Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica
Abstract
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 Ptn/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.
- Authors:
-
- Univ. of Utah, Salt Lake City, UT (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- 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
- OSTI Identifier:
- 1366518
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 1; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Dai, Yang, Gorey, Timothy J., Anderson, Scott L., Lee, Sungsik, Lee, Sungwon, Seifert, Soenke, and Winans, Randall E. Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica. United States: N. p., 2016.
Web. doi:10.1021/acs.jpcc.6b10167.
Dai, Yang, Gorey, Timothy J., Anderson, Scott L., Lee, Sungsik, Lee, Sungwon, Seifert, Soenke, & Winans, Randall E. Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica. United States. https://doi.org/10.1021/acs.jpcc.6b10167
Dai, Yang, Gorey, Timothy J., Anderson, Scott L., Lee, Sungsik, Lee, Sungwon, Seifert, Soenke, and Winans, Randall E. Mon .
"Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica". United States. https://doi.org/10.1021/acs.jpcc.6b10167. https://www.osti.gov/servlets/purl/1366518.
@article{osti_1366518,
title = {Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica},
author = {Dai, Yang and Gorey, Timothy J. and Anderson, Scott L. and Lee, Sungsik and Lee, Sungwon and Seifert, Soenke and Winans, Randall E.},
abstractNote = {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 Ptn/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.},
doi = {10.1021/acs.jpcc.6b10167},
journal = {Journal of Physical Chemistry. C},
number = 1,
volume = 121,
place = {United States},
year = {Mon Dec 12 00:00:00 EST 2016},
month = {Mon Dec 12 00:00:00 EST 2016}
}
Web of Science
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