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Title: Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La1-xSrxCoO3-δ perovskite composite electrodes

Abstract

Perovskite oxides are active room-temperature bifunctional oxygen electrocatalysts in alkaline media, capable of performing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with lower combined overpotentials relative to their precious metal counterparts. However, their semiconducting nature necessitates the use of activated carbons as conductive supports to generate applicably relevant current densities. In efforts to advance the performance and theory of oxide electrocatalysts, the chemical and physical properties of the oxide material often take precedence over contributions from the conductive additive. In this work, we find that carbon plays an important synergistic role in improving the performance of La1-xSrxCoO3-δ (0 ≤ x ≤ 1) electrocatalysts through the activation of O2 and spillover of radical oxygen intermediates, HO2- and O2-, which is further reduced through chemical decomposition of HO2- on the perovskite surface. Here, through a combination of thin-film rotating disk electrochemical characterization of the hydrogen peroxide intermediate reactions (hydrogen peroxide reduction reaction (HPRR), hydrogen peroxide oxidation reaction (HPOR)) and oxygen reduction reaction (ORR), surface chemical analysis, HR-TEM, and microkinetic modeling on La1-xSrxCoO3-δ (0 ≤ x ≤ 1)/carbon (with nitrogen and non-nitrogen doped carbons) composite electrocatalysts, we deconvolute the mechanistic aspects and contributions to reactivity of the oxide and carbonmore » support.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5];  [1]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [8]; ORCiD logo [2]
  1. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry; Univ. of Texas, Austin, TX (United States). Center for Nano and Molecular Science and Technology
  2. Skolkovo Inst. of Science and Technology, Moscow (Russia). Center for Electrochemical Energy Storage CREI
  3. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
  4. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry, and Center for Nano and Molecular Science and Technology, Texas Materials Inst.; Exponent Failure Analysis Associates, Natick, MA (United States)
  5. Skolkovo Inst. of Science and Technology, Moscow (Russia). Center for Electrochemical Energy Storage CREI; Univ. of Antwerp, Antwerp (Belgium)
  6. Univ. of Strasbourg, Strasbourg (France). Inst. de Chimie de Strasbourg
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  8. Univ. of Texas, Austin, TX (United States). Center for Nano and Molecular Science and Technology, Texas Materials Inst., and Dept. of Chemical Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1506782
Alternate Identifier(s):
OSTI ID: 1492463
Grant/Contract Number:  
AC05-00OR22725; F-1529; F-1319
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 21; Journal Issue: 6; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Mefford, J. Tyler, Kurilovich, Aleksandr A., Saunders, Jennette, Hardin, William G., Abakumov, Artem M., Forslund, Robin P., Bonnefont, Antoine, Dai, Sheng, Johnston, Keith P., and Stevenson, Keith J. Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La1-xSrxCoO3-δ perovskite composite electrodes. United States: N. p., 2019. Web. doi:10.1039/C8CP06268D.
Mefford, J. Tyler, Kurilovich, Aleksandr A., Saunders, Jennette, Hardin, William G., Abakumov, Artem M., Forslund, Robin P., Bonnefont, Antoine, Dai, Sheng, Johnston, Keith P., & Stevenson, Keith J. Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La1-xSrxCoO3-δ perovskite composite electrodes. United States. doi:10.1039/C8CP06268D.
Mefford, J. Tyler, Kurilovich, Aleksandr A., Saunders, Jennette, Hardin, William G., Abakumov, Artem M., Forslund, Robin P., Bonnefont, Antoine, Dai, Sheng, Johnston, Keith P., and Stevenson, Keith J. Fri . "Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La1-xSrxCoO3-δ perovskite composite electrodes". United States. doi:10.1039/C8CP06268D. https://www.osti.gov/servlets/purl/1506782.
@article{osti_1506782,
title = {Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La1-xSrxCoO3-δ perovskite composite electrodes},
author = {Mefford, J. Tyler and Kurilovich, Aleksandr A. and Saunders, Jennette and Hardin, William G. and Abakumov, Artem M. and Forslund, Robin P. and Bonnefont, Antoine and Dai, Sheng and Johnston, Keith P. and Stevenson, Keith J.},
abstractNote = {Perovskite oxides are active room-temperature bifunctional oxygen electrocatalysts in alkaline media, capable of performing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with lower combined overpotentials relative to their precious metal counterparts. However, their semiconducting nature necessitates the use of activated carbons as conductive supports to generate applicably relevant current densities. In efforts to advance the performance and theory of oxide electrocatalysts, the chemical and physical properties of the oxide material often take precedence over contributions from the conductive additive. In this work, we find that carbon plays an important synergistic role in improving the performance of La1-xSrxCoO3-δ (0 ≤ x ≤ 1) electrocatalysts through the activation of O2 and spillover of radical oxygen intermediates, HO2- and O2-, which is further reduced through chemical decomposition of HO2- on the perovskite surface. Here, through a combination of thin-film rotating disk electrochemical characterization of the hydrogen peroxide intermediate reactions (hydrogen peroxide reduction reaction (HPRR), hydrogen peroxide oxidation reaction (HPOR)) and oxygen reduction reaction (ORR), surface chemical analysis, HR-TEM, and microkinetic modeling on La1-xSrxCoO3-δ (0 ≤ x ≤ 1)/carbon (with nitrogen and non-nitrogen doped carbons) composite electrocatalysts, we deconvolute the mechanistic aspects and contributions to reactivity of the oxide and carbon support.},
doi = {10.1039/C8CP06268D},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 6,
volume = 21,
place = {United States},
year = {2019},
month = {1}
}

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