金属卟啉化合物光催化反应研究（Ⅲ）──金属卟啉光助氧化甲醇动力学研究

Studies on the Photochemical Reactions Catalyzed by Metalloporphyrin Complexes(Ⅲ)──Kinetics of Photoassisted Oxidation Reaction of Methanol by Metalloporphyrins

研究了６种金属卟啉在有甲醇存在的脱气水或二甲基甲酰胺溶液中的光化学行为，当用高压汞灯照射时，金属卟啉被还原，同时甲醇被氧化成甲醛，以碘化四（对三甲胺基）苯基钴（Ⅲ）卟啉为例详细地研究了影响光助氧化甲醇反应的因素，并对反应机理进行了探讨。

In deaerated solution of water-methanol or water-methanol-pyridine system,trivalent ions(Co(Ⅲ)and Mn(Ⅲ))porphyrins were reduced to divalent ions on illummination of light with simultaneous oxidation of methanol. The kinetic study on the photoreduction revealed that the reduction rate of Co(Ⅲ)followed the pseudo-first-order rate expression at 20℃ and pH 2 to 13 in the presence of excess methanol. The observed rate constants were dependent on [CH3OH] and pH values.The possible mechnisms for the photoreduction of metalloporphyrins were discussed.