Synthesis, characterization and sorption properties of NH2-MIL-47

Karen Leus; Sarah Couck; Matthias Vandichel; Gauthier Vanhaelewyn; Ying-Ya Liu; Guy B. Marin; Isabel Van Driessche; Diederik Depla; Michel Waroquier; Veronique Van Speybroeck; Joeri F. M. Denayer; Pascal Van Der Voort

doi:10.1039/C2CP42137B

Synthesis, characterization and sorption properties of NH₂-MIL-47†

Karen Leus,^a Sarah Couck,^b Matthias Vandichel,^c Gauthier Vanhaelewyn,^d Ying-Ya Liu,^a Guy B. Marin,^e Isabel Van Driessche,^f Diederik Depla,^d Michel Waroquier,^c Veronique Van Speybroeck,^c Joeri F. M. Denayer^b and Pascal Van Der Voort*^a

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^a Department of Inorganic and Physical Chemistry, Center for Ordered Materials, Organometallics and Catalysis, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium
E-mail: pascal.vandervoort@ugent.be
Tel: +32 964 44 42

^b Vrije Universiteit Brussel, Department of Chemical Engineering, Belgium

^c Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052 Zwijnaarde, Belgium

^d Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, 9000 Ghent, Belgium

^e Laboratory for Chemical Technology, Ghent University, Krijgslaan 281-S5, 9000 Ghent, Belgium

^f Department of Inorganic and Physical Chemistry, Ghent University, Sol-gel Center for Research on Inorganic Powders and Thin films Synthesis (SCRiPTS), Krijgslaan 281-S3, 9000 Gent, Belgium

Abstract

An amino functionalized vanadium-containing Metal Organic Framework, NH₂-MIL-47, has been synthesized by a hydrothermal reaction in an autoclave. Alternatively, a synthesis route via microwave enhanced irradiation has been optimized to accelerate the synthesis. The NH₂-MIL-47 exhibits the same topology as MIL-47, in which the V center is octahedrally coordinated. After an exchange procedure in DMF the V^+III center is oxidized to V^+IV, which is confirmed by EPR and XPS measurements. The CO₂ and CH₄ adsorption properties have been evaluated and compared to MIL-47, showing that both MOFs have an almost similar adsorption capacity and affinity for CO₂. DFT-based molecular modeling calculations were performed to obtain more insight into the adsorption positions for CO₂ in NH₂-MIL-47. Furthermore our calculated adsorption enthalpies agree well with the experimental values.

Physical Chemistry Chemical Physics

Synthesis, characterization and sorption properties of NH₂-MIL-47†

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Synthesis, characterization and sorption properties of NH₂-MIL-47

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Physical Chemistry Chemical Physics