Platinum In Alkaline Medium Research Articles

A Systematic Approach to the Determination of Possible Reaction Mechanisms of Oxygen Reduction on Platinum in Alkaline Medium

The reaction mechanisms of oxygen reduction of platinum in alkaline medium are determined once a set of reacting species and elementary reactions is specified. The technique utilized to generate all the possible reaction mechanisms is based upon the principles of combinatorial analysis and linear algebra along with application of the principle of microscopic reversibility. The development of this method by Happel and Sellers has enabled them to study complex mechanisms for some important industrial reactions in heterogeneous catalysis. A preliminary evaluation analysis of the myriad reaction mechanisms for oxygen reduction is accomplished by invoking the concept of a stoichiometric number and a corresponding rate‐determining elementary reaction. The number of mechanisms which are consistent with a given experimentally derived stoichiometric number is considerably less. The resulting set of mechanisms forms an important basis for further investigations.

Evidence for the effect of molecular structure on the electrochemical reactivity of alcohols: Part II. Electrocatalytic oxidation of the butanol isomers on platinum in alkaline medium

The electrocatalytic oxidation of the four butanol isomers on platinum in alkaline medium was investigated by cyclic voltammetry varying the experimental kinetic parameters (sweep rate, temperature, concentration of butanol and hydroxyl ion). The primary isomers, n-butanol and isobutanol, behave relatively similar, whereas s-butanol displays an unusual behaviour, and t-butanol is totally unreactive at room temperature. From the kinetic results obtained, the rate-determining step was tentatively given, and the different electrochemical reactivity of the four isomers was interpreted in a first approach through inductive electronic effects, involving hydrogen atoms linked to the α-carbon.