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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 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 themore » enhanced ORR kinetics of La0.8Sr0.2CoO3-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:
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 = {2016},
month = {2}
}

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Works referenced in this record:

In Situ Ambient Pressure X-ray Photoelectron Spectroscopy of Cobalt Perovskite Surfaces under Cathodic Polarization at High Temperatures
journal, July 2013

  • Crumlin, Ethan J.; Mutoro, Eva; Hong, Wesley T.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 31
  • DOI: 10.1021/jp4051963

Oxygen tracer diffusion in dense Ba0.5Sr0.5Co0.8Fe0.2O3−δ films
journal, February 2009

  • Wang, L.; Merkle, R.; Maier, J.
  • Applied Physics Letters, Vol. 94, Issue 7
  • DOI: 10.1063/1.3085969

Relationship between Cation Segregation and the Electrochemical Oxygen Reduction Kinetics of La0.6Sr0.4CoO3−δ Thin Film Electrodes
journal, January 2011

  • Kubicek, Markus; Limbeck, Andreas; Frömling, Till
  • Journal of The Electrochemical Society, Vol. 158, Issue 6
  • DOI: 10.1149/1.3581114

Photoelectron spectroscopy under ambient pressure and temperature conditions
journal, March 2009

  • Frank Ogletree, D.; Bluhm, Hendrik; Hebenstreit, Eleonore D.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2
  • DOI: 10.1016/j.nima.2008.12.155

Revealing the atomic structure and strontium distribution in nanometer-thick La0.8Sr0.2CoO3−δ grown on (001)-oriented SrTiO3
journal, January 2014

  • Feng, Zhenxing; Yacoby, Yizhak; Hong, Wesley T.
  • Energy & Environmental Science, Vol. 7, Issue 3
  • DOI: 10.1039/c3ee43164a

Surface strontium enrichment on highly active perovskites for oxygen electrocatalysis in solid oxide fuel cells
journal, January 2012

  • Crumlin, Ethan J.; Mutoro, Eva; Liu, Zhi
  • Energy & Environmental Science, Vol. 5, Issue 3
  • DOI: 10.1039/c2ee03397f

Reversible Compositional Control of Oxide Surfaces by Electrochemical Potentials
journal, December 2011

  • Mutoro, Eva; Crumlin, Ethan J.; Pöpke, Hendrik
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 1
  • DOI: 10.1021/jz201523y

Electronic structure of 3 d -transition-metal compounds by analysis of the 2 p core-level photoemission spectra
journal, August 1992


Surface termination and subsurface restructuring of perovskite-based solid oxide electrode materials
journal, January 2014

  • Druce, J.; Téllez, H.; Burriel, M.
  • Energy Environ. Sci., Vol. 7, Issue 11
  • DOI: 10.1039/C4EE01497A

Water Reactivity on the LaCoO 3 (001) Surface: An Ambient Pressure X-ray Photoelectron Spectroscopy Study
journal, August 2014

  • Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 34
  • DOI: 10.1021/jp502970r

Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge
journal, August 2013

  • Jeen, Hyoungjeen; Choi, Woo Seok; Biegalski, Michael D.
  • Nature Materials, Vol. 12, Issue 11
  • DOI: 10.1038/nmat3736

Oxygen non-stoichiometry and electrical conductivity of the binary strontium cobalt oxide SrCoOx
journal, August 1997


XPS and voltammetric studies on La1−xSrxCoO3−δ perovskite oxide electrodes
journal, October 2000


Quantum-mechanics-based design principles for solid oxide fuel cell cathode materials
journal, January 2011

  • Pavone, Michele; Ritzmann, Andrew M.; Carter, Emily A.
  • Energy & Environmental Science, Vol. 4, Issue 12
  • DOI: 10.1039/c1ee02377b

A differentially pumped electrostatic lens system for photoemission studies in the millibar range
journal, November 2002

  • Ogletree, D. Frank; Bluhm, Hendrik; Lebedev, Gennadi
  • Review of Scientific Instruments, Vol. 73, Issue 11
  • DOI: 10.1063/1.1512336

Systematics in band gaps and optical spectra of 3D transition metal compounds
journal, September 1990


Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells
journal, June 2010

  • la O', Gerardo Jose; Ahn, Sung-Jin; Crumlin, Ethan
  • Angewandte Chemie International Edition, Vol. 49, Issue 31
  • DOI: 10.1002/anie.201001922

Electrochemistry of Mixed Oxygen Ion and Electron Conducting Electrodes in Solid Electrolyte Cells
journal, July 2012


Orienting Oxygen Vacancies for Fast Catalytic Reaction
journal, October 2013

  • Jeen, Hyoungjeen; Bi, Zhonghe; Choi, Woo Seok
  • Advanced Materials, Vol. 25, Issue 44
  • DOI: 10.1002/adma.201302919

Surface segregation and restructuring of colossal-magnetoresistant manganese perovskites La 0.65 Sr 0.35 MnO 3
journal, December 2000


Mechanisms and rate laws for oxygen exchange on mixed-conducting oxide surfaces
journal, January 2007


Suppression of Sr surface segregation in La 1−x Sr x Co 1−y Fe y O 3−δ : a first principles study
journal, January 2013

  • Ding, Hepeng; Virkar, Anil V.; Liu, Meilin
  • Phys. Chem. Chem. Phys., Vol. 15, Issue 2
  • DOI: 10.1039/C2CP43148C

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
  • DOI: 10.1039/c1ee01245b

Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes
journal, October 2004


Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions
journal, January 2015

  • Mueller, David N.; Machala, Michael L.; Bluhm, Hendrik
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7097

Chemical Heterogeneities on La 0.6 Sr 0.4 CoO 3−δ Thin Films—Correlations to Cathode Surface Activity and Stability
journal, March 2012

  • Cai, Zhuhua; Kubicek, Markus; Fleig, Jürgen
  • Chemistry of Materials, Vol. 24, Issue 6
  • DOI: 10.1021/cm203501u

Oxygen Electrocatalysis on Epitaxial La 0.6 Sr 0.4 CoO 3- δ Perovskite Thin Films for Solid Oxide Fuel Cells
journal, January 2012

  • Crumlin, Ethan J.; Ahn, Sung-Jin; Lee, Dongkyu
  • Journal of The Electrochemical Society, Vol. 159, Issue 7
  • DOI: 10.1149/2.018207jes

Topotactic Electrochemical Redox Reactions of the Defect Perovskite SrCoO2.5+x
September 1996

  • Nemudry, A.; Rudolf, P.; Schollhorn, R.
  • Chemistry of Materials, Vol. 8, Issue 9, p. 2232-2238
  • DOI: 10.1021/cm950504+

Note: Fixture for characterizing electrochemical devices in-operando in traditional vacuum systems
journal, August 2010

  • Whaley, Josh A.; McDaniel, Anthony H.; El Gabaly, Farid
  • Review of Scientific Instruments, Vol. 81, Issue 8
  • DOI: 10.1063/1.3479384

Cation Size Mismatch and Charge Interactions Drive Dopant Segregation at the Surfaces of Manganite Perovskites
journal, May 2013

  • Lee, Wonyoung; Han, Jeong Woo; Chen, Yan
  • Journal of the American Chemical Society, Vol. 135, Issue 21
  • DOI: 10.1021/ja3125349

Prediction of solid oxide fuel cell cathode activity with first-principles descriptors
journal, January 2011

  • Lee, Yueh-Lin; Kleis, Jesper; Rossmeisl, Jan
  • Energy & Environmental Science, Vol. 4, Issue 10
  • DOI: 10.1039/c1ee02032c

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


Systematic x-ray photoelectron spectroscopic study of La1?xSrx-based perovskite-type oxides
journal, January 2002

  • van der Heide, P. A. W.
  • Surface and Interface Analysis, Vol. 33, Issue 5
  • DOI: 10.1002/sia.1227

Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells
journal, October 2010

  • Crumlin, Ethan J.; Mutoro, Eva; Ahn, Sung-Jin
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 21
  • DOI: 10.1021/jz101217d

Correlation between reconstructive phase transitions and transport properties from SrCoO2.5 brownmillerite: A neutron diffraction study
journal, December 2008


Why are some oxides metallic, while most are insulating?
journal, November 1991

  • Torrance, Jerry B.; Lacorre, Philippe; Asavaroengchai, Chinnarong
  • Physica C: Superconductivity, Vol. 182, Issue 4-6
  • DOI: 10.1016/0921-4534(91)90534-6

Chemical diffusion and oxygen exchange of La0.6Sr0.4Co0.6Fe0.4O3−δ
journal, August 1997