Organic redox transformations at chemically modified surfaces. Progress report, 1984-1985

Technical Report · Tue Jan 01 04:00:00 EST 1985

OSTI ID:6085481

The following studies have led to publication within the last year: (1) Electrochemical Reductions of Olefins Catalyzed by Nickel Complexes, J. Electrochem. Soc., 1985, 132 000. Investigation of the catalytic reduction of olefins mediated by controlled reduction of nickel complexes of varying structure and reduction potential revealed that electrochemical generation of radical ions initiates polymerization of acrylonitrile. The complexes examined were NiL/sub 3/Cl/sub 2/ complexes, where L = bipyridine, substituted bipyridines, phenanthroline, substituted phenanthrolines, biquinoline, substituted biquinolines, and a tetraazamacrocycle. Although all nickel complexes employed can be catalyzed the catalytic reduction of acrylonitrile, only four (with L = bpy, 4,4-diMe(bpy), phen, and 4,7-diMe(phen) demonstrate sufficient chemical reversibility to be useful on a preparative scale; and (2) Polymer Modified Electrodes. Electrochemical and Photoelectrochemical Polymerization of 1-Vinylpyrene, Macromol. 1985, 000. Polymerization of 1-vinylpyrene in acetonitrile was achieved electrochemically at a conducting SnO/sub 2/ electrode by application of anodic potentials and photoelectrochemically at an n-GaAs semiconductor electrode under visible light irradiation. Both polymers exhibited characteristic excimer emission (max - 480 nm) in both films and THF solutions similar to polyvinylpyrene synthesized via a Ziegler-Natta catalyst. The lifetime of the excimer emission was 110 ns. The mechanism of photodegradation was elucidated by using ESR techniques. In addition, several conference papers covering DOE material have been presented. In addition, a great deal of synthetic work has been conducted in the last year, producing several new modified surfaces whose properties will be reported in the ensuing year. The efforts have centered on the synthesis of dyes and on monomers for preparation of polymer-coated electrodes.

• Research Organization: Texas Univ., Austin (USA)
• DOE Contract Number: AS05-77ER05528
• OSTI ID: 6085481
• Report Number(s): DOE/ER/05528-76; ON: DE85006845
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY
140505* -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400500 -- Photochemistry
400600 -- Radiation Chemistry
ACRYLONITRILE
ALKENES
AZINES
BIPYRIDINES
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DECOMPOSITION
DYES
ELECTROCHEMICAL CELLS
ELECTROCHEMISTRY
ELECTRODES
ENERGY LEVELS
EQUIPMENT
EXCITED STATES
FURANS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
MODIFICATIONS
NICKEL COMPLEXES
NITRILES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOELECTROCHEMICAL CELLS
PHOTOLYSIS
POLYMERIZATION
POLYMERS
PYRIDINES
RADICALS
REDUCTION
RESEARCH PROGRAMS
SOLAR EQUIPMENT
SYNTHESIS
TETRAHYDROFURAN
TIN COMPOUNDS
TIN OXIDES
TRANSITION ELEMENT COMPLEXES