Electrocatalysis of anodic oxygen-transfer reactions: Oxidation of phenol and benzene at bismuth-doped lead dioxide electrodes in acidic solutions

Journal Article · Thu Dec 01 04:00:00 EST 1994 · Journal of the Electrochemical Society; (United States)

DOI:https://doi.org/10.1149/1.2059345· OSTI ID:6604876

Kawagoe, K T; Johnson, D C ^[1]

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1. Ames Lab., IA (United States)

The electrocatalytic activities are compared for pure [beta]-lead dioxide electrodes and bismuth-doped lead dioxide electrodes for oxidation of dimethylsulfoxide (DMSO), phenol, and benzene in acidic media. A correlation is observed between the bismuth content of Bi-PbO[sub 2] films on Au disk electrodes and the apparent heterogeneous rate constant for conversion of DMSO to DMSO[sub 2]. The oxidation of phenol occurs at a transport-limited rate for both the PbO[sub 2] and Bi-PbO[sub 2] film electrodes; however, the Bi-PbO[sub 2] electrodes exhibit significantly greater stability against surface fouling by polymeric films. This is a direct benefit of the greater electrocatalytic activity of Bi-PbO[sub 2] electrodes for oxidation of phenol beyond the phenolic radical. A ring-disk experiment for benzene oxidation at a Bi-PbO[sub 2] disk demonstrates that o-benzoquinone and p-benzoquinone are produced at the disk in the ratio ca. 0.25. However, the total ring current for reduction of these products from the disk reaction is significantly below that predicted from the disk current, and it must be concluded that a significant amount of electroinactive species is produced at the disk. This production probably corresponds to a ring-opening reaction with production of one or more organic acids. The product solution from exhaustive electrolysis of benzene contains p-benzoquinone as the only electroactive product; hence, the o-benzoquinone is concluded to undergo further oxidation at the Bi-PbO[sub 2] electrode to one or more electroinactive products. This is part of a larger program motivated by the search for new catalytic anode materials for achieving electrolytic production of useful compounds by oxidation of toxic chemical wastes. Also of interest is the total oxidative degradation of toxic organic wastes to their corresponding elemental oxides (CO[sub 2], etc.), a technology referred to as electrochemical incineration.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6604876
• Journal Information: Journal of the Electrochemical Society; (United States), Journal Name: Journal of the Electrochemical Society; (United States) Vol. 141:12; ISSN JESOAN; ISSN 0013-4651
• Country of Publication: United States
• Language: English

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
320305 -- Energy Conservation
Consumption
& Utilization-- Industrial & Agricultural Processes-- Industrial Waste Management
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
AROMATICS
BENZENE
BISMUTH
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL FEEDSTOCKS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DMSO
DOPED MATERIALS
ELECTROCATALYSTS
ELECTROCHEMICAL CELLS
ELECTROLYSIS
ELEMENTS
HAZARDOUS MATERIALS
HYDROCARBONS
HYDROXY COMPOUNDS
KINETICS
LEAD COMPOUNDS
LEAD OXIDES
LYSIS
MANAGEMENT
MATERIALS
METALS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PERFORMANCE TESTING
PHENOL
PHENOLS
PROCESSING
RAW MATERIALS
REACTION KINETICS
SULFOXIDES
SYNTHESIS
TESTING
TOXIC MATERIALS
WASTE MANAGEMENT
WASTE PROCESSING