Electrocatalysis of anodic oxygen-transfer reactions. Application of an electrochemical quartz crystal microbalance to a study of pure and bismuth-doped beta-lead dioxide film electrodes

Larry A. Larew, James S. Gordon, Yun Lin Hsiao, Dennis C. Johnson, Daniel Buttry

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Ratios of the change in surface mass corresponding to a change in charge (Δm/Δq) were determined for the electrodeposition of thin films of pure PbO2 and Bi-doped PbO2 at Au-film electrodes in 0.1M HClO4, using an electrochemical quartz microbalance. The value Δm/Δq = 1.26 ± 0.04 mg C-1 obtained for pure PbO2 films is in good agreement with the theoretical value of 1.24 mg C-1. A larger value, Δm/Δq = 1.32 ± 0.03 mg C-1, obtained for the Bi-doped PbO2 films, is concluded to result from the co-deposition of some ClO4 - with Bi(V) in the mixed-oxide film. Bismuth(III) was determined to be anodically adsorbed as Bi(V) at pure PbO2 surfaces for E > 1.45V vs. Ag/AgCl with Δm/Δq = 1.72 ± 0.02 mg C-1 in 0.1M HClO4 and 1.30 ± 0.03 mg C-1 in 1M HNO3. The PbO2-film electrodes with adsorbed Bi(V) are active for various anodic oxygen-transfer reactions, including the oxidations of Mn(II) to MnO4 - and DMSO to DMSO2. Experimental results are interpreted to be consistent with a mechanism proposed previously, in which the Bi(V) sites have a lower overpotential for anodic discharge of H2O to produce O2. It has been proposed that adsorbed hydroxyl radicals (·OHads) generated in the O2 evolution mechanism are consumed by oxygen-transfer steps, required in many oxidation processes.

Original languageEnglish (US)
Pages (from-to)3071-3078
Number of pages8
JournalJournal of the Electrochemical Society
Volume137
Issue number10
StatePublished - Oct 1990
Externally publishedYes

Fingerprint

Electrocatalysis
Bismuth
Quartz crystal microbalances
quartz crystals
dioxides
microbalances
bismuth
Lead
Oxygen
Electrodes
electrodes
oxygen
Oxidation
oxidation
Quartz
hydroxyl radicals
mixed oxides
Dimethyl Sulfoxide
Electrodeposition
electrodeposition

ASJC Scopus subject areas

  • Electrochemistry
  • Surfaces, Coatings and Films
  • Surfaces and Interfaces

Cite this

Electrocatalysis of anodic oxygen-transfer reactions. Application of an electrochemical quartz crystal microbalance to a study of pure and bismuth-doped beta-lead dioxide film electrodes. / Larew, Larry A.; Gordon, James S.; Hsiao, Yun Lin; Johnson, Dennis C.; Buttry, Daniel.

In: Journal of the Electrochemical Society, Vol. 137, No. 10, 10.1990, p. 3071-3078.

Research output: Contribution to journalArticle

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abstract = "Ratios of the change in surface mass corresponding to a change in charge (Δm/Δq) were determined for the electrodeposition of thin films of pure PbO2 and Bi-doped PbO2 at Au-film electrodes in 0.1M HClO4, using an electrochemical quartz microbalance. The value Δm/Δq = 1.26 ± 0.04 mg C-1 obtained for pure PbO2 films is in good agreement with the theoretical value of 1.24 mg C-1. A larger value, Δm/Δq = 1.32 ± 0.03 mg C-1, obtained for the Bi-doped PbO2 films, is concluded to result from the co-deposition of some ClO4 - with Bi(V) in the mixed-oxide film. Bismuth(III) was determined to be anodically adsorbed as Bi(V) at pure PbO2 surfaces for E > 1.45V vs. Ag/AgCl with Δm/Δq = 1.72 ± 0.02 mg C-1 in 0.1M HClO4 and 1.30 ± 0.03 mg C-1 in 1M HNO3. The PbO2-film electrodes with adsorbed Bi(V) are active for various anodic oxygen-transfer reactions, including the oxidations of Mn(II) to MnO4 - and DMSO to DMSO2. Experimental results are interpreted to be consistent with a mechanism proposed previously, in which the Bi(V) sites have a lower overpotential for anodic discharge of H2O to produce O2. It has been proposed that adsorbed hydroxyl radicals (·OHads) generated in the O2 evolution mechanism are consumed by oxygen-transfer steps, required in many oxidation processes.",
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N2 - Ratios of the change in surface mass corresponding to a change in charge (Δm/Δq) were determined for the electrodeposition of thin films of pure PbO2 and Bi-doped PbO2 at Au-film electrodes in 0.1M HClO4, using an electrochemical quartz microbalance. The value Δm/Δq = 1.26 ± 0.04 mg C-1 obtained for pure PbO2 films is in good agreement with the theoretical value of 1.24 mg C-1. A larger value, Δm/Δq = 1.32 ± 0.03 mg C-1, obtained for the Bi-doped PbO2 films, is concluded to result from the co-deposition of some ClO4 - with Bi(V) in the mixed-oxide film. Bismuth(III) was determined to be anodically adsorbed as Bi(V) at pure PbO2 surfaces for E > 1.45V vs. Ag/AgCl with Δm/Δq = 1.72 ± 0.02 mg C-1 in 0.1M HClO4 and 1.30 ± 0.03 mg C-1 in 1M HNO3. The PbO2-film electrodes with adsorbed Bi(V) are active for various anodic oxygen-transfer reactions, including the oxidations of Mn(II) to MnO4 - and DMSO to DMSO2. Experimental results are interpreted to be consistent with a mechanism proposed previously, in which the Bi(V) sites have a lower overpotential for anodic discharge of H2O to produce O2. It has been proposed that adsorbed hydroxyl radicals (·OHads) generated in the O2 evolution mechanism are consumed by oxygen-transfer steps, required in many oxidation processes.

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