Fundamental Investigations of Hazardous Gas Uptake and Binding in Metal-Organic Frameworks and Polyurethane Films

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Virginia Tech


The advancements of chemists, engineers, and material scientists has yielded an enormous and diverse library of high-performance materials with varying chemical and physical properties that can be used in a wide array of applications. A molecular-level understanding of the nature of gas–surface interactions is critical to the development of next generation materials for applications such as gas storage and separation, chemical sensing, catalysis, energy conversion, and protective coatings. Quartz crystal microbalance (QCM) and in situ infrared (IR) spectroscopic techniques were employed to probe how topological features of a material as well as structural differences of the analytes affect gas sorption. Detailed studies of the interactions of three categories of molecules: aromatic hydrocarbons, triatomic ambient gases, and chemical warfare agents, with metal-organic frameworks (MOFs) and polyurethane coatings were conducted to build structure–property relationships for the nature and energetics of gas sorption within each material. Differences in the molecular structure of the guest compounds were found to greatly influence how, and to what extent each molecule interacts with the MOF or polyurethane film. Specifically, IR studies revealed that transport of aromatic compounds within the zirconium-based MOF, UiO-66 was limited by steric restrictions as molecules passed through small triangular apertures within the pore environment of the MOF. In contrast, the smaller triatomic molecules, CO2, SO2, and NO2, were able to pass freely through the MOF apertures and instead reversibly adsorbed inside the MOF cavities. Specifically, SO2 and NO2 were observed to preferentially bind to undercoordinated zirconium sites located on the MOF nodes. In addition, uptake of CO2, SO2, and NO2 was also aided by dispersion forces within the confined pore environments and by hydrogen bond formation with μ3 OH groups of the MOFs. Dimethyl chlorophosphate (DMCP), a nerve agent simulant that contains several electronegative moieties, was also found to strongly adsorb to undercoordinated zirconium; however, unlike in the aromatic and triatomic molecule systems, DMCP remained permanently bound to the MOFs, even at high temperatures. Finally, QCM studies of mustard gas simulant uptake into polyurethane films of varying hard:soft segment compositions revealed that dipole-dipole and dipole-induced dipole interactions were responsible for favorable absorption conditions. Furthermore, the ratio of hard and soft segment components of the polyurethane had a minor impact on simulant adsorption. Higher hard-segment content resulted in a more crystalline film that reduced simulant uptake, whereas the rubbery, high soft segment polyurethane allowed for greater vapor absorption. Ultimately, molecular-level insight into how the chemical identity of a guest molecule impacts the mechanism and energetics of vapor sorption into both MOFs and polymeric films can be extended to other relevant systems and may help identify how specific characteristics of each material, such as size, shape, and chemical functionality impact their potential use in targeted applications.



Metal-Organic Framework, Polyurethane, BTX, Chemical Warfare Agent, Diffusion, Adsorption, Vacuum, Infrared Spectroscopy, Quartz Crystal Microbalance