<p>Diesel engines emit toxic gases like NOx and hydrocarbons. These gases need to be treated before they are released out the tailpipe. Thus, an aftertreatment system is installed which comprises of DOC, DPF and SCR. The DOC oxidizes the hydrocarbons and NO, the DPF traps the particulate matter and SCR reduces the NOx by reacting with NH3 at high temperatures. However, since NH3 is also a toxic gas, it cannot be released out the tailpipe in excess. It is important to inject an appropriate amount of NH3 so that it does not slip out the tailpipe. With increasingly stringent regulations on the emission limits of these toxic gases, control of SCR has become more necessary than before.</p> <p>In this thesis, the work done by previous members of the lab research group was improved upon. The objective remained the same, namely, keeping the NH3 slip under 50 ppm while maximizing NOx reduction. On initial inspection, it was realized that the entire controller had been designed and implemented in continuous time. Since the controller would be implemented digitally, with limited hardware sampling time, a discrete-time implementation as done via a DCU was created. The controller switched between two controllers – slip-based and storage-based. The slip-based controller was modified to include a feedforward term in the system so that the response time could be improved along with a feedback controller to eliminate any disturbances and steady-state error, using ammonia slip feedback as measured by an NH3 sensor. It aims at keeping the maximum ammonia slip under 50 ppm. The storage controller is a feedback controller which tries to limit the ammonia storage based on the values fed by a lookup table. This lookup table is a simplified table that determines the maximum ammonia storage at any given instant based on the catalyst bed temperature. The feedback controller gains for both controllers were determined based on a linearized plant model since the initial gains were ineffective with the discretized model. The initial switching mode controller that switches between slip control and storage control switched too frequently between the controllers, thereby affecting controller performance. A switching logic was implemented to limit the number of switches. A switch will be permitted only if the previous switch occurred over a certain time. By implementing all the subparts together in the controller, incremental improvements were prominent. In the end, the performance by implementing the proposed idea was distinctly better. The metrics considered for performance comparison are the number of switches and the ability to maximize slip up to 50 ppm. Parameter error was also studied as well and its effect on the controller performance was analyzed. The data when tested against sets of underestimated, overestimated and mixed estimates for the plant parameters resulted in the underestimated parameters to work within the scope of the objective. The controller was able to compensate for the underdosing. Overestimation caused overdosing in the system which led to spikes in the NH3 slip. Thus, it is better to underestimate the plant parameters than overestimate them.</p>

<p dir="ltr">Metal speciation and structure can be influenced by the deposition method used during synthesis, interactions with the support, and by post-deposition treatments and reaction conditions experienced during its lifetime of carrying out a catalytic reaction. Supported metal particles of different size contain different surface structures and coordination environments, which may not only influence reaction rates but also the interconversion between agglomerated metallic domains and dispersed metal atom or ion sites. Here, we address the influence of post-deposition treatments and support properties on the structural interconversion of Pd and Cu on aluminosilicate chabazite (CHA) zeolites, Pt on gamma-alumina (γ-Al2O3), and Pd on amorphous oxides (γ-Al2O3, La-doped Al2O3, ΘΔ-Al2O3). The fundamental insights from these studies can be used to design catalysts used widely in automotive exhaust aftertreatment systems, including Pd-exchanged zeolites for passive NOx (x = 1,2) adsorbers (PNA), Cu-exchanged zeolites for NOx (x = 1,2) selective catalytic reduction (SCR), Pt/Al2O3 for NH3 oxidation, and Pd/oxides for three-way catalysts (TWC). Incipient wetness impregnation (IWI) and colloidal methods were used to prepare Pd nanoparticles deposited on CHA zeolites with distinct Pd nanoparticle sizes and distributions. These Pd-CHA samples were used to investigate the effects of Pd particle size distribution on structural interconversion between ion-exchanged Pd and agglomerated Pd domains under realistic operating conditions. Smaller Pd nanoparticles had larger fractions of agglomerated Pd that converted to ion-exchanged Pd2+ sites at fixed air treatment temperatures (598–973 K) and H2O pressures (2–6 kPa H2O), consistent with thermodynamic predictions from DFT calculations. Furthermore, the addition of H2O during air treatment of different Pd nanoparticles (2–14 nm) inhibited the formation of ion-exchanged Pd2+ (thermodynamics), but not the rate of redispersion (kinetics). This demonstrates that, regardless of Pd nanoparticle size, water vapor in automotive exhaust streams facilitate metal sintering in PNA applications. Aqueous-phase exchange of Cu on CHA zeolites with varying support properties (i.e., number of paired Al sites in the 6 membered ring) were used to prepare materials with distinct types and numbers of extraframework Cu species (Cu2+, CuOH+). These Cu-CHA materials were used to analyze Cu structural changes before and after exposure to hydrothermal aging conditions. In the absence of H2O, some Cu2+ sites condense to form binuclear Ox-bridged Cu species that can be reduced with H2 to form Cu-hydride sites and reject H2O, leading to a sub-stoichiometric H2 consumption (H2/Cu < 0.5). In the presence of H2O, all nominally isolated Cu2+ species convert to [CuOH]+ structures, which can subsequently be reduced by H2 to form a Cu-hydride and reject H2O, leading to stoichiometric H2 consumption (H2/Cu ~ 0.5). Furthermore, the presence of H2O led to reduction features in H2 temperature programmed reduction (TPR) profiles that were similar among Cu-CHA materials, regardless of the initial Cu2+ speciation, further supporting the proposal that all nominally isolated Cu2+ sites convert to a similar [CuOH]+ motif. This demonstrates how water influences Cu speciation on CHA materials of varying origin or treatment history, aiding in quantifying SCR-active isolated Cu ions and SCR-inactive Cu species (e.g., CuO, CuAl2O4). Pt supported on γ-Al2O3 were prepared with different average Pt particle sizes (2–13 nm) by increasing the temperature of post-deposition air treatment (523–873 K). This suite of materials was interrogated to isolate the effects of Pt particle size on NH3 oxidation rates and selectivities during conditions relevant to NH3 slip applications in diesel exhaust aftertreatment. For all Pt particle sizes, NH3 oxidation rates displayed a hysteresis with temperature, with high rates measured during temperature decreases than during temperature increases. Smaller Pt particles (2 nm) had lower rates (per surface Pt, quantified by CO chemisorption) than larger Pt particles (13 nm), signifying that NH3 oxidation is a structure-sensitive reaction. Furthermore, surfaces of Pt particles restructure under NH3 oxidation reaction conditions, influencing effective Pt oxidation states, surface structures (numbers and types of exposed Pt sites), and surface coverages of intermediates leading to the observed hysteresis in rate. These findings demonstrate that Pt particles undergo dynamic structural changes during reaction, influencing their ability to convert NH3 to environmentally benign products in NH3 slip applications. The influence of treatment conditions, support properties, and initial Pd particle size and distribution on the kinetics of nanoparticle sintering were investigated to identify which material properties allow maintaining high dispersion to maximize metal utilization for three way catalysts (TWC) during the conversion of regulated pollutants (CO, hydrocarbons, NOx). Pd was deposited by IWI methods to generate polydiserse particle size distributions, and using colloidal Pd nanoparticle solutions to generate monodisperse size distributions, onto various supports (γ-Al2O3, La-doped Al2O3, ΘΔ-Al2O3) and subjected to aging under oxidative and reductive conditions relevant for TWC operation. The average Pd particle size for all materials increased with treatment time under both reductive and oxidative environments. For samples prepared with IWI (i.e., log normal distribution of Pd particle sizes), reductive aging treatments led to higher sintering rates than oxidative treatments. In contrast, for samples prepared using colloidal Pd solutions (i.e., normal distribution of Pd particle sizes), oxidative aging treatments led to higher sintering rates than reduction treatments. Furthermore, after the same treatment condition and time, samples prepared with IWI resulted in higher average Pd particle sizes. These results indicate that more monodisperse initial Pd particle size distributions lead to lower sintering rates, providing guidance to design of supported metal TWCs with improved metal utilization during their lifetimes. Here, the combination of synthesis approaches to prepare a suite of model (e.g., powder) supported metal catalysts of varying structure and composition, interrogated using site and structural characterizations and steady-state and transient kinetic measurements, along with predictions from theoretical calculations, enabled unraveling the influence of material properties and gas environments that affect metal speciation, structure, and oxidation state in real-world aftertreatment systems that use more complex catalytic architectures (e.g., layered washcoats) and reactor designs (e.g., monoliths). This approach provides insights into the fundamental thermodynamic and kinetic factors influencing metal restructuring and interconversion under realistic conditions encountered in automotive exhaust aftertreatment applications, and the kinetic and mechanistic factors that underlie complex phenomena (e.g., reaction rate hysteresis) from data measured in the absence of hydrodynamic artifacts. The overall approach used in this work enabled development of synthesis-structure-function relationships on various metal supported catalysts for automotive exhaust aftertreatment applications, which can provide guidance for material design and treatment strategies to form and retain desired metal structures throughout the material lifetime, including synthesis, reaction, and regeneration treatments.</p>