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 O2 environment

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

doi:10.1088/1361-648X/aafcf9

Title: 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 O₂ environment

Journal Article · Mon Feb 11 00:00:00 EST 2019 · Journal of Physics. Condensed Matter

DOI:https://doi.org/10.1088/1361-648X/aafcf9· OSTI ID:1496228

^[1]; Spanu, Leonardo ^[2]; Tyo, Eric C. ^[3]; Yang, Bing ^[3]; Halder, Avik ^[3]; Seifert, Sönke ^[3]; Pellin, Michael J. ^[3];

^[4];

^[1]

Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore (India)
Shell Technology Center, 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)

Here, we have used ab initio density functional theory together with ab initio atomistic thermodynamics, and in situ X-ray absorption near edge spectroscopy (XANES) experiments, to study the oxidation of sub-nanometer clusters of Cu_nO_x supported on a hydroxylated amorphous alumina substrate in an O₂-rich environment. We obtain (p, T) phase diagrams; these differ notably for the nanoclusters compared to the bulk. Both theory and experiment suggest that in the presence of oxygen, the cluster will oxidize from its elemental state to the oxidized state as temperature decreases. We obtain a clear trend for the transition Cu_n → Cu_nO_n/2: we see that smaller the cluster, greater is the tendency toward oxidation. However, we do not see a monotonic size-dependent trend for the transition Cu_nO_n/2→ Cu_nO_n. We suggest that theoretically computed Bader charges constitute a simple yet quantitative way to align experimental measures of XANES edges with theoretical calculations, so as to yield oxidation states for nanoclusters. Our results have important implications for the use of small clusters in fields such as nanocatalysis and nanomedicine.

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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) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR); Shell Global Solutions

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1496228

Journal Information:: Journal of Physics. Condensed Matter, Vol. 31, Issue 14; ISSN 0953-8984

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
DFT
XANES
cluster
copper
oxidation

Title: 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 O2 environment

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Title: 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 O₂ environment