期刊
APPLIED CATALYSIS A-GENERAL
卷 521, 期 -, 页码 68-74出版社
ELSEVIER
DOI: 10.1016/j.apcata.2015.10.033
关键词
Titanium dioxide; Photocatalytic reduction; Hydrogenation; Defluorination; Acetophenone derivatives
资金
- JSPS KAKENHI [15K08120, 25460028]
- Grants-in-Aid for Scientific Research [25460028, 15K08120, 15K07879] Funding Source: KAKEN
Photoreductive transformation of mono- and di-fluoromethyl acetophenone (AP) derivatives on the P25 titanium dioxide (TiO2) has been studied in deaerated ethanol solution under UV irradiation. 2-Monofluoromethyl AP (MFAP) was stable in the dark and existed as keto form in ethanol, whereas 64% of 2,2-difluoromethyl AP (DFAP) transformed into hemiketal form (photocatalytically inactive form) under the same condition. Under the UV irradiation with the TiO2 particles, the reduction of MFAP afforded only the defluorinated ketone, while the reduction of DFAP provided not only defluorinated ketones but also a hydrogenated alcohol. The reduction of carbonyl group and defluorination of DFAP concurrently occurred on TiO2, in which the formation of MFAP was observed as an intermediate of the sequential defluorinations. These two parallel reactions were initiated by electron transfer from the surface defect sites (Ti-sd) to DFAP adsorbed on the TiO2 surface. A possible reaction mechanism for DFAP is proposed and discussed on the basis of thermodynamic data upon the C-F bond cleavage of anion radical species generated during the photocatalysis. (C) 2015 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据