Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects [Controlling the Degree of Oxidation of Copper Clusters Through Size and Support Effects]
Abstract
Having the ability to tune the oxidation state of Cu nanoparticles is essential for their utility as catalysts. The degree of oxidation that maximizes product yield and selectivity is known to vary, depending on the particular reaction. Using first principles calculations and XANES measurements, we show that for sub-nanometer sizes in the gas phase, smaller Cu clusters are more resistant to oxidation. However, this trend is reversed upon deposition on an alumina support. We are able to explain this result in terms of strong cluster-support interactions, which differ significantly for the oxidized and elemental clusters. The stable cluster phases also feature novel oxygen stoichiometries. Finally, our results suggest that one can tune the degree of oxidation of Cu catalysts by optimizing not just their size, but also the support they are deposited on.
- Authors:
-
[1];
[2];
[3];
[3];
[3];
[3];
[3];
[4];
[1]
- Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore (India)
- Shell India Markets Private Limited, Bangalore (India)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1459668
- Alternate Identifier(s):
- OSTI ID: 1414803
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 2018; Journal Issue: 1; Journal ID: ISSN 1434-1948
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray absorption spectroscopy; ab initio calculations; copper; nanoparticles; oxidation; reduction; clusters
Citation Formats
Mammen, Nisha, Spanu, Leonardo, Tyo, Eric C., Yang, Bing, Halder, Avik, Seifert, Sonke, Pellin, Michael J., Vajda, Stefan, and Narasimhan, Shobhana. Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects [Controlling the Degree of Oxidation of Copper Clusters Through Size and Support Effects]. United States: N. p., 2017.
Web. doi:10.1002/ejic.201701355.
Mammen, Nisha, Spanu, Leonardo, Tyo, Eric C., Yang, Bing, Halder, Avik, Seifert, Sonke, Pellin, Michael J., Vajda, Stefan, & Narasimhan, Shobhana. Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects [Controlling the Degree of Oxidation of Copper Clusters Through Size and Support Effects]. United States. https://doi.org/10.1002/ejic.201701355
Mammen, Nisha, Spanu, Leonardo, Tyo, Eric C., Yang, Bing, Halder, Avik, Seifert, Sonke, Pellin, Michael J., Vajda, Stefan, and Narasimhan, Shobhana. Tue .
"Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects [Controlling the Degree of Oxidation of Copper Clusters Through Size and Support Effects]". United States. https://doi.org/10.1002/ejic.201701355. https://www.osti.gov/servlets/purl/1459668.
@article{osti_1459668,
title = {Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects [Controlling the Degree of Oxidation of Copper Clusters Through Size and Support Effects]},
author = {Mammen, Nisha and Spanu, Leonardo and Tyo, Eric C. and Yang, Bing and Halder, Avik and Seifert, Sonke and Pellin, Michael J. and Vajda, Stefan and Narasimhan, Shobhana},
abstractNote = {Having the ability to tune the oxidation state of Cu nanoparticles is essential for their utility as catalysts. The degree of oxidation that maximizes product yield and selectivity is known to vary, depending on the particular reaction. Using first principles calculations and XANES measurements, we show that for sub-nanometer sizes in the gas phase, smaller Cu clusters are more resistant to oxidation. However, this trend is reversed upon deposition on an alumina support. We are able to explain this result in terms of strong cluster-support interactions, which differ significantly for the oxidized and elemental clusters. The stable cluster phases also feature novel oxygen stoichiometries. Finally, our results suggest that one can tune the degree of oxidation of Cu catalysts by optimizing not just their size, but also the support they are deposited on.},
doi = {10.1002/ejic.201701355},
journal = {European Journal of Inorganic Chemistry},
number = 1,
volume = 2018,
place = {United States},
year = {2017},
month = {12}
}
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Works referencing / citing this record:
Perspective: Size selected clusters for catalysis and electrochemistry
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The stability and oxidation of supported atomic-size Cu catalysts in reactive environments
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Using first principles calculations to interpret XANES experiments: extracting the size-dependence of the ( p , T ) phase diagram of sub-nanometer Cu clusters in an O 2 environment
journal, February 2019
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