Multi‐Electron Oxygen Reduction by a Hybrid Visible‐Light‐Photocatalyst Consisting of Metal‐Oxide Semiconductor and Self‐Assembled Biomimetic Complex | Zendy

Naya Shinichi | Zendy; Niwa Tadahiro | Zendy; Negishi Ryo | Zendy; Kobayashi Hisayoshi | Zendy; Tada Hiroaki | Zendy

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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.

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