Adsorption of anions on ultra-thin metal deposits on single-crystal electrodes. II: Voltammetric and radiochemical study of bisulfate adsorption on Pt(111) and Pt(poly) electrodes containing copper adatoms

K. Varga, P. Zelenay, A. Wieckowski

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Abstract

The formation of ultra-thin metal deposits of copper on Pt(111) and polycrystalline platinum electrodes, as well as the adsorption of bisulfate on the copper-covered platinum surfaces, were studied by cyclic voltammetry and radioactive labeling. The highest charge obtained by voltammetry in the underpotential stripping range nearly corresponds to a close-packed monolayer of copper. The radioactive labeling data indicate that there are inactive and active copper adlayers toward bisulfate adsorption. The transition from inactive to active behavior is interpreted in terms of an increase in surface-bisulfate interactions at the expense of surface-perchlorate interactions. Based on recent X-ray absorption near-edge spectroscopy (XANES) analysis of copper deposition onto platinum, the site for bisulfate adsorption is most probably a Cu+ surface species. Combining this spectroscopic information with coulometry shows that an additional electron is confined to surface platinum atom(s) covered by the copper species. The copper film attains bulk copper properties when approximately 2.5 monolayers of copper are deposited.

Original languageEnglish
Pages (from-to)453-467
Number of pages15
JournalJournal of Electroanalytical Chemistry
Volume330
Issue number1-2
DOIs
Publication statusPublished - Jul 24 1992

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Adatoms
Anions
Copper
Negative ions
Deposits
Metals
Single crystals
Adsorption
Electrodes
Platinum
Labeling
Monolayers
Coulometers
X ray absorption
Voltammetry
Cyclic voltammetry
Spectroscopy
Atoms
Electrons

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

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title = "Adsorption of anions on ultra-thin metal deposits on single-crystal electrodes. II: Voltammetric and radiochemical study of bisulfate adsorption on Pt(111) and Pt(poly) electrodes containing copper adatoms",
abstract = "The formation of ultra-thin metal deposits of copper on Pt(111) and polycrystalline platinum electrodes, as well as the adsorption of bisulfate on the copper-covered platinum surfaces, were studied by cyclic voltammetry and radioactive labeling. The highest charge obtained by voltammetry in the underpotential stripping range nearly corresponds to a close-packed monolayer of copper. The radioactive labeling data indicate that there are inactive and active copper adlayers toward bisulfate adsorption. The transition from inactive to active behavior is interpreted in terms of an increase in surface-bisulfate interactions at the expense of surface-perchlorate interactions. Based on recent X-ray absorption near-edge spectroscopy (XANES) analysis of copper deposition onto platinum, the site for bisulfate adsorption is most probably a Cu+ surface species. Combining this spectroscopic information with coulometry shows that an additional electron is confined to surface platinum atom(s) covered by the copper species. The copper film attains bulk copper properties when approximately 2.5 monolayers of copper are deposited.",
author = "K. Varga and P. Zelenay and A. Wieckowski",
year = "1992",
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T1 - Adsorption of anions on ultra-thin metal deposits on single-crystal electrodes. II

T2 - Voltammetric and radiochemical study of bisulfate adsorption on Pt(111) and Pt(poly) electrodes containing copper adatoms

AU - Varga, K.

AU - Zelenay, P.

AU - Wieckowski, A.

PY - 1992/7/24

Y1 - 1992/7/24

N2 - The formation of ultra-thin metal deposits of copper on Pt(111) and polycrystalline platinum electrodes, as well as the adsorption of bisulfate on the copper-covered platinum surfaces, were studied by cyclic voltammetry and radioactive labeling. The highest charge obtained by voltammetry in the underpotential stripping range nearly corresponds to a close-packed monolayer of copper. The radioactive labeling data indicate that there are inactive and active copper adlayers toward bisulfate adsorption. The transition from inactive to active behavior is interpreted in terms of an increase in surface-bisulfate interactions at the expense of surface-perchlorate interactions. Based on recent X-ray absorption near-edge spectroscopy (XANES) analysis of copper deposition onto platinum, the site for bisulfate adsorption is most probably a Cu+ surface species. Combining this spectroscopic information with coulometry shows that an additional electron is confined to surface platinum atom(s) covered by the copper species. The copper film attains bulk copper properties when approximately 2.5 monolayers of copper are deposited.

AB - The formation of ultra-thin metal deposits of copper on Pt(111) and polycrystalline platinum electrodes, as well as the adsorption of bisulfate on the copper-covered platinum surfaces, were studied by cyclic voltammetry and radioactive labeling. The highest charge obtained by voltammetry in the underpotential stripping range nearly corresponds to a close-packed monolayer of copper. The radioactive labeling data indicate that there are inactive and active copper adlayers toward bisulfate adsorption. The transition from inactive to active behavior is interpreted in terms of an increase in surface-bisulfate interactions at the expense of surface-perchlorate interactions. Based on recent X-ray absorption near-edge spectroscopy (XANES) analysis of copper deposition onto platinum, the site for bisulfate adsorption is most probably a Cu+ surface species. Combining this spectroscopic information with coulometry shows that an additional electron is confined to surface platinum atom(s) covered by the copper species. The copper film attains bulk copper properties when approximately 2.5 monolayers of copper are deposited.

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