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- W4281487966 abstract "The ongoing transition to renewable energy sources and the implementation of artificial photosynthetic setups call for an efficient and stable water oxidation catalyst (WOC). Here, we heterogenize a molecular all-inorganic [CoIIICoII(H2O)W11O39]7- ({CoIIICoIIW11}) Keggin-type polyoxometalate (POM) onto a model TiO2 surface, employing a 3-aminopropyltriethoxysilane (APTES) linker to form a novel heterogeneous photosystem for light-driven water oxidation. The {CoIIICoIIW11}-APTES-TiO2 hybrid is characterized using a set of spectroscopic and microscopic techniques to reveal the POM integrity and dispersion to elucidate the POM/APTES and APTES/TiO2 binding modes as well as to visualize the attachment of individual clusters. We conduct photocatalytic studies under heterogeneous and homogeneous conditions and show that {CoIIICoIIW11}-APTES-TiO2 performs as an active light-driven WOC, wherein {CoIIICoIIW11} acts as a stable co-catalyst for water oxidation. In contrast to the homogeneous WOC performance of this POM, the heterogenized photosystem yields a constant WOC rate for at least 10 h without any apparent deactivation, demonstrating that TiO2 not only stabilizes the POM but also acts as a photosensitizer. Complementary studies using photoluminescence (PL) emission spectroscopy elucidate the charge transfer mechanism and enhanced WOC activity. The {CoIIICoIIW11}-APTES-TiO2 photocatalyst serves as a prime example of a hybrid homogeneous-heterogeneous photosystem that combines the advantages of solid-state absorbers and well-defined molecular co-catalysts, which will be of interest to both scientific communities and applications in photoelectrocatalysis and CO2 reduction." @default.
- W4281487966 created "2022-05-26" @default.
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- W4281487966 date "2022-05-25" @default.
- W4281487966 modified "2023-10-18" @default.
- W4281487966 title "Immobilization of a [Co<sup>III</sup>Co<sup>II</sup>(H<sub>2</sub>O)W<sub>11</sub>O<sub>39</sub>]<sup>7–</sup> Polyoxoanion for the Photocatalytic Oxygen Evolution Reaction" @default.
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- W4281487966 doi "https://doi.org/10.1021/acsmaterialsau.2c00025" @default.
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