Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells
Abstract
Nitrogen-coordinated single atom iron sites (FeN4) embedded in carbon (Fe–N–C) are the most active platinum group metal-free oxygen reduction catalysts for proton-exchange membrane fuel cells. Still, current Fe–N–C catalysts lack sufficient long-term durability and are not yet viable for practical applications. Here we report a highly durable and active Fe–N–C catalyst synthesized using heat treatment with ammonia chloride followed by high-temperature deposition of a thin layer of nitrogen-doped carbon on the catalyst surface. We propose that catalyst stability is improved by converting defect-rich pyrrolic N-coordinated FeN4 sites into highly stable pyridinic N-coordinated FeN4 sites. The stability enhancement is demonstrated in membrane electrode assemblies using accelerated stress testing and a long-term steady-state test (>300 h at 0.67 V), approaching a typical Pt/C cathode (0.1 mgPt cm-2). The encouraging stability improvement represents a critical step in developing viable Fe–N–C catalysts to overcome the cost barriers of hydrogen fuel cells for numerous applications.
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- State Univ. of New York (SUNY), Buffalo, NY (United States)
- Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), Indianapolis, IN (United States); Purdue Univ., West Lafayette, IN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Univ. of Pittsburgh, PA (United States)
- Oregon State Univ., Corvallis, OR (United States)
- Carnegie Mellon Univ., Pittsburgh, PA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
- Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), Indianapolis, IN (United States)
- Giner, Inc., Newton, MA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Univ. at Buffalo, NY (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Nuclear Energy (NE), Nuclear Fuel Cycle and Supply Chain. Fuel Cycle Research and Development Program; National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1881116
- Alternate Identifier(s):
- OSTI ID: 1897111; OSTI ID: 1969732
- Grant/Contract Number:
- AC05-00OR22725; EE0008076; EE0008417; AC02-06CH11357; CBET-1604392; 1804326; CBET-1949870; 2016192
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Energy
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2058-7546
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; electrocatalysis; fuel cells; hydrogen energy; 08 HYDROGEN
Citation Formats
Liu, Shengwen, Li, Chenzhao, Zachman, Michael J., Zeng, Yachao, Yu, Haoran, Li, Boyang, Wang, Maoyu, Braaten, Jonathan, Liu, Jiawei, Meyer, III, Harry M., Lucero, Marcos, Kropf, A. Jeremy, Alp, E. Ercan, Gong, Qing, Shi, Qiurong, Feng, Zhenxing, Xu, Hui, Wang, Guofeng, Myers, Deborah J., Xie, Jian, Cullen, David A., Litster, Shawn, and Wu, Gang. Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells. United States: N. p., 2022.
Web. doi:10.1038/s41560-022-01062-1.
Liu, Shengwen, Li, Chenzhao, Zachman, Michael J., Zeng, Yachao, Yu, Haoran, Li, Boyang, Wang, Maoyu, Braaten, Jonathan, Liu, Jiawei, Meyer, III, Harry M., Lucero, Marcos, Kropf, A. Jeremy, Alp, E. Ercan, Gong, Qing, Shi, Qiurong, Feng, Zhenxing, Xu, Hui, Wang, Guofeng, Myers, Deborah J., Xie, Jian, Cullen, David A., Litster, Shawn, & Wu, Gang. Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells. United States. https://doi.org/10.1038/s41560-022-01062-1
Liu, Shengwen, Li, Chenzhao, Zachman, Michael J., Zeng, Yachao, Yu, Haoran, Li, Boyang, Wang, Maoyu, Braaten, Jonathan, Liu, Jiawei, Meyer, III, Harry M., Lucero, Marcos, Kropf, A. Jeremy, Alp, E. Ercan, Gong, Qing, Shi, Qiurong, Feng, Zhenxing, Xu, Hui, Wang, Guofeng, Myers, Deborah J., Xie, Jian, Cullen, David A., Litster, Shawn, and Wu, Gang. Thu .
"Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells". United States. https://doi.org/10.1038/s41560-022-01062-1. https://www.osti.gov/servlets/purl/1881116.
@article{osti_1881116,
title = {Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells},
author = {Liu, Shengwen and Li, Chenzhao and Zachman, Michael J. and Zeng, Yachao and Yu, Haoran and Li, Boyang and Wang, Maoyu and Braaten, Jonathan and Liu, Jiawei and Meyer, III, Harry M. and Lucero, Marcos and Kropf, A. Jeremy and Alp, E. Ercan and Gong, Qing and Shi, Qiurong and Feng, Zhenxing and Xu, Hui and Wang, Guofeng and Myers, Deborah J. and Xie, Jian and Cullen, David A. and Litster, Shawn and Wu, Gang},
abstractNote = {Nitrogen-coordinated single atom iron sites (FeN4) embedded in carbon (Fe–N–C) are the most active platinum group metal-free oxygen reduction catalysts for proton-exchange membrane fuel cells. Still, current Fe–N–C catalysts lack sufficient long-term durability and are not yet viable for practical applications. Here we report a highly durable and active Fe–N–C catalyst synthesized using heat treatment with ammonia chloride followed by high-temperature deposition of a thin layer of nitrogen-doped carbon on the catalyst surface. We propose that catalyst stability is improved by converting defect-rich pyrrolic N-coordinated FeN4 sites into highly stable pyridinic N-coordinated FeN4 sites. The stability enhancement is demonstrated in membrane electrode assemblies using accelerated stress testing and a long-term steady-state test (>300 h at 0.67 V), approaching a typical Pt/C cathode (0.1 mgPt cm-2). The encouraging stability improvement represents a critical step in developing viable Fe–N–C catalysts to overcome the cost barriers of hydrogen fuel cells for numerous applications.},
doi = {10.1038/s41560-022-01062-1},
journal = {Nature Energy},
number = 7,
volume = 7,
place = {United States},
year = {Thu Jul 07 00:00:00 EDT 2022},
month = {Thu Jul 07 00:00:00 EDT 2022}
}
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Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction
journal, November 2019
- Li, Jiazhan; Zhang, Hanguang; Samarakoon, Widitha
- Angewandte Chemie International Edition, Vol. 58, Issue 52
In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts
journal, October 2016
- Malko, Daniel; Kucernak, Anthony; Lopes, Thiago
- Nature Communications, Vol. 7, Issue 1
Atomically dispersed metal catalysts for the oxygen reduction reaction: synthesis, characterization, reaction mechanisms and electrochemical energy applications
journal, January 2019
- Liu, Minmin; Wang, Linlin; Zhao, Kangning
- Energy & Environmental Science, Vol. 12, Issue 10
PGM‐Free Cathode Catalysts for PEM Fuel Cells: A Mini‐Review on Stability Challenges
journal, December 2018
- Shao, Yuyan; Dodelet, Jean‐Pol; Wu, Gang
- Advanced Materials, Vol. 31, Issue 31
pyMCR: A Python Library for Multivariate Curve Resolution Analysis with Alternating Regression (MCR-AR)
journal, January 2019
- Camp, Charles H.
- Journal of Research of the National Institute of Standards and Technology, Vol. 124
Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction
journal, April 2017
- Chen, Yuanjun; Ji, Shufang; Wang, Yanggang
- Angewandte Chemie International Edition, Vol. 56, Issue 24
ElectroCat: DOE's approach to PGM-free catalyst and electrode R&D
journal, June 2018
- Thompson, Simon T.; Wilson, Adria R.; Zelenay, Piotr
- Solid State Ionics, Vol. 319
New roads and challenges for fuel cells in heavy-duty transportation
journal, March 2021
- Cullen, David A.; Neyerlin, K. C.; Ahluwalia, Rajesh K.
- Nature Energy, Vol. 6, Issue 5
Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells
journal, January 2012
- Kramm, Ulrike I.; Herranz, Juan; Larouche, Nicholas
- Physical Chemistry Chemical Physics, Vol. 14, Issue 33
High Durability of a 14-Membered Hexaaza Macrocyclic Fe Complex for an Acidic Oxygen Reduction Reaction Revealed by In Situ XAS Analysis
journal, September 2021
- Ohyama, Junya; Moriya, Makoto; Takahama, Ryo
- JACS Au, Vol. 1, Issue 10
High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011
- Wu, G.; More, K. L.; Johnston, C. M.
- Science, Vol. 332, Issue 6028, p. 443-447
Status and challenges for the application of platinum group metal-free catalysts in proton-exchange membrane fuel cells
journal, February 2021
- Osmieri, Luigi; Park, Jaehyung; Cullen, David A.
- Current Opinion in Electrochemistry, Vol. 25
Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts
journal, August 2016
- Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.
- Nature Communications, Vol. 7, Issue 1
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells
journal, October 2018
- Li, Jiazhan; Chen, Mengjie; Cullen, David A.
- Nature Catalysis, Vol. 1, Issue 12
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Step-by-Step Synthesis of Non-Noble Metal Electrocatalysts for O2 Reduction under Proton Exchange Membrane Fuel Cell Conditions
journal, December 2007
- Herranz, Juan; Lefèvre, Michel; Larouche, Nicholas
- The Journal of Physical Chemistry C, Vol. 111, Issue 51
Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells
journal, March 2019
- Wan, Xin; Liu, Xiaofang; Li, Yongcheng
- Nature Catalysis, Vol. 2, Issue 3
Single Atomic Iron Site Catalysts via Benign Aqueous Synthesis for Durability Improvement in Proton Exchange Membrane Fuel Cells
journal, April 2021
- Chen, Mengjie; Cullen, David A.; Karakalos, Stavros
- Journal of The Electrochemical Society, Vol. 168, Issue 4
Exploring the Single Atom Spin State by Electron Spectroscopy
journal, November 2015
- Lin, Yung-Chang; Teng, Po-Yuan; Chiu, Po-Wen
- Physical Review Letters, Vol. 115, Issue 20
Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation
journal, January 2020
- Zhao, Di; Zhuang, Zewen; Cao, Xing
- Chemical Society Reviews, Vol. 49, Issue 7
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites
journal, January 2019
- Zhang, Hanguang; Chung, Hoon T.; Cullen, David A.
- Energy & Environmental Science, Vol. 12, Issue 8
Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials
journal, August 2015
- Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa
- Nature Materials, Vol. 14, Issue 9
Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
journal, July 2019
- Wang, Xiao Xia; Swihart, Mark T.; Wu, Gang
- Nature Catalysis, Vol. 2, Issue 7
Probing active sites in iron-based catalysts for oxygen electro-reduction: A temperature-dependent 57 Fe Mössbauer spectroscopy study
journal, March 2016
- Sougrati, Moulay Tahar; Goellner, Vincent; Schuppert, Anna K.
- Catalysis Today, Vol. 262
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Fundamental Concepts in Heterogeneous Catalysis
book, January 2014
- Nørskov, Jens K.; Studt, Felix; Abild-Pedersen, Frank
- John Wiley & Sons, Inc.
PGM-Free Oxygen-Reduction Catalyst Development for Proton-Exchange Membrane Fuel Cells: Challenges, Solutions, and Promises
journal, January 2022
- He, Yanghua; Wu, Gang
- Accounts of Materials Research, Vol. 3, Issue 2
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
journal, September 2017
- Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu
- Journal of the American Chemical Society, Vol. 139, Issue 40
A pyridinic Fe-N4 macrocycle models the active sites in Fe/N-doped carbon electrocatalysts
journal, October 2020
- Marshall-Roth, Travis; Libretto, Nicole J.; Wrobel, Alexandra T.
- Nature Communications, Vol. 11, Issue 1
Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction
journal, November 2017
- Wang, Jing; Huang, Zhengqing; Liu, Wei
- Journal of the American Chemical Society, Vol. 139, Issue 48
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
(Invited) Kinetic Models for the Degradation Mechanisms of PGM-Free ORR Catalysts
journal, June 2018
- Yin, Xi; Zelenay, Piotr
- ECS Transactions, Vol. 85, Issue 13
Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement
journal, January 2020
- He, Yanghua; Liu, Shengwen; Priest, Cameron
- Chemical Society Reviews, Vol. 49, Issue 11
Versatile Strategy for Tuning ORR Activity of a Single Fe-N 4 Site by Controlling Electron-Withdrawing/Donating Properties of a Carbon Plane
journal, March 2019
- Mun, Yeongdong; Lee, Seonggyu; Kim, Kyeounghak
- Journal of the American Chemical Society, Vol. 141, Issue 15
Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells
journal, January 2020
- Shi, Qiurong; He, Yanghua; Bai, Xiaowan
- Energy & Environmental Science, Vol. 13, Issue 10
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction
journal, December 2018
- Martinez, Ulises; Komini Babu, Siddharth; Holby, Edward F.
- Advanced Materials, Vol. 31, Issue 31
US Department of Energy hydrogen and fuel cell technologies perspectives
journal, January 2020
- Miller, Eric L.; Thompson, Simon T.; Randolph, Katie
- MRS Bulletin, Vol. 45, Issue 1
Mapping chemical and bonding information using multivariate analysis of electron energy-loss spectrum images
journal, October 2006
- Bosman, M.; Watanabe, M.; Alexander, D. T. L.
- Ultramicroscopy, Vol. 106, Issue 11-12, p. 1024-1032
Resolving the Dilemma of Fe–N–C Catalysts by the Selective Synthesis of Tetrapyrrolic Active Sites via an Imprinting Strategy
journal, October 2021
- Menga, Davide; Low, Jian Liang; Li, Yan-Sheng
- Journal of the American Chemical Society, Vol. 143, Issue 43
Chemical vapour deposition of Fe–N–C oxygen reduction catalysts with full utilization of dense Fe–N4 sites
journal, June 2021
- Jiao, Li; Li, Jingkun; Richard, Lynne LaRochelle
- Nature Materials
Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells
journal, December 2020
- Li, Jingkun; Sougrati, Moulay Tahar; Zitolo, Andrea
- Nature Catalysis, Vol. 4, Issue 1
Fe-based catalysts for the reduction of oxygen in polymer electrolyte membrane fuel cell conditions: determination of the amount of peroxide released during electroreduction and its influence on the stability of the catalysts
journal, August 2003
- Lefèvre, Michel; Dodelet, Jean-Pol
- Electrochimica Acta, Vol. 48, Issue 19, p. 2749-2760
In Situ X-ray Absorption Spectroscopy to Monitor the Degradation of Fe/N/C Cathode Catalyst in Proton Exchange Membrane Fuel Cells
journal, January 2021
- Nabae, Y.; Yuan, Q.; Nagata, S.
- Journal of The Electrochemical Society, Vol. 168, Issue 1
Theoretically probing the possible degradation mechanisms of an FeNC catalyst during the oxygen reduction reaction
journal, January 2021
- Yang, Na; Peng, Lanlan; Li, Li
- Chemical Science, Vol. 12, Issue 37
Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells
journal, August 2011
- Proietti, Eric; Jaouen, Frédéric; Lefèvre, Michel
- Nature Communications, Vol. 2, Issue 1
Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion
journal, November 2019
- Zhu, Yuanzhi; Sokolowski, Joshua; Song, Xiancheng
- Advanced Energy Materials, Vol. 10, Issue 11
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells
journal, April 2009
- Lefèvre, Michel; Proietti, Eric; Jaouen, Frédéric
- Science, Vol. 324, Issue 5923, p. 71-74
Solving the activity–stability trade-off riddle
journal, January 2021
- Liu, Shengwen; Shi, Qiurong; Wu, Gang
- Nature Catalysis, Vol. 4, Issue 1
Fourteen-Membered Macrocyclic Fe Complexes Inspired by FeN4-Center-Embedded Graphene for Oxygen Reduction Catalysis
journal, August 2020
- Moriya, Makoto; Takahama, Ryo; Kamoi, Kazuki
- The Journal of Physical Chemistry C, Vol. 124, Issue 38
Understanding Active Sites in Pyrolyzed Fe–N–C Catalysts for Fuel Cell Cathodes by Bridging Density Functional Theory Calculations and 57 Fe Mössbauer Spectroscopy
journal, September 2019
- Mineva, Tzonka; Matanovic, Ivana; Atanassov, Plamen
- ACS Catalysis, Vol. 9, Issue 10