The first study investigated the deposition and characterization of the CoO and Co3O4 phases of cobalt oxide. It was determined that both phases can be easily distinguishable by XPS, LEED and EELS and grown by only altering the oxygen partial pressure during MBE deposition. This fundamental knowledge gives a foundation for further experiments involving graphene growth on cobalt oxides. The second study focused on the layer-by-layer growth of graphene on another metal oxide, MgO. Past research gives promise of favorable interfacial interactions at the graphene/MgO interface though the exact growth mechanism is unknown. Layer by layer growth by MBE resulted in the characterization of a complex graphene oxide/buckled graphene/ graphene heterostructure confirmed by XPS, AES, LEED and EELS and supported by DFT calculations performed by the project's collaborators at the California Institute of Technology. This detailed look into graphene growth give valuable information that can be allied to graphene growth on similar oxide surfaces. The last project deviates from graphene-based studies and instead focused on interfacial interactions between two metal oxides, chrome oxide and titanium oxide. A corundum phase TiO2-x film was grown on Al2O3 via MBE and characterized using XPS, AES, LEED, and EELS. Data taken gives evidence of the presence of a two-dimensional election gas at the TiO2-x surface because of oxygen vacancies present after deposition. Deposition of chrome in UHV results in the formation of an oxidized chrome overlayer by abstraction of oxygen from the TiO2-x underlayer increasing the number of vacancies present. MOKE measurements taken by the project's collaborators at the University of Nebraska-Lincoln indicate that there is an interfacial exchange bias at the interface of the two oxides, a favorable property for magnetic device applications.

A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Doctor of Philosophy. Johannesburg, March, 2018 / Reduction behavior of South African Mamatwan manganese ore using methane-argon- hydrogen gas mixture was investigated experimentally in the temperature range of 1050ºC to 1250ºC. The effect of changing gas mixture composition, time and temperature was studied using a vertical tube furnace. After each test, three representative samples were prepared; one was analyzed by chemical analysis to obtain metallization results as a function of each reducing condition for each time interval over the total reduction period of two hours. Second sample was analyzed by X-ray diffraction to determine the progress of phase changes; the third sample was mounted, polished and submitted for SEM-EDAX in order to examine the morphology of the ore and its changes in the course of reduction. It was seen that CH4 was an effective reductant as it cracked, supplying the reaction site with hydrogen gas and very fine solid carbon. The excess carbon from cracking of methane ensures regeneration of reductants CO and H2 from reaction product gases of CO2 and H2O ensuring low partial pressure of oxygen at the reaction site. Hydrogen gas may also be involved in the reduction of iron oxide components of the ore. Moreover, depending upon temperature and CH4/H2 ratio in the gas phase the activity of carbon in the system reaches values much higher than unity, shifting the reduction reaction by carbon to lower temperatures. It was observed that bulk of the metallization occurred in the first thirty to forty minutes and the metallization reached some kind of a reduction maximum at 73% metallization. The Mn/Fe ratios in the resulting alloy were higher than those in ordinary carbothermic solid-state reduction, indicating the simultaneous reduction of Fe and Mn at these low reducing temperatures due to a low oxygen potential set up by the methane bearing gas mixtures. It was seen that metallization of Mamatwan ore proceed in two stages. First, reduction of the higher oxides to MnO and metallic iron. Second, reduction of any remaining oxides and MnO to mixed carbide of iron and manganese. During first stage values of effective CO-CO2 diffusivities generated by the model were found to lie in the range from 1.45 *10-6 cm2sec-1 to 8.43*10-6 cm2sec-1 at 1100ºC. Apparent activation energy for first stage calculated in the temperature range of 1050ºC to 1250ºC varied from 1.47 kJ/mol to 24.72 kJ/mol indicating possibility of diffusional control. For the second stage the experimental curves could be duplicated with the mathematical model reasonably well with a maximum difference between the experimental and predicted values being about 5 percent. Rate of metallization values during the second stage (Ms) changed between 1.83*10-8 mol.sec-1.cm-2 and 8.55*10-8 mol.sec-1.cm-2. Specific rate constant values (ks) for the second stage, varied from 5.53*10-6 cm/sec to 3.16*10-5 cm/sec which are much smaller than specific rate constant for the first stage of reduction (kf), which varied from 1.64*10-4 cm/sec to 1.15*10-4 cm/sec, as the rate of second stage of the reduction is much slower than the rate of the first stage. X ray analysis revealed that manganese ore was reduced primarily to carbide Mn7C3 at lower temperature range of the experiments, but at 1200ºC the dominant reaction product was Mn5C2 in both mixtures of methane-argon and methane-hydrogen. The S.E.M images revealed that the product metallic phase occurred all throughout the surface, with globular formation in case of reduction where hydrogen was the carrier gas. / MT 2018

In this dissertation, I present four projects on the fundamental study of the surface configurations and reactivity of the metal oxides using density functional theory computational method. In the first project, we studied the formaldehyde adsorption and diffusion on rutile TiO2 (110) surface. By comparing the adsorption of formaldehyde on stoichiometric and defective TiO2 surfaces under the same condition, we evaluated the effect of surface oxygen vacancy on their interaction with formaldehyde. The project involved close collaboration with Dr. Zhenrong Zhang’s group of Baylor University who studied the formaldehyde chemistry on rutile TiO2(110) surface using a combination of STM and other surface science techniques. In the second project, we compared the surface chemistries of formaldehyde and formic acid on rutile TiO2 and SnO2, two structurally similar but chemically different oxides. We analyzed the oxidation of formaldehyde to formic acid on two oxides and assessed the role of surface oxygen in the oxidation. In the third project, we studied the oxygen evolution reaction (OER) catalyzed by γ-FeOOH (010) under the alkaline condition. The OER process was divided into four elementary steps and the potential energy profiles of these steps on three terminations of the γ-FeOOH (010) surface were mapped out. Based on the computed reaction energies, we determined the most probable OER reaction pathway on each surface termination. We found that partially exposed surface Fe sites were the active sites for the OER process. In the fourth project, we studied the potential of iron oxides (FeOx) and iron-titanium mixed oxides (FeTiOx) as solid oxygen carriers for the chemical looping combustion (CLC) process. As oxygen carriers for CLC, FeOx and FeTiOx in fully oxidized forms went through a series of reduction steps by reacting with the fuel molecules. The reduced oxides were then re-oxidized in an air reactor to restore their oxygen. By studying the surface oxygen vacancy formation and oxygen diffusion, we gained insights into the initial stage of reduction process and activities of FeOx and FeTiOx as well as the effect of Ti on oxygen carrying properties of FeTiOx for CLC.

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