High catalytic activity of heteropolynuclear cyanide complexes containing cobalt and platinum ions: visible-light driven water oxidation.

A near-stoichiometric amount of O2 was evolved as observed in the visible-light irradiation of an aqueous buffer (pH 8) containing [Ru(II) (2,2'-bipyridine)3 ] as a photosensitizer, Na2 S2 O8 as a sacrificial electron acceptor, and a heteropolynuclear cyanide complex as a water-oxidation catalyst. The heteropolynuclear cyanide complexes exhibited higher catalytic activity than a polynuclear cyanide complex containing only Co(III) or Pt(IV) ions as C-bound metal ions. The origin of the synergistic effect between Co and Pt ions is discussed in relation to electronic and local atomic structures of the complexes.