The influence of Fe substitution in lanthanum calcium cobalt oxide on the oxygen evolution reaction in alkaline media

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

doi:10.1149/2.1311609jes

The influence of Fe substitution in lanthanum calcium cobalt oxide on the oxygen evolution reaction in alkaline media

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

Nanomaterials Chemistry Group

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19 Scopus citations

Abstract

The effect due to systematic substitution of cobalt by iron in La_0.6Ca_0.4CoO₃ perovskites on 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 and neutron powder diffraction analysis. The apparent OER activity was evaluated by quasisteady state current measurements in alkaline media using a traditional three-electrode system. X-ray photoelectron spectroscopy shows an increase in Fe substitution causes an increase in the surface concentration of various Co oxidation states. A Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order for OH- near unity were found for the unsubstituted compounds. A decrease in the Tafel slope to 49 mV/decade was observed when iron is incorporated in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction; however, the dependence of specific current density with Fe fraction is not linear.We believe that the iron incorporation in the La_0.6Ca_0.4CoO₃ perovskites decreases the electron transfer barrier and facilitates the formation of cobalt-hydroxides.

Original language	English
Pages (from-to)	F1124-F1132
Journal	Journal of the Electrochemical Society
Volume	163
Issue number	9
DOIs	https://doi.org/10.1149/2.1311609jes
State	Published - 2016

Bibliographical note

Publisher Copyright:
© The Author(s) 2016. Published by ECS.

Funding

This research has been supported by the NSF-IGERT DGE-0966089 at the University of Rochester, NY. A portion of this research at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U. S. Department of Energy. Support (MPP and CAB) for neutron characterizations was provided by U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. DAT acknowledges support by the New Energy and Industrial Development Organization (NEDO) of Japan. Notice: This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).

Funders	Funder number
DOE Public Access Plan
NSF-IGERT	DGE-0966089
Scientific User Facilities Division
United States Government
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Division of Materials Sciences and Engineering
New Energy and Industrial Technology Development Organization	DE-AC05-00OR22725

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Abreu-Sepulveda, M. A., Dhital, C., Huq, A., Li, L., Bridges, C. A., Paranthaman, M. P., Narayanan, S. R., Quesnel, D. J., Tryk, D. A., & Manivannan, A. (2016). The influence of Fe substitution in lanthanum calcium cobalt oxide on the oxygen evolution reaction in alkaline media. Journal of the Electrochemical Society, 163(9), F1124-F1132. https://doi.org/10.1149/2.1311609jes

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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 La0.6Ca0.4CoO3 perovskites on 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 and neutron powder diffraction analysis. The apparent OER activity was evaluated by quasisteady state current measurements in alkaline media using a traditional three-electrode system. X-ray photoelectron spectroscopy shows an increase in Fe substitution causes an increase in the surface concentration of various Co oxidation states. A Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order for OH- near unity were found for the unsubstituted compounds. A decrease in the Tafel slope to 49 mV/decade was observed when iron is incorporated in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction; however, the dependence of specific current density with Fe fraction is not linear.We believe that the iron incorporation in the La0.6Ca0.4CoO3 perovskites decreases the electron transfer barrier and facilitates the formation of cobalt-hydroxides.",

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

note = "Publisher Copyright: {\textcopyright} The Author(s) 2016. Published by ECS.",

year = "2016",

doi = "10.1149/2.1311609jes",

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AU - Abreu-Sepulveda, Maria A.

AU - Dhital, Chetan

AU - Huq, Ashfia

AU - Li, Ling

AU - Bridges, Craig A.

AU - Paranthaman, M. Parans

AU - Narayanan, S. R.

AU - Quesnel, David J.

AU - Tryk, Donald A.

AU - Manivannan, A.

PY - 2016

Y1 - 2016

N2 - The effect due to systematic substitution of cobalt by iron in La0.6Ca0.4CoO3 perovskites on 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 and neutron powder diffraction analysis. The apparent OER activity was evaluated by quasisteady state current measurements in alkaline media using a traditional three-electrode system. X-ray photoelectron spectroscopy shows an increase in Fe substitution causes an increase in the surface concentration of various Co oxidation states. A Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order for OH- near unity were found for the unsubstituted compounds. A decrease in the Tafel slope to 49 mV/decade was observed when iron is incorporated in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction; however, the dependence of specific current density with Fe fraction is not linear.We believe that the iron incorporation in the La0.6Ca0.4CoO3 perovskites decreases the electron transfer barrier and facilitates the formation of cobalt-hydroxides.

AB - The effect due to systematic substitution of cobalt by iron in La0.6Ca0.4CoO3 perovskites on 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 and neutron powder diffraction analysis. The apparent OER activity was evaluated by quasisteady state current measurements in alkaline media using a traditional three-electrode system. X-ray photoelectron spectroscopy shows an increase in Fe substitution causes an increase in the surface concentration of various Co oxidation states. A Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order for OH- near unity were found for the unsubstituted compounds. A decrease in the Tafel slope to 49 mV/decade was observed when iron is incorporated in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction; however, the dependence of specific current density with Fe fraction is not linear.We believe that the iron incorporation in the La0.6Ca0.4CoO3 perovskites decreases the electron transfer barrier and facilitates the formation of cobalt-hydroxides.

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The influence of Fe substitution in lanthanum calcium cobalt oxide on the oxygen evolution reaction in alkaline media

Abstract

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