Selective Partial Oxidation of Hydrocarbons by the Cell Reaction System

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New oxidation methods for the partial oxidtion od alenes at low temperature (<373K) using gaseous alkene-OィイD22ィエD2 fuel cell systems and for the hydroxykation of alkanes and aromatics applying HィイD22ィエD2-OィイD22ィエD2 fuel cell reactions were studied. Catalytic oxidation systems can be converted into electrochemical cells which control the reaction rate and selectivity by a variable resister or potentiostat in the outer circuit, as shown for the Wacker type and π-allyl type oxidations.Direct oxygenation of aromatics to phenols, C6 alkanes and light alkanes to alcohols and aldehydes are realized at the cathode during HィイD22ィエD2-OィイD22ィエD2 fuel cell reactions at room temperature. The topics are the ω-oxidation of n-hexane with (FeClィイD23ィエD2 + α-cyclodextrin) /graphite cathode, the synergism of Pd-black and iron compounds for the formation of phenol on (Pd-black+FeィイD23ィエD2OィイD24ィエD2)/Carbon-Whisker (CW) cathode, cogeneration of phenol and electricity by using CuSOィイD24ィエD2/CW cathode, the synergism of different carbon materials in the cathode for the product selectivity in the oxidation of toluene on (CW + Active Carbon) cathodes, and the oxidation of propane over (Pal-black +VO(acac)ィイD22ィエD2)/Carbon-Fiber cathodes in the gas phase. Reductive activation of oxygen on the cathode is essential for these oxygenations. For most of the electrocatalytic systems used in this work, the oxygenations of alkanes and aromatics can be explained on the basis of Fenton Chemistry assuming HO・ as the active oxygen species, except for the SmClィイD23ィエD2/graphite cathode.