In situ EPR studies of reaction pathways in Titania photocatalyst-promoted alkylation of alkenes.

In situ EPR studies of reaction pathways in Titania photocatalyst-promoted alkylation of alkenes.
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DOI:
10.3390/molecules20034055
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发表时间:
2015-03-03
期刊:
Molecules (Basel, Switzerland)
影响因子:
--
通讯作者:
Howe RF
Howe RF
中科院分区:
其他
文献类型:
--
作者:
Rhydderch S;Howe RF

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低温下的原位EPR光谱已被用于观察和识别当二氧化钛在与t-丁基羧酸或苯氧乙酸光催化马来酰亚胺烷基化的反应物存在下辐照时产生的顺磁物质。结果表明,马来酰亚胺是导电带电子的受体。价带空穴将t-丁基羧酸氧化为t-丁基自由基,将苯氧乙酸氧化为苯氧乙酸自由基阳离子。在马来酰亚胺存在下,苯氧乙酸形成苯氧甲基。讨论了这些观察结果与二氧化钛光催化剂催化烯烃烷基化反应机理的相关性。
In situ EPR spectroscopy at cryogenic temperatures has been used to observe and identify paramagnetic species produced when titania is irradiated in the presence of reactants used in the photocatalytic alkylation of maleimide with t-butyl carboxylic acid or phenoxyacetic acid. It is shown that maleimide acts as an acceptor of conduction band electrons. Valence band holes oxidise t-butyl carboxylic acid to the t-butyl radical and phenoxyacetic acid to the phenoxyacetic acid radical cation. In the presence of maleimide, the phenoxymethyl radical is formed from phenoxyacetic acid. The relevance of these observations to the mechanisms of titania photocatalyst-promoted alkylation of alkenes is discussed.
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