二氧化碳光催化利用.pdfVIP

Published on Web 01/19/2008 Development of an Efficient Photocatalytic System for CO2 Reduction Using Rhenium(I) Complexes Based on Mechanistic Studies Hiroyuki Takeda,† Kazuhide Koike,‡ Haruo Inoue,§, and Osamu Ishitani*,†, Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1-E1-9 O-okayama, Meguro-ku, Tokyo, 152-8551, Japan, National Institute of Ad anced Industrial Science and Technology, 16-1 Onogawa, Tsukuba, Ibaraki, 305-8569, Japan, Department of Applied Chemistry, Graduate Course of Urban En ironmental Sciences, Tokyo Metropolitan Uniersity, 1-1 Minamiosawa, Hachioji, Tokyo, 192-0364, Japan, and SORST, Japan Science and Technology Agency (JST), Japan Received October 9, 2007; E-mail: ishitani@chem.titech.ac.jp Abstract: The reaction mechanism of photocatalytic CO2 reduction using rhenium(I) complexes has been investigated by means of a detailed comparison of the photocatalyses of three rhenium(I) complexes, fac- [Re(bpy)(CO)3L] (L SCN (1-NCS), Cl (1-Cl), and CN (1-CN)). The corresponding one-electron-reduced species (OER) of the complexes play two important roles in the reaction: (a) capturing CO2 after loss of the monodentate ligand (L) and (b) donation of the second electron to CO2 by another OER without loss of L. In the case of 1-NCS, the corresponding OER has both of the capab