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

The effect due to systematic substitution of cobalt by iron in La 0.6Ca 0.4Co 1-xFe xO 3 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 La 0.6Ca 0.4CoO 3. 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, La 0.6Ca 0.4Co 0.2Fe 0.8O 3 and La 0.6Ca 0.4Co 0.1Fe 0.9O 3 showed higher area specific activity towards OER than La 0.6Ca 0.4CoO 3 or La 0.6Ca 0.4FeO 3. Finally, we believe iron inclusion inmore » 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.« less
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  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)
Publication Date:
Grant/Contract Number:
AC05-00OR22725; DGE-0966089
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 163; Journal Issue: 9; Journal ID: ISSN 0013-4651
The Electrochemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalyst; oxygen evolution; transition metal perovskites; water electrolytes
OSTI Identifier: