Considering the requirements for the commercial production of metal-organic frameworks (MOFs), we investigated the aqueous synthesis of zirconium MOFs. A highly versatile route was identified employing ZrOCl 2 ·8H 2 O, H 2 O, acetic acid and the respective linker molecule as starting materials. These synthesis conditions are suitable to obtain zirconium MOFs with different topologies like UiO-66-(OH) 2 , zirconium fumarate, zirconium mesaconate, DUT-67 or MOF-808 with synthesis times of 1 to 5 h under microwave irradiation. The scalability of the synthesis of zirconium fumarate was demonstrated [a]

Metal-organic frameworks of general composition [M(OH)(O)(PDC)(Cl)(HO)] with M = Zr, Ce, Hf; PDC = 2,5-pyridinedicarboxylate and 0 ≤ x ≤ 2 were obtained under reflux using formic, nitric or acetic acid as an additive. Rietveld refinements carried out using a fixed occupancy of the linker molecules according to the results of thermogravimetric measurements confirmed that the MOFs crystallize in the UiO-66 type structure and demonstrate that the structural models describe the data well. Further characterization was carried out by NMR spectroscopy, thermogravimetric analysis, Zr K-edge EXAFS- and Ce L-edge XANES measurements. To highlight the influence of the additional nitrogen atom of the pyridine ring, luminescence and vapour sorption measurements were carried out. The hydrophilisation of the MOFs was shown by the adsorption of water at lower p/p (<0.2) values compared to the corresponding BDC-MOFs (0.3). For water and methanol stability cycling adsorption experiments were carried out to evaluate the MOFs as potential adsorbents in heat transformation applications.

A new, microporous Zr-MOF was obtained using 2,5-pyrazinedicarboxylic acid (HPzDC). The linker leads to the formation of a new 1D inorganic building unit composed of μ-OH bridged {ZrO(OH)} clusters which are arranged in a hexagonal array and connected by the PzDC ions. The structure was determined from powder X-ray diffraction data.

Heterogeneous palladium single-site MOF catalysts for the oxidative coupling of arenes via C–H/C–H: superior TONs due to active site isolation.