Exploiting parameter space in MOFs: A 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2

Michael J. Katz, Su Young Moon, Joseph E. Mondloch, M. Hassan Beyzavi, Casey J. Stephenson, Joseph T. Hupp, Omar K. Farha

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The hydrolysis of nerve agents is of primary concern due to the severe toxicity of these agents. Using a MOF-based catalyst (UiO-66), we have previously demonstrated that the hydrolysis can occur with relatively fast half-lives of 50 minutes. However, these rates are still prohibitively slow to be efficiently utilized for some practical applications (e.g., decontamination wipes used to clean exposed clothing/skin/vehicles). We thus turned our attention to derivatives of UiO-66 in order to probe the importance of functional groups on the hydrolysis rate. Three UiO-66 derivatives were explored; UiO-66-NO2 and UiO-66-(OH)2 showed little to no change in hydrolysis rate. However, UiO-66-NH2 showed a 20 fold increase in hydrolysis rate over the parent UiO-66 MOF. Half-lives of 1 minute were observed with this MOF. In order to probe the role of the amino moiety, we turned our attention to UiO-67, UiO-67-NMe2 and UiO-67-NH2. In these MOFs, the amino moiety is in close proximity to the zirconium node. We observed that UiO-67-NH2 is a faster catalyst than UiO-67 and UiO-67-NMe2. We conclude that the role of the amino moiety is to act as a proton-transfer agent during the catalytic cycle and not to hydrogen bond or to form a phosphorane intermediate. This journal is

Original languageEnglish
Pages (from-to)2286-2291
Number of pages6
JournalChemical Science
Issue number4
Publication statusPublished - Apr 1 2015


ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Katz, M. J., Moon, S. Y., Mondloch, J. E., Beyzavi, M. H., Stephenson, C. J., Hupp, J. T., & Farha, O. K. (2015). Exploiting parameter space in MOFs: A 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2. Chemical Science, 6(4), 2286-2291. https://doi.org/10.1039/c4sc03613a