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Title: Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy

Abstract

Compared to nanomaterials exposing nonpolar facets, polar-faceted nanocrystals often exhibit unexpected and interesting properties. The electrostatic instability arising from the intrinsic dipole moments of polar facets, however, leads to different surface configurations in many cases, making it challenging to extract detailed structural information and develop structure-property relations. The widely used electron microscopy techniques are limited because the volumes sampled may not be representative, and they provide little chemical bonding information with low contrast of light elements. With ceria nanocubes exposing (100) facets as an example, here we show that the polar surface structure of oxide nanocrystals can be investigated by applying 17O and 1H solid-state NMR spectroscopy and dynamic nuclear polarization, combined with DFT calculations. Both CeO 4-termination reconstructions and hydroxyls are present for surface polarity compensation and their concentrations can be quantified. These results open up new possibilities for investigating the structure and properties of oxide nanostructures with polar facets.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [1]; ORCiD logo [3];  [3];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [4];  [1];  [5];  [3]; ORCiD logo [1]
  1. Nanjing Univ. (China)
  2. East China Univ. of Science and Technology, Shanghai (China); Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of Cambridge (United Kingdom)
  4. Univ. of Nottingham (United Kingdom)
  5. East China Univ. of Science and Technology, Shanghai (China)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1591836
Grant/Contract Number:  
[AC02-05CH11231; SC0012583]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
[ Journal Volume: 10; Journal Issue: 1]; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; characterization and analytical techniques; nanoparticles; solid-state NMR

Citation Formats

Chen, Junchao, Wu, Xin-Ping, Hope, Michael A., Qian, Kun, Halat, David M., Liu, Tao, Li, Yuhong, Shen, Li, Ke, Xiaokang, Wen, Yujie, Du, Jia-Huan, Magusin, Pieter C. M. M., Paul, Subhradip, Ding, Weiping, Gong, Xue-Qing, Grey, Clare P., and Peng, Luming. Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy. United States: N. p., 2019. Web. doi:10.1038/s41467-019-13424-7.
Chen, Junchao, Wu, Xin-Ping, Hope, Michael A., Qian, Kun, Halat, David M., Liu, Tao, Li, Yuhong, Shen, Li, Ke, Xiaokang, Wen, Yujie, Du, Jia-Huan, Magusin, Pieter C. M. M., Paul, Subhradip, Ding, Weiping, Gong, Xue-Qing, Grey, Clare P., & Peng, Luming. Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy. United States. doi:10.1038/s41467-019-13424-7.
Chen, Junchao, Wu, Xin-Ping, Hope, Michael A., Qian, Kun, Halat, David M., Liu, Tao, Li, Yuhong, Shen, Li, Ke, Xiaokang, Wen, Yujie, Du, Jia-Huan, Magusin, Pieter C. M. M., Paul, Subhradip, Ding, Weiping, Gong, Xue-Qing, Grey, Clare P., and Peng, Luming. Thu . "Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy". United States. doi:10.1038/s41467-019-13424-7. https://www.osti.gov/servlets/purl/1591836.
@article{osti_1591836,
title = {Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy},
author = {Chen, Junchao and Wu, Xin-Ping and Hope, Michael A. and Qian, Kun and Halat, David M. and Liu, Tao and Li, Yuhong and Shen, Li and Ke, Xiaokang and Wen, Yujie and Du, Jia-Huan and Magusin, Pieter C. M. M. and Paul, Subhradip and Ding, Weiping and Gong, Xue-Qing and Grey, Clare P. and Peng, Luming},
abstractNote = {Compared to nanomaterials exposing nonpolar facets, polar-faceted nanocrystals often exhibit unexpected and interesting properties. The electrostatic instability arising from the intrinsic dipole moments of polar facets, however, leads to different surface configurations in many cases, making it challenging to extract detailed structural information and develop structure-property relations. The widely used electron microscopy techniques are limited because the volumes sampled may not be representative, and they provide little chemical bonding information with low contrast of light elements. With ceria nanocubes exposing (100) facets as an example, here we show that the polar surface structure of oxide nanocrystals can be investigated by applying 17O and 1H solid-state NMR spectroscopy and dynamic nuclear polarization, combined with DFT calculations. Both CeO4-termination reconstructions and hydroxyls are present for surface polarity compensation and their concentrations can be quantified. These results open up new possibilities for investigating the structure and properties of oxide nanostructures with polar facets.},
doi = {10.1038/s41467-019-13424-7},
journal = {Nature Communications},
number = [1],
volume = [10],
place = {United States},
year = {2019},
month = {11}
}

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