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Issue 33, 2012
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Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance

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Abstract

The photochemical properties of homo- and heterometallic molybdate-based Lindqvist polyoxometalate clusters are investigated in a comparative study and it is shown that vanadium substitution can be used as a facile synthetic tool to optimize the visible light absorption and photocatalytic activity of the cluster. The mono-vanadium substituted unit, [VMo5O19]3− shows light absorption up to 480 nm whereas the light absorption of the molybdate analogue [Mo6O19]2− is mainly in the UV region below 400 nm. The electronic absorption properties of both clusters are further investigated using TD-DFT calculations which show that vanadium incorporation leads to the formation of low-energy O → V LMCT transitions. In comparative photochemical dye decomposition test reactions under UV and Vis irradiation, a higher reactivity is observed for [VMo5O19]3− together with turnover numbers of more than 1600. In addition it is shown that under anaerobic conditions, the photoreaction proceeds faster than in the presence of oxygen, suggesting that oxygen acts as a quencher in one of the photoredox steps.

Graphical abstract: Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance

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Publication details

The article was received on 10 Feb 2012, accepted on 20 Mar 2012 and first published on 22 Mar 2012


Article type: Paper
DOI: 10.1039/C2DT30304C
Citation: Dalton Trans., 2012,41, 9938-9943
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    Metal substitution in a Lindqvist polyoxometalate leads to improved photocatalytic performance

    J. Tucher, Y. Wu, L. C. Nye, I. Ivanovic-Burmazovic, M. M. Khusniyarov and C. Streb, Dalton Trans., 2012, 41, 9938
    DOI: 10.1039/C2DT30304C

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