Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex

Tomoya Ishizuka, Atsuko Watanabe, Hiroaki Kotani, Dachao Hong, Kenta Satonaka, Tohru Wada, Yoshihito Shiota, Kazunari Yoshizawa, Kazuaki Ohara, Kentaro Yamaguchi, Satoshi Kato, Shunichi Fukuzumi, Takahiko Kojima

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

A bis-hydroxo-bridged dinuclear CoIII-pyridylmethylamine complex (1) was synthesized and the crystal structure was determined by X-ray crystallography. Complex 1 acts as a homogeneous catalyst for visible-light-driven water oxidation by persulfate (S2O82-) as an oxidant with [RuII(bpy)3]2+ (bpy = 2,2′-bipyridine) as a photosensitizer affording a high quantum yield (44%) with a large turnover number (TON = 742) for O2 formation without forming catalytically active Co-oxide (CoOx) nanoparticles. In the water-oxidation process, complex 1 undergoes proton-coupled electron-transfer (PCET) oxidation as a rate-determining step to form a putative dinuclear bis-μ-oxyl CoIII complex (2), which has been suggested by DFT calculations. Catalytic water oxidation by 1 using [RuIII(bpy)3]3+ as an oxidant in a H216O and H218O mixture was examined to reveal an intramolecular O-O bond formation in the two-electron-oxidized bis-μ-oxyl intermediate, prior to the O2 evolution.

Original languageEnglish
Pages (from-to)1154-1164
Number of pages11
JournalInorganic Chemistry
Volume55
Issue number3
DOIs
Publication statusPublished - Feb 1 2016

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Oxidation
oxidation
Water
Oxidants
water
Photosensitizing Agents
Electrons
X ray crystallography
Quantum yield
Discrete Fourier transforms
Oxides
crystallography
Protons
electron transfer
Crystal structure
Nanoparticles
catalysts
nanoparticles
Catalysts
crystal structure

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Ishizuka, T., Watanabe, A., Kotani, H., Hong, D., Satonaka, K., Wada, T., ... Kojima, T. (2016). Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex. Inorganic Chemistry, 55(3), 1154-1164. https://doi.org/10.1021/acs.inorgchem.5b02336

Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex. / Ishizuka, Tomoya; Watanabe, Atsuko; Kotani, Hiroaki; Hong, Dachao; Satonaka, Kenta; Wada, Tohru; Shiota, Yoshihito; Yoshizawa, Kazunari; Ohara, Kazuaki; Yamaguchi, Kentaro; Kato, Satoshi; Fukuzumi, Shunichi; Kojima, Takahiko.

In: Inorganic Chemistry, Vol. 55, No. 3, 01.02.2016, p. 1154-1164.

Research output: Contribution to journalArticle

Ishizuka, T, Watanabe, A, Kotani, H, Hong, D, Satonaka, K, Wada, T, Shiota, Y, Yoshizawa, K, Ohara, K, Yamaguchi, K, Kato, S, Fukuzumi, S & Kojima, T 2016, 'Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex', Inorganic Chemistry, vol. 55, no. 3, pp. 1154-1164. https://doi.org/10.1021/acs.inorgchem.5b02336
Ishizuka, Tomoya ; Watanabe, Atsuko ; Kotani, Hiroaki ; Hong, Dachao ; Satonaka, Kenta ; Wada, Tohru ; Shiota, Yoshihito ; Yoshizawa, Kazunari ; Ohara, Kazuaki ; Yamaguchi, Kentaro ; Kato, Satoshi ; Fukuzumi, Shunichi ; Kojima, Takahiko. / Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex. In: Inorganic Chemistry. 2016 ; Vol. 55, No. 3. pp. 1154-1164.
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