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Title: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through 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 subnanometer 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. 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:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [5]; ORCiD logo [1]
  1. Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, -560064 Bangalore India
  2. Shell Technology Center, Shell India Markets Private Limited, -560048 Bangalore India
  3. Materials Science Division, Argonne National Laboratory, 60439 Argonne IL USA
  4. X-ray Science Division, Argonne National Laboratory, 60439 Argonne IL USA
  5. Materials Science Division, Argonne National Laboratory, 60439 Argonne IL USA; Institute for Molecular Engineering, The University of Chicago, 60637 Chicago IL USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1415999
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: European Journal of Inorganic Chemistry; Journal Volume: 2018; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
X-ray absorption spectroscopy; ab initio calculations; copper; nanoparticles; oxidation; reduction

Citation Formats

Mammen, Nisha, Spanu, Leonardo, Tyo, Eric C., Yang, Bing, Halder, Avik, Seifert, Sönke, Pellin, Michael J., Vajda, Stefan, and Narasimhan, Shobhana. Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through 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, Sönke, Pellin, Michael J., Vajda, Stefan, & Narasimhan, Shobhana. Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects. United States. doi:10.1002/ejic.201701355.
Mammen, Nisha, Spanu, Leonardo, Tyo, Eric C., Yang, Bing, Halder, Avik, Seifert, Sönke, Pellin, Michael J., Vajda, Stefan, and Narasimhan, Shobhana. Fri . "Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects". United States. doi:10.1002/ejic.201701355.
@article{osti_1415999,
title = {Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects: Reversing Size-Dependent Trends in the Oxidation of Copper Clusters through Support Effects},
author = {Mammen, Nisha and Spanu, Leonardo and Tyo, Eric C. and Yang, Bing and Halder, Avik and Seifert, Sönke 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 subnanometer 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. 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 = {Fri Dec 22 00:00:00 EST 2017},
month = {Fri Dec 22 00:00:00 EST 2017}
}