Deciphering the Mechanism of Crystallization of UiO‐66 Metal‐Organic Framework

Abstract Zirconium‐containing metal‐organic framework (MOF) with UiO‐66 topology is an extremely versatile material, which finds applications beyond gas separation and catalysis. However, after more than 10 years after the first reports introducing this MOF, understanding of the molecular‐level mechanism of its nucleation and growth is still lacking. By means of in situ time‐resolved high‐resolution mass spectrometry, Zr K‐edge X‐ray absorption spectroscopy, magic‐angle spinning nuclear magnetic resonance spectroscopy, and X‐ray diffraction it is showed that the nucleation of UiO‐66 occurs via a solution‐mediated hydrolysis of zirconium chloroterephthalates, whose formation appears to be autocatalytic. Zirconium‐oxo nodes form directly and rapidly during the synthesis, the formation of pre‐formed clusters and stable non‐stoichiometric intermediates are not observed. The nuclei of UiO‐66 possess identical to the crystals local environment, however, they lack long‐range order, which is gained during the crystallization. Crystal growth is the rate‐determining step, while fast nucleation controls the formation of the small crystals of UiO‐66 with a narrow size distribution of about 200 nanometers.