Electrocatalysis of anodic, oxygen-transfer reactions at noble metal electrodes
Voltammetry at rotated disk and rotated ring-disk electrodes was applied to the study of several aspects of anodic, oxygen-transfer reactions at noble electrodes. Anodic reactions which involve the transfer of oxygen from H{sub 2}O to the oxidation products generally exhibit a voltammetric response characterized by severe kinetic limitations. Mechanistic studies were performed at noble electrodes in order to contrive strategies for improving the kinetics of these reactions. Competitive adsorption studies were used to devise an adsorption hierarchy for Au rotated disk electrodes. It was concluded that adsorption was a prerequisite for oxidations involving the transfer of oxygen present on the electrodes surface as adsorbed hydroxyl radicals. The electrogenerated chemiluminescence (ECL) of luminol was studied at Au, Pt, Pd, glassy carbon, PbO{sub 2}, and Bi-doped PbO{sub 2} electrodes. The ECL intensity was determined to be inversely related to electrochemical activity for the oxidation of luminol. It was concluded that the oxygen-transfer oxidation of luminol to 3-aminophthalate ( n = 4 eq mol{sup {minus}1}) corresponded to the dark reaction, whereas the electron-transfer oxidation of luminol with n = 1 eq mol{sup {minus}1} initiated the chemiluminescent reaction in solution.
- Research Organization:
- Ames Lab., IA (United States)
- Sponsoring Organization:
- USDOE; USDOE, Washington, DC (United States)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5021436
- Report Number(s):
- IS-T-1569; ON: DE92016308
- Resource Relation:
- Other Information: Thesis (Ph.D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HYDROXYL RADICALS
TRANSFER REACTIONS
LUMINOL
CHEMILUMINESCENCE
WATER
OXIDATION
CARBON
ELECTRODES
ELECTRON TRANSFER
GOLD
PLATINUM METALS
VOLTAMETRY
AMINES
AZINES
CHEMICAL REACTIONS
DIRECT REACTIONS
ELEMENTS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
LUMINESCENCE
METALS
NONMETALS
NUCLEAR REACTIONS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHTHALAZINES
PYRIDAZINES
RADICALS
TRANSITION ELEMENTS
400400* - Electrochemistry