One Step Backward Is Two Steps Forward: Enhancing the Hydrolysis Rate of UiO-66 by Decreasing [OH-]

The rapid destruction of chemical threats, such as phosphate-based nerve agents, is of considerable current interest. The hydrolysis of the nerve-agent simulant methylparaoxon, as catalyzed by UiO-66 and UiO-67, was examined as a function of pH. Surprisingly, even though typical phosphate ester hydrolysis mechanisms entail nucleophilic attack of the simulant by aqueous hydroxide, the rate of hydrolysis accelerates as the solution pH is lowered. The unexpected behavior is attributed to a pH-dependent composition change followed by ligand substitution at the Zr-6-based node.