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Highly efficient photocatalytic oxygenation reactions using water as an oxygen source

Nature Chemistry volume 3, pages 38–41 (2011)Cite this article

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Abstract

The effective utilization of solar energy requires photocatalytic reactions with high quantum efficiency. Water is the most abundant reactant that can be used as an oxygen source in efficient photocatalytic reactions, just as nature uses water in an oxygenic photosynthesis. We report that photocatalytic oxygenation of organic substrates such as sodium p-styrene sulfonate occurs with nearly 100% quantum efficiency using manganese(III) porphyrins as an oxygenation catalyst, [RuII(bpy)3]2+ (bpy = 2,2′-bipyridine) as a photosensitized electron-transfer catalyst, [CoIII(NH3)5Cl]2+ as a low-cost and weak one-electron oxidant, and water as an oxygen source in a phosphate buffer solution (pH 7.4). A high-valent manganese-oxo porphyrin is proposed as an active oxidant that effects the oxygenation reactions.

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Figure 1: Determination of quantum yields.
Figure 2: Proposed reaction mechanism of photocatalytic oxygenations.
Figure 3: Time-resolved absorption spectra of (TMPS)MnIII(OH).

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Acknowledgements

This work was supported by a Grant-in-Aid (no. 20108010 to S.F.) and a Global COE program, ‘the Global Education and Research Center for Bio-Environmental Chemistry’ from the Ministry of Education, Culture, Sports, Science and Technology, Japan (to S.F.), and The National Research Foundation (NRF) and the Ministry of Education and Science Technology (MEST) of Korea through the WCU (R31-2008-000-10010-0) and GRL (2010-00353) Programs (to S.F. and W.N.) and the Creative Research Initiatives Program (to W.N.).

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Authors and Affiliations

  1. Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, SORST, Japan Science and Technology Agency (JST), Suita, 565-0871, Osaka, Japan

    Shunichi Fukuzumi, Takashi Kishi & Hiroaki Kotani

  2. Department of Bioinspired Science, Ewha Womans University, Seoul, 120-750, Korea

    Shunichi Fukuzumi, Yong-Min Lee & Wonwoo Nam

  3. Department of Chemistry and Nano Science, Center for Biomimetic Systems, Ewha Womans University, Seoul, 120-750, Korea

    Yong-Min Lee & Wonwoo Nam

Authors
  1. Shunichi Fukuzumi
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  2. Takashi Kishi
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  3. Hiroaki Kotani
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  4. Yong-Min Lee
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Contributions

S.F., T.K. and W.N. conceived and designed the experiments. T.K. and H.K. performed the experiments. T.K. and H.K. analysed the data. Y.M.L. contributed materials/analysis tools. S.F. and W.N. co-wrote the paper.

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Correspondence to Shunichi Fukuzumi or Wonwoo Nam.

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The authors declare no competing financial interests.

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Fukuzumi, S., Kishi, T., Kotani, H. et al. Highly efficient photocatalytic oxygenation reactions using water as an oxygen source. Nature Chem 3, 38–41 (2011). https://doi.org/10.1038/nchem.905

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