Surface-structure sensitivity of CeO2 nanocrystals in photocatalysis and enhancing the reactivity with nanogold
Abstract
Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this research, using aberration-corrected scanning transmission electron microscopy (STEM), the atomic surface structures of well-defined one-dimensional (1D) CeO2 nanorods (NRs) and 3D nanocubes (NCs) are directly visualized at subangstrom resolution. CeO2 NCs predominantly expose the {100} facet, with {110} and {111} as minor cutoff facets at the respective edges and corners. Notably, the outermost surface layer of the {100} facet is nearly O-terminated. Neither surface relaxations nor reconstructions on {100} are observed, indicating unusual polarity compensation, which is primarily mediated by near-surface oxygen vacancies. The surface of CeO2 NRs is highly stepped, with the enclosed {110} facet exposing Ce cations and O anions on terraces. On the basis of STEM profile-view imaging and electronic structure analysis, the photoreactivity of CeO2 nanocrystals toward aqueous methyl orange degradation under UV is revealed to be surface-structure-sensitive, following the order: {110} >> {100}. The underlying surface-structure sensitivity can be attributed to the variation in low-coordinate surface cerium cations between {110} and {100} facets. To further enhance light absorption, Au nanoparticles (NPs) are deposited on CeO2 NRs to form Au/CeO2 plasmonic nanocomposites, which dramatically promotes the photoreactivity that is Au particle size- and excitation lightmore »
- Authors:
-
- National Center for Nanoscience and Technology, Beijing (China)
- Chinese Academy of Sciences, Beijing (China)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1222610
- Report Number(s):
- BNL-108402-2015-JA
Journal ID: ISSN 2155-5435; R&D Project: CO009; KC0302010
- Grant/Contract Number:
- 51272048
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 7; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; surface structure; CeO2; aberration-corrected STEM; photocatalysis; surface plasmon resonance; nanogold
Citation Formats
Lei, Wanying, Zhang, Tingting, Gu, Lin, Liu, Ping, Rodriguez, José A., Liu, Gang, and Liu, Minghua. Surface-structure sensitivity of CeO2 nanocrystals in photocatalysis and enhancing the reactivity with nanogold. United States: N. p., 2015.
Web. doi:10.1021/acscatal.5b00620.
Lei, Wanying, Zhang, Tingting, Gu, Lin, Liu, Ping, Rodriguez, José A., Liu, Gang, & Liu, Minghua. Surface-structure sensitivity of CeO2 nanocrystals in photocatalysis and enhancing the reactivity with nanogold. United States. https://doi.org/10.1021/acscatal.5b00620
Lei, Wanying, Zhang, Tingting, Gu, Lin, Liu, Ping, Rodriguez, José A., Liu, Gang, and Liu, Minghua. Fri .
"Surface-structure sensitivity of CeO2 nanocrystals in photocatalysis and enhancing the reactivity with nanogold". United States. https://doi.org/10.1021/acscatal.5b00620. https://www.osti.gov/servlets/purl/1222610.
@article{osti_1222610,
title = {Surface-structure sensitivity of CeO2 nanocrystals in photocatalysis and enhancing the reactivity with nanogold},
author = {Lei, Wanying and Zhang, Tingting and Gu, Lin and Liu, Ping and Rodriguez, José A. and Liu, Gang and Liu, Minghua},
abstractNote = {Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this research, using aberration-corrected scanning transmission electron microscopy (STEM), the atomic surface structures of well-defined one-dimensional (1D) CeO2 nanorods (NRs) and 3D nanocubes (NCs) are directly visualized at subangstrom resolution. CeO2 NCs predominantly expose the {100} facet, with {110} and {111} as minor cutoff facets at the respective edges and corners. Notably, the outermost surface layer of the {100} facet is nearly O-terminated. Neither surface relaxations nor reconstructions on {100} are observed, indicating unusual polarity compensation, which is primarily mediated by near-surface oxygen vacancies. The surface of CeO2 NRs is highly stepped, with the enclosed {110} facet exposing Ce cations and O anions on terraces. On the basis of STEM profile-view imaging and electronic structure analysis, the photoreactivity of CeO2 nanocrystals toward aqueous methyl orange degradation under UV is revealed to be surface-structure-sensitive, following the order: {110} >> {100}. The underlying surface-structure sensitivity can be attributed to the variation in low-coordinate surface cerium cations between {110} and {100} facets. To further enhance light absorption, Au nanoparticles (NPs) are deposited on CeO2 NRs to form Au/CeO2 plasmonic nanocomposites, which dramatically promotes the photoreactivity that is Au particle size- and excitation light wavelength-dependent. The mechanisms responsible for the enhancement of photocatalytic activity are discussed, highlighting the crucial role of photoexcited charge carrier transfer.},
doi = {10.1021/acscatal.5b00620},
journal = {ACS Catalysis},
number = 7,
volume = 5,
place = {United States},
year = {Fri Jun 19 00:00:00 EDT 2015},
month = {Fri Jun 19 00:00:00 EDT 2015}
}
Web of Science
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