Herein, we report two new COOH-functionalized metal-organic frameworks (MOFs) of composition [M6 O4 (OH)6 (PMA)2 (H2 PMA)]×H2 O, M=Zr, Hf), denoted CAU-61, synthesized by using pyromellitic acid (H4 PMA), a tetracarboxylic acid, as the linker and acetic acid as the solvent. The structure was determined from powder X-ray diffraction data and one-dimensional inorganic building units are connected through tetracarboxylate as well as dicarboxylate linker molecules, resulting in highly stable microporous framework structures with limiting and maximum pore diameter of ∼3.6 and ∼5.0 Å, respectively, lined with -COOH groups. Thermal stabilities of up to 400 °C in air, chemical stability in water at pH 1 to 12 and water uptake of 17 mol/mol prompted us to study the proton exchange of the μ2 -OH, μ3 -OH of the IBU and -COOH groups of the linker by titration with LiOH. Comparison of the pKa values with three UiO-66 derivatives confirms distinct pKa value ranges and trends for the different acidic protons. Furthermore, the preparation of Zr-CAU-61 membranes and first results on permeation of dyes and ions in aqueous solutions are presented.
Keywords: LiOH titration; acidity; metal-organic framework; osmosis; zirconium.
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.