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Title: Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La (1- x ) Sr x CrO 3

Abstract

The oxidation and reduction of metal oxides and their interaction with the environment play a critical role in material stability and the ability to catalyze reactions. The local change in valence and formation of surface adsorbates affect the oxide electronic structure and chemical reactivity, yet are challenging to probe experimentally. Here we present a detailed study of the oxidation and reduction of Cr in the perovskite oxide family of La(1-x)SrxCrO3 using ambient pressure X-ray photoelectron spectroscopy. The incorporation of Sr increases the propensity to oxidize the surface, leading to the presence of Cr4+ and Cr6+ principally confined to the top unit cell when in equilibrium with O2 gas. These acidic sites are readily reduced to Cr3+ in equilibrium with H2O vapor, and the resultant amount of hydroxyls formed from the dissociation of H2O is directly proportional to the density of surface sites which had been oxidized. Our quantification of the redox stability of La(1-x)SrxCrO3 and the relationship between the extent of oxidation, reduction, and hydroxylation with Sr yields important insight into the surface functionality during electrochemical applications.

Authors:
ORCiD logo [1];  [1];  [2];  [3];  [4];  [5];  [5];  [5];  [6];  [1]
  1. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99352 USA
  2. Beamline Research Division, Pohang Kyungbuk 37673 Republic of Korea
  3. Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 China
  4. State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 China; Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley CA 94720 USA
  5. School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis OR 97331 USA
  6. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley CA 94720 USA
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1439687
Report Number(s):
PNNL-SA-129951
Journal ID: ISSN 2196-7350; 49306
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Advanced Materials Interfaces; Journal Volume: 5; Journal Issue: 6
Country of Publication:
United States
Language:
English
Subject:
ambient pressure X-ray photoelectron spectroscopy; surface oxidation; surface reduction; chromium oxides; hydroxylation; Environmental Molecular Sciences Laboratory

Citation Formats

Stoerzinger, Kelsey A., Du, Yingge, Ihm, Kyuwook, Zhang, Kelvin H. L., Cai, Jun, Diulus, J. Trey, Frederick, Ryan T., Herman, Gregory S., Crumlin, Ethan J., and Chambers, Scott A. Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La (1- x ) Sr x CrO 3. United States: N. p., 2018. Web. doi:10.1002/admi.201701363.
Stoerzinger, Kelsey A., Du, Yingge, Ihm, Kyuwook, Zhang, Kelvin H. L., Cai, Jun, Diulus, J. Trey, Frederick, Ryan T., Herman, Gregory S., Crumlin, Ethan J., & Chambers, Scott A. Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La (1- x ) Sr x CrO 3. United States. doi:10.1002/admi.201701363.
Stoerzinger, Kelsey A., Du, Yingge, Ihm, Kyuwook, Zhang, Kelvin H. L., Cai, Jun, Diulus, J. Trey, Frederick, Ryan T., Herman, Gregory S., Crumlin, Ethan J., and Chambers, Scott A. Wed . "Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La (1- x ) Sr x CrO 3". United States. doi:10.1002/admi.201701363.
@article{osti_1439687,
title = {Impact of Sr-Incorporation on Cr Oxidation and Water Dissociation in La (1- x ) Sr x CrO 3},
author = {Stoerzinger, Kelsey A. and Du, Yingge and Ihm, Kyuwook and Zhang, Kelvin H. L. and Cai, Jun and Diulus, J. Trey and Frederick, Ryan T. and Herman, Gregory S. and Crumlin, Ethan J. and Chambers, Scott A.},
abstractNote = {The oxidation and reduction of metal oxides and their interaction with the environment play a critical role in material stability and the ability to catalyze reactions. The local change in valence and formation of surface adsorbates affect the oxide electronic structure and chemical reactivity, yet are challenging to probe experimentally. Here we present a detailed study of the oxidation and reduction of Cr in the perovskite oxide family of La(1-x)SrxCrO3 using ambient pressure X-ray photoelectron spectroscopy. The incorporation of Sr increases the propensity to oxidize the surface, leading to the presence of Cr4+ and Cr6+ principally confined to the top unit cell when in equilibrium with O2 gas. These acidic sites are readily reduced to Cr3+ in equilibrium with H2O vapor, and the resultant amount of hydroxyls formed from the dissociation of H2O is directly proportional to the density of surface sites which had been oxidized. Our quantification of the redox stability of La(1-x)SrxCrO3 and the relationship between the extent of oxidation, reduction, and hydroxylation with Sr yields important insight into the surface functionality during electrochemical applications.},
doi = {10.1002/admi.201701363},
journal = {Advanced Materials Interfaces},
number = 6,
volume = 5,
place = {United States},
year = {Wed Jan 17 00:00:00 EST 2018},
month = {Wed Jan 17 00:00:00 EST 2018}
}