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Title: The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.1311609jes· OSTI ID:1286965
 [1];  [2];  [2];  [2];  [2];  [2];  [3];  [1]; ORCiD logo [4];  [5]
  1. Univ. of Rochester, NY (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Soutehrn California, Los Angeles, CA (United States)
  4. Univ. of Yamanashi, Kofu (Japan)
  5. West Virginia Univ., Morgantown, WV (United States)
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The effect due to systematic substitution of cobalt by iron in La0.6Ca0.4Co1-xFexO3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order towards OH- near unity were achieved for the unsubstituted La0.6Ca0.4CoO3. Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La0.6Ca0.4Co0.2Fe0.8O3 and La0.6Ca0.4Co0.1Fe0.9O3 showed higher area specific activity towards OER than La0.6Ca0.4CoO3 or La0.6Ca0.4FeO3. Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; DGE-0966089
OSTI ID:
1286965
Journal Information:
Journal of the Electrochemical Society, Vol. 163, Issue 9; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Cited By (2)

Electrosynthesis of high-entropy metallic glass nanoparticles for designer, multi-functional electrocatalysis journal June 2019
Impact of Strontium-Substitution on Oxygen Evolution Reaction of Lanthanum Nickelates in Alkaline Solution journal January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalyst
oxygen evolution
transition metal perovskites
water electrolytes