Browsing by Author "Van Heerden, Tracey"

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    Characterization of gold catalysts for methanol synthesis
    (2012) Van Heerden, Tracey; Van Steen, Eric; Case, Jenni
    The activity (per mass of catalyst) of supported gold catalysts across a range of reduction and oxidation reactions is significantly affected by the average crystallite size of the gold crystallites in the catalyst. Supported gold catalysts are most commonly characterized for particle size using TEM and XRD. Both of these methods can have a large degree of inaccuracy associated with them at low metal loadings and for catalysts containing small gold crystallites. In this study oxygen chemisorption was used as an additional method to characterize supported gold catalysts to complement electron microscope techniques. Agreement between the results from these different methods was obtained only with regard to the order of magnitude range of crystallite size. The oxygen chemisorption can be used to estimate the mass fraction of gold present as nano-crystallites (typically less than 1%) implying a large room for improvement in catalyst preparation technique. In this study a range of supported gold catalysts were prepared by ion exchange, varying a range of preparation variables, including gold concentration in the precursor solution, washing procedure using an aqueous ammonia solution, as well as drying and calcination procedures. The washing procedure and in particular the concentration of ammonia and the duration affected the final metal loading of the catalyst. TEM analyses show crystallite size distributions between 2-5nm for all catalysts excepting those which were not washed using an aqueous ammonia solution and which did not show any small crystallites. Only the total omission of the ammonia wash resulted in a significant change in the gold crystallite sizes observed on TEM-images. Further characterization with SEM showed that catalysts that appeared identical on the TEM-images also contained large 50-500nm crystallites. This additional method of characterisation using SEM allowed for the identification of significant differences between catalysts upon varying the preparation method. Catalyst drying was also shown to be a crucial step in the catalyst preparation method, with SEM images displaying only small well-distributed gold crystallites for catalysts dried in the rotary evaporator. Two of the catalysts were then tested for their activity and selectivity in the hydrogenation of CO or CO 2. Although it has been shown that the production of methanol from CO (and CO 2) can be catalysed by gold particles with crystallite sizes below 5nm (Haruta, 1997), this reaction has received comparatively little attention compared to the more extensively studied CO oxidation reaction. Testing was done over a range of temperatures (200 - 350°C) at a pressure of 30bar. The obtained methanol yields and selectivities are comparable to reported values in literature. The hydrogenation of CO 2 was shown to have higher yields and selectivities to methanol than the hydrogenation of CO over the same catalyst. The preparation of the catalyst was shown to have an effect on the activity and selectivity, with the catalyst dried in the rotary evaporator having a higher yield and selectivity to methanol, while also forming a larger variety of products than the catalyst dried in the oven.
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    MAX phases as an electrocatalyst support material: a DFT study
    (2019) Gertzen, Jonathan; Rampai, Tokoloho; Van Heerden, Tracey; Levecque, Pieter
    The insatiable global demand for energy cannot be sustained by fossil fuels without irreparable damage to the environment. Various alternative energy sources are being investigated to provide renewable clean energy. One promising technology is the hydrogen fuel cell, which uses hydrogen and oxygen to produce electricity. However, the currently used catalyst support material, carbon black, corrodes in the low pH and oxidative environment. Therefore, new catalyst support materials are being sought. A new class of material, called MAX phases, shows potential because some possess a combination of properties of metals and ceramics. Three of them, Ti2AlC, Ti3AlC2, and Ti3SiC2, show good electrical conductivity and oxidation resistance. These MAX phases have been investigated using density functional theory (DFT) in this thesis to determine their properties. The density of states show that they are electrically conductive, with a continuous band over the Fermi level primarily from the Ti d orbital. Calculating the Boltzmann transport properties, yielded electrical resistivity values of 0.460 µΩ m for Ti2AlC, 0.370 µΩ m for Ti3AlC2, and 0.268 µΩ m for Ti3SiC2 at 300 K. Therefore, Ti3SiC2 should be the most electrically conductive of the three. The vacancy formation energy of an A group atom was investigated using a 2 x 2 x 2 supercell. The vacancy formation energies were calculated to be 2.882 eV for Ti2AlC, 2.812 eV for Ti3AlC2, and 2.167 eV for Ti3SiC2. The formation of a vacancy increases the electrical resistivity of the bulk MAX phases. As a catalyst support material, a MAX phase particle will have surfaces present. Due to the layered structure of the MAX phases, multiple terminations of (0 0 0 1) surfaces could be possible, which were investigated. It was shown that terminations where the Ti-C cage structure remained intact produced the lowest cleavage energies. For Ti2AlC, the two low cleavage energy surfaces are Al(Ti) and Ti(C), for Ti3AlC2, Al(Ti2) and Ti2(C), and for Ti3SiC2, Si(Ti2) and Ti2(C). The surfaces with the lowest cleavage energy should be more stable than other surfaces and would therefore be expected to be present on a MAX phase particle. Vacancies were also formed in the surface systems. The surfaces with the vacancy in the surface layer had the lowest vacancy formation energy, with that of Si(Ti2) being positive. The surface slabs generally showed a higher electrical resistivity than the bulk systems, while the formation of a vacancy generally increased the resistivity, in agreement with the bulk vacancy trend. These MAX phases are electrically conductive, however a quantifiable oxidation resistance was not able to be calculated. They do however show signs of being good electrocatalyst support materials.