Browsing by Subject "Heterogeneous catalysis"
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Item Heterogeneous N₂O₅ chemistry in the Houston atmosphere(2008-08) Simon, Heather Aliza, 1979-; Allen, David T.Heterogeneous reactions have the potential to significantly impact urban ozone formation and total reactivity of the atmosphere. This dissertation used comparisons between photochemical modeling predictions and field measurements to examine heterogeneous N₂O₅ chemistry in Southeast Texas. Heterogeneous reactions of N₂O₅ can lead to two different products: nitric acid (HNO₃) and nitryl chloride (ClNO₂). The formation of HNO₃ results in a loss of reactive nitrogen from the atmosphere. In contrast ClNO₂ photolysis forms Cl radicals and NO₂, both of which promote ozone formation in the troposphere. Preliminary modeling identified key uncertainties and the need to perform more refined modeling which included updated PM emissions estimates, an updated gas-phase N₂O₅ hydrolysis reaction rate constant, updated reactive uptake coefficients, and the inclusion of ClNO₂ as a product of heterogeneous N₂O₅ uptake. Refined modeling which incorporated all of these improvements was carried out and was the first comprehensive modeling of this chemistry performed for an urban air pollution episode. Comparisons of aerosol surface area concentrations, N₂O₅ concentrations, HNO₃ concentrations, and ClNO₂ concentrations with ambient data showed that model predictions were reasonable. The exceptions to this were 1) over-predictions of aerosol surface area concentration peaks at altitudes above 1500 meters and 2) over-prediction of N₂O₅ concentrations in the Houston Ship Channel. Further analysis is needed to identify the reasons for these over-predictions. Other key findings from this modeling include the model prediction of inland chlorine concentrations high enough to form ClNO₂ and the prediction that a large portion of atmospheric chlorine is cycled through ClNO₂, therefore making the inclusion of ClNO₂ into photochemical models essential for properly simulating chlorine chemistry. In addition, modeling suggested that the chemistry leads to significant increases of NO[subscript x] at night, but decreases in daytime NO[subscript x] concentrations and that the overall effect was to decrease ozone concentrations. Further investigation into the effect of ClNO₂ as a chlorine source showed that likely ozone increases in the Houston area caused by the presence of this compound are on the order of several ppb. Further analyses showed that vertical dispersion and local atmospheric composition moderated the effect of nitryl chloride on ozone mixing ratios.Item The development of metal-organic frameworks using palladium metal complexes for catalysis and the utilization of a dihaloimidazolidinedione for easy acid chloride generation(2016-08) Nguyen, An Ngoc-Michael; Humphrey, Simon M.; Jones, Richard APart 1. Metal-Organic Frameworks (MOFs) have been extensively studied due to their functional versatility and well-defined, porous structures. It is, however, exceptionally rare to find MOFs that use late transition metal complexes as a building block. Incorporation of these complexes would have immediate applications in catalysis and enhanced gas adsorption/storage. Furthermore, because of the MOF’s well-defined structures, heterogeneous catalysis properties can be more readily studied and improved. Herein, 1,2-bis(bi(para-carboxyl)phenylphosphino)benzene palladium dichlo-ride’s (PdCl2(BBCB)) catalytic ability is studied using the Mizoroki-Heck reaction, and 1,2-bis(bi(4-carboxy-biphenyl-4’-phosphino))ethane palladium dichloride (PdCl2(BBCE-1L)) is used to make a MOF with an enlarged pore size and greater catalytic ability. BBCB, a tetra-para-carboxylic acid derivative of dppb, is used to form a palladium dichloride bis(phosphine) complex. This complex was found to perform a Mizoroki-Heck reaction in decent yields despite formation of palladium black. BBCE-1L, a tetra-4-carboxylic acid biphenyl derivative of dppe, was then developed to deter palladium black formation and enlarge the pore size of the MOF. A MOF was made using a Zn(II) paddlewheel as the metal node and PdCl2(BBCE-1L) as the organic linker. This MOF was found to have moderate thermal stability and potentially high pore volume. Part 2. Acid chloride generation is a widely researched field for the synthesis of amides and esters, motifs found throughout nature and pharmaceuticals. Recently, we found that dihaloimidazolidinediones could substitute a variety of alcohols with halogens through an amide-stabilized carbocation. As an extension of this chemistry, we were able to activate most carboxylic acids into the corresponding acid chloride with near quantitative yields. Mechanistic studies of electronic and steric effects suggest that the rate-determining step is the nucleophilic attack of a free chloride ion on the carbonyl center to produce the corresponding acid chloride. Electronic effects of ring size on electrophilicity was also observed and explained through analysis of a simplified Walsh diagram.