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

Research output: Contribution to journalArticle

108 Citations (Scopus)

Abstract

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
Volume6
Issue number4
DOIs
Publication statusPublished - Apr 1 2015

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Hydrolysis
Esters
Phosphates
Phosphoranes
Derivatives
Catalysts
Proton transfer
Decontamination
Functional groups
Toxicity
Skin
Hydrogen bonds

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

Exploiting parameter space in MOFs : A 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2. / Katz, Michael J.; Moon, Su Young; Mondloch, Joseph E.; Beyzavi, M. Hassan; Stephenson, Casey J.; Hupp, Joseph T; Farha, Omar K.

In: Chemical Science, Vol. 6, No. 4, 01.04.2015, p. 2286-2291.

Research output: Contribution to journalArticle

Katz, MJ, Moon, SY, Mondloch, JE, Beyzavi, MH, Stephenson, CJ, Hupp, JT & Farha, OK 2015, 'Exploiting parameter space in MOFs: A 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2', Chemical Science, vol. 6, no. 4, pp. 2286-2291. https://doi.org/10.1039/c4sc03613a
Katz, Michael J. ; Moon, Su Young ; Mondloch, Joseph E. ; Beyzavi, M. Hassan ; Stephenson, Casey J. ; Hupp, Joseph T ; Farha, Omar K. / Exploiting parameter space in MOFs : A 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2. In: Chemical Science. 2015 ; Vol. 6, No. 4. pp. 2286-2291.
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