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首页> 外文期刊>Catalysis science & technology >Direct cyanomethylation of aliphatic and aromatic hydrocarbons with acetonitrile over a metal loaded titanium oxide photocatalyst
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Direct cyanomethylation of aliphatic and aromatic hydrocarbons with acetonitrile over a metal loaded titanium oxide photocatalyst

机译：脂肪族和芳香族的直接cyanomethylation碳氢化合物与乙腈的金属加载氧化钛光催化剂

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A platinum-loaded TiO2 (Pt/TiO2) photocatalyst promoted cyanomethylation of aliphatic hydrocarbons, namely cyclohexane and cyclohexene, with acetonitrile, where the photogenerated hole oxidatively dissociates the C-H bond of both the acetonitrile and the aliphatic hydrocarbons to form each corresponding radical species before their radical cross-coupling. The Pt/TiO2 photocatalyst was more active than the Pd/TiO2 photocatalyst in these reactions. In contrast, the cyanomethylation of benzene was promoted by the Pd/TiO2 photocatalyst or a physical mixture of the Pt/TiO2 photocatalyst and a Pd catalyst supported by Al2O3, while it was hardly promoted by the Pt/TiO2 photocatalyst alone. The temperature dependence of the reaction rate proved that the Pd nanoparticles on the TiO2 photocatalyst thermally function as a metal catalyst. These results clearly suggest that the Pd metal catalyst is necessary for the cyanomethylation of benzene. However, in the cyanomethylation of aliphatic hydrocarbons, the catalytic effect of the metal particles was not observed, meaning that the radical coupling takes place without the metal catalysis. Thus, it is concluded that in the case of the benzene cyanomethylation the Pd nanoparticles play dual roles, as a catalyst to catalyse the substitution reaction of benzene with the cyanomethyl radical, and as an electron receiver to reduce the recombination of the photoexcited electrons and holes in the TiO2 photocatalyst, although they could not contribute as a catalyst to the cyanomethylation of aliphatic hydrocarbons.
机译：platinum-loaded二氧化钛(Pt /二氧化钛光催化剂促进了脂肪族的cyanomethylation碳氢化合物,即环己烷、环己烯与乙腈,photogenerated洞氧化水解的碳氢键乙腈和脂肪族碳氢化合物形式对应每一个激进的物种他们的激进的交叉耦合。比Pd /二氧化钛光催化剂更活跃光催化剂在这些反应。苯的cyanomethylation被提拔Pd /二氧化钛光催化剂或物理混合物Pt /二氧化钛光催化剂和钯催化剂支持的氧化铝,而这是很难推广由Pt /二氧化钛光催化剂。依赖于温度的反应速率证明了Pd在二氧化钛纳米颗粒光催化剂金属热功能催化剂。Pd金属催化剂是必要的cyanomethylation苯。脂肪族碳氢化合物cyanomethylation,金属粒子的催化效果观察到,这意味着需要激进的耦合没有金属催化。得出的结论是,在苯cyanomethylation Pd纳米粒子双玩角色,作为催化剂,催化替换反应的苯cyanomethyl激进,作为一个电子接收器来减少光激电子和重组孔二氧化钛光催化剂,尽管他们不能作为催化剂,贡献吗cyanomethylation的脂肪族碳氢化合物。

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