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

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Publication date 2012
Author Car Pierre-Emmanuel, Guttentag Miguel, Baldridge Kim K, Alberto Roger, Patzke Greta R,
Project Homogeneous photocatalytic water splitting
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Original article (peer-reviewed)

Journal Green Chemistry
Volume (Issue) 14(6)
Page(s) 1680 - 1688
Title of proceedings Green Chemistry
DOI 10.1039/c2gc16646a


The trivacant triruthenium-substituted polyoxometalate α-K 6Na[{Ru3O3(H2O)Cl 2}(SiW9O34)]·17H2O (1) and two sandwich-type Co- and Ni-containing silicotungstates K11Na 1[M4(H2O)2(SiW9O 34)2]·nH2O (M = Co2+, Ni 2+) (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 (POM-PS). These POM-PS complexes are formed in the initial phase of the reaction, and they prevent POM decomposition into colloidal oxide catalysts. This journal is © The Royal Society of Chemistry.