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Selective H2 and CO production with rhenium(I) biscarbonyl complexes as photocatalyst |
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| Authors: | Tatsuki Morimoto Junji Tanabe Kazuhiko Sakamoto Kazuhide Koike Osamu Ishitani |
| Institution: | 1. Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama 2-12-1-NE-1, Meguro-ku, Tokyo, 152-8551, Japan 2. PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi-shi, Saitama, 332-0012, Japan 3. Graduate School of Science and Engineering, Saitama University, 255 Shimo-Okubo, Saitama, 338-8570, Japan 4. National Institute of Advanced Industrial Science and Technology, 16-1 Onogawa, Tsukuba, Ibaraki, 305-8569, Japan 5. ALCA, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi-shi, Saitama, 332-0012, Japan |
| Abstract: | Rhenium(I) biscarbonyl complexes with two phosphine ligands photocatalyzed not only CO2 reduction under CO2 atmosphere but also H2 evolution under Ar. The reductant 1-benzyl-1,4-dihydronicotinamide (BNAH) worked only as a one-electron donor, and it was quantitatively converted to its corresponding oxidized dimer (BNA2). The photocatalytic reactions required addition of a base such as triethanolamine, because deprotonation from the oxidized BNAH (BNAH?+) is essential for the suppression of the back electron transfer from the reduced rhenium(I) complex to BNAH?+. 1H, 13C, and 31P NMR studies under vacuum or 13CO2 atmosphere indicated that the rhenium(I) complex is relatively stable under the CO2 reduction conditions, but it is converted to some other complexes under the H2 evolution conditions. |
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