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Title: Surface-reaction induced structural oscillations in the subsurface

Abstract

Surface and subsurface are commonly considered as separate entities because of the difference in the bonding environment and are often investigated separately due to the experimental challenges in differentiating the surface and subsurface effects. Using in-situ atomic-scale transmission electron microscopy to resolve the surface and subsurface at the same time, we show that the hydrogen-CuO surface reaction results in structural oscillations in deeper atomic layers via the cycles of ordering and disordering of oxygen vacancies in the subsurface. Together with atomistic calculations, we show that the structural oscillations in the subsurface are induced by the hydrogen oxidation induced cyclic loss of oxygen from the oxide surface. These results demonstrate the propagation of the surface reaction dynamics into the deeper layers in inducing nonstoichiometry in the subsurface and have significant implications in modulating various chemical processes involving surface-subsurface mass transport such as heterogeneous catalysis, oxidation, corrosion and carburization.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. State Univ. of New York (SUNY), Binghamton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
State Univ. of New York (SUNY), Binghamton, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1593988
Grant/Contract Number:  
SC0001135; SC0012704; OCI-1053575
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Sun, Xianhu, Zhu, Wenhui, Wu, Dongxiang, Li, Chaoran, Wang, Jianyu, Zhu, Yaguang, Chen, Xiaobo, Boscoboinik, Jorge Anibal, Sharma, Renu, and Zhou, Guangwen. Surface-reaction induced structural oscillations in the subsurface. United States: N. p., 2020. Web. doi:10.1038/s41467-019-14167-1.
Sun, Xianhu, Zhu, Wenhui, Wu, Dongxiang, Li, Chaoran, Wang, Jianyu, Zhu, Yaguang, Chen, Xiaobo, Boscoboinik, Jorge Anibal, Sharma, Renu, & Zhou, Guangwen. Surface-reaction induced structural oscillations in the subsurface. United States. doi:10.1038/s41467-019-14167-1.
Sun, Xianhu, Zhu, Wenhui, Wu, Dongxiang, Li, Chaoran, Wang, Jianyu, Zhu, Yaguang, Chen, Xiaobo, Boscoboinik, Jorge Anibal, Sharma, Renu, and Zhou, Guangwen. Thu . "Surface-reaction induced structural oscillations in the subsurface". United States. doi:10.1038/s41467-019-14167-1. https://www.osti.gov/servlets/purl/1593988.
@article{osti_1593988,
title = {Surface-reaction induced structural oscillations in the subsurface},
author = {Sun, Xianhu and Zhu, Wenhui and Wu, Dongxiang and Li, Chaoran and Wang, Jianyu and Zhu, Yaguang and Chen, Xiaobo and Boscoboinik, Jorge Anibal and Sharma, Renu and Zhou, Guangwen},
abstractNote = {Surface and subsurface are commonly considered as separate entities because of the difference in the bonding environment and are often investigated separately due to the experimental challenges in differentiating the surface and subsurface effects. Using in-situ atomic-scale transmission electron microscopy to resolve the surface and subsurface at the same time, we show that the hydrogen-CuO surface reaction results in structural oscillations in deeper atomic layers via the cycles of ordering and disordering of oxygen vacancies in the subsurface. Together with atomistic calculations, we show that the structural oscillations in the subsurface are induced by the hydrogen oxidation induced cyclic loss of oxygen from the oxide surface. These results demonstrate the propagation of the surface reaction dynamics into the deeper layers in inducing nonstoichiometry in the subsurface and have significant implications in modulating various chemical processes involving surface-subsurface mass transport such as heterogeneous catalysis, oxidation, corrosion and carburization.},
doi = {10.1038/s41467-019-14167-1},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {1}
}

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