期刊
ACS MATERIALS AU
卷 2, 期 4, 页码 505-515出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsmaterialsau.2c00025
关键词
heterogeneous photocatalysis; homogeneous photocatalysis; polyoxometalate; molecular metal oxide; water oxidation catalysis; co-catalyst; cluster; APTES; surface modification
资金
- Austrian Science Fund (FWF)
- University of Vienna
This study successfully heterogenized a molecular all-inorganic polyoxometalate catalyst onto a TiO2 surface, creating a novel heterogeneous photosystem for efficient and stable light-driven water oxidation. The hybrid photosystem exhibited constant catalytic rate for at least 10 hours, demonstrating the stability provided by TiO2 and its role as a photosensitizer.
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 [(CoCoII)-Co-III(H2O)W11O39](7-) ({(CoCoW11)-Co-III-W-II}) 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 {(CoCoW11)-Co-III-W-II}-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 {(CoCoW11)-Co-III-W-II}-APTES-TiO2 performs as an active light-driven WOC, wherein {(CoCoW11)-Co-III-W-II} 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 {(CoCoW11)-Co-III-W-II}-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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