| 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 |
