U.S. Department of Energy Office of Scientific and Technical Information
Density functional analysis of fluorite-structured (Ce, Zr)O2/CeO2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O2/CeO2 interfaces: Implications for catalysis and energy applications]
Journal Article·· Journal of Physical Chemistry. C
The structures and properties of Ce1–xZrxO2 (x = 0–1) solid solutions, selected Ce1–xZrxO2 surfaces, and Ce1–xZrxO2/CeO2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O2 phases, indicating a significant rise in microhardness from CeO2 to ZrO2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energy of Ce1–xZrxO2(111)/CeO2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce1–xZrxO2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce1–xZrxO2/CeO2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce0.25Zr0.75O2/CeO2 interfaces.
Weck, Philippe F., et al. "Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces: Implications for catalysis and energy applications]." Journal of Physical Chemistry. C, vol. 121, no. 27, Jun. 2017. https://doi.org/10.1021/acs.jpcc.7b03902
Weck, Philippe F., Juan, Pierre -Alexandre, Dingreville, Remi, & Kim, Eunja (2017). Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces: Implications for catalysis and energy applications]. Journal of Physical Chemistry. C, 121(27). https://doi.org/10.1021/acs.jpcc.7b03902
Weck, Philippe F., Juan, Pierre -Alexandre, Dingreville, Remi, et al., "Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces: Implications for catalysis and energy applications]," Journal of Physical Chemistry. C 121, no. 27 (2017), https://doi.org/10.1021/acs.jpcc.7b03902
@article{osti_1372358,
author = {Weck, Philippe F. and Juan, Pierre -Alexandre and Dingreville, Remi and Kim, Eunja},
title = {Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O<sub>2</sub>/CeO<sub>2</sub> interfaces: Implications for catalysis and energy applications]},
annote = {The structures and properties of Ce1–xZrxO2 (x = 0–1) solid solutions, selected Ce1–xZrxO2 surfaces, and Ce1–xZrxO2/CeO2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O2 phases, indicating a significant rise in microhardness from CeO2 to ZrO2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energy of Ce1–xZrxO2(111)/CeO2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce1–xZrxO2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce1–xZrxO2/CeO2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce0.25Zr0.75O2/CeO2 interfaces.},
doi = {10.1021/acs.jpcc.7b03902},
url = {https://www.osti.gov/biblio/1372358},
journal = {Journal of Physical Chemistry. C},
issn = {ISSN 1932-7447},
number = {27},
volume = {121},
place = {United States},
publisher = {American Chemical Society},
year = {2017},
month = {06}}
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 221, Issue 582-593https://doi.org/10.1098/rsta.1921.0006