The use of electropolymerization to prepare electrocatalytically and photocatalytically active electrodes for water oxidation is described. Electropolymerization of the catalyst Ru(II)(bda)(4-vinylpyridine)2 (bda=2,2'-bipyridine-6,6'-dicarboxylate) on planar electrodes results in films containing semirigid polymer networks. In these films there is a change in the water oxidation mechanism compared to the solution analogue from bimolecular to single-site. Electro-assembly construction of a chromophore-catalyst structure on mesoporous, nanoparticle TiO2 films provides the basis for a dye-sensitized photoelectrosynthesis cell (DSPEC) for sustained water splitting in a pH 7 phosphate buffer solution. Photogenerated oxygen was measured in real-time by use of a two-electrode cell design.
Keywords: electropolymerization; photoelectrochemistry; proton-coupled electron transfer; solar fuels; water oxidation.
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