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<div class="csl-entry">Nandan, S. P., Gumerova, N., Schubert, J. S., Saito, H., Rompel, A., Cherevan, A., & Eder, D. (2022). Immobilization of a [Co<sup>I</sup><sup>I</sup><sup>I</sup>Co<sup>I</sup><sup>I</sup>(H₂O)W₁₁O₃₉]<sup>7</sup><sup>−</sup> Polyoxoanion for the Photocatalytic Oxygen Evolution Reaction. <i>ACS Materials Au</i>, <i>2</i>(4), 505–515. https://doi.org/10.1021/acsmaterialsau.2c00025</div>
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dc.identifier.uri
http://hdl.handle.net/20.500.12708/81176
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dc.description.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.
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dc.language.iso
en
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dc.publisher
American Chemical Society (ACS)
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dc.relation.ispartof
ACS Materials Au
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dc.subject
APTES
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dc.subject
cluster
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dc.subject
co-catalyst
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dc.subject
heterogeneous photocatalysis
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dc.subject
homogeneous photocatalysis
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dc.subject
molecular metal oxide
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dc.subject
polyoxometalate
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dc.subject
surface modification
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dc.subject
water oxidation catalysis
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dc.title
Immobilization of a [CoᴵᴵᴵCoᴵᴵ(H₂O)W₁₁O₃₉]⁷⁻ Polyoxoanion for the Photocatalytic Oxygen Evolution Reaction