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

Sunday, 29 May 2016: 16:00
Indigo Ballroom A (Hilton San Diego Bayfront)
M. Abreu-Sepulveda (University of Rochester), C. A. Bridges (Oak Ridge National Laboratory), A. Manivannan (U.S. Department of Energy), M. P. Paranthaman (ORNL), and D. J. Quesnel (University of Rochester)
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. These compounds were synthesized 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. 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. 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.