Electrocatalysis of anodic oxygen-transfer reactions; Activation of PbO sub 2 -film electrodes in 1. 0M HClO sub 4 by addition of Bismuth(III) and Arcenic(III,V)

Journal Article · Wed Aug 01 04:00:00 EDT 1990 · Journal of the Electrochemical Society; (USA)

OSTI ID:6386426

Johnson, D C ^[1]; Chang, H ^[2]

---

1. Ames Lab. and Dept. of Chemistry, Iowa State Univ., Ames, IA (US)
2. Dept. of Chemistry, Univ of Texas, Austin, TX (US)

The electrocatalytic effect of added Bi{sup 3+} was studied for the anodic response of dimethyl sulfoxide (DMSO) at PbO{sub 2}-film electrodes in 1.0M HClO{sub 4}. DMSO was virtually unreactive at pure PbO{sub 2}-film electrodes electrodeposited from acidic media. However, well-defined anodic waves with transport-limited current plateaus were obtained for up to 100 mM DMSO by addition of as little as 10 {mu}M Bi{sup 3+}. The product of DMSO oxidation was determined to be dimethyl sulfone (DMSO{sub 2}). The electrode activity is concluded to be the result of adsorbed Bi{sup 3+} and/or Bi{sup 5+} which function to mediate the oxygen-transfer step in the anodic reaction mechanism. The E{sub 1/2} values for DMSO and several additional compounds were determined to be virtually equivalent (1.65-1.71 V vs SCE) in spite of large differences in the E{degree} values for the respective half reactions. This is explained as the consequence of a common rate-controlling step which is the discharge of H{sub 2}O at the Bi sites to produce adsorbed hydroxyl radicals (OH{sub ads}) which are subsequently consumed in the oxidation process.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6386426
• Journal Information: Journal of the Electrochemical Society; (USA), Journal Name: Journal of the Electrochemical Society; (USA) Vol. 137:8; ISSN JESOA; ISSN 0013-4651
• Country of Publication: United States
• Language: English

Related Subjects

25 ENERGY STORAGE
250903* -- Energy Storage-- Batteries-- Materials
Components
& Auxiliaries
36 MATERIALS SCIENCE
360204 -- Ceramics
Cermets
& Refractories-- Physical Properties
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400 -- Electrochemistry
ALLOYS
ANODES
ARSENIC ADDITIONS
ARSENIC ALLOYS
BISMUTH ADDITIONS
BISMUTH ALLOYS
CATALYSTS
CHALCOGENIDES
CHEMISTRY
DMSO
ELECTROCATALYSTS
ELECTROCHEMISTRY
ELECTRODES
FILMS
HYDROXYL RADICALS
LEAD COMPOUNDS
LEAD OXIDES
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RADICALS
SULFOXIDES
THIN FILMS