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J Am Chem Soc. 2009 May 27;131(20):6936-7. doi: 10.1021/ja902121f.

Cobalt-oxo core of a water-oxidizing catalyst film.

Author information

1
Freie Universit├Ąt Berlin, FB Physik, Arminallee 14, 14195 Berlin, Germany.

Abstract

In photosynthesis, water is oxidized at a protein-bound Mn(4)Ca complex. Artificial water-oxidation catalysts that are similarly efficient and based on inexpensive and abundant materials are of great interest. Recently, assembly of a catalyst as an amorphous layer on inert cathodes by electrodeposition starting from an aqueous solution of cobalt ions and potassium phosphate has been reported. X-ray absorption spectroscopy on the cobalt catalyst film (CoCF) suggests that its central structural unit is a cluster of interconnected complete or incomplete Co(III)-oxo cubanes. Potassium ligation to Co-bridging oxygens could result in Co(3)K(mu-O)(4) cubanes, in analogy to the Mn(3)Ca(mu-O)(4) cubane motif proposed for the photosynthetic Mn complex. The similarities in function and oxidative self-assembly of CoCF and the catalytic Mn complex in photosynthesis are striking. Our study establishes a close analogy also with respect to the metal-oxo core of the catalyst.

PMID:
19419168
DOI:
10.1021/ja902121f
[Indexed for MEDLINE]

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