The complexation of zinc tetraphenylporphyrintrisulfonate by viologen and its role in photoredox processes.
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概要
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The formation of the cation radicals of viologen dyes was established when an aqueous solution containing zinc tetraphenylporphyrintrisulfonate (Zn–TPPS<SUB>3</SUB>), viologen dye, and 2-mercaptoethanol was irradiated by visible light. The reduction of viologen has been studied kinetically; its reduction rate may be expressed as follows:<BR><I>v</I>=\fracd[V<SUP>+</SUP>]d<I>t</I>=\left(\frac<I>k</I><SUB>3</SUB>[Zn−TPPS<SUB>3</SUB>]<SUB>0</SUB>1+<I>K</I><SUB>1</SUB>[V<SUP>2+</SUP>]+<I>K</I><SUB>2</SUB>[V<SUP>+</SUP>]\right)\left(\frac<I>k</I><SUB>4</SUB>[V<SUP>2+</SUP>]<I>k</I><SUB><SUP>−</SUP>3</SUB>+<I>k</I><SUB>4</SUB>[V<SUP>2+</SUP>]\right)\left(\frac<I>k</I><SUB>6</SUB>[RSH]<I>k</I><SUB>5</SUB>[V<SUP>+</SUP>]+<I>k</I><SUB>6</SUB>[RSH]\right),<BR>where [V<SUP>2+</SUP>], [V<SUP>+</SUP>], and [RSH] are the concentrations of the oxidized form and the reduced form of viologen, and 2-mercaptoethanol respectively. On the basis of the rate expression, a reaction mechanism containing the complexation of Zn–TPPS<SUB>3</SUB> by viologen was proposed. On the addition of hydrogenase to the above photoirradiation system, hydrogen evolution was observed by the irradiation of visible light.
- 公益社団法人 日本化学会の論文
著者
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Okura Ichiro
Department Of Bioengineering Tokyo Institute Of Technology
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Aono Shigetoshi
Department Of Bioengineering Tokyo Institute Of Technology
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Kusunoki Shin
Department of Chemical Engineering, Tokyo Institute of Technology
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