Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films
Abstract
The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce3+ concentration while decreasing the dopant ionic radius from La3+ to Yb3+ was observed, thus explaining the measured increased activation energy and enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce3+ ionic radius allows promoting the formation of oxygen vacancies and Ce3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.
- Authors:
-
[3];
[5];
[3]
- ShanghaiTech Univ, Shanghai (China)
- Univ. of Salerno (Italy); TASC National Lab, Trieste (Italy)
- Univ. of Rome Tor Vergata (Italy)
- TASC National Lab, Trieste (Italy)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Milano (Italy)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1376532
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 16; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Yang, Nan, Orgiani, Pasquale, Di Bartolomeo, Elisabetta, Foglietti, Vittorio, Torelli, Piero, Ievlev, Anton V., Rossi, Giorgio, Licoccia, Silvia, Balestrino, Giuseppe, Kalinin, Sergei V., and Aruta, Carmela. Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b00386.
Yang, Nan, Orgiani, Pasquale, Di Bartolomeo, Elisabetta, Foglietti, Vittorio, Torelli, Piero, Ievlev, Anton V., Rossi, Giorgio, Licoccia, Silvia, Balestrino, Giuseppe, Kalinin, Sergei V., & Aruta, Carmela. Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films. United States. https://doi.org/10.1021/acs.jpcc.7b00386
Yang, Nan, Orgiani, Pasquale, Di Bartolomeo, Elisabetta, Foglietti, Vittorio, Torelli, Piero, Ievlev, Anton V., Rossi, Giorgio, Licoccia, Silvia, Balestrino, Giuseppe, Kalinin, Sergei V., and Aruta, Carmela. Mon .
"Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films". United States. https://doi.org/10.1021/acs.jpcc.7b00386. https://www.osti.gov/servlets/purl/1376532.
@article{osti_1376532,
title = {Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films},
author = {Yang, Nan and Orgiani, Pasquale and Di Bartolomeo, Elisabetta and Foglietti, Vittorio and Torelli, Piero and Ievlev, Anton V. and Rossi, Giorgio and Licoccia, Silvia and Balestrino, Giuseppe and Kalinin, Sergei V. and Aruta, Carmela},
abstractNote = {The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce3+ concentration while decreasing the dopant ionic radius from La3+ to Yb3+ was observed, thus explaining the measured increased activation energy and enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce3+ ionic radius allows promoting the formation of oxygen vacancies and Ce3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.},
doi = {10.1021/acs.jpcc.7b00386},
journal = {Journal of Physical Chemistry. C},
number = 16,
volume = 121,
place = {United States},
year = {Mon Apr 17 00:00:00 EDT 2017},
month = {Mon Apr 17 00:00:00 EDT 2017}
}
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Works referencing / citing this record:
Defect evolution in Eu 3+ , Nb 5+ doped and co-doped CeO 2 : X-ray diffraction, positron annihilation lifetime and photoluminescence studies
journal, January 2019
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