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

doi:10.1021/acs.inorgchem.5b02336

Homogeneous Photocatalytic Water Oxidation with a Dinuclear Co^III-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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

72 Scopus citations

Abstract

A bis-hydroxo-bridged dinuclear Co^III-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 (S₂O₈^2-) as an oxidant with [Ru^II(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 (CoO_x) 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 Co^III complex (2), which has been suggested by DFT calculations. Catalytic water oxidation by 1 using [Ru^III(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 language	English
Pages (from-to)	1154-1164
Number of pages	11
Journal	Inorganic Chemistry
Volume	55
Issue number	3
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02336
State	Published - 1 Feb 2016

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Publisher Copyright:
© 2016 American Chemical Society.

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10.1021/acs.inorgchem.5b02336

Cite this

@article{838a537d3e9240eda21ddec558bcbe59,

title = "Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex",

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.",

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

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T1 - Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex

AU - Ishizuka, Tomoya

AU - Watanabe, Atsuko

AU - Kotani, Hiroaki

AU - Hong, Dachao

AU - Satonaka, Kenta

AU - Wada, Tohru

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Ohara, Kazuaki

AU - Yamaguchi, Kentaro

AU - Kato, Satoshi

AU - Fukuzumi, Shunichi

AU - Kojima, Takahiko

PY - 2016/2/1

Y1 - 2016/2/1

N2 - 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.

AB - 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.

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