Nanoscaled M-MOF-74 Materials Prepared at Room Temperature

This paper describes the preparation and characterization of nanoscaled M-MOF-74/CPO-27-M (M = Mg, Mn, Co, Ni, and Zn) materials at room temperature. Some of the so-formed crystals are the smallest ones of any metal–organic framework (MOF) material (and, to the best of our knowledge, of any microporous material) ever reported. They are at the limit of being able to diffract, particularly those forming the Co- and Ni-MOF-74 samples. Consequently, unequivocal identification as the crystalline MOF-74 phase was deduced by combining other characterization techniques rather than powder X-ray diffraction. These small crystals are unstable as isolated ones, so they form steady and robust aggregates, whose mechanical properties strongly depend on the crystal size. The particles that result from the “fusion” of nanocrystals smaller than 10 nm (more properly denoted as nanodomains) could not be disaggregated by conventional ultrasonic and graining techniques. On the contrary, agglomerates of crystals larger than 10 nm are dissociable in discrete crystals. It allows characterizing Zn-MOF-74 nanocrystals by advanced electron microscopy methods. Cs-corrected scanning transmission electron microscopy (STEM) provided, for the first time, “quasi” atomic resolution images of MOFs, which are especially unstable under electronic radiation. The magnitude of the crystal size of M-MOF-74 is tentatively associated with the solubility of the metal source.