Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica

Dai, Yang; Gorey, Timothy J.; Anderson, Scott L.; Lee, Sungsik; Lee, Sungwon; Seifert, Soenke; Winans, Randall E.

doi:10.1021/acs.jpcc.6b10167

Title: Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica

Journal Article · Mon Dec 12 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b10167· OSTI ID:1366518

Dai, Yang ^[1]; Gorey, Timothy J. ^[1];

^[1]; Lee, Sungsik ^[2]; Lee, Sungwon ^[2]; Seifert, Soenke ^[2];

^[2]

Univ. of Utah, Salt Lake City, UT (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

X-ray absorption near-edge structure (XANES) is commonly used to probe the oxidation state of metal-containing nanomaterials, however, as the particle size in the material drops below a few nanometers, it becomes important to consider inherent size effects on the electronic structure of the materials. In this paper, we analyze a series of size-selected Pt_n/SiO₂ samples, using X-ray photoelectron spectroscopy (XPS), low energy ion scattering, grazing-incidence small angle X-ray scattering, and XANES. The oxidation state and morphology are characterized both as-deposited in UHV, and after air/O₂ exposure and annealing in H₂. Here, the clusters are found to be stable during deposition and upon air exposure, but sinter if heated above ~150 °C. XANES shows shifts in the Pt L₃ edge, relative to bulk Pt, that increase with decreasing cluster size, and the cluster samples show high white line intensity. Reference to bulk standards would suggest that the clusters are oxidized, however, XPS shows that they are not. Instead, the XANES effects are attributable to development of a band gap and localization of empty state wavefunctions in small clusters.

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

Sponsoring Organization:: Air Force Research Laboratory (AFRL), Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1366518

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 1; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 45 works

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