Macromorphological Control of Zr-Based Metal-Organic Frameworks for Hydrolysis of a Nerve Agent Simulant

Zirconium-based metal-organic frameworks (MOFs) have become one of the most promising materials for the adsorption and destruction of chemical warfare agents. While numerous studies have shown differences in reactivity based on MOF topology and postsynthetic modification, the understanding of how modifying MOF macromorphology is less understood. MOF xerogels demonstrate modified defect levels and larger porosity, which increase the number of and access to potential active sites. Indeed, UiO-66 and NU-901 xerogels display reaction rates 2 and 3 times higher, respectively, for the hydrolysis of DMNP relative to their powder morphologies. Upon recycling, MOF-808 xerogel outperforms MOF-808 powder, previously noted as the fastest Zr₆ MOF for hydrolysis of organophosphate nerve agents. The increase in reactivity is largely driven by a higher external surface area and the introduction of mesoporosity to previously microporous materials.