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Multi‐Electron Oxygen Reduction by a Hybrid Visible‐Light‐Photocatalyst Consisting of Metal‐Oxide Semiconductor and Self‐Assembled Biomimetic Complex
Author(s) -
Naya Shinichi,
Niwa Tadahiro,
Negishi Ryo,
Kobayashi Hisayoshi,
Tada Hiroaki
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201408352
Subject(s) - photocatalysis , visible spectrum , photochemistry , reagent , chemistry , density functional theory , adsorption , metal , aqueous solution , oxide , semiconductor , irradiation , materials science , catalysis , organic chemistry , computational chemistry , optoelectronics , physics , nuclear physics
Adsorption experiments and density functional theory (DFT) simulations indicated that Cu(acac) 2 is chemisorbed on the monoclinic sheelite (ms)‐BiVO 4 surface to form an O 2 ‐bridged binuclear complex (OBBC/BiVO 4 ) like hemocyanin. Multi‐electron reduction of O 2 is induced by the visible‐light irradiation of the OBBC/BiVO 4 in the same manner as a blue Cu enzyme. The drastic enhancement of the O 2 reduction renders ms‐BiVO 4 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.