Water splitting with polyoxometalate-treated photoanodes: enhancing performance through sensitizer design

Visible light driven water oxidation has been demonstrated at near-neutral pH using photoanodes based on nanoporous films of TiO₂, polyoxometalate (POM) water oxidation catalyst [{Ru₄O₄(OH)₂(H₂O)₄}(γ-SiW₁₀O₃₆)₂]^10- (1), and both known photosensitizer [Ru(bpy)₂(H₄dpbpy)]²⁺ (P2) and the novel crown ether functionalized dye [Ru(5-crownphen)₂(H₂dpbpy)](H). Both triads, containing catalyst 1, and catalyst-free dyads, produce O₂ with high faradaic efficiencies (80 to 94%), but presence of catalyst enhances quantum yield by up to 190% (maximum 0.39%). New sensitizer H absorbs light more strongly than P2, and increases O₂ quantum yields by up to 270%. TiO₂-2 based photoelectrodes are also more stable to desorption of active species than TiO₂-P2: losses of catalyst 1 are halved when pH > TiO₂ point-of-zero charge (pzc), and losses of sensitizer reduced below the pzc (no catalyst is lost when pH < pzc). For the triads, quantum yields of O₂ are higher at pH 5.8 than at pH 7.2, opposing the trend observed for 1 under homogeneous conditions. This is ascribed to lower stability of the dye oxidized states at higher pH, and less efficient electron transfer to TiO₂, and is also consistent with the 4^th1-to-dye electron transfer limiting performance rather than catalyst TOF_max. Transient absorption reveals that TiO₂-2-1 has similar 1^st electron transfer dynamics to TiO₂-P2-1, with rapid (ps timescale) formation of long-lived TiO₂(e^-)-2-1(h⁺) charge separated states, and demonstrates that metallation of the crown ether groups (Na⁺/Mg²⁺) has little or no effect on electron transfer from 1 to 2. The most widely relevant findings of this study are therefore: (i) increased dye extinction coefficients and binding stability significantly improve performance in dye-sensitized water splitting systems; (ii) binding of POMs to electrode surfaces can be stabilized through use of recognition groups; (iii) the optimal homogeneous and TiO₂-bound operating pHs of a catalyst may not be the same; and (iv) dye-sensitized TiO₂ can oxidize water without a catalyst.