Triosmium Clusters on a Support: Determination of Structure by X-Ray Absorption Spectroscopy and High-Resolution Microscopy

Shareghe, Mehraeen; Chi, Miaofang; Browning, N. D.

doi:10.1002/chem.201000860

Title: Triosmium Clusters on a Support: Determination of Structure by X-Ray Absorption Spectroscopy and High-Resolution Microscopy

Journal Article · Sat Jan 01 00:00:00 EST 2011 · Chemistry—A European Journal

DOI:https://doi.org/10.1002/chem.201000860· OSTI ID:1049786

Shareghe, Mehraeen ^[1];

^[2]; Browning, N. D. ^[1]

University of California, Davis
ORNL

The structures of small, robust metal clusters on a solid support were determined by a combination of spectroscopic and microscopic methods: extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning transmission electron microscopy (STEM), and aberration-corrected STEM. The samples were synthesized from [Os{sub 3}(CO){sub 12}] on MgO powder to provide supported clusters intended to be triosmium. The results demonstrate that the supported clusters are robust in the absence of oxidants. Conventional high-angle annular dark-field (HAADF) STEM images demonstrate a high degree of uniformity of the clusters, with root-mean-square (rms) radii of 2.03 {+-} 0.06 {angstrom}. The EXAFS OsOs coordination number of 2.1 {+-} 0.4 confirms the presence of triosmium clusters on average and correspondingly determines an average rms cluster radius of 2.02 {+-} 0.04 {angstrom}. The high-resolution STEM images show the individual Os atoms in the clusters, confirming the triangular structures of their frames and determining OsOs distances of 2.80 {+-} 0.14 {angstrom}, matching the EXAFS value of 2.89 {+-} 0.06 {angstrom}. IR and EXAFS spectra demonstrate the presence of CO ligands on the clusters. This set of techniques is recommended as optimal for detailed and reliable structural characterization of supported clusters.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1049786

Journal Information:: Chemistry—A European Journal, Vol. 17, Issue 3

Country of Publication:: United States

Language:: English

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Title: Triosmium Clusters on a Support: Determination of Structure by X-Ray Absorption Spectroscopy and High-Resolution Microscopy

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