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Ag-oxide signature in Ag 3d photoelectron spectra : A study on free nanoparticles

Tzomos, E. ; Mikkelä, M. H. LU ; Öhrwall, G. LU orcid ; Björneholm, O. LU and Tchaplyguine, M. LU (2023) In Surface Science 733.
Abstract

Over decades the Ag 3d-level binding energy has been puzzling researchers with its unusual sign and value in silver oxides. For the absolute majority of metals, the metal-to-oxide binding energy shifts are positive and depend significantly on the oxidation state, while in Ag-oxides the oxide shift was time after time reported negative, small, and close for the two very different Ag(I) and Ag(III) oxidation states. In the current work, a photoelectron spectroscopy (PES) investigation on the in-situ created free nanoparticles simultaneously containing both metallic silver and silver-oxide parts provided the grounds to reconsider the old consensus on the Ag-oxide shifts. The Ag 3d energies for the metallic and the oxide parts established... (More)

Over decades the Ag 3d-level binding energy has been puzzling researchers with its unusual sign and value in silver oxides. For the absolute majority of metals, the metal-to-oxide binding energy shifts are positive and depend significantly on the oxidation state, while in Ag-oxides the oxide shift was time after time reported negative, small, and close for the two very different Ag(I) and Ag(III) oxidation states. In the current work, a photoelectron spectroscopy (PES) investigation on the in-situ created free nanoparticles simultaneously containing both metallic silver and silver-oxide parts provided the grounds to reconsider the old consensus on the Ag-oxide shifts. The Ag 3d energies for the metallic and the oxide parts established in the current experimental work allowed estimating a ≈ 1.2 eV positive shift for the realized oxidation state. This estimate was made possible by using a beam of free nanoparticles with finely controlled composition. The PES experiments on such a beam allowed for a continuous and fast renewal of the poorly conducting sample and for a reliable and accurate calibration relative to vacuum. The constant oxide shift observed at several different oxidation conditions, as well as the relatively narrow and symmetric oxide peaks, point to one dominating oxidation state being present in the particles.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Surface Science
volume
733
article number
122307
publisher
Elsevier
external identifiers
  • scopus:85152619001
ISSN
0039-6028
DOI
10.1016/j.susc.2023.122307
language
English
LU publication?
yes
id
3a2f4014-5fdb-40c7-af1c-cf7dc58e8c0d
date added to LUP
2023-07-12 14:43:42
date last changed
2023-07-12 14:43:42
@article{3a2f4014-5fdb-40c7-af1c-cf7dc58e8c0d,
  abstract     = {{<p>Over decades the Ag 3d-level binding energy has been puzzling researchers with its unusual sign and value in silver oxides. For the absolute majority of metals, the metal-to-oxide binding energy shifts are positive and depend significantly on the oxidation state, while in Ag-oxides the oxide shift was time after time reported negative, small, and close for the two very different Ag(I) and Ag(III) oxidation states. In the current work, a photoelectron spectroscopy (PES) investigation on the in-situ created free nanoparticles simultaneously containing both metallic silver and silver-oxide parts provided the grounds to reconsider the old consensus on the Ag-oxide shifts. The Ag 3d energies for the metallic and the oxide parts established in the current experimental work allowed estimating a ≈ 1.2 eV positive shift for the realized oxidation state. This estimate was made possible by using a beam of free nanoparticles with finely controlled composition. The PES experiments on such a beam allowed for a continuous and fast renewal of the poorly conducting sample and for a reliable and accurate calibration relative to vacuum. The constant oxide shift observed at several different oxidation conditions, as well as the relatively narrow and symmetric oxide peaks, point to one dominating oxidation state being present in the particles.</p>}},
  author       = {{Tzomos, E. and Mikkelä, M. H. and Öhrwall, G. and Björneholm, O. and Tchaplyguine, M.}},
  issn         = {{0039-6028}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Surface Science}},
  title        = {{Ag-oxide signature in Ag 3d photoelectron spectra : A study on free nanoparticles}},
  url          = {{http://dx.doi.org/10.1016/j.susc.2023.122307}},
  doi          = {{10.1016/j.susc.2023.122307}},
  volume       = {{733}},
  year         = {{2023}},
}