| dc.description.abstract | Organophosphates are ubiquitous in uses ranging from chemical warfare agents
(CWA’s) to detergents. In between these two extreme uses lie organophosphorus-based
agrichemicals, primarily pesticides, which are applied in multi-tonne amounts each year.
Metal-organic frameworks, especially the UiO-6x family, are known to interact, sequester,
and/or break down organophosphate nerve gases.
This thesis presents the synthesis and characterization of UiO-6x MOFs,
comparing standing solvothermal with microwave methods, which appear (by powder Xray diffraction, X-ray photoelectron spectroscopy, and solid-state nuclear magnetic
resonance (SS-NMR) analysis) to give equally high-quality products. Preparation of the
UiO-6x MOFs were conducted using 1 molar equivalent of ZrCl4 to 1 equivalent of organic
ligand in the presence of equal volumes of dimethyl formamide (DMF) and glacial acetic
acid (GAA) for both solvothermal and microwave methods. Yields ranged from 41-63%
for our synthesized MOFs (UiO-66, UiO-67 and UiO-67-bipy).
The prepared MOFs are then reacted with organophosphate nerve agent
simulants and agrichemicals in reactions followed by GC or HPLC; it appears that the
studied agrichemicals are less-reactive than their chemical warfare agent equivalents
with only (2-chloroethyl) phosphonic acid and glyphosate showing reactivity with UiO-67
and UiO-66 respectively whereas UiO-67-bipy was shown to nearly completely
degrade/sequester dimethyl methylphosphonate. Also presented are preliminary SSNMR spectra on UiO-66 post-reaction with glyphosate. The line-broadening and
restricted rotation that occurs on the combined spectrum suggests the pesticide is
incorporated whole into the MOF without degrading. | en_US |
