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Zhu J.;Walsh J.;Bond A.;Keyes T.;Forster R.
Ruthenium metallopolymer: Dawson polyoxomolybdate α-[Mo 18O 54(SO 4) 2] 4- adduct films: Sensitization for visible photoelectrocatalysis
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Thin films of the adduct formed from the electrostatic association of the metallopolymer, [Ru(bpy) 2(PVP) 10] 2+, and the Dawson polyoxomolybdate α-[Mo 18O 54(SO 4) 2] 4-, POMo, have been formed on ITO electrodes using an alternate immersion approach. The Ru/POMo ratio is 4.5:1, which exceeds the 2:1 ratio expected on the basis of the charges of the Ru 2+ and POMo 4- building blocks. This behavior arises because of the polymeric character of the cation. In the presence of a substrate that has an abstractable proton such as benzyl alcohol, these ruthenium-sensitized polyoxomolybdate films generate significant photocurrents under visible irradiation. Significantly, increasing the surface coverage of the adduct from 1.4 × 10 -10 to 8.1 × 10 -10 mol cm -2 does not measurably increase the photocurrent observed. Scan-rate-dependent cyclic voltammetry reveals that the rate of homogeneous charge transport through the film is slow, which most likely results in only a fraction of the film thickness being active for photoelectrocatalysis. The photocurrent increases markedly when the driving force for the oxidation of POMo 5-, created by the photoelectrocatalytic oxidation of benzyl alcohol, is increased. This result is consistent with the dynamics of heterogeneous electron transfer being centrally important to the regeneration of the photoelectrocatalyst. A system in which the surface coverage and applied overpotential are optimized produces a photocurrent density of 190 ± 18 nA cm -2 under 480 ± 5 nm irradiation. © 2012 American Chemical Society.
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