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Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats
Published on: June 13, 2018
New functionalized flexible Al-MIL-53-X (X = -Cl, -Br, -CH3, -NO2, -(OH)2) solids: syntheses, characterization,
Shyam Biswas1, Tim Ahnfeldt, Norbert Stock
1Institut für Anorganische Chemie, Christian-Albrechts-Universität, Max-Eyth-Strasse 2, 24118 Kiel, Germany.
Abstract:
Five new flexible functionalized aluminum hydroxo terephthalates [Al(OH)(BDC-X)]·n(guests) (BDC = 1,4-benzene-dicarboxylate; X = -Cl, 1-Cl; -Br, 2-Br; -CH(3), 3-CH(3); -NO(2), 4-NO(2); -(OH)(2), 5-OH(2)) were synthesized under solvothermal conditions. The as synthesized (Al-MIL-53-X-AS) as well as the activated compounds were characterized by X-ray powder diffraction (XRPD), IR spectroscopy, thermogravimetric (TG), and elemental analysis. Activation, that is, removal of unreacted H(2)BDC-X molecules and/or occluded solvent molecules, followed by hydration in air at room temperature, led to the narrow pore (NP) form of the title compounds [Al(OH)(BDC-X)]·n(H(2)O) (Al-MIL-53-X). Thermogravimetric analysis (TGA) and temperature-dependent XRPD (TDXRPD) experiments performed on the NP-form of the compounds indicate high thermal stability in the range 325-500 °C. As verified by N(2), CO(2), or H(2)O sorption measurements, most of the thermally activated compounds exhibit significant microporosity. Similar to pristine Al-MIL-53, the present compounds retain their structural flexibility depending on the nature of guest molecules and temperature, as verified by cell parameter determination from XRPD data. The breathing behavior of the functionalized frameworks upon dehydration-rehydration, investigated by temperature and time-dependent XRPD measurements, differs significantly compared to parent Al-MIL-53.
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