Nanoscale oxygen defect gradients in UO2+x surfaces
Abstract
Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in surfaces. We observe large image contrast and spectral changes that reflect the presence of sizable gradients in interstitial oxygen content at the nanoscale, which we quantify through first-principles calculations and image simulations. These findings reveal an unprecedented level of excess oxygen incorporated in a complex near-surface spatial distribution, offering additional insight into defect formation pathways and kinetics during surface oxidation.
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1582609
- Alternate Identifier(s):
- OSTI ID: 1564069
- Report Number(s):
- PNNL-SA-141717
Journal ID: ISSN 0027-8424; TRN: US2102037
- Grant/Contract Number:
- AC05-76RL01830; AC02-05CH11231; EAR-1634415; FG02-94ER14466; SC0019108
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 116; Journal Issue: 35; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; actinide oxides; uraninite; surface oxidation; scanning transmission electron; microscopy; electron energy loss spectroscopy
Citation Formats
Spurgeon, Steven R., Sassi, Michel, Ophus, Colin, Stubbs, Joanne E., Ilton, Eugene S., and Buck, Edgar C. Nanoscale oxygen defect gradients in UO2+x surfaces. United States: N. p., 2019.
Web. doi:10.1073/pnas.1905056116.
Spurgeon, Steven R., Sassi, Michel, Ophus, Colin, Stubbs, Joanne E., Ilton, Eugene S., & Buck, Edgar C. Nanoscale oxygen defect gradients in UO2+x surfaces. United States. https://doi.org/10.1073/pnas.1905056116
Spurgeon, Steven R., Sassi, Michel, Ophus, Colin, Stubbs, Joanne E., Ilton, Eugene S., and Buck, Edgar C. Fri .
"Nanoscale oxygen defect gradients in UO2+x surfaces". United States. https://doi.org/10.1073/pnas.1905056116. https://www.osti.gov/servlets/purl/1582609.
@article{osti_1582609,
title = {Nanoscale oxygen defect gradients in UO2+x surfaces},
author = {Spurgeon, Steven R. and Sassi, Michel and Ophus, Colin and Stubbs, Joanne E. and Ilton, Eugene S. and Buck, Edgar C.},
abstractNote = {Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in UO2+x surfaces. We observe large image contrast and spectral changes that reflect the presence of sizable gradients in interstitial oxygen content at the nanoscale, which we quantify through first-principles calculations and image simulations. These findings reveal an unprecedented level of excess oxygen incorporated in a complex near-surface spatial distribution, offering additional insight into defect formation pathways and kinetics during UO2 surface oxidation.},
doi = {10.1073/pnas.1905056116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 35,
volume = 116,
place = {United States},
year = {Fri Aug 09 00:00:00 EDT 2019},
month = {Fri Aug 09 00:00:00 EDT 2019}
}
Web of Science
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