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]

Mammen, Nisha; Spanu, Leonardo; Tyo, Eric C.; Yang, Bing; Halder, Avik; Seifert, Sonke; Pellin, Michael J.; Vajda, Stefan; Narasimhan, Shobhana

doi:10.1002/ejic.201701355

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]

Journal Article · Tue Dec 05 00:00:00 EST 2017 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201701355· OSTI ID:1459668

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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)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1459668

Alternate ID(s):: OSTI ID: 1414803

Journal Information:: European Journal of Inorganic Chemistry, Vol. 2018, Issue 1; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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Cited By (3)

Perspective: Size selected clusters for catalysis and electrochemistry Halder, Avik; Curtiss, Larry A.; Fortunelli, Alessandro The Journal of Chemical Physics, Vol. 148, Issue 11 https://doi.org/10.1063/1.5020301	journal	March 2018
The stability and oxidation of supported atomic-size Cu catalysts in reactive environments Iyemperumal, Satish Kumar; Fenton, Thomas G.; Gillingham, Samantha L. The Journal of Chemical Physics, Vol. 151, Issue 5 https://doi.org/10.1063/1.5110300	journal	August 2019
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 Mammen, Nisha; Spanu, Leonardo; Tyo, Eric C. Journal of Physics: Condensed Matter, Vol. 31, Issue 14 https://doi.org/10.1088/1361-648x/aafcf9	journal	February 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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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]

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