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Issue 6, 2012
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Synthesis and characterization of open and sandwich-type polyoxometalates reveals visible-light-driven water oxidationvia POM-photosensitizer complexes

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Abstract

The trivacant triruthenium-substituted polyoxometalate α-K6Na[{Ru3O3(H2O)Cl2}(SiW9O34)]·17H2O (1) and two sandwich-type Co- and Ni-containing silicotungstates K11Na1[M4(H2O)2(SiW9O34)2nH2O (M = Co2+, Ni2+) (2, 3) based on the same Keggin-type building block were obtained through variation of a solution-based protocol. All compounds were investigated with respect to their performance as visible-light-driven water oxidation catalysts (WOCs). Analytical characterizations and photocatalytic reactivity of (1) are correlated with results of B97D/Def2-TZVP computation. The WOC activity of (1) and (2) was found to arise from their immobilization into a recyclable POM–photosensitizer complex (POMPS). These POM–PS complexes are formed in the initial phase of the reaction, and they prevent POM decomposition into colloidal oxide catalysts.

Graphical abstract: Synthesis and characterization of open and sandwich-type polyoxometalates reveals visible-light-driven water oxidation via POM-photosensitizer complexes

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Supplementary files

Article information


Submitted
22 Dec 2011
Accepted
19 Mar 2012
First published
05 Apr 2012

Green Chem., 2012,14, 1680-1688
Article type
Paper

Synthesis and characterization of open and sandwich-type polyoxometalates reveals visible-light-driven water oxidation via POM-photosensitizer complexes

P. Car, M. Guttentag, K. K. Baldridge, R. Alberto and G. R. Patzke, Green Chem., 2012, 14, 1680
DOI: 10.1039/C2GC16646A

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