Small Molecules, Big Effects: Tuning Adsorption and Catalytic Properties of Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have emerged as a highly tunable class of porous materials, and in particular, zirconium-based MOFs (Zr-MOFs) have demonstrated the potential to address challenges in a variety of practical applications due to their excellent chemical and thermal stabilities. However, Zr-MOFs are typically synthesized using flammable and toxic organic solvents. An effective, green, scalable route to obtain high-quality Zr-MOFs has yet to be developed as these procedures typically yield Zr-MOFs with relatively lower crystallinities and porosities than those obtained via the former route. Herein, we report the aqueous synthesis of MOF-808, a versatile Zr-MOF, that yields products with high crystallinities and porosities that are comparable to those of solvothermally synthesized MOF-808. We demonstrate that modifying the carboxylic acid-based modulator used in this hydrothermal procedure enables the straightforward tuning of the pore environment in MOF-808. This approach can be leveraged to tune both the water adsorption properties of MOF-808 and the solid-state catalytic performance of MOF-808 toward the hydrolysis of a nerve agent simulant. We anticipate that the insight gained here extends beyond MOF-808 and that it will lead to similar advancements for other Zr-MOFs.