Effect of Synthesis Conditions on Formation Pathways of Metal Organic Framework (MOF-5) Crystals

Metal Organic Frameworks (MOFs) represent a class of nanoporous crystalline materials with far reaching potential in gas storage, catalysis, and medical devices. We investigated the effects of synthesis process parameters on production of MOF-5 from terephthalic acid and zinc nitrate in diethylformamide. Under favorable synthesis conditions, we systematically mapped a solid formation diagram in terms of time and temperature for both stirred and unstirred conditions. The synthesis of MOF-5 has been previously reported as a straightforward reaction progressing from precursor compounds in solution directly to the final MOF-5 solid phase product. However, we show that the solid phase formation process is far more complex, invariably transferring through metastable intermediate crystalline phases before the final MOF-5 phase is reached, providing new insights into the formation pathways of MOFs. We also identify process parameters suitable for scale-up and continuous manufacturing of high purity MOF-5.