Thesis (Ph. D.)--University of Missouri-Columbia, 1999. / Typescript. Vita. Includes bibliographical references (leaves 304-307). Also available on the Internet.

The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

Philosophiae Doctor - PhD / Light olefins are some of the main raw materials for the petrochemical industry. With the rise in oil prices and increasing demand for olefins, there is an increasing interest in finding cheaper alternatives for processes in the petrochemical industry (PETROSA 2017). Research into the dehydrogenation of light alkanes has received significant attention. This dehydrogenation process represents a route to obtain olefins from inexpensive hydrocarbon feedstocks. The use of inexpensive hydrocarbons as a feedstock in the petrochemical industry could reduce the dependence on oil. Commercially used catalysts based on chromium or platinum have major disadvantages, including the harmful effects of chromium and the high cost of platinum, which limit their application to a certain extent. Therefore, research into developing efficient dehydrogenation systems using environmentally friendly and inexpensive metals have become highly desirable. Sulfide-containing metal catalysts have gained significant research interest for use in the dehydrogenation process and display interesting catalytic activity. / 2024

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The buckling constant for neutron moderators in the shape of an elliptic cylinder, hemisphere, and"piggy-back" cylinder has been determined by experimental measurements using paraffin as a moderator. The pulsed neutron sources technique was used throughout the work; a fast neutron burst of short duration was injected into regular paraffin shapes (cylinders with diameter and height ratio equal approximately to one). An empirical curve of decay constant of the neutron population versus the buckling was obtained. The measured decay constant, λ, was fitted by the method of least square to a parabola in B² of the form: λ=Σ_av+ B²D - CB⁴ where λ= the decay constant B² = the buckling constant Σ_a = the macroscopic absorption cross section v = the neutron velocity D = diffusion coefficient C = diffusion cooling coefficient The resulting values of the diffusion parameters are: Σ_a v = 4858 ± 162 sec⁻¹ D = 25911 ± 202 sec⁻¹ cm² C = 1186 ± 2558 sec⁻¹ cm⁴ By measuring the decay constant, the buckling of the moderators with irregular shapes were determined from the above parameters. The result was in general accord with the theoretical approximations for such shapes. / Master of Science

In many catalytic systems, the catalytic performance of a metal supported catalyst would be affected by the size and shape of the metals, and this phenomena is called structure sensitivity. Generally, the structure sensitivity effect is considered being led by a combination of geometric property change and electronic property change of the surface metals. The particle size variation is an effective way to change the surface structure of the supported metal catalyst, leading to different fractions of the active sites exposing on the support that would take effect on catalyzing the reaction. In this project, a series of Ir/MgAl₂O₄ catalysts with different particle sizes that less than 2nm were utilized for ethane and n-butane hydrogenolysis reactions to study the structure sensitivity effect as well as the potential reaction mechanism. The results show that the activity on the catalysts with nanoparticles and mostly single atoms is evidently higher than that with the subnanometer clusters in both reactions, but the selectivity to the target product of ethane is not quite dependent on the particle size in the n-butane hydrogenolysis. After the fundamental analysis, it is proposed that the reaction mechanism of alkanes hydrogenolysis on the single atom catalysts including single active sites is probably distinctive from that generally accepted on the large particles containing multiple active sites from literature. For n-butane hydrogenolysis, the parallel reaction pathway of central C-C bond cleavage is dominant at low temperature or in the low conversion range. As the temperature going up or the conversion increasing at a certain temperature, the parallel reaction pathway of terminal C-C bond cleavage becomes more and more competitive. The series reaction pathway of hydrogenolysis on propane intermediate would always take place, but the level would be drastically enhanced when the conversion keeps increasing in the very high range. The C-C bond cleavage on the ethane product would not easily happen unless the conversion is close to 100%. / M. S. / Shale gas is natural gas trapped in shale rocks. Among all the countries that have abundant shale gas reserves, the US, benefited from advanced extraction technology, has the largest production of it. What’s more, the production rate will keep increasing at least for the coming 20 years, and shale gas will eventually become the largest source for natural gas. After extraction, there is a series of treatments shale gas has to go through before it can be utilized, catalytic reaction of alkanes (molecules found in most fuels) is one of these essential procedures. Although they are among the most important compositions of shale gas, different types of alkanes are difficult to separate and purify through traditional methods like condensation. To overcome this obstacle, this thesis focuses on exploring efficient catalysts to convert the n-butane (a straight chain alkane with 4 carbon atoms) to ethane (alkane with 2 carbon atoms). Two reactions are involved: n-butane hydrogenolysis and ethane hydrogenolysis. Catalysts are some specific materials that can accelerate certain chemical reactions. The catalysts discussed in this thesis are tiny metal (iridium) particles attached to the support material (magnesium aluminate). In this study, the performance of these catalysts with different particle sizes were tested for the above mentioned hydrogenolysis reactions. The results show that changing the particle size of the catalysts considerably affects the rate of these catalytic reactions. The fundamentals of the catalytic system presented in this work can also help the researchers to rationally design the catalysts aiming at higher efficiency and lower cost in the future work.

With the use of grand canonical molecular dynamics, we studied the slow ompression(0.01m/s) of very thin liquid films made of equimolar mixtures of short and long alkane chains (hexane and hexadecane), and branched and unbranched alkanes (phytane and hexadecane). Besides comparing how these mixtures behave under constant speed compression, we will compare their properties with the behavior and structure of the pure systems undergoing the same type of slow compression. To understand the arrangement of the molecules inside the confinement, we present segmental and molecular density profiles, average length and orientation of the molecules inside well layered gaps. To observe the effects of the compression on the fluids, we present the number of confined molecules, the inlayer orientation, the solvation force and the inlayer diffusion coefficient, versus the thickness of the gap. We observe that pure hexadecane, although liquid at this temperature, starts presenting strong solid-like behavior when it is compressed to thicknesses under 3nm, while pure hexane and pure phytane continue to behave liquid-like except at 1.3nm when they show some weak solid-like features. When hexadecane is mixed with the short straight hexane, it remains liquid down to 2.8nm at which point this mixture behaves solid-like with an enhanced alignment of the long molecules not seen in its pure form; but when hexadecane is mixed with the branched phytane the system does not present the solid-like features seen when hexadecane is compressed pure.

Les alcanes et les alcènes sont des hydrocarbures non cycliques important dans l’industrie. Ils sont synthétisés à partir d'acides gras par une grande variété d’organismes mais les connaissances à ce sujet sont très limitées chez les microalgues. Le but de ces travaux était donc de rechercher la présence d’alcanes ou d’alcènes dans diverses microalgues modèles, et d’essayer d’identifier la ou les enzymes responsables de la synthèse de ces composés. Nous avons mis en évidence la présence d’hydrocarbures linéaires en C15-C17 chez les microalgues Chlorella et Chlamydomonas. Ces composés étaient synthétisés uniquement en présence de lumière. L’absence dans le génome de ces microalgues d’homologues de gènes codant pour des enzymes connues de synthèse d’alcanes/alcènes a permis de conclure à la présence d’un nouveau système de synthèse d’hydrocarbures. Des purifications enzymatique et des analyses protéomique ont permis d’identifier une enzyme candidate qui exprimée chezE. coli est suffisante à la synthèse d’hydrocarbures. L'étude de cette enzyme révella qu'il s'agissait d'une photoenzyme utilisant l'énergie des photons bleue pour décarboxyler les acides grass en alca(e)ne. La structure de cette photoenzyme montre la présence un tunnel hydrophobe contenant l’acide gras et le cofacteur FAD. Cette nouvelle enzyme nommée « alcane photosynthase » amène de nombreuses question: qu'elle est la fonction des hydrocarbures chez ces microorganismes? Quel est le mécanisme catalytique de l’alcane photosynthase? Enfin, elle offre de nouvelles possibilités pour la production de biocarburants utilisant directement l’énergie solaire. / Alkanes and alkenes are important in industry. Alkanes and alkenes are synthesized from fatty acids by a variety of organisms, such as plants and insects. However, the presence in microalgae of enzymes converting fatty acids into hydrocarbons has been poorly studied. The aim of this work was to investigate the presence of alkanes and alkenes in various microalgae models, and try to identify the enzymes responsible for the synthesis of these compounds.We have first demonstrated the presence of linear hydrocarbons C15-C17 in microalgae Chlorella and Chlamydomonas. Then we have shown that the main hydrocarbon formed in Chlorella and Chlamydomonas was derived from cis-vaccenic acid and was synthesized only in the presence of light. Absence of homologues of genes coding for known alkane/alkene biosynthetic enzymes in the genome of Chlorella and Chlamydomonas indicate the presence of an unknown pathway. Enzymatic purification and proteomic analysis allowed to identify a candidate enzyme which, expressed in E. coli lead to the formation of hydrocarbons with variable chain lengths, thus demonstrating that it was really an synthase alkane. Characterization showed that the enzyme was a photoenzyme, which used blue light to catalyse the decarboxylation of fatty acid to an alka(e)ne. The three-dimensional structure of this enzyme revealed a hydrophobic tunnel containing the fatty acid and the FAD cofactor.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy