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Title: In operando studies of CO oxidation on epitaxial SrCoO 2.5+δ thin films

Abstract

The high abundance and fast kinetics of select transition metal oxide catalysts are attractive features for many chemical and electrochemical device applications. However, the activity of such catalysts can be accompanied by phase instabilities that prevent their widespread usage. Furthermore, complexities associated with variations in phase behavior and oxygen stoichiometry have hindered studies on the true origins of catalytic activity. Here, we explore the interactions between activity, phase stability, and microstructure using in operando synchrotron X-ray techniques and gas chromatography/mass spectroscopy (GCMS) to probe the behavior of model SrCoO 2.5+δ (SCO) catalysts. Pulsed laser deposition was used to prepare SCO thin films on (001) SrTiO 3, (111) SrTiO 3, and pseudocubic (001) DyScO 3 substrates. The GCMS catalytic measurements were performed with a custom-built microreactor compatible with a synchrotron X-ray diffractometer at the Advanced Photon Source. The activity for carbon monoxide oxidation was determined as a function of temperature from 500 °C to 800 °C. We show that the SrCoO 2.5+δ films are active for CO oxidation, most likely by direct reaction with lattice oxygen; consequently, the activity was observed to increase as the films become less stable, with the most active film being the one exhibiting the lowest surfacemore » and crystal quality. All films decompose at high temperatures, with in operando diffraction indicating the gradual formation of Sr-rich hexagonal and CoO phases. We find that real-time studies of model oxide systems with synchrotron X-rays is a powerful means of gaining insight into the varied processes taking place at catalytic surfaces.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [1];  [5]; ORCiD logo [1]; ORCiD logo [6]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Chung-Ang Univ., Seoul (South Korea)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pusan National Univ., Busan (Korea)
  4. Argonne National Lab. (ANL), Argonne, IL (United States); Empa, Swiss Federal Labs for Materials Science and Technology, Gallen (Switzerland)
  5. Northern Illinois Univ., DeKalb, IL (United States)
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1560385
Alternate Identifier(s):
OSTI ID: 1559362; OSTI ID: 1569463
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
APL Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 8; Journal ID: ISSN 2166-532X
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Folkman, Chad M., Chang, Seo Hyoung, Jeen, Hyoungjeen, Perret, Edith, Baldo, Peter M., Thompson, Carol, Eastman, Jeffrey A., Lee, Ho Nyung, and Fong, Dillon D. In operando studies of CO oxidation on epitaxial SrCoO2.5+δ thin films. United States: N. p., 2019. Web. doi:10.1063/1.5108957.
Folkman, Chad M., Chang, Seo Hyoung, Jeen, Hyoungjeen, Perret, Edith, Baldo, Peter M., Thompson, Carol, Eastman, Jeffrey A., Lee, Ho Nyung, & Fong, Dillon D. In operando studies of CO oxidation on epitaxial SrCoO2.5+δ thin films. United States. doi:10.1063/1.5108957.
Folkman, Chad M., Chang, Seo Hyoung, Jeen, Hyoungjeen, Perret, Edith, Baldo, Peter M., Thompson, Carol, Eastman, Jeffrey A., Lee, Ho Nyung, and Fong, Dillon D. Thu . "In operando studies of CO oxidation on epitaxial SrCoO2.5+δ thin films". United States. doi:10.1063/1.5108957. https://www.osti.gov/servlets/purl/1560385.
@article{osti_1560385,
title = {In operando studies of CO oxidation on epitaxial SrCoO2.5+δ thin films},
author = {Folkman, Chad M. and Chang, Seo Hyoung and Jeen, Hyoungjeen and Perret, Edith and Baldo, Peter M. and Thompson, Carol and Eastman, Jeffrey A. and Lee, Ho Nyung and Fong, Dillon D.},
abstractNote = {The high abundance and fast kinetics of select transition metal oxide catalysts are attractive features for many chemical and electrochemical device applications. However, the activity of such catalysts can be accompanied by phase instabilities that prevent their widespread usage. Furthermore, complexities associated with variations in phase behavior and oxygen stoichiometry have hindered studies on the true origins of catalytic activity. Here, we explore the interactions between activity, phase stability, and microstructure using in operando synchrotron X-ray techniques and gas chromatography/mass spectroscopy (GCMS) to probe the behavior of model SrCoO2.5+δ (SCO) catalysts. Pulsed laser deposition was used to prepare SCO thin films on (001) SrTiO3, (111) SrTiO3, and pseudocubic (001) DyScO3 substrates. The GCMS catalytic measurements were performed with a custom-built microreactor compatible with a synchrotron X-ray diffractometer at the Advanced Photon Source. The activity for carbon monoxide oxidation was determined as a function of temperature from 500 °C to 800 °C. We show that the SrCoO2.5+δ films are active for CO oxidation, most likely by direct reaction with lattice oxygen; consequently, the activity was observed to increase as the films become less stable, with the most active film being the one exhibiting the lowest surface and crystal quality. All films decompose at high temperatures, with in operando diffraction indicating the gradual formation of Sr-rich hexagonal and CoO phases. We find that real-time studies of model oxide systems with synchrotron X-rays is a powerful means of gaining insight into the varied processes taking place at catalytic surfaces.},
doi = {10.1063/1.5108957},
journal = {APL Materials},
issn = {2166-532X},
number = 8,
volume = 7,
place = {United States},
year = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

FIG. 1 FIG. 1: Description of the in operando apparatus and materials systems. (a) Schematic of the microreactor allowing both catalytic studies and X-ray diffraction measurements. The sample is mounted atop a quartz tube affixed to both rotational and translational motors. We depict a symmetrical scattering geometry with incoming and outgoing wavevectorsmore » k and scattering vector Q, but off-specular geometries can also be employed. The gas flow direction is indicated. (b) Image of the Be-domed microreactor as mounted on a six-circle diffractometer. Lines for water cooling and gas handling are visible. (c) Cross-sectional views of the SrCoO2.5 crystal structure for SCO films grown on STO (001) (top), DSO (001)p (middle), and STO (111) (bottom) substrates. Oxygen octahedra are colored light blue, and oxygen tetrahedra are colored dark blue. The arrows indicate the direction along the surface normal.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.