Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

Varnell, Jason A.; Tse, Edmund C.  M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

doi:10.1038/ncomms12582

Title: Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

Journal Article · Fri Aug 19 00:00:00 EDT 2016 · Nature Communications

DOI:https://doi.org/10.1038/ncomms12582· OSTI ID:1623846

Varnell, Jason A. ^[1]; Tse, Edmund C. M. ^[1]; Schulz, Charles E. ^[2]; Fister, Tim T. ^[3]; Haasch, Richard T. ^[4]; Timoshenko, Janis ^[5]; Frenkel, Anatoly I. ^[5]; Gewirth, Andrew A. ^[6]

Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Chemistry
Knox College, Galesburg, Illinois (United States). Dept. of Physics
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Univ. of Illinois at Urbana-Champaign, IL (United States). Frederick Seitz Materials Research Laboratory
Yeshiva University, New York, New York (United States). Dept. of Physics
Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Chemistry; Kyushu University, Fukuoka, (Japan). International Institute for Carbon Neutral Energy Research (WPI-I2CNER)

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; FG02-07ER46453; FG02-07ER46471

OSTI ID:: 1623846

Journal Information:: Nature Communications, Vol. 7, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Fe, N, S-codoped carbon frameworks derived from nanocrystal superlattices towards enhanced oxygen reduction activity Zou, Jinxiang; Wang, Biwei; Zhu, Baixu Nano Convergence, Vol. 6, Issue 1 https://doi.org/10.1186/s40580-019-0174-5	journal	February 2019
The Challenge of Achieving a High Density of Fe-Based Active Sites in a Highly Graphitic Carbon Matrix Li, Jingkun; Jia, Qingying; Mukerjee, Sanjeev Catalysts, Vol. 9, Issue 2 https://doi.org/10.3390/catal9020144	journal	February 2019
Warped graphitic layers generated by oxidation of fullerene extraction residue and its oxygen reduction catalytic activity Takigami, Machiko; Kobayashi, Rieko; Ishii, Takafumi Beilstein Journal of Nanotechnology, Vol. 10 https://doi.org/10.3762/bjnano.10.137	journal	January 2019
⁵⁷ Fe Mössbauer Spectroscopy Characterization of Electrocatalysts Kramm, Ulrike I.; Ni, Lingmei; Wagner, Stephan Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201805623	journal	December 2018
Unraveling the Nature of Sites Active toward Hydrogen Peroxide Reduction in Fe-N-C Catalysts Choi, Chang Hyuck; Choi, Won Seok; Kasian, Olga Angewandte Chemie, Vol. 129, Issue 30 https://doi.org/10.1002/ange.201704356	journal	June 2017
Homogenous Meets Heterogenous and Electro‐Catalysis: Iron‐Nitrogen Molecular Complexes within Carbon Materials for Catalytic Applications Li, Alain; Nicolae, Sabina A.; Qiao, Mo ChemCatChem, Vol. 11, Issue 16 https://doi.org/10.1002/cctc.201900910	journal	June 2019
Self-Sacrificial Template Synthesis of a Nitrogen-Doped Microstructured Carbon Tube as Electrocatalyst for Oxygen Reduction Yang, Limeng; Zeng, Yachao; Tang, Xuejun ChemElectroChem, Vol. 5, Issue 23 https://doi.org/10.1002/celc.201801050	journal	October 2018
Engineering the Interface of Carbon Electrocatalysts at the Triple Point for Enhanced Oxygen Reduction Reaction Qiao, Mo; Titirici, Maria‐Magdalena Chemistry – A European Journal, Vol. 24, Issue 69 https://doi.org/10.1002/chem.201804610	journal	June 2018
Metal‐Organic Framework Derived N/C Supported Austenite Nanoparticles as Efficient Oxygen Reduction Catalysts Yang, Jiao‐Jiao; Mi, Jian‐Li; Yang, Xue‐Jing ChemNanoMat, Vol. 5, Issue 4 https://doi.org/10.1002/cnma.201800629	journal	January 2019
Improving the Activity of M−N ₄ Catalysts for the Oxygen Reduction Reaction by Electrolyte Adsorption Svane, Katrine L.; Reda, Mateusz; Vegge, Tejs ChemSusChem, Vol. 12, Issue 23 https://doi.org/10.1002/cssc.201902443	journal	November 2019
Electronic structure modulation of bifunctional oxygen catalysts for rechargeable Zn–air batteries Yang, Jian; Chang, Le; Guo, Heng Journal of Materials Chemistry A, Vol. 8, Issue 3 https://doi.org/10.1039/c9ta11654k	journal	January 2020
Key Single-Atom Electrocatalysis in Metal-Organic Framework (MOF)-Derived Bifunctional Catalysts Zhao, Wanpeng; Wan, Gang; Peng, Chunlei ChemSusChem, Vol. 11, Issue 19 https://doi.org/10.1002/cssc.201801473	journal	August 2018
Synthesis and Characterization of Betti Bases Derivatives via Green Mannich Reaction by NS-PCS and FHS as the Catalyst Mansoori, Aida; Eshghi, Hossein; Lari, Jalil Taylor & Francis https://doi.org/10.6084/m9.figshare.7642472.v1	text	January 2019
Identification of Catalytic Sites for Oxygen Reduction in Metal/Nitrogen‐Doped Carbons with Encapsulated Metal Nanoparticles Chen, Ming‐Xi; Zhu, Mengzhao; Zuo, Ming Angewandte Chemie, Vol. 132, Issue 4 https://doi.org/10.1002/ange.201912275	journal	November 2019
Nanoscaffold effects on the performance of air-cathodes for microbial fuel cells: Sustainable Fe/N-carbon electrocatalysts for the oxygen reduction reaction under neutral pH conditions Iannaci, Alessandro; Ingle, Swapnil; Domínguez, Carlota Bioelectrochemistry, Vol. 142 https://doi.org/10.1016/j.bioelechem.2021.107937	journal	December 2021
Zirconium Oxynitride-Catalyzed Oxygen Reduction Reaction at Polymer Electrolyte Fuel Cell Cathodes Chisaka, Mitsuharu; Ishihara, Akimitsu; Morioka, Hiroyuki ACS Omega, Vol. 2, Issue 2 https://doi.org/10.1021/acsomega.6b00555	journal	February 2017
A pyridinic Fe-N4 macrocycle models the active sites in Fe/N-doped carbon electrocatalysts Marshall-Roth, Travis; Libretto, Nicole J.; Wrobel, Alexandra T. Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-18969-6	journal	October 2020