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.

Organophosphorus nerve agents are amongst the most toxic chemicals known to human beings. 9 They interfere with the central nervous system, resulting in continuous muscle contractions, 10 paralysis and even death. Prohibition by many countries around the world cannot disguise the 11 remaining presence of nerve agents in stockpile storage and governmental deployment, 12 highlighting the dire need for an efficient catalyst to degrade and detoxify nerve agents by 13 hydrolysis. Metal-organic frameworks (MOFs) have raised a few eyebrows for their permanent 14 porosity, precise tunability, and lasting stability. Modern Reticular Chemistry fosters the design and 15 synthesis of well-defined crystalline MOFs with open Lewis acidic metal sites that can catalytically 16 hydrolyze nerve agents both in aqueous solution and in solid state systems, unveiling unparalleled 17 potential for MOF-based personal protection gears. In this review, a summary of the representative 18 catalytically active MOFs in nerve agent hydrolysis is discussed. MOFs are categorized by their 19 reticular structure, emphasizing the capability and mechanistic insights of each single MOF in nerve 20 agent hydrolysis. The author’s perspective on the current challenges and future directions of MOF- 21 based catalysts in real-world protection applications is also provided, which hopefully could shed some 22 light on the future development of commercially available MOF protection suits.