Fundamental Studies of the Uptake and Diffusion of Sulfur Mustard Simulants within Zirconium-based Metal-Organic Frameworks

dc.contributor.authorSharp, Conor Haysen
dc.contributor.committeechairMorris, John R.en
dc.contributor.committeememberTroya, Diegoen
dc.contributor.committeememberMorris, Amanda J.en
dc.contributor.committeememberKarim, Ayman M.en
dc.description.abstractThe threat of chemical warfare agent (CWA) attacks has persisted into the 21st century due to the actions of terror groups and rogue states. Traditional filtration strategies for soldier protection rely on high surface area activated carbon, but these materials merely trap CWAs through weak physisorption. Metal-organic frameworks (MOFs) have emerged as promising materials to catalyze the degradation of CWAs into significantly less toxic byproducts. The precise synthetic control over the porosity, defect density, and chemical functionality of MOFs offer exciting potential of for use in CWA degradation as well as a wide variety of other applications. Developing a molecular-level understanding of gas-MOF interactions can allow for the rational design of MOFs optimized for CWA degradation. Our research investigated the fundamental interfacial interactions between CWA simulant vapors, specifically sulfur mustard (HD) simulants, and zirconium-based MOFs (Zr-MOFs). Utilizing a custom-built ultrahigh vacuum chamber with infrared spectroscopic and mass spectrometric capabilities, the adsorption mechanism, diffusion energetics, and diffusion kinetics of HD simulants were determined. For 2-chloroethyl ethyl sulfide (2-CEES), a widely used HD simulant, infrared spectroscopy revealed that adsorption within Zr-MOFs primarily proceeded through hydrogen bond formation between 2-CEES and the bridging hydroxyls on the secondary building unit of the MOFs. Through the study of 1-chloropentane and diethyl sulfide adsorption, we determined that 2-CEES forms hydrogen bonds through its chlorine atom likely due to geometric constraints within the MOF pore environment. Temperature-programmed desorption experiments aimed at determining desorption energetics reveal that 2-CEES remain adsorbed within the pores of the MOFs until high temperatures, but traditional methods of TPD analysis fail to accurately measure both the enthalpic and entropic interactions of 2-CEES desorption from a single adsorption site. Infrared spectroscopy was able to measure the diffusion of adsorbates within MOFs by tracking the rate of decrease in overall adsorbate concentrations at several temperatures. The results indicate that 2-CEES diffusion through the pores of the MOFs is a slow, activated process that is affected by the size of the pore windows and presence of hydrogen bonding sites. We speculate that diffusion is the rate limiting step in the desorption of HD simulants through Zr-MOFs at lower temperatures. Stochastic simulations were performed in an attempt to deconvolute TPD data in order to extract desorption parameters. Finally, a combination of vacuum-based and ambient-pressure spectroscopic techniques were employed to study the reaction between 2-CEES and an amine-functionalized MOF, UiO-66-NH2. Although the presence of water adsorbed within UiO 66 NH2 under ambient conditions may assist in the reactive adsorption of 2-CEES, the reaction proceeded under anhydrous conditions.en
dc.description.abstractgeneralChemical warfare agents (CWAs) are some of the most toxic chemicals on the planet and their continued use by terror groups and rogue nations threaten the lives of both civilians and the warfighter. Our work was motivated by a class of high surface area, highly porous materials that have shown the ability to degrade CWAs, specifically mustard gas, into less harmful byproducts. By determining the adsorption mechanism (how and where mustard gas “sticks” to the material), diffusion rates (how quickly mustard gas can travel through the pores of to reach the binding sites), and desorption energies (how strongly mustard gas “sticks” to the binding sites), we can alter the structure of these materials and to efficiently trap mustard gas and render it harmless. In the research described in this dissertation, we examined these fundamental interactions for a series of molecules that mimic the structure of mustard gas. and linear alkanes within several metal-organic frameworks with varying pore size. We observed the size of the pore environment affects the orientation that a given molecule sticks to binding sites as well as how quickly these compounds diffuse through the MOF. While the majority of these studies were conducted in a low-pressure environment that eliminated the presence of gas molecules in the atmosphere, research that exposed a MOF to a mustard gas mimic in an ambient environment demonstrated that gas molecules present in the atmosphere, especially water, can greatly impact the chemical interactions between mustard gas and zirconium-based MOFs.en
dc.description.degreeDoctor of Philosophyen
dc.publisherVirginia Techen
dc.rightsIn Copyrighten
dc.subjectSurface Scienceen
dc.subjectMetal-Organic Frameworksen
dc.subjectChemical Warfare Agentsen
dc.titleFundamental Studies of the Uptake and Diffusion of Sulfur Mustard Simulants within Zirconium-based Metal-Organic Frameworksen
dc.typeDissertationen Polytechnic Institute and State Universityen of Philosophyen
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