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Title: Enhanced oxidation resistance of active nanostructures via dynamic size effect

A major challenge limiting the practical applications of nanomaterials is that the activities of nanostructures (NSs) increase with reduced size, often sacrificing their stability in the chemical environment. Under oxidative conditions, NSs with smaller sizes and higher defect densities are commonly expected to oxidize more easily, since high-concentration defects can facilitate oxidation by enhancing the reactivity with O 2 and providing a fast channel for oxygen incorporation. Here, using FeO NSs as an example, we show to the contrary, that reducing the size of active NSs can drastically increase their oxidation resistance. A maximum oxidation resistance is found for FeO NSs with dimensions below 3.2 nm. Rather than being determined by the structure or electronic properties of active sites, the enhanced oxidation resistance originates from the size-dependent structural dynamics of FeO NSs in O 2. We find this dynamic size effect to govern the chemical properties of active NSs.
Authors:
 [1] ;  [2] ;  [1] ;  [2] ;  [2] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [3] ;  [2]
  1. State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences (China); University of Chinese Academy of Sciences, Beijing (China)
  2. State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Department
Publication Date:
Report Number(s):
BNL-113821-2017-JA
Journal ID: ISSN 2041-1723; R&D Project: CO027; KC0302010
Grant/Contract Number:
SC0012704; AC02-05CH11231; 21303195; 21473191; 91545204
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Catalysis; Nanoparticles; Surface chemistry
OSTI Identifier:
1358014

Liu, Yun, Yang, Fan, Zhang, Yi, Xiao, Jianping, Yu, Liang, Liu, Qingfei, Ning, Yanxiao, Zhou, Zhiwen, Chen, Hao, Huang, Wugen, Liu, Ping, and Bao, Xinhe. Enhanced oxidation resistance of active nanostructures via dynamic size effect. United States: N. p., Web. doi:10.1038/ncomms14459.
Liu, Yun, Yang, Fan, Zhang, Yi, Xiao, Jianping, Yu, Liang, Liu, Qingfei, Ning, Yanxiao, Zhou, Zhiwen, Chen, Hao, Huang, Wugen, Liu, Ping, & Bao, Xinhe. Enhanced oxidation resistance of active nanostructures via dynamic size effect. United States. doi:10.1038/ncomms14459.
Liu, Yun, Yang, Fan, Zhang, Yi, Xiao, Jianping, Yu, Liang, Liu, Qingfei, Ning, Yanxiao, Zhou, Zhiwen, Chen, Hao, Huang, Wugen, Liu, Ping, and Bao, Xinhe. 2017. "Enhanced oxidation resistance of active nanostructures via dynamic size effect". United States. doi:10.1038/ncomms14459. https://www.osti.gov/servlets/purl/1358014.
@article{osti_1358014,
title = {Enhanced oxidation resistance of active nanostructures via dynamic size effect},
author = {Liu, Yun and Yang, Fan and Zhang, Yi and Xiao, Jianping and Yu, Liang and Liu, Qingfei and Ning, Yanxiao and Zhou, Zhiwen and Chen, Hao and Huang, Wugen and Liu, Ping and Bao, Xinhe},
abstractNote = {A major challenge limiting the practical applications of nanomaterials is that the activities of nanostructures (NSs) increase with reduced size, often sacrificing their stability in the chemical environment. Under oxidative conditions, NSs with smaller sizes and higher defect densities are commonly expected to oxidize more easily, since high-concentration defects can facilitate oxidation by enhancing the reactivity with O2 and providing a fast channel for oxygen incorporation. Here, using FeO NSs as an example, we show to the contrary, that reducing the size of active NSs can drastically increase their oxidation resistance. A maximum oxidation resistance is found for FeO NSs with dimensions below 3.2 nm. Rather than being determined by the structure or electronic properties of active sites, the enhanced oxidation resistance originates from the size-dependent structural dynamics of FeO NSs in O2. We find this dynamic size effect to govern the chemical properties of active NSs.},
doi = {10.1038/ncomms14459},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {2}
}