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Title: Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films

Abstract

Transition metal perovskite oxides are promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, but a lack of fundamental understanding of oxide surfaces impedes the rational design of novel catalysts with improved device efficiencies. In particular, understanding the surface chemistry of oxides is essential for controlling both catalytic activity and long-term stability. Thus, elucidating the physical nature of species on perovskite surfaces and their catalytic enhancement would generate new insights in developing oxide electrocatalysts. In this article, we perform near-ambient pressure XPS of model brownmillerite Sr 2Co 2O 5 (SCO) epitaxial thin films with different crystallographic orientations. Detailed analysis of the Co 2p spectra suggests that the films lose oxygen as a function of temperature. Moreover, deconvolution of the O 1s spectra shows distinct behavior for (114)-oriented SCO films compared to (001)-oriented SCO films, where an additional bulk oxygen species is observed. These findings indicate a change to a perovskite-like oxygen chemistry that occurs more easily in (114) SCO than (001) SCO, likely due to the orientation of oxygen vacancy channels out-of-plane with respect to the film surface. This difference in surface chemistry is responsible for the anisotropy of the oxygen surface exchange coefficient of SCO and maymore » contribute to the enhanced ORR kinetics of La 0.8Sr 0.2CoO 3-δ thin films by SCO surface particles observed previously.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [3];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1261344
Alternate Identifier(s):
OSTI ID: 1379119
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 59; Journal Issue: 5; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ambient pressure XPS; Strontium cobaltite; Solid oxide fuel cells; Oxygen reduction; Electrocatalysis

Citation Formats

Hong, Wesley T., Stoerzinger, Kelsey, Crumlin, Ethan J., Mutoro, Eva, Jeen, Hyoung Jeen, Lee, Ho Nyung, and Shao-Horn, Yang. Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films. United States: N. p., 2016. Web. doi:10.1007/s11244-015-0532-4.
Hong, Wesley T., Stoerzinger, Kelsey, Crumlin, Ethan J., Mutoro, Eva, Jeen, Hyoung Jeen, Lee, Ho Nyung, & Shao-Horn, Yang. Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films. United States. doi:10.1007/s11244-015-0532-4.
Hong, Wesley T., Stoerzinger, Kelsey, Crumlin, Ethan J., Mutoro, Eva, Jeen, Hyoung Jeen, Lee, Ho Nyung, and Shao-Horn, Yang. Thu . "Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films". United States. doi:10.1007/s11244-015-0532-4. https://www.osti.gov/servlets/purl/1261344.
@article{osti_1261344,
title = {Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films},
author = {Hong, Wesley T. and Stoerzinger, Kelsey and Crumlin, Ethan J. and Mutoro, Eva and Jeen, Hyoung Jeen and Lee, Ho Nyung and Shao-Horn, Yang},
abstractNote = {Transition metal perovskite oxides are promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, but a lack of fundamental understanding of oxide surfaces impedes the rational design of novel catalysts with improved device efficiencies. In particular, understanding the surface chemistry of oxides is essential for controlling both catalytic activity and long-term stability. Thus, elucidating the physical nature of species on perovskite surfaces and their catalytic enhancement would generate new insights in developing oxide electrocatalysts. In this article, we perform near-ambient pressure XPS of model brownmillerite Sr2Co2O5 (SCO) epitaxial thin films with different crystallographic orientations. Detailed analysis of the Co 2p spectra suggests that the films lose oxygen as a function of temperature. Moreover, deconvolution of the O 1s spectra shows distinct behavior for (114)-oriented SCO films compared to (001)-oriented SCO films, where an additional bulk oxygen species is observed. These findings indicate a change to a perovskite-like oxygen chemistry that occurs more easily in (114) SCO than (001) SCO, likely due to the orientation of oxygen vacancy channels out-of-plane with respect to the film surface. This difference in surface chemistry is responsible for the anisotropy of the oxygen surface exchange coefficient of SCO and may contribute to the enhanced ORR kinetics of La0.8Sr0.2CoO3-δ thin films by SCO surface particles observed previously.},
doi = {10.1007/s11244-015-0532-4},
journal = {Topics in Catalysis},
number = 5,
volume = 59,
place = {United States},
year = {Thu Feb 11 00:00:00 EST 2016},
month = {Thu Feb 11 00:00:00 EST 2016}
}

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Works referenced in this record:

Enhanced oxygen reduction activity on surface-decorated perovskite thin films for solid oxide fuel cells
journal, January 2011

  • Mutoro, Eva; Crumlin, Ethan J.; Biegalski, Michael D.
  • Energy & Environmental Science, Vol. 4, Issue 9, p. 3689-3696
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Topotactic Electrochemical Redox Reactions of the Defect Perovskite SrCoO2.5+x
September 1996

  • Nemudry, A.; Rudolf, P.; Schollhorn, R.
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  • DOI: 10.1021/cm950504+

Crystallographic and magnetic structure of SrCoO 2.5 brownmillerite: Neutron study coupled with band-structure calculations
journal, August 2008