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This content will become publicly available on December 5, 2018

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]

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.
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [4] ; ORCiD logo [1]
  1. Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore (India)
  2. Shell India Markets Private Limited, Bangalore (India)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2018; Journal Issue: 1; Journal ID: ISSN 1434-1948
ChemPubSoc Europe
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-ray absorption spectroscopy; ab initio calculations; copper; nanoparticles; oxidation; reduction; clusters
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1414803