Nanoscale oxygen defect gradients in UO2+x surfaces

Spurgeon, Steven R.; Sassi, Michel; Ophus, Colin; Stubbs, Joanne E.; Ilton, Eugene S.; Buck, Edgar C.

doi:10.1073/pnas.1905056116

Title: Nanoscale oxygen defect gradients in UO_2+x surfaces

Journal Article · Fri Aug 09 00:00:00 EDT 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1905056116· OSTI ID:1582609

^[1]; Sassi, Michel ^[1]; Ophus, Colin ^[2];

^[3]; Ilton, Eugene S. ^[1];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of Chicago, IL (United States)

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 ${U O}_{2 + x}$ 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 ${U O}_{2}$ surface oxidation.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231; EAR-1634415; FG02-94ER14466; SC0019108

OSTI ID:: 1582609

Alternate ID(s):: OSTI ID: 1564069

Report Number(s):: PNNL-SA-141717; TRN: US2102037

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 116, Issue 35; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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Title: Nanoscale oxygen defect gradients in UO2+x surfaces

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Title: Nanoscale oxygen defect gradients in UO_2+x surfaces