Encapsulation of the vanadium substituted Keggin polyoxometalates α-PVW11O404- and α-PV2W10O405- in HKUST-1

Two POM@MOF hybrid materials composed of a copper-based metal-organic framework (MOF) [Cu3(C9H3O6)2(H2O)3]n (HKUST-1) encapsulating vanadium-substituted Keggin polyoxometalates (POM), [α-PVW11O40]4- (PVW11) and [α-PV2W10O40]5- (PV2W10), were prepared and characterized. PVW11@HKUST-1 and PV2W10@HKUST-1 were synthesized hydrothermally by self-assembly of HKUST-1 in the presence of the preformed POMs, [α-PVW11O40]4- and [α-PV2W10O40]5-, respectively. The two POM@MOF composites were characterized by X-ray diffraction, TGA, BET surface area analysis and FT-IR and Raman spectroscopy. The electronic structure of the POM@MOF materials and their respective constituents is surveyed using solid state UV-vis reflectance spectroscopy. The UV-vis spectra order the oxidizing strength of the POM constituents ([α-PV2W10O40]5- > [α-PVW11O40]4-) and reveal the distinct electronic structure of the POM@MOF materials obtained by synthetic encapsulation of mono- and di-vanadium substituted Keggin polyoxotungstates in HKUST-1.Two POM@MOF hybrid materials composed of a copper-based metal-organic framework (MOF) [Cu3(C9H3O6)2(H2O)3]n (HKUST-1) encapsulating vanadium-substituted Keggin polyoxometalates (POM), [α-PVW11O40]4- (PVW11) and [α-PV2W10O40]5- (PV2W10), were prepared and characterized. PVW11@HKUST-1 and PV2W10@HKUST-1 were synthesized hydrothermally by self-assembly of HKUST-1 in the presence of the preformed POMs, [α-PVW11O40]4- and [α-PV2W10O40]5-, respectively. The two POM@MOF composites were characterized by X-ray diffraction, TGA, BET surface area analysis and FT-IR and Raman spectroscopy. The electronic structure of the POM@MOF materials and their respective constituents is surveyed using solid state UV-vis reflectance spectroscopy. The UV-vis spectra order the oxidizing strength of the POM constituents ([α-PV2W10O40]5- > [α-PVW11O40]4-) and reveal the distinct electronic structure of the POM@MOF materials obtained by synthetic encapsulation of mono- and di-vanadium substituted Keggin polyoxotungstates in HKUST-1.