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Title: Understanding Structure–Activity Relationships in Sr1–xYxCoO3–δ through in Situ Neutron Diffraction and Electrochemical Measurements

Abstract

In this study, we report a systematic study on temperature-dependent local structural evolution, oxygen stoichiometry, and electrochemical properties of an oxygen-deficient perovskite Sr0.7Y0.3CoO3–δ (SYC30) for oxygen electrocatalysis. The obtained results are then closely compared with its analogue Sr0.9Y0.1CoO3–δ (SYC10) of different crystal structures to establish structure–activity relationships. The comparison shows that both SYC30 and SYC10 consist of alternate layers of oxygen-deficient Co1-polyhedra and oxygen-saturated Co2-octahedra with Co1-polyhedra being responsible for Vo•• migration. It is also found that the distribution and concentration of oxygen vacancies within the Co1-layer are, respectively, less symmetrical and lower in SYC30 than those in SYC10, making the former unfavorable for oxygen transport. A molecular orbital energy analysis reveals that the energy gap between Fermi level and O 2p level in the active Co1-polyhedra is larger in SYC30 than that in SYC10, further suggesting that SYC10 is a better oxide-ion conductor and thus a better electrocatalyst for oxygen reduction reaction, which is unambiguously confirmed by the subsequent electrochemical measurements.

Authors:
 [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1483181
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 42; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; neutron diffraction; oxygen electrocatalyst; oxygen migration; perovskite; solid oxide fuel cell

Citation Formats

Yang, Tianrang, Matthews, Allison H., Xu, Nansheng, Chen, Yan, An, Ke, Ma, Dong, and Huang, Kevin. Understanding Structure–Activity Relationships in Sr1–xYxCoO3–δ through in Situ Neutron Diffraction and Electrochemical Measurements. United States: N. p., 2018. Web. https://doi.org/10.1021/acsami.8b12943.
Yang, Tianrang, Matthews, Allison H., Xu, Nansheng, Chen, Yan, An, Ke, Ma, Dong, & Huang, Kevin. Understanding Structure–Activity Relationships in Sr1–xYxCoO3–δ through in Situ Neutron Diffraction and Electrochemical Measurements. United States. https://doi.org/10.1021/acsami.8b12943
Yang, Tianrang, Matthews, Allison H., Xu, Nansheng, Chen, Yan, An, Ke, Ma, Dong, and Huang, Kevin. Tue . "Understanding Structure–Activity Relationships in Sr1–xYxCoO3–δ through in Situ Neutron Diffraction and Electrochemical Measurements". United States. https://doi.org/10.1021/acsami.8b12943. https://www.osti.gov/servlets/purl/1483181.
@article{osti_1483181,
title = {Understanding Structure–Activity Relationships in Sr1–xYxCoO3–δ through in Situ Neutron Diffraction and Electrochemical Measurements},
author = {Yang, Tianrang and Matthews, Allison H. and Xu, Nansheng and Chen, Yan and An, Ke and Ma, Dong and Huang, Kevin},
abstractNote = {In this study, we report a systematic study on temperature-dependent local structural evolution, oxygen stoichiometry, and electrochemical properties of an oxygen-deficient perovskite Sr0.7Y0.3CoO3–δ (SYC30) for oxygen electrocatalysis. The obtained results are then closely compared with its analogue Sr0.9Y0.1CoO3–δ (SYC10) of different crystal structures to establish structure–activity relationships. The comparison shows that both SYC30 and SYC10 consist of alternate layers of oxygen-deficient Co1-polyhedra and oxygen-saturated Co2-octahedra with Co1-polyhedra being responsible for Vo•• migration. It is also found that the distribution and concentration of oxygen vacancies within the Co1-layer are, respectively, less symmetrical and lower in SYC30 than those in SYC10, making the former unfavorable for oxygen transport. A molecular orbital energy analysis reveals that the energy gap between Fermi level and O 2p level in the active Co1-polyhedra is larger in SYC30 than that in SYC10, further suggesting that SYC10 is a better oxide-ion conductor and thus a better electrocatalyst for oxygen reduction reaction, which is unambiguously confirmed by the subsequent electrochemical measurements.},
doi = {10.1021/acsami.8b12943},
journal = {ACS Applied Materials and Interfaces},
number = 42,
volume = 10,
place = {United States},
year = {2018},
month = {9}
}

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Figures / Tables:

Figure 1 Figure 1: Unit cell of the RT crystal structure of (a) SYC30 (SG I4/ mmm) and (b) SYC10 (SG P4/mmm).

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Works referenced in this record:

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    Works referencing / citing this record:

    Nickel-substituted Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3−δ : a highly active perovskite oxygen electrode for reduced-temperature solid oxide fuel cells
    journal, January 2019

    • Li, Lu; Yang, Hua; Gao, Zhenghui
    • Journal of Materials Chemistry A, Vol. 7, Issue 19
    • DOI: 10.1039/c9ta02548k