GREEN SYNTHESIS OF ZIRCONIUM-MOFs

The synthesis of Zr-MOFs under green, industrially feasible conditions was investigated. Two new compounds with bcu-topology and the fluorinated analogue of UiO-66 exhibiting fcu-topology were obtained and characterised. All products exhibit permanent porosity. In the bcu-frameworks the interaction with sulfate anions apparently induces an unusual eightfold connectivity of the Zr cluster. Access the research article here.

DETAILED STRUCTURE ANALYSIS OF ATOMIC POSITIONS AND DEFECTS IN ZIRCONIUM METAL-ORGANIC FRAMEWORKS

We report the structure of the Zr metal–organic frameworks (MOFs) UiO-66 and UiO-67 to very fine detail using synchrotron single-crystal X-ray diffraction and the synthesis method used to obtain single crystals. Zr terephthalate MOF UiO-66 is known to have missing linkers, and the nature of these are shown to be coordinating water and solvent molecules. Single crystals of the isoreticular material UiO-67 does not show such missing linker defects. Access the research article here.

TUNED TO PERFECTION: IRONING OUT THE DEFECTS IN METAL-ORGANIC FRAMEWORKS UiO-66

This systematic study has demonstrated the dramatic yet logical impact that the synthesis conditions can have on the properties of UiO-66. Seven potential pitfalls regarding sample ideality were investigated, affording the conclusion that the material systematically becomes more “ideal” when the BDC:Zr ratio and/or synthesis temperature are increased. Such gravitation toward ideality makes sense when one notes that linker deficiencies are the underlying cause of the majority of pitfalls. We suggest that increasing the synthesis temperature and/or BDC:Zr ratio shifts the solution equilibrium in favor of BDC-Zr bonds, aiding the “ironing out” of linker deficiencies. This approach ultimately yields “ideal” UiO-66 with unsurpassed thermal stability when the synthesis is performed with a 2:1 BDC:Zr ratio at 220 °C. Access the research article here.

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