The importance of platinum group metals for catalytic and microelectronic applications has prompted research into the development of novel molecular precursors for chemical vapor deposition of thin films of these metals. A variety of molecular architectures, ligand systems, as well as deposition conditions are investigated and related to the morphology and composition of the resultant films. For example, amorphous thin films of ruthenium and phosphorus alloys are deposited using single source metal hydride precursors, while use of the 3,5-di-substituted pyrazolate ligand in conjunction with various rhodium starting materials leads to a variety of different volatile monomeric and dimeric complexes. Synthesis of pyrazole and pyrazolate complexes of tungsten and palladium are also explored. In a related research area, progress towards the development of novel synthetic routes to mesostructured transition metal phosphides and borates for Li-ion battery electrode applications is summarized. Traditional routes to these materials involve high-temperature syntheses, allowing limited control over morphology. Identification of low-temperature reaction conditions necessary to afford a desired composition, morphology and electrochemical performance of the bulk material are the main goals of this project, and results are discussed with various early transition metals. / text

M.Sc. / Please refer to full text to view abstract

Includes abstract. / Includes bibliographical references (leaves 74-79). / Historically the platinum group metals (PGMs) have been, and are still being dissolved by means of rather aggressive methods, e.g. aqua regia. Limited research has been conducted into the dissolution of the PGMs using different oxidizing agents. The dissolution of gold on the other hand has been afforded extensive research, and numerous papers and review articles have been published on the subject. The last number of years has seen the biggest application by volume of the PGMs as part of autocatalysts towards the degradation of harmful motor vehicle exhaust gases. This has subsequently sparked research into the recovery of specifically platinum, palladium, and rhodium from spent autocatalysts. Currently pyrometallurgical recovery of PGMs is being employed predominantly. A hydrometallurgical process on the other hand is, based on current technology, still a rather aggressive process that makes for high maintenance costs and an unpleasant environment. Gold has traditionally been dissolved by making use of cyanide, which is still the major route for gold dissolution. Due to environmental concerns lixiviants such as thiosulphate (S2O3 2-), thiourea (H2NCSNH2), and thiocyanate (SCN-) are gaining acceptance due to them being more environmentally friendly and giving good recoveries. These ‘softer’ alternatives have however not been tested on the PGMs. It is therefore the aim of this study to obtain an improved understanding of the leaching of the PGMs using lixiviants less aggressive than aqua-regia. These lixiviants include (i) SCN-, (ii) S2O3 2-, (iii) H2NCSNH2, and (iv) AlCl3/HCl. A thermodynamic study highlighted the fact that thermodynamic data for platinum-, palladium- and rhodium complexes are basically non-existent. To therefore obtain a clearer thermodynamic understanding of the leaching of the platinum group metals by means of these alternative lixiviants, future detailed speciation and thermodynamic investigations need to be conducted. An exploratory electrochemical investigation focusing on open circuit potentials and potentiodynamic scans, showed AlCl3 / HCl / NaOCl to be a good candidate for the leaching of the platinum group metals followed by SCN- / Fe3+ and CS(NH2)2 / Fe3+. Actual leach results, employing virgin autocatalysts as sample material, again highlighted the potential of AlCl3 / HCl / NaOCl as being a good lixiviant system. The surprise package, however, has been SCN- / Fe3+ that rendered very good results for Pd and Pt.

Platinum-Group Metal (PGM) nanostructures as advantageous alternatives to natural peroxidases have drawn great attention because of their superior catalytic activities, which can effectively enhance performance of enzyme-based in vitro diagnostics. The catalytic activity of metal nanoparticle peroxidase mimics can depend on their size, shape, elemental composition, and surface ligand of PGM nanostructures. Therefore, to develop optimal peroxidase mimics for a few bioanalytical and diagnostic applications, such as enzyme-linked immunosorbent assay (ELISA), it is important to investigate how structural aspects of PGM nanoparticles correlate with the ability of the nanoparticles to serve as functional mimics of protein peroxidase enzymes. In summary, this dissertation has studied: 1) iridium (Ir), platinum (Pt) and Ir/Pt bimetallic nanowire structures as peroxidase mimics, and the effect of different wires' length on their peroxidase-like activities and certain application of sandwich ELISA for the detection of carcinoembryonic antigen (CEA, a cancer biomarker); 2) ultra-small Ir nanoparticles, with an average size of 1.1 nm, supported by WO2.72 nanowire with high catalytic activity. Those Ir nanoparticles were applied to sandwich ELISA and competitive ELISA for sensitive detection of CEA and aflatoxin B1 (AFB1, a carcinogenic toxin), respectively; 3) the size effect of peroxidase mimics on their catalytic activities and performance in biosensing application, where Pd-Ir core-shell nanoparticles were used as a type of model peroxidase mimics. These studies may significantly stimulate further investigations of PGM nanostructures as peroxidase mimics and other potential applications in in vitro diagnostics.

The world energy supply and demand, together with limited available resources have resulted in the need to develop alternative energy sources to ensure sustainable and expanding economies. Hydrogen is being considered a viable option with particular application to fuel cells. The Hybrid Sulphur cycle has been identified as a process to produce clean hydrogen (carbon free process) and can have economic benefits when coupled to nuclear reactors (High Temperature Gas Reactor) or solar heaters for the supply of the required process energy. The sulphur trioxide decomposition reactor producing sulphur dioxide for the electrolytic cells in a closed loop system has been examined, but it is clear that development with respect to a more durable active catalyst in a reactor operating under severe conditions needs to be investigated. A suitable sulphur trioxide reactor needs to operate at a high temperature with efficient heating in view of the endothermic reaction, and has to consist of special materials of construction to handle the very corrosive reactants and products. This investigation was undertaken to address (1) the synthesis, characterisation, reactivity and stability of a suitable catalyst (2), determination the reaction rate of the chosen catalyst with a suitable micro reactor (3) construction and evaluation of a packed bed reactor for the required reaction, and (4) the development and validation of a reactor model using computational fluid dynamics with associated chemical reactions. A supported catalyst consisting of 0.5 wt% platinum and 0.5 wt% palladium on rutile (TiO2, titania) was prepared by the sintering of an anatase/rutile supported catalyst with the same noble metal composition, synthesized according to an incipient impregnation procedure using cylindrical porous pellets (±1.7 mm diameter and ±5 mm long). Characterization involving: surface area, porosity, metal composition, - dispersion, - particle size, support phase and sulphur content was carried out and it was found from reactivity determinations that the sintered catalyst, which was very different from the synthesized catalyst, had an acceptable activity and stability which was suitable for further evaluation. A micro pellet reactor was constructed and operated and consisted of a small number of pellets (five) placed apart from each other in a two-stage quartz reactor with sulphur trioxide generated from sulphuric acid in the first stage and the conversion of sulphur trioxide in the second stage, respectively. Attention was only confined to the second stage involving the conversion of sulphur trioxide with the supported catalyst. The overall reaction kinetics of the pellets involving momentum, heat and mass transfer and chemical reaction was evaluated and validated with constants obtained from literature and with an unknown reaction rate equation for which constants were obtained by regression. As result of the complexity of the flow, mass and heat transfer fields in the micro pellet reactor it was necessary to use a CFD model with chemical reactions which was accomplished with a commercial code COMSOL MultiPhysics® 4.3b. A reversible reaction rate equation was used and a least squares regression procedure was used to evaluate the activation energy and pre-exponential factor. The activation energy obtained for the first order forward reaction was higher than values obtained from literature for a first order reaction rate (irreversible reaction) for the platinum group metals on titania catalysts. Detailed analyses of the velocity, temperature and concentration profile revealed the importance of using a complex model for determination of the reaction parameters. A fixed bed reactor system consisting of a sulphuric acid vaporizer, a single reactor tube (1 m length, 25 mm OD) heated with a surrounding electrical furnace followed, by a series of condensers for the analysis of the products was constructed and operated. Three process variables were investigated, which included the inlet temperature, the weight hourly velocity and the residence time in order to assess the performance of the reactor and generate results for developing a model. The results obtained included the wall and reactor centreline temperature profiles together with average conversion. As a result of the complexity of the chemistry and the phases present containing the products from the reactor a detailed calculation was done using vapour/liquid equilibrium with the accompanying mass balance (Aspen-Plus®) to determine the distribution of sulphur trioxide, sulphur dioxide, oxygen and steam. A mass balance was successfully completed with analyses including SO2 with a GC, O2 with a paramagnetic cell analyser, acid/base titrations with sodium hydroxide, SO2 titrations with iodine and measurement of condensables (mass and volume). The results obtained showed that a steady state (constant conversion) was obtained after approximately six hours and that it was possible to obtain sulphur trioxide conversion approaching equilibrium conditions for bed lengths of 100 mm with very low weight hourly space velocities. A heterogeneous 2D model consisting of the relevant continuity, momentum, heat transfer and mass transfer and the reaction rate equation determined in this investigation was developed and solved with the use of the commercial code COMSOL MultiPhysics® 4.3b with an appropriate mesh structure. The geometry of the packed bed (geometry) was accomplished by generating a randomly packed bed with a commercial package DigiPac™. The model predicted results that agreed with experimental results with conversions up to 56%, obtained over the following ranges: weight hourly space velocity equal to 15 h-1, temperatures between 903 K and 1053 K and residence times between 0.1 and 0.07 seconds. The post-processing results were most useful for assessing the effect of the controlling mechanisms and associated parameters. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

The world energy supply and demand, together with limited available resources have resulted in the need to develop alternative energy sources to ensure sustainable and expanding economies. Hydrogen is being considered a viable option with particular application to fuel cells. The Hybrid Sulphur cycle has been identified as a process to produce clean hydrogen (carbon free process) and can have economic benefits when coupled to nuclear reactors (High Temperature Gas Reactor) or solar heaters for the supply of the required process energy. The sulphur trioxide decomposition reactor producing sulphur dioxide for the electrolytic cells in a closed loop system has been examined, but it is clear that development with respect to a more durable active catalyst in a reactor operating under severe conditions needs to be investigated. A suitable sulphur trioxide reactor needs to operate at a high temperature with efficient heating in view of the endothermic reaction, and has to consist of special materials of construction to handle the very corrosive reactants and products. This investigation was undertaken to address (1) the synthesis, characterisation, reactivity and stability of a suitable catalyst (2), determination the reaction rate of the chosen catalyst with a suitable micro reactor (3) construction and evaluation of a packed bed reactor for the required reaction, and (4) the development and validation of a reactor model using computational fluid dynamics with associated chemical reactions. A supported catalyst consisting of 0.5 wt% platinum and 0.5 wt% palladium on rutile (TiO2, titania) was prepared by the sintering of an anatase/rutile supported catalyst with the same noble metal composition, synthesized according to an incipient impregnation procedure using cylindrical porous pellets (±1.7 mm diameter and ±5 mm long). Characterization involving: surface area, porosity, metal composition, - dispersion, - particle size, support phase and sulphur content was carried out and it was found from reactivity determinations that the sintered catalyst, which was very different from the synthesized catalyst, had an acceptable activity and stability which was suitable for further evaluation. A micro pellet reactor was constructed and operated and consisted of a small number of pellets (five) placed apart from each other in a two-stage quartz reactor with sulphur trioxide generated from sulphuric acid in the first stage and the conversion of sulphur trioxide in the second stage, respectively. Attention was only confined to the second stage involving the conversion of sulphur trioxide with the supported catalyst. The overall reaction kinetics of the pellets involving momentum, heat and mass transfer and chemical reaction was evaluated and validated with constants obtained from literature and with an unknown reaction rate equation for which constants were obtained by regression. As result of the complexity of the flow, mass and heat transfer fields in the micro pellet reactor it was necessary to use a CFD model with chemical reactions which was accomplished with a commercial code COMSOL MultiPhysics® 4.3b. A reversible reaction rate equation was used and a least squares regression procedure was used to evaluate the activation energy and pre-exponential factor. The activation energy obtained for the first order forward reaction was higher than values obtained from literature for a first order reaction rate (irreversible reaction) for the platinum group metals on titania catalysts. Detailed analyses of the velocity, temperature and concentration profile revealed the importance of using a complex model for determination of the reaction parameters. A fixed bed reactor system consisting of a sulphuric acid vaporizer, a single reactor tube (1 m length, 25 mm OD) heated with a surrounding electrical furnace followed, by a series of condensers for the analysis of the products was constructed and operated. Three process variables were investigated, which included the inlet temperature, the weight hourly velocity and the residence time in order to assess the performance of the reactor and generate results for developing a model. The results obtained included the wall and reactor centreline temperature profiles together with average conversion. As a result of the complexity of the chemistry and the phases present containing the products from the reactor a detailed calculation was done using vapour/liquid equilibrium with the accompanying mass balance (Aspen-Plus®) to determine the distribution of sulphur trioxide, sulphur dioxide, oxygen and steam. A mass balance was successfully completed with analyses including SO2 with a GC, O2 with a paramagnetic cell analyser, acid/base titrations with sodium hydroxide, SO2 titrations with iodine and measurement of condensables (mass and volume). The results obtained showed that a steady state (constant conversion) was obtained after approximately six hours and that it was possible to obtain sulphur trioxide conversion approaching equilibrium conditions for bed lengths of 100 mm with very low weight hourly space velocities. A heterogeneous 2D model consisting of the relevant continuity, momentum, heat transfer and mass transfer and the reaction rate equation determined in this investigation was developed and solved with the use of the commercial code COMSOL MultiPhysics® 4.3b with an appropriate mesh structure. The geometry of the packed bed (geometry) was accomplished by generating a randomly packed bed with a commercial package DigiPac™. The model predicted results that agreed with experimental results with conversions up to 56%, obtained over the following ranges: weight hourly space velocity equal to 15 h-1, temperatures between 903 K and 1053 K and residence times between 0.1 and 0.07 seconds. The post-processing results were most useful for assessing the effect of the controlling mechanisms and associated parameters. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.

<p>In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.</p>

<p>In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.</p>

In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.