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Title: Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?

Abstract

There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A n-1A 2'BnO 3n+1, A n-1A 2'BnX 3n+1; LaSrCo 0.5Fe 0.5O 4-δ (n = 1), La 0.3Sr 2.7CoFeO 7-δ (n = 2) and LaSr 3Co 1.5Fe 1.5O 10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is inmore » contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.« less

Authors:
 [1];  [1];  [2];  [1]
  1. Lehigh Univ., Bethlehem, PA (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 Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1261476
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 182; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tomkiewicz, Alex C., Tamimi, Mazin A., Huq, Ashfia, and McIntosh, Steven. Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?. United States: N. p., 2015. Web. doi:10.1039/C5FD00014A.
Tomkiewicz, Alex C., Tamimi, Mazin A., Huq, Ashfia, & McIntosh, Steven. Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?. United States. doi:10.1039/C5FD00014A.
Tomkiewicz, Alex C., Tamimi, Mazin A., Huq, Ashfia, and McIntosh, Steven. Mon . "Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?". United States. doi:10.1039/C5FD00014A. https://www.osti.gov/servlets/purl/1261476.
@article{osti_1261476,
title = {Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?},
author = {Tomkiewicz, Alex C. and Tamimi, Mazin A. and Huq, Ashfia and McIntosh, Steven},
abstractNote = {There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form An-1A2'BnO3n+1, An-1A2'BnX3n+1; LaSrCo0.5Fe0.5O4-δ (n = 1), La0.3Sr2.7CoFeO7-δ (n = 2) and LaSr3Co1.5Fe1.5O10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.},
doi = {10.1039/C5FD00014A},
journal = {Faraday Discussions},
issn = {1359-6640},
number = ,
volume = 182,
place = {United States},
year = {2015},
month = {3}
}

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