Macromorphological\nControl of Zr-Based Metal–Organic\nFrameworks for Hydrolysis of a Nerve Agent Simulant

Zirconium-based metal–organic frameworks (MOFs)\nhave become\none of the most promising materials for the adsorption and destruction\nof chemical warfare agents. While numerous studies have shown differences\nin reactivity based on MOF topology and postsynthetic modification,\nthe understanding of how modifying MOF macromorphology is less understood.\nMOF xerogels demonstrate modified defect levels and larger porosity,\nwhich increase the number of and access to potential active sites.\nIndeed, UiO-66 and NU-901 xerogels display reaction rates 2 and 3\ntimes higher, respectively, for the hydrolysis of DMNP relative to\ntheir powder morphologies. Upon recycling, MOF-808 xerogel outperforms\nMOF-808 powder, previously noted as the fastest Zr<sub>6</sub> MOF\nfor hydrolysis of organophosphate nerve agents. The increase in reactivity\nis largely driven by a higher external surface area and the introduction\nof mesoporosity to previously microporous materials.