chemistry and electrochemical oxidation of small organic molecules

chemistry and electrochemical oxidation of small organic molecules
SMART,MARSHALL C.,PH.D. THE UNIVERSITY OF SOUTHERN CALIFORNIA ,1998.267PP.
CHAIR. G.K.S. PRAKASH
Direct oxidation fuel cells using proton-exchange membrane electrolytes have long been recongnized as being an atactive mode of a power generation. The current work addresses the electro-oxidation characteristics of a number of potential fuels on Pt-based electrodes which can be used in direct oxidation fuel cells,including hydrocarbons and oxygenated molecules,such as alcohols,formates,ethers,and acetals.Promising alternative fuels which were identified,such as trimethoxymethane and dimethoxymethane,were then investigate in liquid-free PEM-based fuel cells. Inaddtion to investigating the nature of the anodic electro-oxidation of organic fuels,effort was also devoted to developing novel polymer electrolyte membrane which have low permeability to organic molecules ,such as methanol. This research was initiatated wish the expectation of reducing the extent of fuel crossover from the anode to the cathode in the liquid-feed design fuel cell which results in lower fuel efficiency and performance.Other work involving efforts to improve the performance of direct oxidation fuel cell includes research focused upon improving the kinetics of oxygen reduction.
There is continued interest in the identification of new,safe,non-toxic,and inexpensive reagents which can be used in the oxidation of organic compounds.Urea-hydrogen peroxide(UHP),a hydrogen bonded adduct, has been shown to serve as a valuable source of hydogen peroxide in a range of reactions. UHP has been shown to be ideal for the monohydroxylation of aromatics,including toluene,ethylbenzene p-xylene,m-xylene.and mesitylene,as well as benzene,in the presence of trifluoromethanesulfonic acid.It was also found that aniline was converted to a mixture containing primarily azobenaene, azoxybenzene and nitrobenzene when eated with UHP in glacial acetic acid. A number of aniline derivatives have been investigated and it was observed that the corresponding azoxybenzene derivatives could be geneate as the major products in good excellent yield. The oxidation of othe organic substrates was also investigated using urea-hydrogen peroxide as an oxidation reagent,including cyclohexylamine,1-adamantaneamine,and adamantane.

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