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Title: Stabilization of Oxidized Copper Nanoclusters in Confined Spaces

Abstract

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silica film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.

Authors:
 [1];  [1];  [2];  [2];  [3];  [2];  [2];  [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1425038
Report Number(s):
BNL-200027-2018-JAAM
Journal ID: ISSN 1022-5528
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 61; Journal Issue: 5-6; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Akter, Nusnin, Wang, Mengen, Zhong, Jian-Qiang, Liu, Zongyuan, Kim, Taejin, Lu, Deyu, Boscoboinik, J. Anibal, and Stacchiola, Dario J. Stabilization of Oxidized Copper Nanoclusters in Confined Spaces. United States: N. p., 2018. Web. doi:10.1007/s11244-017-0879-9.
Akter, Nusnin, Wang, Mengen, Zhong, Jian-Qiang, Liu, Zongyuan, Kim, Taejin, Lu, Deyu, Boscoboinik, J. Anibal, & Stacchiola, Dario J. Stabilization of Oxidized Copper Nanoclusters in Confined Spaces. United States. doi:10.1007/s11244-017-0879-9.
Akter, Nusnin, Wang, Mengen, Zhong, Jian-Qiang, Liu, Zongyuan, Kim, Taejin, Lu, Deyu, Boscoboinik, J. Anibal, and Stacchiola, Dario J. Thu . "Stabilization of Oxidized Copper Nanoclusters in Confined Spaces". United States. doi:10.1007/s11244-017-0879-9. https://www.osti.gov/servlets/purl/1425038.
@article{osti_1425038,
title = {Stabilization of Oxidized Copper Nanoclusters in Confined Spaces},
author = {Akter, Nusnin and Wang, Mengen and Zhong, Jian-Qiang and Liu, Zongyuan and Kim, Taejin and Lu, Deyu and Boscoboinik, J. Anibal and Stacchiola, Dario J.},
abstractNote = {Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silica film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu2+ cations.},
doi = {10.1007/s11244-017-0879-9},
journal = {Topics in Catalysis},
issn = {1022-5528},
number = 5-6,
volume = 61,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
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Figures / Tables:

Figure 1. Figure 1.: Auger Spectroscopy of (from top to bottom) Ru(0001) (green), oxygen pre-covered Ru(0001) (black), silica/O/Ru(0001) (blue) and Cu/silica/O/Ru(0001) (red). In the bottom inserted box is the zoom-in spectra of the region showing the presence of ~1% ML of copper.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.