Selective electrocatalysis of anodic oxygen-transfer reactions at chemically modified, thin-film lead dioxide electrodes
The strategy to modify PbO{sub 2} electrodes for electrocatalysis of oxygen-transfer (O-t) reactions is to incorporate spatially separated catalytic sites into the PbO{sub 2} surface. The rate of OH radical formation is promoted at these sites, as is the rate of the O-t reaction, for the latter was demonstrated to be proportional to the former. Chemically modified PbO{sub 2} is electrodeposited by addition of Bi{sup 3+}, As(III), or Cl{sup {minus}} to the Pb{sup 2+} plating bath. The electrochemical stability and catalytic activity of the Bi-doped PbO{sub 2} (Bi-PbO{sub 2}) increase with increased Bi/Pb atomic ratio in the mixed oxide which were determined with x-ray photoelectron spectroscopy. Microcracked, ultra-thin films of Bi-PbO{sub 2} were found at Au, Pt, GC, and Ti electrodes after consecutive deposition and stripping of the thick oxide films. The surface of pure PbO{sub 2} can be modified by Bi{sup 3+}, As(V), and Cl{sup {minus}} by electroadsorption. The adsorption method to modify PbO{sub 2} is fast and efficient for screening new catalysts. An O-t mediation mechanism was proposed for the electrocatalysis observed at the chemically modified PbO{sub 2}. 31 refs., 12 figs.
- Research Organization:
- Ames Lab., IA (USA)
- Sponsoring Organization:
- DOE/ER
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 6974822
- Report Number(s):
- IS-T-1437; ON: DE90011747
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360201* -- Ceramics
Cermets
& Refractories-- Preparation & Fabrication
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
BISMUTH
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
DEPOSITION
ELECTROCATALYSTS
ELECTRODEPOSITION
ELECTRODES
ELECTROLYSIS
ELEMENTS
FILMS
KINETICS
LEAD COMPOUNDS
LEAD OXIDES
LYSIS
METALS
MODIFICATIONS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
SUBSTRATES
SURFACE COATING
SURFACES
THIN FILMS