Organic dyestuffs as catalysts for fuel cells.
Electrocatalysis in fuel cells requires as well substances capable of catalyzing the anodic oxidation of fuels as catalysts for the cathodic reduction of oxygen. Several dyestuffs that catalyze oxygen reduction are known, but up to now only one has been described as active in anodic reactions. All these dyestuffs are N4-chelates. Comparative studies have shown that chelates with other types of coordination, in particular N202-, 04-, N2S2- and S4-chelates, are able to catalyze the reduction of oxygen, though they are considerably less active than the N4-compounds. With a given type of coordination, the nature of the central atom has a decisive influence on the catalytic activity of the dyestuff, whereas substitution on the organic skeleton has only a slight effect. Thermal pretreatment of the N4-chelates can considerably increase their stability in electrolytes containing sulfuric acid. All the experimental results point to the conclusion that, with electrocatalysts, as with natural oxygen carriers, the interaction essential for catalysis takes place between the oxygen and the central metal ion. Various assumptions may be made as to the nature of the rate-determining step. The cathodic reduction of oxygen can be regarded as redox catalysis, or it can be considered from the standpoint of molecular orbital theory. The models hitherto suggested for the mechanism of oxygen reduction are tested against the experimental results and a modified model based on MO theory is put forward.
Organic dyestuffs as catalysts for fuel cells. Electrocatalysis in fuel cells requires as well substances capable of catalyzing the anodic oxidation of fuels as catalysts for the cathodic reduction of oxygen. Several dyestuffs that catalyze oxygen reduction are known, but up to now only one has been described as active in anodic reactions. All these dyestuffs are N4-chelates. Comparative studies have shown that chelates with other types of coordination, in particular N202-, 04-, N2S2- and S4-chelates, are able to catalyze the reduction of oxygen, though they are considerably less active than the N4-compounds. With a given type of coordination, the nature of the central atom has a decisive influence on the catalytic activity of the dyestuff, whereas substitution on the organic skeleton has only a slight effect. Thermal pretreatment of the N4-chelates can considerably increase their stability in electrolytes containing sulfuric acid. All the experimental results point to the conclusion that, with electrocatalysts, as with natural oxygen carriers, the interaction essential for catalysis takes place between the oxygen and the central metal ion. Various assumptions may be made as to the nature of the rate-determining step. The cathodic reduction of oxygen can be regarded as redox catalysis, or it can be considered from the standpoint of molecular orbital theory. The models hitherto suggested for the mechanism of oxygen reduction are tested against the experimental results and a modified model based on MO theory is put forward.