Photooxidation at Platinum Colloidal TiO₂ Aqueous-Solution Interfaces. I. Ethylenediaminetetraacetic Acid and Related-Compounds

Abstract

The photooxidation of ethylenediaminetetraacetic acid ( edta ) and related glycine derivatives, at Pt/TiO₂/aqueous solution interfaces, has been monitored via the production of hydrogen and carbon dioxide. Yields are consistent with the exhaustive oxidation of methoxycarbonyl groups and the rate varied with the number and distribution of such groups. A photooxidation pathway is proposed which involves the oxidation of intermediate carbonium ions. Plausible molecular intermediates, such as formic acid and formaldehyde in the case of edta , have been shown in separate experiments to be photooxidized according to the proposed pathway. The maximum rate of oxidation for each donor depends on its oxidation potential and its tendency to adsorb on TiO₂ surfaces. Desorption due to pH increase, as well as consumption of the donor, causes the rate to decline rapidly with illumination time.

Acetic and malonic acids gave some hydrogen but underwent mainly (> c. 80%) photo-Kolbe decarboxylation to yield carbon dioxide and methane. By contrast the oxidation of oxomalonic, pyruvic and lactic acids proceeded mainly via a H₂ producing pathway similar to that established for edta. The oxidation of pyruvic and lactic acids ceased at a yield of one mole of CO₂ per mole of acid.