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Zhu J, Walsh JJ, Bond AM, et al. Ruthenium metallopolymer: Dawson polyoxomolybdate α-[Mo18O54(SO4)2]4- adduct films: sensitization for visible photoelectrocatalysis. Langmuir. 2012;28(37):13536-41doi: 10.1021/la300886s.
Zhu, J., Walsh, J. J., Bond, A. M., Keyes, T. E., & Forster, R. J. (2012). Ruthenium metallopolymer: Dawson polyoxomolybdate α-[Mo18O54(SO4)2]4- adduct films: sensitization for visible photoelectrocatalysis. Langmuir : the ACS journal of surfaces and colloids, 28(37), 13536-41. https://doi.org/10.1021/la300886s
Zhu, Jie, et al. "Ruthenium metallopolymer: Dawson polyoxomolybdate α-[Mo18O54(SO4)2]4- adduct films: sensitization for visible photoelectrocatalysis." Langmuir : the ACS journal of surfaces and colloids vol. 28,37 (2012): 13536-41. doi: https://doi.org/10.1021/la300886s
Zhu J, Walsh JJ, Bond AM, Keyes TE, Forster RJ. Ruthenium metallopolymer: Dawson polyoxomolybdate α-[Mo18O54(SO4)2]4- adduct films: sensitization for visible photoelectrocatalysis. Langmuir. 2012 Sep 18;28(37):13536-41. doi: 10.1021/la300886s. Epub 2012 Sep 04. PMID: 22812386.
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Langmuir. 2012 Sep 18;28(37):13536-41. doi: 10.1021/la300886s. Epub 2012 Sep 04.

Ruthenium metallopolymer: Dawson polyoxomolybdate α-[Mo18O54(SO4)2]4- adduct films: sensitization for visible photoelectrocatalysis.

Langmuir : the ACS journal of surfaces and colloids

Jie Zhu, James J Walsh, Alan M Bond, Tia E Keyes, Robert J Forster

Affiliations

  1. School of Chemical Science, Dublin City University, Dublin, Ireland.

PMID: 22812386 DOI: 10.1021/la300886s

Abstract

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(18)O(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.

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