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

Abreu-Sepulveda, Maria A.; Dhital, Chetan; Huq, Ashfia; Li, Ling; Bridges, Craig A.; Paranthaman, M. Parans; Narayanan, S. R.; Quesnel, David J.; Tryk, Donald A.; Manivannan, A.

doi:10.1149/2.1311609jes

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

Abstract

The effect due to systematic substitution of cobalt by iron in La_0.6Ca_0.4Co_1-xFe_xO₃ 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_0.4CoO₃. 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, La_0.6Ca_0.4Co_0.2Fe_0.8O₃ and La_0.6Ca_0.4Co_0.1Fe_0.9O₃ showed higher area specific activity towards OER than La_0.6Ca_0.4CoO₃ or La_0.6Ca_0.4FeO₃. 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 mechanismsmore »« less

Authors:

Abreu-Sepulveda, Maria A. ^[1]; Dhital, Chetan ^[2]; Huq, Ashfia ^[2]; Li, Ling ^[2]; Bridges, Craig A. ^[2]; Paranthaman, M. Parans ^[2]; Narayanan, S. R. ^[3]; Quesnel, David J. ^[1];

^[4]; Manivannan, A. ^[5]

Univ. of Rochester, NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Soutehrn California, Los Angeles, CA (United States)
Univ. of Yamanashi, Kofu (Japan)
West Virginia Univ., Morgantown, WV (United States)

Publication Date:: Sat Jul 30 00:00:00 EDT 2016

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1286965

Grant/Contract Number:: AC05-00OR22725; DGE-0966089

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the Electrochemical Society

Additional Journal Information:: Journal Volume: 163; Journal Issue: 9; Journal ID: ISSN 0013-4651

Publisher:: The Electrochemical Society

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Abreu-Sepulveda, Maria A., Dhital, Chetan, Huq, Ashfia, Li, Ling, Bridges, Craig A., Paranthaman, M. Parans, Narayanan, S. R., Quesnel, David J., Tryk, Donald A., and Manivannan, A. The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media.  United States: N. p., 2016. 
Web.  doi:10.1149/2.1311609jes.

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                    Abreu-Sepulveda, Maria A., Dhital, Chetan, Huq, Ashfia, Li, Ling, Bridges, Craig A., Paranthaman, M. Parans, Narayanan, S. R., Quesnel, David J., Tryk, Donald A., & Manivannan, A. The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media.  United States.  https://doi.org/10.1149/2.1311609jes

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                    Abreu-Sepulveda, Maria A., Dhital, Chetan, Huq, Ashfia, Li, Ling, Bridges, Craig A., Paranthaman, M. Parans, Narayanan, S. R., Quesnel, David J., Tryk, Donald A., and Manivannan, A. Sat .  
"The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media".  United States.  https://doi.org/10.1149/2.1311609jes.  https://www.osti.gov/servlets/purl/1286965.

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@article{osti_1286965,

  title        = {The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media},

  author       = {Abreu-Sepulveda, Maria A. and Dhital, Chetan and Huq, Ashfia and Li, Ling and Bridges, Craig A. and Paranthaman, M. Parans and Narayanan, S. R. and Quesnel, David J. and Tryk, Donald A. and Manivannan, A.},

  abstractNote = {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.},

  doi          = {10.1149/2.1311609jes},

  journal      = {Journal of the Electrochemical Society},

  number       = 9,

  volume       = 163,

  place        = {United States},

  year         = {Sat Jul 30 00:00:00 EDT 2016},

  month        = {Sat Jul 30 00:00:00 EDT 2016}

}

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Abstract

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