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Title: In Situ X-ray Absorption Spectroscopy of a Synergistic Co–Mn Oxide Catalyst for the Oxygen Reduction Reaction

Abstract

Identifying the catalytically active site(s) in the oxygen reduction reaction (ORR), under real-time electrochemical conditions, is critical to the development of fuel cells and other technologies. We have employed in situ synchrotron-based X-ray absorption spectroscopy (XAS) to explore the synergistic interaction of a Co–Mn oxide catalyst which exhibits impressive ORR activity in alkaline fuel cells. X-ray absorption near edge structure (XANES) was used to track the dynamic structural changes of Co and Mn under both steady state (constant applied potential) and nonsteady state (potentiodynamic cyclic voltammetry, CV). Under steady state conditions, both Mn and Co valences decreased at lower potentials, suggesting the conversion from Mn-(III,IV) and Co(III) to Mn(II,III) and Co(II), respec-tively. Rapid X-ray data acquisition, combined with a slow sweep rate in CV, enabled a 3 mV resolution in the applied potential, approaching a nonsteady (potentiody-namic) state. Changes in the Co and Mn valence states were simultaneous and exhibited periodic patterns that tracked the cyclic potential sweeps. To the best of our knowledge, this represents the first study, using in situ XAS, to resolve the synergistic catalytic mechanism of a bimetallic oxide. Strategies developed/described herein can offer an enticing approach to unveil the reaction mechanism for other multimetallic electrocatalysts.

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Cornell Univ., Ithaca, NY (United States)
  2. Wuhan Univ. (China)
Publication Date:
Research Org.:
Cornell Univ., Ithaca, NY (United States). Energy Frontier Research Center (EFRC) Center for Alkaline-Based Energy+B11:C29 Solutions (CABES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1566594
Grant/Contract Number:  
SC0019445
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 4; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yang, Yao, Wang, Ying, Xiong, Yin, Huang, Xin, Shen, Luxi, Huang, Rong, Wang, Hongsen, Pastore, James P., Yu, Seung-Ho, Xiao, Li, Brock, Joel D., Zhuang, Lin, and Abruña, Héctor D. In Situ X-ray Absorption Spectroscopy of a Synergistic Co–Mn Oxide Catalyst for the Oxygen Reduction Reaction. United States: N. p., 2019. Web. doi:10.1021/jacs.8b12243.
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Yang, Yao, Wang, Ying, Xiong, Yin, Huang, Xin, Shen, Luxi, Huang, Rong, Wang, Hongsen, Pastore, James P., Yu, Seung-Ho, Xiao, Li, Brock, Joel D., Zhuang, Lin, & Abruña, Héctor D. In Situ X-ray Absorption Spectroscopy of a Synergistic Co–Mn Oxide Catalyst for the Oxygen Reduction Reaction. United States. https://doi.org/10.1021/jacs.8b12243
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Yang, Yao, Wang, Ying, Xiong, Yin, Huang, Xin, Shen, Luxi, Huang, Rong, Wang, Hongsen, Pastore, James P., Yu, Seung-Ho, Xiao, Li, Brock, Joel D., Zhuang, Lin, and Abruña, Héctor D. Tue . "In Situ X-ray Absorption Spectroscopy of a Synergistic Co–Mn Oxide Catalyst for the Oxygen Reduction Reaction". United States. https://doi.org/10.1021/jacs.8b12243. https://www.osti.gov/servlets/purl/1566594.
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@article{osti_1566594,
title = {In Situ X-ray Absorption Spectroscopy of a Synergistic Co–Mn Oxide Catalyst for the Oxygen Reduction Reaction},
author = {Yang, Yao and Wang, Ying and Xiong, Yin and Huang, Xin and Shen, Luxi and Huang, Rong and Wang, Hongsen and Pastore, James P. and Yu, Seung-Ho and Xiao, Li and Brock, Joel D. and Zhuang, Lin and Abruña, Héctor D.},
abstractNote = {Identifying the catalytically active site(s) in the oxygen reduction reaction (ORR), under real-time electrochemical conditions, is critical to the development of fuel cells and other technologies. We have employed in situ synchrotron-based X-ray absorption spectroscopy (XAS) to explore the synergistic interaction of a Co–Mn oxide catalyst which exhibits impressive ORR activity in alkaline fuel cells. X-ray absorption near edge structure (XANES) was used to track the dynamic structural changes of Co and Mn under both steady state (constant applied potential) and nonsteady state (potentiodynamic cyclic voltammetry, CV). Under steady state conditions, both Mn and Co valences decreased at lower potentials, suggesting the conversion from Mn-(III,IV) and Co(III) to Mn(II,III) and Co(II), respec-tively. Rapid X-ray data acquisition, combined with a slow sweep rate in CV, enabled a 3 mV resolution in the applied potential, approaching a nonsteady (potentiody-namic) state. Changes in the Co and Mn valence states were simultaneous and exhibited periodic patterns that tracked the cyclic potential sweeps. To the best of our knowledge, this represents the first study, using in situ XAS, to resolve the synergistic catalytic mechanism of a bimetallic oxide. Strategies developed/described herein can offer an enticing approach to unveil the reaction mechanism for other multimetallic electrocatalysts.},
doi = {10.1021/jacs.8b12243},
journal = {Journal of the American Chemical Society},
number = 4,
volume = 141,
place = {United States},
year = {Tue Jan 15 00:00:00 EST 2019},
month = {Tue Jan 15 00:00:00 EST 2019}
}
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https://doi.org/10.1021/jacs.8b12243
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    Works referencing / citing this record:

    Octahedral spinel electrocatalysts for alkaline fuel cells
    journal, November 2019

    • Yang, Yao; Xiong, Yin; Holtz, Megan E.
    • Proceedings of the National Academy of Sciences, Vol. 116, Issue 49
    • DOI: 10.1073/pnas.1906570116

    Rational Design of Spinel Cobalt Vanadate Oxide Co 2 VO 4 for Superior Electrocatalysis
    journal, January 2020

    Co–Mn spinel supported self-catalysis induced N-doped carbon nanotubes with high efficiency electron transport channels for zinc–air batteries
    journal, January 2019

    • Su, Hang; Wang, Xiao-Tong; Hu, Jing-Xiao
    • Journal of Materials Chemistry A, Vol. 7, Issue 39
    • DOI: 10.1039/c9ta08064c

    Gadolinium‐Induced Valence Structure Engineering for Enhanced Oxygen Electrocatalysis
    journal, March 2020

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