Photocatalytic isomerization of butenes over TiO2. Photo-formed active species and characteristics of reaction.

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概要

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• It has been found that UV irradiation of powdered TiO<SUB>2</SUB> catalysts in the presence of butene molecules leads to both cis-trans and double bond shift isomerization reactions with high efficiency. In the photocatalytic isomerization the reactivity of 2-butene is much higher than that of 1-butene, being in contrast to the feature in the thermal isomerization. The addition of O<SUB>2</SUB> or NO molecules leads to the complete inhibition of photocatalytic isomerization of butenes. The effect of adsorbed water on the photocatalytic isomerization has been investigated. From these results together with the ESR measurements under UV irradiation of TiO<SUB>2</SUB> at 77 K in the presence of butene as well as O<SUB>2</SUB> or NO, the following conclusion emerges: The interaction of the photo-formed O<SUP>−</SUP> species or [Ti<SUP>3+</SUP>–O<SUP>−</SUP>] pairs results in opening of the C=C bond of butene, i.e. formation of a radical species, which acts as the intermediate in the photocatalytic isomerization. The O<SUP>−</SUP> as well as surface OH<SUP>−</SUP> species participates in the hydrogen shift, i.e. the double bond shift isomerization. Thus, the reaction mechanism which has been proposed for the photocatalytic isomerization of butene over ZnO has been confirmed over TiO<SUB>2</SUB>.

• 公益社団法人 日本化学会の論文

著者

• Anpo Masakazu

  Department Of Applied Chemistry Colledge Of Engineering University Of Osaka Prefecture

• Kubokawa Yutaka

  Department of Applied Chemistry College of Engineering University of Osaka Prefecture

• Yabuta Masaaki

  Department of Applied Chemistry, College of Engineering, University of Osaka Prefecture

• Kodama Sukeya

  Department of Applied Chemistry, College of Engineering, University of Osaka Prefecture

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