Thesis (M.S.)--Ohio University, August, 2006. / Title from PDF t.p. Includes bibliographical references.

Masters of Science / The electrochemical oxidation of ammonia has attracted much attention as an efficient green method for application in direct ammonia fuel cells (DAFCs) and the production of high purity hydrogen. However, the insufficient performance and high costs of platinum has hindered the large scale application of ammonia (NH₃) electro-oxidation technologies. Therefore, there is a need for the fabrication of efficient electrocatalysts for NH₃ electrooxidation with improved activity and lower Pt loading. Owing to their unique catalytic properties, nanoalloys of platinum group metals (PGMs) are being designated as possible electrocatalysts for NH₃ oxidation. This study presents for the first time a chemical synthesis of unsupported ternary PGM based nanoalloys such as Cu@Pt@Ir with multi-shell structures and Cu-Pt-Ir mixed nanoalloys for electro-catalysis of NH3 oxidation. The nanoalloys were stabilised with polyvinylpyrrolidone (PVP) as the capping agent. The structural properties of the nanoalloys were studied using ultraviolet-visible (UV-Vis) and fourier transform infra-red (FTIR) spectroscopic techniques. The elemental composition, average particle size and morphology of the materials were evaluated by high resolution transmission electron microscopy (HRTEM) coupled to energy dispersive X-ray (EDX) spectroscopy. High resolution scanning electron microscopy (HRSEM) was used for morphological characterisation. Additionally, scanning auger nanoprobe microscopy (NanoSAM) was employed to provide high performance auger (AES) spectral analysis and auger imaging of complex multi-layered Cu@Pt@Ir nanoalloy surface. X-ray diffraction (XRD) spectroscopy was used to investigate the crystallinity of the nanoalloys. The electrochemistry of the nanoalloy materials was interrogated with cyclic voltammetry (CV) and square wave voltammetry (SWV). The electrocatalytic activity of novel Cu-Pt-Ir trimetallic nanoalloys for the oxidation of ammonia was tested using CV. UV-Vis spectroscopy confirmed the complete reduction of the metal precursors to the respective nanoparticles. FTIR spectroscopy confirmed the presence of the PVP polymer as well as formation of a bond between the polymer (PVP) chains and the metal surface for all nanoparticles (NPs). Furthermore, HRTEM confirmed that the small irregular interconnected PVP stabilised Cu@Pt@Ir NPs were about 5 nm in size. The elemental composition of the alloy nanoparticles measured using EDX also confirmed the presence of Cu, Pt and Ir. Cyclic voltammetry indicated that both the GCE|Cu-Pt-Ir NPs and GCE|Cu@Pt@Ir NPs are active electrocatalysts for NH3 oxidation as witnessed by the formation of a well-defined anodic peak around -0.298 V (vs. Ag/AgCl). Thus the GCE|Cu-Pt-Ir NPs was found to be a suitable electrocatalyst that enhances the kinetics of oxidation of ammonia at reduced overpotential and high peak current in comparison with GCE|Cu@Pt@Ir NPs, GCE|Pt NPs, GCE|Ir NPs and GCE|Cu NPs electrocatalysts. The presence of the crystalline phases in each sample was confirmed by XRD analysis. The surface analysis of Cu@Pt@Ir nanoalloy with AES surveys revealed the presence of Pt, Ir and Cu elements in all probed spots suggesting some mixing between the layers of the nanoalloy. Yet, analysis of nanoalloys by CV and XRD confirmed the presence of Cu-Pt and Pt-Ir solid solutions in the Cu-Pt-Ir and Cu@Pt@Ir nanoalloys respectively.

Les nanoparticules de platine (Pt) représentent environ la moitié du coût de fabrication des piles à combustible à membrane échangeuses de protons (PEMFC), ce qui constitue un frein à leur commercialisation à grande échelle. La récupération du Pt contenu dans les piles usagées apparaît donc nécessaire. Les voies de traitement habituellement mises en œuvre pour le recyclage de catalyseurs à base de Pt sont des procédés pyro-hydrométallurgiques, générateurs d’émissions polluantes (CO2, NO2). Une voie de traitement électrochimique en milieu liquide ionique (LI), plus respectueuse de l'environnement, est proposée ici. Elle combine dans une seule cellule la lixiviation du Pt par dissolution anodique et sa récupération par électrodéposition, dans des conditions de température "douces", sans émission de gaz nocifs. L’étude de nombreux électrolytes a permis de sélectionner les mélanges BMIMTFSI + BMIMCl (bis(trifluorométhylsulfonyl) imidure + chlorure de 1-butyl-3-méthylimidazolium), en raison du caractère complexant des chlorures facilitant la lixiviation du Pt et de la bonne stabilité électrochimique du BMIMTFSI. L’anion TFSI-, peu coordonnant, permet de moduler le caractère complexant de l’électrolyte, paramètre clé du procédé influant sur la nature et la stabilité électrochimique du complexe de Pt formé par lixiviation. Au cours de ce travail, les conditions expérimentales permettant de lixivier et d’électrodéposer le Pt dans une cellule unitaire ont été définies et appliquées avec succès aux électrodes de PEMFC. L’électrolyte sélectionné, faiblement hygroscopique, permet la récupération du Pt en atmosphère ambiante / The platinum nanoparticles used as catalyst in Proton Exchange Membrane Fuel Cells (PEMFCs) represent around the half of the total price of the cell and is one of the limitations for their large scale commercialization. The treatment of spent PEMFC through the recovery of platinum catalyst is a major concern for their development. Usual recovery routes for platinum-containing catalysts are pyro-hydrometallurgical processes that generate pollutant emissions (CO2, NO2). An electrochemical recovery route by coupling electrochemical leaching and electrodeposition in ionic liquids (ILs) is proposed here, more environmentally friendly, performed in "soft" temperature conditions and without any gases emission. Studies of several electrolytes lead us to select BMIMTFSI + BMIMCl melts (bis(trifluorométhylsulfonyl) imidure + 1-butyl-3-méthylimidazolium chloride), due to the complexing ability of chloride against platinum and the good electrochemical stability of the RMIM+ cation. TFSI-, a weakly coordinate anion, allows us to modulate the complexing ability of the electrolyte, which is a key parameter affecting the nature and the electrochemical stability of the Pt complex formed after leaching. The optimal conditions of the leaching and electrodeposition steps have been determined during this work and successfully applied to PEMFC’s electrode. The selected electrolyte, which is weakly hygroscopic, allows the Pt recovery under ambient atmosphere

M.Sc. / This study focuses on the Merensky Reef (MR) occurring within the Two Rivers Platinum mine property in the farm Dwarsriver 372 KT, on the Southern sector of the Eastern Limb of the Bushveld Complex. Five MR exploratory drill core intersections were obtained. Petrographic and mineral chemical characteristics of these drill core samples focused on the characterization of minerals like clinopyroxene, orthopyroxene, plagioclase, chromite and olivine. Data of the cryptic variation of orthopyroxene, plagioclase and chromite, from a 10 m interval (approximate thickness of the section studied); from footwall through the MR to the hangingwall lithologies at Dwarsriver are described in this study. Locally the vertical cryptic variation of these minerals is broadly consistent with regional trends of the RLS. The lateral variation (i.e. along strike) is less pronounced; however, locally these minerals appear to be chemically evolving moving to the south of the property. Footwall orthopyroxene compositions vary from a minimum of En66 and reach a maximum of En84. Those of the MR range from En71 to En85. Hangingwall orthopyroxene compositions range from En60 and reach a maximum of En80. Plagioclase compositions in the footwall units range from a minimum of An69 and reach a maximum of An85. Those of the MR range from a minimum of An35 to a maximum of An84. This wide range in plagioclase compositions is believed to be as a result of the increased presence of fluids within the MR interval. The hangingwall plagioclase compositions range from An64 to An84. By analogy of the Western Limb, where the lithologies of the Northwestern sector are believed to be proximal to the feeder of this limb; the local lateral variation in the present study suggests that the lithologies of either the Central or Western sectors are most probably proximal to the feeder for the Eastern Limb. PGM assemblages associated with and adjacent to the MR chromitite stringers were evaluated using an MLA. Data obtained from this technique is in broad agreement with regional studies of the MR. With the aid of wholerock PGE assays the MLA technique has proven to be a powerful tool in evaluating PGM assemblages relatively quickly, from a few carefully selected samples. The mineralogical associations of the PGM with the gangue and host minerals have shown three main associations. These are the associations of chromite, BMS and silicates with the PGM, of which the base metal sulfide (BMS) association is remarkable given that these have a relatively low modal abundance. The relatively high mineralogical association of the BMS with PGM has been explained by a model involving a base metal sulfide liquid which possibly scavenged chalcophile and siderophile elements. Chromite chemistry and modal analyses of MR secondary silicate phases, which peak adjacent to the chromitite stringers, suggests elevated fluid overprinting within and adjacent to the chromitite stringers. The upper chromitite stringers, however, have higher abundances of PGM phases that are believed to be secondary in origin relative to the basal chromitite stringers. Generally the PGM associated with the upper chromitite stringers are also bigger in size averaging 70 μm as opposed to 27 μm for those associated with the basal chromitite stringers. The increase in grain size of the PGM along with the higher modal abundance of secondary PGM phases associated with the upper stringers is believed to be as a result of fluids. These fluids although affecting both the upper and basal chromitite stringers, appear to have had a relatively higher influence on the upper chromitite stringers. The most common PGMs encountered in this study are isoferroplatinum, sperrylite, michenerite, maslovite, cooperite, laurite and braggite.

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

Please read the abstract in the section 00front of this document / Thesis (PhD (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

The Uitkomst Complex is a mineralized, layered basic to ultrabasic intrusion, hosted by sedimentary rocks of the lower part of the Transvaal Supergroup. It is situated on the farms Uitkomst 541JT and Slaaihoek 540JT, about 25 km north of Badplaas and 50 km east of the eastern limb of the Bushveld Complex in the Mpumalanga province of South Africa. The intrusion plunges between 8 to 10º to the northwest with an established length of 12 km and a total thickness of 850 m. It is divided into seven lithological Units (from base to top), the Basal Gabbro (BGAB), Lower Harzburgite (LHZBG), Chromitiferous Harzburgite (PCR), Main Harzburgite (MHZBG), Pyroxenite (PXT), Gabbronorite (GN) and Upper Gabbro units (UGAB). A detailed petrographic and geochemical investigation of borehole core SH176, which provided a complete intersection of the Uitkomst Complex was carried out. The study shows that the Complex may have crystallized in a dynamic magma conduit setting. The whole rock geochemical trends indicate that there is a reversed fractionation in the basal portion of the Complex and a lack of fractionation in much of the MHZBG. Trace and REE variations show a decrease in concentration with height, contrary to what is expected of a progressively differentiating magma in a close system. Further, the platinum-group element concentration of the four basal units show no depletion with increasing height, suggesting that the individual units are not related to each other by means of in situ fractionation. Instead, a model whereby the individual units crystallized from distinct pulses of magma best explains the data. By comparing Nd isotopes and ratios of highly incompatible trace elements like [Th/La]n and [Sm/Ta]n from the Uitkomst Complex and Bushveld Complex it is seen that the Uitkomst magmas are of a similar lineage as the B1 magma of the Bushveld Complex, supporting a genetic link between the two complexes. The upper portion of the Uitkomst Complex shows values more akin to B3 magmas indicating the possible presence of more than one type of magma. Based on the available S isotope and trace element data, the sulphides of the Complex appear to have formed within the Complex, probably in response to contamination of the magma with dolomite. Entrainment of sulphides from depth is considered unlikely. The relatively low Cu/Ni ratios of the sulphides in the LHZBG, PCR and MHZBG (Cu/Ni 0.03 to 0.8) may be modelled by sulphide segregation from B1 magma and not from fractionation of sulphides that were later entrained in the streaming magma. / Dissertation (MSc)--University of Pretoria, 2006. / Geography, Geoinformatics and Meteorology / Unrestricted

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.

<p> Sulfide-poor platinum-group element (PGE) mineralization occurs within the Archean Boston Creek Flow ferropicrite, Abitibi greenstone belt, Canada. The PGE mineralization (∑PGE+Au = up to 1000 ppb) is manifest as metre-scale platinum-group mineral-bearing pods of disseminated chalcopyrite and pyrite (< 1 modal%) within titaniferous magnetite-rich gabbroic rock at the base of its central gabbroic layer. This mineralization is distinct in character from well known PGE mineralization associated with massive Fe-Ni-Cu sulfides at the base of komatiite flows at Kambalda, Western Australia and elsewhere. Exploration strategies presently used to search for PGE in mafic and ultramafic volcanic rock terrains are based on the geological and geophysical characteristics of sulfide-rich PGE mineralization. Consequently, refinements in exploration strategies are required if economic concentrations of sulfide-poor PGE mineralization are to be discovered in volcanic terrains.</p> <p> To begin development of such exploration criteria, ground-based magnetic and VLF surveys were conducted over the PGE mineralization along a single cross-section through the BCF. Drill core samples were collected along this transect to characterize the volume magnetic susceptibility and natural remanent magnetization (NRM) of the mineralization. Magnetic highs ranging in intensity from 64000 to 65000 nT were recorded for the base of the gabbroic layer, including mineralized outcrops. Susceptibilities of up to 9700 cgs and high remanence values with variable directions were determined. VLF, as expected, was not useful in identifying the mineralized horizons. The peridotite at the base of the flow appears to be the only conductive rock in the BCF.</p> <p> The magnetic highs associated with the base of the gabbroic layer define a positive anomaly that appears to be podiform in outline and up to ten metres in maximum dimension. This result suggests that the titaniferous magnetite-rich rock is itself podiform, like the enclosed PGE mineralization. This magnetic anomaly is not extensive enough to be evident on a regional scale aeromagnetic map as a separate anomaly within the BCF, and is not evident through VLF techniques. The rocks hosting the PGE mineralization is defined by the paleomagnetic results but this is not a practical field method.</p> <p> The geophysical characterization of the PGE mineralization host rocks, and of the BCF in general, demonstrates the potential of detailed magnetic and susceptibility mapping, together with petrographic and petrologic studies, in the search for economic PGE concentrations of sulfide-poor PGE mineralization in other volcanic and possibly plutonic rocks as well. Specifically, the results suggest that podiform magnetic anomalies within titaniferous magnetite-rich pyroxenites and gabbroic rocks may have potential use in the exploration for economic sulfide-poor PGE mineralization. Although the paleomagnetic methods used in this study are probably not of direct use in exploration, they were able to distinguish the different lithologies in the BCF. This substantiates the results of the susceptibility measurements in characterizing PGE mineralized, titaniferous magnetite-bearing rocks. The results of the paleomagnetic study also show that the NRM of the Ghost Range intrusive complex is not primary and therefore the Archean apparent polar wander path as it is currently defined is incorrect.</p> / Thesis / Bachelor of Science (BSc)

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.