Abstract
The synthesis and characterization of a Keggin-type mono-rhenium(V)- substituted polyoxotungstate are described. The dimethylammonium salt [Me2NH2]4[PW11ReVO40] was obtained as analytically pure homogeneous black-purple crystals by reacting mono-lacunary Keggin polyoxotungstate with [ReIVCl6]2- in water, followed by crystallization from acetone at ca. 5 °C. Single-crystal X-ray structural analysis of [PW11ReVO40]4- revealed a monomeric structure with overall Td symmetry. Characterization of [Me2NH2]4[PW11ReVO40] was also accomplished by elemental analysis, magnetic susceptibility, TG/DTA, FTIR, UV-vis, diffuse reflectance (DR) UV-vis, and solution 31P-NMR spectroscopy. Furthermore, [PW11ReVO40]4- and the Dawson-type dirhenium(V)-oxido-bridged polyoxotungstate [O{ReV(OH)(α2-P2W17O61)}2]14- were supported onto anatase TiO2 surface by the precipitation methods using CsCl and Pt(NH3)4Cl2. With these materials, hydrogen evolution from water in the presence of EDTA·2Na (ethylenediamine tetraacetic acid disodium salt) under visible light irradiation (≥400 nm) was achieved.
Highlights
Molecular hydrogen is known to be a clean-burning fuel free of CO2 emissions; it is considered a promising candidate to mitigate the current energy problems [1,2]
[PW11ReVO40]4- (2) as a sensitizer to investigate the influence of molecular structures of rhenium(V)-containing polyoxometalates for hydrogen evolution from water under visible light irradiation
The photocatalytic activities of these materials were demonstrated for hydrogen evolution from water in the presence of EDTA⋅2Na under visible light irradiation (≥400 nm)
Summary
Molecular hydrogen is known to be a clean-burning fuel free of CO2 emissions; it is considered a promising candidate to mitigate the current energy problems [1,2]. Noble-metal/Cr2O3 (core/shell) nanoparticles as co-catalysts [8] These materials are powerful photocatalysts for water splitting under visible light irradiation; research on using other materials as visible-light-responsive photocatalysts still holds considerable interest. The material showed activity for hydrogen evolution from water vapor under visible light irradiation (≥400 and ≥420 nm); the surface silane coupling reagent was decomposed by the visible light irradiation [18]. We focused on using the Keggin-type mono-rhenium(V)-substituted POM [PW11ReVO40]4- (2) as a sensitizer to investigate the influence of molecular structures of rhenium(V)-containing polyoxometalates for hydrogen evolution from water under visible light irradiation. The photocatalytic activities of these materials were demonstrated for hydrogen evolution from water in the presence of EDTA⋅2Na (ethylenediamine tetraacetic acid disodium salt) under visible light irradiation (≥400 nm). The WO6 and internal PO4 groups are represented by white octahedra and yellow tetrahedra, respectively
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