The Modulating Effect of Ethanol on the Morphology of a Zr-based Metal-Organic Framework under Room Temperature in the Cosolvent System

We report that ethanol, used together with water, plays a crucial role in tuning the structures of a zirconium-based Metal-Organic Framework, the 12-connected MOF-801, and the possible mechanisms of this modulating effect. By employing the cosolvent system of ethanol and water just under room temperature without the presence of a monotopic carboxylic acid as the modulator, MOF-801 in various morphologies of different sizes can be synthesized. The linear correlation between the ethanol/water ratio and the crystal sizes is also demonstrated. The growth mechanism is mainly explained by ethanol’s binding with the metal ion clusters and the Marangoni Flow Effect. Ethanol competes with the linker molecules in coordinating with the Zr metal clusters, a role similar to that of the modulators. The Marangoni Flow Effect, which dominates at a certain solvent ratio, further promotes the 1-D alignment of the MOF-801 crystals.