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Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH

Author

Listed:
  • Akira Yamaguchi

    (The University of Tokyo)

  • Riko Inuzuka

    (The University of Tokyo)

  • Toshihiro Takashima

    (Clean Energy Research Center, University of Yamanashi)

  • Toru Hayashi

    (The University of Tokyo)

  • Kazuhito Hashimoto

    (The University of Tokyo)

  • Ryuhei Nakamura

    (Biofunctional Catalyst Research Team, RIKEN Center for Sustainable Resource Science)

Abstract

Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH.

Suggested Citation

  • Akira Yamaguchi & Riko Inuzuka & Toshihiro Takashima & Toru Hayashi & Kazuhito Hashimoto & Ryuhei Nakamura, 2014. "Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH," Nature Communications, Nature, vol. 5(1), pages 1-6, September.
    • Handle: RePEc:nat:natcom:v:5:y:2014:i:1:d:10.1038_ncomms5256
    DOI: 10.1038/ncomms5256
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