Cobalt-Oxo Core of a Water-Oxidizing Catalyst Film

In photosynthesis, water is oxidized at a protein-bound Mn4Ca 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 Co3K(mu-O)(4) cubanes, in analogy to the Mn3Ca(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.