Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell.

A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO2/TiO2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore-catalyst assembly. The assembly, [(4,4'-(PO3H2)2bpy)2Ru(4-Mebpy-4'-bimpy)Ru(tpy)(OH2)](4+) ([Ru(a) (II)-Ru(b) (II)-OH2](4+), combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al2O3 or TiO2 overlayers. Illumination of the resulting fluorine-doped tin oxide (FTO)|SnO2/TiO2|-[Ru(a) (II)-Ru(b) (II)-OH2](4+)(Al2O3 or TiO2) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H2 and O2. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO2/TiO2 core/shell compared with nanoITO/TiO2 with the same assembly results in photocurrent enhancements of ∼ 5. Systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm(2) with 445-nm, ∼ 90-mW/cm(2) illumination in a phosphate buffer at pH 7.