NO_x (NO, NO₂) is one of the most harmful air-pollutants from exhaust, resulting in series of environmental problems as well as severe healthy issues for human beings. Selective catalytic reduction (SCR) system is a common approach to eliminate NO_x onboard by using ammonia as a reductant. However, ammonia storage unit has been one of the restriction factors for the NO_x conversion efficiency because of insufficient ammonia dosing rate and the corrosive and hazardous nature of ammonia. Thus, a reliable ammonia storage and delivery system is of high scientific and commercial desire.

In this thesis, novel composites were fabricated and studied based on MgCl₂ and SrCl₂, two commercial alkaline earth metal halides (AEMH) for ammonia storage. In order to reduce the melting issue and enhance the kinetics of the ammonia sorption, carbon materials, graphite (Gt) and graphene nanoplatelets aggregates (GNA) were added to MgCl₂ at 1 wt.%, 10 wt.% and 20 wt.%. With ball milling and hydraulic pressing, the aforementioned carbon-MgCl₂ composites were structured into pellets for various characterization. With real-time recording in the tube furnace at 1073 K, we observed that with 20% carbon additives, the pelletized composites maintained their structure with 95% mass retention, while the pure MgCl₂ completely melted and disintegrated. According to the SEM images, carbon materials separated MgCl₂ so that the molten MgCl₂ cannot form large droplet to spread out. Furthermore, the 20 wt.% GNA-80 wt.% MgCl₂ (GNA20) composites demonstrated enhanced kinetics in both absorption and desorption of ammonia, which is 83% faster in ammonia absorption and 73% faster in desorption in the first two minutes compared to the pure MgCl₂. The BET surface area and mercury intrusion porosimetry results explains the kinetic elevation by the GNA by introducing extra reaction surface and nanopores as the diffusion path for ammonia. The enhancement of both structural stabilityand kinetics make the GNA20 composite a robust ammonia carrier.

During the chemical absorption process, SrCl₂ uptakes 8 ammonia molecules resulting in 4 times volume expansion. This dramatic expansion and shrinkage during the absorption and desorption will destroy the structure and disintegrate the SrCl₂ into powder, which could bring the dust explosion risk for many applications. Based on the carbon-salts composites, a novel porous SrCl₂ structure is designed and fabricated with graphene oxide as skeleton by freeze casting process. Porous SrCl₂ structure is feasible for various geometries with different molds at a wide SrCl₂ load from 0 wt.% to 96 wt.%. The ammonia capacity of the porous SrCl₂ is linear proportional to the SrCl₂ load. During the ammonia absorption and desorption cycles, the graphene oxide skeleton could self-adjust along with the volume swing to within its flexibility. This porous SrCl₂ demonstrates excellent tolerance of volume swing and enhanced kinetics as a promising ammonia storage material. Our approach and results may cast light on the obstacles of structuring self-expansion and shrinkage materials as well as on enhancing the gas sorption properties.

Air quality has been one of the long-term focuses in society and has raised people’s concern regarding its amelioration in the post coronavirus disease 2019 (COVID-19) pandemic era. Nitrogen oxides (NO_x), including NO and NO₂, as one of the most harmful air pollutants, have been stringently monitored in most countries due to their devastating impact on the environment and human health. The transport sector, as the primary source of NO_x, therefore, is regulated with ever-evolving NO_x emission standards for vehicles. One typical approach to abate NO_x from vehicle exhaust is using ammonia (NH₃) to reduce NO_x and produce environmentally friendly nitrogen (N₂) and water (H₂O) by selective catalytic reduction (SCR). Conventional urea-based SCR systems using urea as an indirect ammonia source have presented a series of problems, including low conversion efficiency with the lowering of exhaust temperature, freezing of urea solution in low-temperature regions, and emission of carbon dioxide (CO₂) as a by-product.

Solid SCR systems have emerged as a new direction for NO_x reduction (DeNO_x) in both industry and research, owing to their high NO_x converting efficiency at low exhaust temperatures with direct ammonia dosing. In solid SCR systems, the ammonia storage and delivery unit is a critical part influencing DeNO_x performance. The most popular ammonia carriers in solid SCR systems are alkaline earth metal halides (AEMHs), such as MgCl₂, CaCl₂, and SrCl₂. AEMHs face two main challenges as ammonia carriers: (1) low kinetics of ammonia absorption and desorption for urban driving and engine idle scenarios; (2) poor structural stability in terms of thermal melting spread due to heat accumulation and dramatic volume expansion/shrinkage during ammonia absorption-desorption cycles.

In this thesis, various physisorbents and chemisorbents, including metal-organic frameworks (MOFs), zeolites, and carbon-reinforced AEMHs, are designed, fabricated, and evaluated as optimized ammonia carriers for solid SCR systems.

MOFs [M₂(adc)₂(dabco)] (M = Co, Ni, Cu, Zn) in this research have demonstrated physisorption of ammonia and superior kinetics of adsorption and desorption compared to MgCl₂. Among the synthesized MOFs, Ni₂(adc)₂(dabco) possessed the highest ammonia uptake capacity, resulting from its high specific surface area. Ni₂(adc)₂(dabco) released 6 times the mole fraction of ammonia in the first 10 minutes compared to Mg(NH₃)₆Cl₂, indicating that physisorbents can offer a solution to shorten the buffer time for ammonia dosing in SCR. To combine the physisorption of microporous materials with the chemisorption of AEMHs, SrCl₂-impregnated zeolite granules as well as three-dimensional (3D) printed zeolite units to carry AEMHs were designed. By optimizing the parameters in the ion exchange and impregnation process, the fabricated SrCl₂-impregnated zeolite granules showed two stages of ammonia sorption, including a rapid adsorption stage from the zeolites and an abundant absorption stage from SrCl₂. The SrCl₂-impregnated zeolite A granules retained 73% of the compressive strength of the pristine CaA granules after ammonia cycles, indicating excellent structural stability of the composite granules. The feasibility of applying 3D printing technology to co-structure AEMHs and zeolites was examined by designing zeolite NaX units to carry MgCl₂. A 3D-printed NaX scaffold was successfully fabricated with an optimal formulation of zeolite NaX ink after rheological studies.

Carbon materials were selected to form composites with AEMHs, including graphite (Gt), graphene nanoplatelets aggregates (GNA) as additives, and graphene networks as the scaffold. The pelletized carbon-MgCl₂ composites containing 20 wt% Gt/GNA presented high structural integrity up to 800 °C above the melting point of MgCl₂. Besides, the introduction of nanopores from GNA could promote ammonia diffusion in the MgCl₂, resulting in enhanced kinetics of ammonia sorption and desorption. A porous SrCl₂ structure scaffolded by graphene networks was fabricated by freeze-casting. The optimized porous SrCl₂ with 80 wt% SrCl₂ loading maintained its macro- and micro-structure, accommodating the volume swing after 20 ammonia sorption–desorption cycles without disintegration. Furthermore, the porous SrCl₂ demonstrated superior kinetics of ammonia sorption and desorption by possessing more surface sites for ammonia adsorption and a shorter diffusion length in the SrCl₂ particles. This structuring approach was verified with other AEMHs, including MgCl₂ and CaCl₂.The results from this thesis offer several solutions to structure AEMHs and their composites as ammonia carriers for SCR, with rapid kinetics and enhanced structural stability. Potential directions for optimizing the ammonia carriers are suggested, such as combining physisorbents (MOFs, zeolites, etc.) and chemisorbents (AEMHs) in flexible networks and optimizing the volumetric ammonia uptake capacity while maintaining the structural stability of the ammonia carriers.