Inverse Kinetic Solvent Isotope Effect in TiO2 Photocatalytic Dehalogenation of Non-adsorbable Aromatic Halides: A Proton-Induced Pathway
文献类型：期刊论文
| 作者 | Chang, Wei1; Sun, Chunyan1,2; Pang, Xibin1; Sheng, Hua1; Li, Yue1; Ji, Hongwei1; Song, Wenjing1; Chen, Chuncheng1; Ma, Wanhong1; Zhao, Jincai1 |
| 刊名 | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
 |
| 出版日期 | 2015-02-09 |
| 卷号 | 54期号:7页码:2052-2056 |
| 关键词 | Electron Transfer Isotope Effects Photocatalysis Surface Chemistry Titanium |
| ISSN号 | 1433-7851 |
| DOI | 10.1002/anie.201409392 |
| 英文摘要 | An efficient redox reaction between organic substrates in solution and photoinduced h(vb)(+)/e(cb)(-) on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE >= 1). Reported herein is a universal inverse KSIE (0.6-0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D-0]methanol/[D-4]methanol solution. Combined with in situ ATR-FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H+/D+ from solvent oxidation, accompanies a change in hybridization from sp(2) to sp(3) at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows. |
| 语种 | 英语 |
| WOS记录号 | WOS:000349391000004 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/53499]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Ma, Wanhong |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Key Lab Photochem, Beijing 100190, Peoples R China 2.Shaoxing Univ, Dept Chem, Shaoxing 312000, Zhejiang, Peoples R China |
| 推荐引用方式 GB/T 7714 | Chang, Wei,Sun, Chunyan,Pang, Xibin,et al. Inverse Kinetic Solvent Isotope Effect in TiO2 Photocatalytic Dehalogenation of Non-adsorbable Aromatic Halides: A Proton-Induced Pathway[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2015,54(7):2052-2056. |
| APA | Chang, Wei.,Sun, Chunyan.,Pang, Xibin.,Sheng, Hua.,Li, Yue.,...&Zhao, Jincai.(2015).Inverse Kinetic Solvent Isotope Effect in TiO2 Photocatalytic Dehalogenation of Non-adsorbable Aromatic Halides: A Proton-Induced Pathway.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,54(7),2052-2056. |
| MLA | Chang, Wei,et al."Inverse Kinetic Solvent Isotope Effect in TiO2 Photocatalytic Dehalogenation of Non-adsorbable Aromatic Halides: A Proton-Induced Pathway".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 54.7(2015):2052-2056. |
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来源：化学研究所
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