Due to the use of fertilizers, concentrations of harmful nitrate have increased in groundwater and surface waters globally in the last century. Water treatment plants primarily use separation techniques for nitrate treatment, but these technologies create a high nitrate concentration brine that is costly to dispose of. This dissertation focuses on catalytic hydrogenation, an emerging technology capable of reducing nitrate to nitrogen gas using hydrogen gas (H2). This technology reduces nitrate at rates >95% and is an improvement over technologies used at water treatment plants, because the nitrate is chemically transformed with harmless byproducts and no nitrate brine. The goal of this dissertation is to upgrade the maturity of catalytic nitrate hydrogenation systems by overcoming several barriers hindering the scale-up of this technology. Objective 1 is to compare different methods of attaching the bimetallic catalyst to a hollow-fiber membrane surface to find a method that results in 1) minimized catalyst loss, and 2) repeatable nitrate removal over several cycles. Results showed that the In-Situ MCfR-H2 deposition was successful in reducing nitrate at a rate of 1.1 min-1gPd-1 and lost less than 0.05% of attached Pd and In cumulatively over three nitrate treatment cycles. Objective 2 is to synthesize catalyst-films with varied In3+ precursor decorated over a Pd0 surface to show the technology can 1) reliably synthesize In-Pd catalyst-films with varied bimetallic ratios, and 2) optimize nitrate removal activity by varying In-Pd ratio. Results showed that nitrate removal activity was optimized with a rate constant of 0.190 mg*min-1L-1 using a catalyst-film with a 0.045 In-Pd ratio. Objective 3 is to perform nitrate reduction in a continuous flow reactor for two months to determine if nitrate removal activity can be sustained over extended operation and identify methods to overcome catalyst deactivation. Results showed that a combination of increased hydraulic residence time and reduced pH was successful in increasing the nitrate removal and decreasing harmful nitrite byproduct selectivity to 0%. These objectives increased the technology readiness of this technology by enabling the reuse of the catalyst, maximizing nitrate reduction activity, and achieving long-term nitrate removal.

While understanding of failure mechanisms for polymeric composites have improved vastly over recent decades, the ability to successfully monitor early failure and subsequent prevention has come of much interest in recent years. One such method to detect these failures involves the use of mechanochemistry, a field of chemistry in which chemical reactions are initiated by deforming highly-strained bonds present in certain moieties. Mechanochemistry is utilized in polymeric composites as a means of stress-sensing, utilizing weak and force-responsive chemical bonds to activate signals when embedded in a composite material. These signals can then be detected to determine the amount of stress applied to a composite and subsequent potential damage that has occurred due to the stress. Among mechanophores, the cinnamoyl moiety is capable of stress response through fluorescent signal under mechanical load. The cinnamoyl group is fluorescent in its initial state and capable of undergoing photocycloaddition in the presence of ultraviolet (UV) light, followed by subsequent reversion when under mechanical load. Signal generation before the yield point of the material provides a form of damage precursor detection.This dissertation explores the implementation of mechanophores in novel approaches to overcome some of the many challenges within the mechanochemistry field. First, new methods of mechanophore detection were developed through utilization of Fourier transform infrared (FTIR) spectroscopy signals and in-situ stress sensing. Developing an in-situ testing method provided a two-fold advantage of higher resolution and more time efficiency over current methods involving image analysis with a fluorescent microscope. Second, bonding mechanophores covalently into the backbone of an epoxy matrix mitigated property loss due to mechanophore incorporation. This approach was accomplished through functionalizing either the resin or hardener component of the matrix. Finally, surface functionalization of fibers was performed and allowed for unaltered fabrication procedures of composite layups as well as provided increased adhesion at the fiber-matrix interphase. The developed materials could enable a simple, non-invasive, and non-detrimental structural health monitoring approach.