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    the design of zr metal-organic frameworks in the detection and neutralization of organophosphorus based nerve agents and pesticides

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    moored2022m-1a.pdf (2.259mb)
    date
    2022
    author
    moore, devin scott
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    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.
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    https://knowledgecommons.lakeheadu.ca/handle/2453/5045
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