A Green, Solvent-Free Route to Functionalised Metal-Organic Frameworks with UiO-66 Topology

We report a solvent-free procedure for the high-yield synthesis of metal-organic frameworks of UiO-66 topology starting from a range of commercial Zr(IV) precursors and various substituted dicarboxylic linkers. The syntheses are carried out by simply grinding the reagents in the presence of a small volume of acetic acid as modulator, followed by incubation at either room temperature or 120 °C. Use of a ball mill for the grinding step is demonstrated to enable facile scale up of the synthesis. High acidity of the linker is found to be a crucial factor in affording materials of quality comparable to that of products obtained in solvo- or hydrothermal conditions.