Adjusting the Stability of Metal–Organic Frameworks under Humid Conditions by Ligand Functionalization

The practical use of metal–organic frameworks (MOFs) in applications ranging from adsorption separations to controlled storage and release hinges on their stability in humid or aqueous environments. The sensitivity of certain MOFs under humid conditions is well-known, but systematic studies of water adsorption properties of MOFs are lacking. This information is critical for developing design criteria for directing future synthesis efforts. The goal of this work is to understand the influence of the extent of Zn–O bond shielding on the relative stabilities of MOFs belonging to same family of isostructural, noncatenated pillared MOFs [Zn(L)(DABCO)₀.₅], where L is the functionalized BDC (1,4-benzenedicarboxylic acid) linker. The different extent of Zn–O bond shielding is provided by incorporating a broad range of functional groups on the BDC ligand. The resulting MOFs have varying surface areas, pore sizes, and pore volumes. Stability is assessed through water vapor adsorption isotherms combined with powder X-ray diffraction (PXRD) experiments and surface area analyses. Our study demonstrates that integration of polar functional groups (e.g., nitro, bromo, chloro, hydroxy, etc.) on the dicarboxylate linker renders these MOFs water unstable compared to the parent MOF as these polar functional groups have a negative shielding effect; i.e., they facilitate hydrolysis of the Zn–O bond. On the other hand, placing nonpolar groups (e.g., methyl) on the BDC ligand results in structurally robust MOFs because the Zn–O bond is effectively shielded from attack by water molecules. Therefore, the anthracene- and tetramethyl-BDC MOFs do not lose crystallinity or surface area after water exposure, in spite of the large amount of water adsorption due to capillary condensation at ∼20% relative humidity (RH). This has been observed rarely in the MOF literature. The results of this work show that by ligand functionalization it is possible to adjust the water stability of a pillared MOF in both the positive and negative directions and, thus, provide an important step toward understanding the water adsorption behavior of MOFs.