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Multi‐Electron Oxygen Reduction by a Hybrid Visible‐Light‐Photocatalyst Consisting of Metal‐Oxide Semiconductor and Self‐Assembled Biomimetic Complex |
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| Authors: | Dr Shin‐ichi Naya Tadahiro Niwa Ryo Negishi Prof?Dr Hisayoshi Kobayashi Prof?Dr Hiroaki Tada |
| Institution: | 1. Environmental Research Laboratory, Kinki University, 3‐4‐1, Kowakae, Higashi‐Osaka, Osaka 577‐8502 (Japan);2. Department of Applied Chemistry, School of Science and Engineering, Kinki University, 3‐4‐1, Kowakae, Higashi‐Osaka, Osaka 577‐8502 (Japan);3. Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo‐ku, Kyoto, 606‐8585 (Japan) |
| Abstract: | Adsorption experiments and density functional theory (DFT) simulations indicated that Cu(acac)2 is chemisorbed on the monoclinic sheelite (ms)‐BiVO4 surface to form an O2‐bridged binuclear complex (OBBC/BiVO4) like hemocyanin. Multi‐electron reduction of O2 is induced by the visible‐light irradiation of the OBBC/BiVO4 in the same manner as a blue Cu enzyme. The drastic enhancement of the O2 reduction renders ms‐BiVO4 to work as a good visible‐light photocatalyst without any sacrificial reagents. As a model reaction, we show that this biomimetic hybrid photocatalyst exhibits a high level of activity for the aerobic oxidation of amines to aldehydes in aqueous solution and imines in THF solution at 25 °C giving selectivities above 99 % under visible‐light irradiation. |
| Keywords: | biomimetic complex oxidation photocatalysis oxygen reduction visible light |