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 SnO 2 /TiO 2 core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO 3 H 2 ) 2 bpy) 2 Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH 2 )] 4+ ([Ru a II -Ru b II -OH 2 ] 4+ , combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO 2 shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al 2 O 3 or TiO 2 overlayers. Illumination of the resulting fluorine-doped tin oxide (FTO)|SnO 2 /TiO 2 |-[Ru a II -Ru b II -OH 2 ] 4+ (Al 2 O 3 or TiO 2 ) 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 H 2 and O 2 . The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO 2 /TiO 2 core/shell compared with nano ITO/TiO 2 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.