-free oxygen-reduction catalysts, but they suffer from a low density of active metal sites and the so-called activity–stability trade-off. Here we report an Fe–N–C catalyst prepared by adding an optimal amount of H2 to the traditional inert atmosphere during the thermal activation. The presence of H2 significantly increases the total density of FeN4 sites, suppressing the unstable pyrrolic-N-coordinated S1 sites and favouring the stable pyridinic-N-coordinated S2 sites with shortened Fe–N bond lengths. We propose that the intrinsically stable S2 sites are probably arranged in well-graphitized carbon layers, and the S1 sites exist in less-graphitized carbon. H2 could remove unstable S1 sites and retain stable S2 sites during the pyrolysis to break the challenging activity–stability trade-off. The Fe–N–C catalyst in membrane electrode assemblies maintains a current density of 67 mA cm−2 at 0.8 V (H2–air) after 30,000 voltage cycles (0.60 to 0.95 V under H2–air), achieving encouraging durability and performance simultaneously. [Figure not available: see fulltext.].

AB - Fe–N–C catalysts are the most promising platinum group metal-free oxygen-reduction catalysts, but they suffer from a low density of active metal sites and the so-called activity–stability trade-off. Here we report an Fe–N–C catalyst prepared by adding an optimal amount of H2 to the traditional inert atmosphere during the thermal activation. The presence of H2 significantly increases the total density of FeN4 sites, suppressing the unstable pyrrolic-N-coordinated S1 sites and favouring the stable pyridinic-N-coordinated S2 sites with shortened Fe–N bond lengths. We propose that the intrinsically stable S2 sites are probably arranged in well-graphitized carbon layers, and the S1 sites exist in less-graphitized carbon. H2 could remove unstable S1 sites and retain stable S2 sites during the pyrolysis to break the challenging activity–stability trade-off. The Fe–N–C catalyst in membrane electrode assemblies maintains a current density of 67 mA cm−2 at 0.8 V (H2–air) after 30,000 voltage cycles (0.60 to 0.95 V under H2–air), achieving encouraging durability and performance simultaneously. [Figure not available: see fulltext.].

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JO - Nature Catalysis

JF - Nature Catalysis

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ER -

Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts

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