Jump to main content
Jump to site search

Issue 24, 2014
Previous Article Next Article

Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity

Author affiliations

Abstract

During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O2 and solar fuels, such as H2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn2II,III catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O–O bond formation.

Graphical abstract: Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity

Back to tab navigation

Publication details

The article was received on 13 Nov 2013, accepted on 27 Jan 2014 and first published on 27 Jan 2014


Article type: Paper
DOI: 10.1039/C3CP54800G
Phys. Chem. Chem. Phys., 2014,16, 11950-11964
  • Open access: Creative Commons BY license
  •   Request permissions

    Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity

    W. A. A. Arafa, M. D. Kärkäs, B. Lee, T. Åkermark, R. Liao, H. Berends, J. Messinger, P. E. M. Siegbahn and B. Åkermark, Phys. Chem. Chem. Phys., 2014, 16, 11950
    DOI: 10.1039/C3CP54800G

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements