No description available.

L’industrie microélectronique en perpétuelle évolution impose de nouvelles spécifications pour les futures générations de microbatteries au lithium. Pour ces dispositifs, il est désormais impératif d’améliorer la capacité volumique des matériaux actifs d’électrode positive ainsi que d’abaisser leur tension de fonction-nement aux alentours de 1,5 V. Ce travail propose d’étudier le comportement de sulfures de métaux de transition de formule MSx (M = Fe, Co, Ni, Ti ; x = 1, 2), réagissant vis-à-vis du lithium selon un mécanisme de conversion, à un potentiel adapté à l’application. Déposés sous forme de couches minces par pulvérisa-tion cathodique radiofréquence à cathode à effet magnétron, ces sulfures ont été caractérisés en termes de composition, morphologie et structure. Dans la plupart des cas, des films cristallisés avec une incorpo-ration minime d’oxygène ont été obtenus sans chauffage intentionnel des substrats. L’utilisation d’une configuration en couches minces et d’un électrolyte solide, propres aux microbatteries, permet une bonne réversibilité des réactions ainsi qu’une prévention des réactions parasites généralement observées pour ces sulfures en électrolyte liquide. Une caractérisation fine des propriétés électrochimiques de ces matériaux en microbatterie tout-solide au lithium a donc pu être réalisée, permettant de corréler la réver-sibilité des cycles d’insertion / extraction du lithium avec la nature du cation de métal de transition mais aussi avec la concentration en soufre dans l’électrode. / The overgoing evolution of the microelectronics industry implies new specifications when it comes to next generations of lithium microbatteries. It is now of utmost importance for these devices to increase the volumetric capacity of the positive electrode material and bring the working potential down to approxi-mately 1.5 V. Hence, this work is aimed at studying the behavior of transition metal sulfides, of formula MSx (M = Fe, Co, Ni ; x = 1, 2), which react towards lithium through conversion reaction mechanism at an adapted potential. Thin films of these materials, prepared via non-reactive radiofrequency magnetron sputtering were structurally, morphologically and compositionally characterized prior to their integration in microbatteries. In most cases, crystallized films were obtained without any intentional heating of the substrates. Also, very low oxygen incorporation within the deposited materials was observed. Thanks to the combined use of thin film and all-solid-state configuration in the microbatteries, good reversibility of the reactions is allowed and parasitic reactions generally observed for transition metal sulfides electrodes in conventionally used liquid electrolytes cells can be avoided. Thus, deep electrochemical characteriza-tions were successfully conducted on the microbatteries. For these materials, it was shown that the re-versibility of the lithium insertion / extraction cycles during operation is directly linked to the nature of the transition metal cation and to the overall sulfur concentration in the electrode material.

Bisacetylenic cabamates/carbonates are most useful compounds in finger mark development, for the synthesis of polymeric gels and other material applications. Organochalogen derivatives are the organic compounds containing chalcogen (S, Se) atoms. They have been used as chiral ligands for enatioselective catalysis, glycosyl donors and in the synthesis of heterocyclic compounds etc. This thesis describes our efforts towards synthesis of bisacetylenic cabamates/carbonates and development new synthetic strategies using rongalite (Na+HOCH2SO2-) and benzyltriethyl ammonium tetrathiomolybate [BnEt3N]2MoS4 as a reducing agents led to obtain various organochalcogen derivatives. We developed a new reagent, hexa-2,4-diyne-1,6-bisoxycarbonyl chloride [Hbc Cl] for the synthesis of symmetrical diacetylenic biscarbamates/biscarbonates and further studied the solid state structures using X-ray crystallography. Later we described a stereoselective method for the hydrothiolation of buta-1,3-diynes derivatives using diaryldichalcogenides in the presence of rongalite and K2CO3. The buta-1,3-diynes underwent stereoselective addition reaction with in situ generated chalocgenate anion from diaryl dichalcogenides which afforded the corresponding (Z)-chalcogenynes. The reactivity of buta-1,3-diynes with diaryl dichalcogenides was further studied at higher temperature led to a mixture of mono chalcogenated and bischalcogenated products. Then an efficient method was developed for the synthesis of enatiopure β-amino sulfides/selenides via ring opening of sulfamidates using diarylchalcogenides with rongalite as reducing agent. Further we synthesized chalcogeno derivatives of sugars from glycosyl halides and diaryl dichalcogenides in the presence rongalite. In addition, the synthesis of mixed glycosyl dichalcogenides has been demonstrated using [BnEt3N]2MoS4 as sulfur transfer agent as well as reducing agent. Finally the reactivity of [BnEt3N]2MoS4 was studied in detail with various isatioc anhydrides which led to the formation of S-benzyl 2-aminobenzothioate derivatives. Further we synthesized S-alkyl/aryl 2-aminobenzothioate derivatives via ring opening of isatoic anhydrides and diaryl/dialkyl chalcogenides by mean of [BnEt3N]2MoS4 as a reducing agent. We extended this method in a one-pot, tandem fashion with various alkyl halides. In this thesis, details of all of the above studies have been described.

Ce travail de thèse porte sur l'élaboration de luminophores (La₂O₂S:Er,Yb, La₂O₂S:Nd, Lu₂O₂S:Nd, CaLa₂S₄:Nd) et céramiques optiques infra-rouges (ZnS et CaLa₂S₄). Il a consisté, en premier lieu, à développer des méthodes de synthèse de poudres de très grande pureté, principalement par méthode de combustion suivie de traitement sous H₂S(/N₂). Des nanopoudres de La₂O₂S:Er,Yb (50-200nm) se sont révélées être des luminophores très efficaces pour l'up‐conversion. Des nanopoudres de La₂O₂S: Nd (~250 nm) présentent un effet laser avec une énergie émise de 2,5 mJ et un rendement supérieur à 15%. L'étude de la densification (par hot pressing, HP) de poudres de ZnS préparées selon trois voies de synthèse (précipitation, synthèse par combustion et réaction en bain fondu) a permis d'élaborer des céramiques transparentes ZnS de qualité CVD‐HIP, avec des transmissions maximales supérieures à 73% à 12μm (précipitation) et la transmission maximale théorique de 75% à 10μm (combustion). Le frittage par HP de poudres de CaLa₂S₄, entre 1100°C et 1300°C, conduit, à cause d'une contamination par le carbone de la matrice de frittage et/ou d'une perte de soufre, à des céramiques noires et opaques en IR. CaLa₂S₄ comme nouveau matériau de matrice tolère des taux de dopage élevés en Nd. Après excitation à 815nm, il présente deux émissions intenses à 900nm et 1060nm, ainsi qu'une émission plus faible à 1350nm avec une intensité de luminescence qui augmente jusqu'à 10% molaire en Nd. / This thesis deals with the elaboration of phosphors (La₂O₂S:Er,Yb, La₂O₂S:Nd, Lu₂O₂S:Nd, CaLa₂S₄:Nd) and optical IR ceramics (ZnS and CaLa₂S₄). First, the routes for the synthesis of high purity powders have been developed, mainly by combustion method followed by H₂S(/N₂) treatment. La₂O₂S:Er, Yb nanopowders (50-200 nm) proved to be very efficient phosphors for up-conversion. La₂O₂S: Nd nanopowders (~250 nm) have a laser effect with a 2.5 mJ output energy and a yield higher than 15%. The densification by hot pressing of ZnS powders prepared following three synthesis routes (precipitation, combustion synthesis and reaction melt) has developed ZnS transparent ceramic of CVD‐HIP quality, with maximum transmission greater than 73% at 12μm (from powders obtained by precipitation) and with the theoretical maximum transmission of 75% at 10μm (from powders obtained by combustion). Hot pressing of CaLa₂S₄ powders, between 1100°C and 1300°C, leads to IR opaque ceramics with black color, due to carbon diffusion from the sintering matrix and/or to sulfur loss. CaLa₂S₄ as new phosphor matrix material tolerates high Nd doping level. After excitation at 815 nm, it shows two intense emissions at 900 nm and 1060 nm, and a lower transmission at 1350nm with a luminescence intensity that increases up to 10% (mol) Nd.

Le massif du Mayo Kebbi, situé au sud-ouest du Tchad entre le craton du Congo au Sud, le craton Ouest Africain à l’Ouest et le Métacraton du Sahara à l’Est, expose un segment de croûte juvenile néoprotérozoïque accrété dans la ceinture orogénique d’Afrique Centrale durant l’orogène Pan-Africaine. Il est constitué de deux ceintures de roches vertes (Zalbi et Goueygoudoum) séparées par le batholithe calco-alcalin du Mayo Kebbi et recoupées par des plutons à signature calco-alcaline hyperpotassique. Le tout est recouvert par des formations sédimentaires phanérozoïques. Les ceintures de roches vertes contiennent des zones minéralisées en sulfures encaissées par les roches métaplutoniques (granodiorites) et métavolcanosédimentaires (métabasaltes). La minéralisation est constituée d’un assemblage métallique à pyrite, pyrrhotite, arsénopyrite, chalcopyrite, pentlandite, pentlandite argentifère, pentlandite cobaltifère, sphalérite, de cobaltite. Les sulfures se trouvent à l’état disséminé ou sous forme de remplissage de fissures. Les roches vertes comprennent également des filons de quartz à calcite-chlorite et encaissant des minéralisations à pyrite, chalcopyrite, galène et or. L’analyse de l’or indique une association systématique avec l’argent. Le pluton calco-alcalin hyperpotassique de Zabili contient des indices de minéralisations en Uranium liés à la superposition de : (1) déformation ductile et altération métasomatique impliquant l'interaction entre les minéraux magmatiques avec un fluide riche en Na, d'origine magmatique, contemporain au dépôt d’oxydes d'uranium, (2) une déformation fragile et le dépôt de silicates hydratés d'uranium secondaires impliquant un fluide riche en Na-Ca. La minéralisation en uranium s’exprime sous forme d’uraninite, d’ekanite, de kasolite, de brannerite, et de silicates d’uranium tels que la coffinite. Un âge U-Th-Pb de 599 +/- 4 Ma a été obtenu sur des grains de monazite hydrothermales. Ces minéralisations d'uranium représentent l'expression extrême de la différenciation de la croûte, suite à la remobilisation de ce segment de croûte juvénile Néoprotérozoïque au cours de l’orogénèse Pan-Africaine / The Mayo Kebbi massiflocated in southwestern Chad between the Congo craton in the South, the West African craton in the west and the Sahara metacraton to the east exposes a segment of Neoproterozoic juvenile crust accreted in the Central African orogenic belt during the Pan African orogeny. It consists of two greenstone belts (Zalbi and Goueygoudoum) separated by the May Kebbi calc-alkaline batholith complexes and intruded by calc-alkaline high-K granitic plutons. The whole is covered by Phanerozoic sedimentary formations. The greenstone belts contain sulphide zones hosted mainly by metaplutonic rocks (granodiorites) and metabasalts and metavolcaniclastics. The mineralization comprises pyrite, pyrrhotite, arsenopyrite, chalcopyrite, pentlandite, pentlandite silver, pentlandite cobaltiferous, sphalerite, cobaltite. These sulphides are disseminated, aggregated in form of layers or are filling veins and cracks. The greenstones also contain quartz veins with calcite and chlorite comprising a mineralization made of pyrite, chalcopyrite, galena and gold. Gold is present both as native crystals and as electrum. The high-K calc-alkaline Zabili granitic pluton hosts uranium mineralization related to a superposition of: (1) ductile deformation and metasomatic alteration implying the interaction between magmatic minerals with a Na-rich fluid, of potential magmatic origin, coeval to the main deposition of uranium oxides, followed by (2) brittle deformation and deposition of secondary hydrated uranium silicates involving a Na-Ca-rich fluid. We propose that these uranium mineralizations represent the extreme expression of crustal differentiation as a result of Pan-African reworking of a Neoproterozoic juvenile crustal segment

No description available.

Unsaturated sugars constitute as an important category of carbohydrate precursors in synthesis. Specifically, 1,2- and 2,3-unsaturated glycosides are excellent intermediates to derivatize monosaccharides and as building blocks in organic synthesis. For example, a major utility of 1,2-unsaturated sugars, namely glycals, is the addition reactions to afford 2-deoxy glycosides under acidic conditions and rearrangement reactions to produce 2,3-unsaturated glycosides. Lewis acids favour the formation of 2,3-unsaturated glycosides, whereas, Brønsted acids lead to normal addition products. A mixture of both the product is obtained often, depending on the nucleophiles and the stereochemistry of glycal. Chapter 1 of the thesis describes (i) reactivities of glycals under acidic condition and (ii) a general survey of reactions involving on C2-C3 carbons of monosaccharides. Glycals are useful precursors to derive a number of functionalized monosaccharide derivatives. A well-known acid catalyzed reaction of glycals is their conversion to 2,3¬unsaturated glycosides, known as the Ferrier products. In a research programme, reactivity switching and selective activation of C-1 or C-3 of 2,3-unsaturated thioglycosides under acid catalyzed condition was undertaken. Thioglycosides are excellent glycosyl donors and can be activated easily. In identifying the reactivities of 2,3-unsaturated thioglycosides, obtained through Ce(IV)-mediated reaction of a glycal, it was intended to study the glycosylation reaction and also the reactivity control of C1-C3 carbons during a glycosylation reaction. Experiments showed that a reactivity switching was possible through activation of either C-1 or C-3. Thus, C-1 glycosylation with alcohol acceptors occurred in the presence of NIS/TfOH, without the acceptors reacting at C-3. On the other hand, reaction of 2,3-unsaturated thioglycosides with alcohols mediated by triflic acid alone led to a transposition of C-1 ethylthio-moiety to C-3 intramolecularly, to form 3-ethylthio-glycals. Resulting glycals underwent glycosylation with alcohols to afford 3-ethylthio-2-deoxy glycosides. However, when thiol was used as an acceptor, only a stereoselective addition at C-3 resulted, so as to form C-1, C-3 dithio-substituted 2-deoxypyranosides. Oxocarbenium ion is the reactive intermediate during activation of a glycosyl donor, and in the case of a 2,3-unsaturated thioglycosides, the oxocarbenium ion may stabilize further by the presence of a C2-C3 unsaturation. Reaction of a nucleophile with allylic oxocarbenium ion may lead to two regio-isomers. Initially, NIS/TfOH was attempted on 2,3–unsaturated sugar with various alcohols and it was found that C-1 was the preferred reactive centre (Scheme 1) Scheme 1 In order to optimize the reaction for selective nucleophilic attack at C-3, further study was continued by using stoichiometric TfOH, in presence of acceptors alcohols with the intension to activate the double bond. The reaction led to the formation of 2-deoxy O-glycosides with the concomitant transposition of C-1 ethylthio-moiety to C-3 (Scheme 2). Scheme 2 An important observation was that the transposition of thioethyl group from C-1 to C-3 was highly regioselective. For example, with thiocresol as the nucleophile, there was an addition across the C-2-C-3 double bond to afford C-1, C-3-dithio derivative (Scheme 2). Thus, hard-soft nature of the nucleophiles, as well as, carbon centres helped to rationalize the reactivites. It was also observed that the intramolecular transposition of thioethyl group is highly stereo-controlled by equatorial C-4 acetoxy group. Thus, thioethyl nucleophile approached selectively at C-3 and afforded trans-diequatorial products. This rationalization was further confirmed through (i) reaction of benzyl protected 2,3-unsaturated thioglycoside, wherein a C-3 epimeric mixture was observed in 1:1 ratio; (ii) galactosyl derivative under similar reaction condition afforded anomeric mixture of 3-(4-methylphenylthio)-O-glycosides, with trans-diaxial orientation of substituent at C-3 (Scheme 3). Scheme 3 These reactions confirmed the role of C-4 substituent on the carbocation at C-3, through the presence or absence of a neighbouring group participation. In summary, in Chapter 2 the selective activation of either anomeric carbon or C-3 with proper choice of activation and reactivity control at each carbon will be described. Thioglycosides are excellent glyosyl donor and their glycosylation reactions were well explored. Upon indentifying the intramolecular transposition of thioalkyl/aryl functionality from C-1 to C-3, further investigations was undertaken to utilize the newly formed carbon sulfur bonds at C-3. Realizing a potential for such 3-alkyl/aryl thio 2-deoxy sugar, the Pummerer rearrangement was investigated. For this purpose, the thioalkyl/aryl moiety at C-3 was oxidized first to a sulfoxide. The resulting sulfoxide was allowed to undergo Pummerer rearrangement to afford vinyl sulfide (Scheme 4), resulting from the elimination of HOAc in the thioacetal formed in situ. Having implemented Pummerer rearrangement on a sugar substrate, synthetic utility of the rearrangement product, namely vinyl sulfide was undertaken. An effort to implement conjugate addition reaction was undertaken, which required the conversion of vinyl sulfide to vinyl sulfoxide in the first step. The conjugate addition reactions were first conducted with alkoxide nucleophiles. The reaction showed that addition of nucleophiles occurred from axial face to furnish manno-configured derivatives as a single diastereomer at sulfinyl sulfur in a moderate yield along with O-deacetylated product. It was also found that O-benzyl protected sugar vinyl sulfoxide was totally resistant to the conjugate addition reaction (Scheme 4). Scheme 4 In order to find the influence of the substituents in sulfoxide moiety in the addition of nucleophiles, additional study was conducted in which a less hindered thioethyl moiety was installed in place of p-tolylthio moiety. To install ethylthio moiety, a similar sequence of reaction was undertaken as described previously in Scheme 4. Conjugate addition reaction with alkoxide nucleophiles was conducted and analysis of the reaction showed that the addition of alkoxides remained similar, leading to the formation of manno-configuration of substituents (Scheme 5). Scheme 5 The configuration of the Michael adducts were ascertained from 1H NMR, as well as 2D NMR spectroscopies. H-1 of all adducts appeared as an apparent singlet, consistent with very small J1,2 values. Aryl vinyl sulfoxide afforded conjugate addition product at much higher ratio than corresponding alkyl vinyl sulfoxide. Thus, among aryl and alkyl vinyl sulfoxides, conjugate addition occurred better with the aryl vinyl sulfoxide, indicating a strong electronic effect of aryl group in stabilizing the conjugate anion which would form in situ during nucleophilic addition with vinyl sulfoxide. Therefore, p-tolylthio substituted vinyl sulfoxide served as a more efficient Michael acceptor when compared to the thioethyl substituted vinyl sulfoxide. Asymmetric environment of vinyl sulfoxides play a vital role during the reaction. Vinyl sulfoxides can exist in two stereochemically distinct conformation which makes the vinyl group electronically dissimilar. In one of the conformer S-O and C-C bonds are coplanar, whereas in the other conformation, these two bonds are opposite to each other. It is agreed generally that vinyl sulfoxides generally try to adopt the most reactive conformer during the reaction in which the C-C and S-O bonds are syn to each other. Thus, the preference for an axial attack would originate from a face anti to the lone pair of electrons on the sulfur of sulfoxide functionality, leading to the formation of the product with manno-configuration. As O-deacetylated vinyl sulfoxide was obtained along with the Michael adducts, it was assumed that one of the epimers of vinyl sulfoxide appeared to be more reactive when compared to the other. Chapter 3 describes implementation of a Pummerer rearrangement in order to synthesize a sugar vinyl sulfoxide and its conjugate addition reactions with alkoxide nucleophiles. The nucleophilic addition reactions of vinyl sulfoxide with other nucleophiles were studied further. The effect of the substituents of chiral sulfoxides in conjugate addition reactions was also incorporated in the course of reactions. Reactions of amines, carbon and sulfur nucleophiles were undertaken with p-tolylthio-substituted vinyl sulfoxides. The reactions showed formation of the addition-elimination products (Scheme 6). All primary amines, carbon and sulfur nucleophiles afforded C-2 axial epimer, namely, threo-epimer exclusively, wherein secondary amines furnished the equatorial vs axial epimer in 3:1 ratio. Scheme 6 In order to assess the course of the reaction, vinyl sulfoxide presenting a p-cumenethio¬moiety was installed in place of p-tolylthio moiety. Conjugate addition reactions were performed with both primary as well as secondary amines that showed formation of the C-2 epimeric mixtures. With both the primary and secondary amines C-2 equatorial epimer was found to be as the major product (Scheme 7). Scheme 7 In conjugate addition of vinyl sulfoxides, nucleophiles approach the olefinic face preferentially, which is anti to the electron rich sulfur lone pair of electrons and syn to the bulky aryl group. Therefore, C-2 axial epimer was observed as most favourable product. However, secondary amines remarkably influenced the pattern as well as selectivity of the reaction. Steric considerations were likely to dictate the overall reactivity with secondary amines which was even more pronounced when using p-cumenethio-substituted vinyl sulfoxide. Chapter 4 describes the conjugate additions as well as remote effect of aryl substituent on the selectivity of addition of amines on sugar sulfoxide In summary, the Thesis establishes: A new reactivity of switching and a selective activation of 2,3-unsaturated thioglycoside; A Pummerer rearrangement route in order to synthesize sugar vinyl sulfide for the first time, which on selective oxidation furnish a sugar vinyl sulfoxide, a useful precursor for conjugate addition reactions; An assessment of the stereoelectronic, as well as, steric effect of the chiral vinyl sulfoxide with various nucleophiles in conjugate addition reactions; Influence of the protecting groups were also studied in conjugate addition reactions. Overall the study presented in the Thesis provides a new insight to unsaturated sugars. The salient features of the present findings also showed that the intermediates such as C-3 substituted thioalkyl/aryl glycosides, vinyl sulfides, a variety of new C-2 substituted vinyl sulfoxides are also the potential sites for many types of modifications in monosaccharides. (For structural formula pl see the pdf file)

Thesis (PhD)--University of Stellenbosch, 2004. / ENGLISH ABSTRACT: The Gamsberg Zn-Pb deposit is a metamorphosed and multiply deformed sediment-hosted base metal deposit in the central Namaqua Province of South Africa. The deposit is hosted by the Bushmanland Group, a late Palaeoproterozoic (2000-1600 Ma) supracrustal succession of quartzite, metapelitic schist and interbedded metavolcanic rocks. Mineralisation occurs within the central part of the Gams Formation, a heterogeneous sequence of metamorphosed metalliferous sediments and fine-grained organic-rich shales. The ore horizon is subdivided into a lower unit of metapelite-hosted ore, an intermediate layer of phosphorite-hosted ore, and an upper unit of banded garnet-apatite ore. The ore body is enveloped by unmineralised silicate-, carbonate- and oxide-facies metalliferous rocks, which originally represented mixtures of Fe-Mn-rich hydrothermal precipitates, authigenic carbonate, and variable concentrations of detrital material. Based on mineralogical and geochemical characteristics, the metalliferous host rocks are subdivided into iron formations, coticules, Fe-Mn silicates, impure marbles and barite/Ba-rich quartzite. Minerals of the Gams Formation mostly represent solid solution between the Fe and Mn end-members of garnet, pyroxene, pyroxenoid, amphibole, olivine, spinel and ilmenite. Calcium-rich rock types are a typical feature and characterized by the occurrence of manganoan calcite, clinopyroxene, andradite-rich garnet and titanite. A successive increase in the (Mn+Ca):Fe value of rocks and minerals is evident with increasing distance from the ore horizon. Amphibole is restricted to Fe-rich ore-bearing assemblages, whereas orthopyroxene, clinopyroxene, Fe-rich pyroxenoid and olivine are present in intermediate assemblages, and Mn-rich rhodonite and pyroxmangite in the most manganiferous assemblages. These variations are mimicked by an increase in the Mn:Fe value of coexisting garnet and ilmenite group minerals with increasing distance from ore. LA-ICP-MS analyses have been used to constrain the REE patterns of garnet and apatite. In the ore-body, these minerals display a positive Eu anomaly, which is interpreted to reflect a distinct hydrothermal signature. In contrast, garnet and apatite in unmineralised metalliferous rocks display nil or a negative Eu anomaly. Primary features of the Gams Formation, such as REE patterns, the banded nature of garnet-apatite ore, the presence of diagenetic apatite nodules, and the distribution of the redox-sensitive elements Ba and Mn have been used to constrain palaeo-environmental conditions. The results indicate that metapelitehosted ore has been deposited in a stratified ocean that was characterised by anoxic bottom waters and precipitation of Fe and Zn sulphides into organic matter-rich shales. These rocks were superceded by phosphorite-hosted ore, garnet-apatite ore and metalliferous host rocks that developed in a suboxic to oxic environment. The large size of the deposit, the internal lamination of the ores and the predominance of sphalerite and barite are consistent with a vent-distal setting and precipitation of the ore-forming constituents from dense and reduced hydrothermal fluids, which originated due to reactivation of dormant growth faults. Collectively, the geological evidence indicates that Gamsberg is bridging the gap betweenthe SEDEX and BHT classifications. The relationships demonstrate that differences between these two classes of sediment-hosted Zn-Pb deposits are predominantly related to environmental conditions within localised third order basins and not to fundamental differences in ore-forming processes. / AFRIKAANSE OPSOMMING: Die Gamsberg Zn-Pb afsetting is ‘n meerfasig vervormde en gemetamorfiseerde sedimentgesetelde onedel metaal afsetting in die sentrale Namakwa Provinsie van Suid Afrika. Die afsetting word geherberg deur die Boesmanland Groep, ‘n laat Paleoproterosoïse (2000 – 1600 Ma) bokors-opeenvolging van kwartsiet, metapelitiese skis en tussengelaagde metavulkaniese gesteente. Mineralisasie word gevind in the sentrale deel van die Gams Formasie. Die Gams Formasie is ‘n heterogene opeenvolging van gemetamorfiseerde metaalhoudende sediment en fynkorrelrige organiese skalie. Die erts horison word onderverdeel in ‘n onderste laag van metapeliet-gesetelde erts, n sentrale laag van fosforiet-gesetelde erts, en ‘n boonste laag van gebande granaat-apatiet erts. Die erts-liggaam word omhuls deur ongemineraliseerde silikaat-, karbonaat- en oksied-fasies metal-ryke rotse. Hierdie gesteentes word geinterpreteer as oorspronklike mengsels van Fe-Mn-ryke hidrotermale partikels, outigeniese karbonaat, en verskeie hoeveelhede detritale materiaal. Gebaseer op mineralogiese en geochemiese kenmerke word hierdie rotse onderverdeel in ysterformasies, „coticules“, Fe-Mn silikate, onsuiwer marmer en barite/Ba-ryke kwartsiet. Minerale van die Gams Formasie form meestal soliede oplossingsreekse tussen die Fe en Mn endlede van granaat, pirokseen, piroksenoid, amfibool, olivien, spinel en ilmeniet. Kalsium-ryke rots tipes is ‘n tipiese kenmerk van die Gams Formasie en word gekenmerk deur mangaan-ryke kalsiet, klinopirokseen, andradiet-ryke granaat en sfeen. Daar word ‘n stapsgewyse vergroting van die (Mn+Ca):Fe verhouding in gesteentes en minerale gevind met toeneemende afstand van die erts horison. Amfibool is beperk tot Fe-ryke ertsdraende gesteentes, ortopirokseen, klinopirokseen, Fe-ryke piroksenoid en olivien tot intermediêre gesteentes, en Mn-ryke rodoniet en piroksmangiet tot Mn-ryke gesteentes. Hierdie variasies gaan gepaard met vergroting van die Mn:Fe verhouding in granaat en ilmeniet-groep minerale met toeneemende afstand van die erts. LA-ICP-MS analises was gebruik om die skaars-aarde element patrone van granaat en apatiet te bepaal. In die erts-liggaam wys hierdie minerale ‘n positiewe Eu anomalie, wat geinterpreteerd word as ‘n hidrotermale kenmerk. In ongemineraliseerde gasheer gesteentes wys granaat en apatiet geen of ‘n negatiewe Eu anomalie. Primêre kenmerke van die Gams Formasie, soos skaars-aarde patrone, the gebande voorkoms van granaat-apatiet erts, die teenwoordigheid van diagenetiese apatiet knolle, en die verspreiding van die redox-sensitiewe elemente Ba en Mn, was gebruik om afleidings oor die paleo-omgewing te maak. Die resultate het gewys dat metapeliet-gesetelde erts afgeset was onder anoksiese bodem water deur presipitasie van Fe en Zn sulfiedes in organiese skalie. Hierdie erts gaan oor in fosforiet-gesetelde erts, granaat-apatiet erts en metaal-ryke gasheer gesteente wat in ‘n suboksiese tot oksiese omgewing ontstaan het. Die grootte van die afsetting, die interne gelaagdheid van die erts, asook die teenwoordigheid van sfaleriet en bariet dui op ‘n distale omgewing relatief tot die hidrotermale bron en presipitasie van die ertsuit digte en gereduseerde hidrotermale vloeistowwe, wat ontstaan het deur die heraktiveering van rustende groeiverskuiwings. Gesaamentlik bewys die geologiese kenmerke van Gamsberg dat gemetamorfiseerde SEDEX en Broken Hill-tipe mineralisasie binne die perke van ‘n enkele afsetting kan voorkom. Die geologiese verhoudings dui aan dat verskille tussen hierdie twee tipes van sedimentgesetelde afsettings meestal veroorsaak word deur omgewings-toestande binne in gelokaliseerde derde orde komme en nie deur fundamentele verskille in ertsvormende prosesse nie.

Ce travail de thèse étudie l’influence de la morphologie des feuillets de sulfure de molybdène sur la sélectivité des catalyseurs d’hydrotraitement. Les feuillets de phase active présentent en effet deux types de bords appelés « M-edge » et « S-edge » susceptibles de conduire à des réactivités différentes. Le changement de la morphologie 2D des feuillets pourrait modifier les proportions de bords M et S exposés et ainsi les propriétés catalytiques des catalyseurs sulfures. Pour cela, des catalyseurs non promus (Mo) et promus (CoMo), supportés sur alumine ont été préparés par imprégnation à sec puis sulfurés dans des conditions variées (gaz et température). Des tests catalytiques en hydrodésulfuration (HDS) sélective des essences de FCC (sélectivité HDS/HYD) ont ensuite permis d’évaluer l’impact de la morphologie en s’appuyant sur des modèles géométriques construits à partir de calculs DFT et de caractérisations expérimentales (TEM, IR (CO), TPR, XPS). Les résultats obtenus pour les catalyseurs de type Mo semblent ainsi confirmer l’influence de la morphologie 2D sur la sélectivité HDS/HYD, le bord M paraissant être le plus sélectif pour les catalyseurs non promus. Ils mettent également en évidence l’importance de la réductibilité plus ou moins marquée des bords sur les propriétés catalytiques, notamment sur le bord M. Le changement des conditions de sulfuration semble donc affecter la morphologie des particules mais également les propriétés chimiques propres à chaque bord. En ce qui concerne les catalyseurs promus, la variation des conditions de sulfuration semble agir essentiellement au niveau de la répartition du promoteur entre les bords M et S. Cependant, les interactions avec le support paraissent constituer un frein aux effets de promotion. Dans ce contexte, les sulfurations à haute température sous H2S pur permettent d’obtenir des gains significatifs en activité et sélectivité. Ces résultats semblent dus à de faibles interactions avec le support et une décoration privilégiée du bord S qui pourrait favoriser la réaction d’HDS et limiter la réaction d’HYD. Au final, les interprétations effectuées en terme de morphologie 2D tendent à confirmer que ce paramètre peut constituer un axe de développement intéressant pour les catalyseurs d’hydrotraitement. L'optimisation des conditions de sulfuration permettraient bien de faire varier la morphologie et le taux de décoration du promoteur des catalyseurs, améliorant ainsi significativement l'activité et la sélectivité / This thesis examines the influence of the morphology of particles of molybdenum sulfide on selectivity of hydrotreating catalysts. Nanoparticles of active phase present two types of edges called “M-edge” and “S-edge” which may lead to different reactivities. The change in morphology of the 2D sheets could change the proportions of M and S edges exposed and thus the catalytic properties of sulfide catalysts. For this, non-promoted (Mo) and promoted (CoMo) catalysts, supported on alumina were prepared by dry impregnation and sulfide in various conditions (gas and temperature). Catalytic tests in selective hydrodesulfurization (HDS) of FCC gasoline (selectivity HDS /HYD) were then used to assess the impact of the morphology based on geometrical models which were constructed with DFT calculations and experimental characterizations (TEM, IR (CO), TPR, XPS). The results for Mo catalysts seem to confirm the influence of the 2D morphology selectivity HDS / HYD, M-edge appearing to be the most selective for non-promoted catalysts. They also highlight the importance of the reducibility more or less pronounced of the edges on the catalytic properties, especially on the M-edge. The different conditions of sulfidation seem to affect the morphology of the particles but also the specific chemical properties at each edge. Regarding to the promoted catalysts, the different conditions of sulfidation appear to act primarily at the distribution of the promoter between the M and S edges. However, interactions with the carrier appear to constitute an obstacle to promoting effects. In this context, sulfidations at high temperature in pure H2S lead to obtain significant gains in activity and selectivity. These results appear to be due to weak interactions with the carrier and to the presence of the promoter on the S-edge which could promote the HDS reaction and limit the HYD reaction. Finally, the interpretations made in terms of 2D morphology tend to confirm that this parameter can be an interesting line of development for hydrotreating catalysts. Optimization of the sulfidation conditions could effectively allow to vary the morphology and the rate of decoration of promoted catalysts which significantly improve the activity and selectivity

L'ouverture sélective de cycle (OSC) d'hydrocarbures polycycliques vise à augmenter le nombre de cétane des carburants diesel. OSC efficace peut être atteint par l'hydroconversion sur des catalyseurs bifonctionnels métal noble/fonction acide. La décaline et, à plus faible mesure, le perhydroindane, le butylcyclohexane et la tétraline, ont été utilisés comme molécules modèles pour l'étude des l'OSC de sulfures de métaux de transition (TMSs) supportés sur zéolithes ou silice-alumine amorphe dans un réacteur à lit fixe sous haute pression (5 MPa) avec une concentration élevée d'H2S dans la charge réactionnelle (1 %). Les nombreux produits d'hydroconversion ont été identifiés grâce à la chromatographie gazeuse bidimensionnelle, qui nous a permis de mieux comprendre les mécanismes de réaction. Ce travail a consisté à l'étude de la nature et la charge du SMT et la nature du support. Comparé à la zéolithe seule, le catalyseur RuSx/HY (qui sert de référence) est plus stable et dix fois plus actif avec une sélectivité en produits d'ouverture proche des 30% à 240 °C. Les produits les plus abondants restent les produits d'isomérisation, ce qui suggère que l'acidité du support domine le schéma réactionnel. Quant à l'ajout de TMS, leur rôle est d'activer l'hydrogène, de favoriser les réactions d'hydrogénation/déshydrogénation et limiter le cokage des sites acides. NiSx/HY est aussi performant que les catalyseurs à base de Ru, Ir ou Rh et un effet de synergie est observé pour les catalyseurs ternaires Ni-Ru et Ni-Rh. Toutefois, comparé aux métaux nobles comme l'Ir et le Ru étudiés sans H2S, les catalyseurs sulfures sont quasiment non-hydrogénolysants. Enfin, la zéolithe HY présente des performances proches a la H-Beta mais avec moins de craquage / The selective ring opening (SRO) of polycyclic hydrocarbons aims at increasing the cetane numbers of diesel fuels. Efficient SRO can be achieved through hydroconversion over bifunctional noble metal/acid catalysts. Decalin and, to lower extents, perhydroindan, butylcyclohexane and tetralin, have been used as model molecules to investigate the SRO performances of transition metal sulfides (TMSs) supported on zeolites or amorphous silica-alumina in a high-pressure (5 MPa) flow-fixed bed reactor with a high concentration of H2S in the reactant feed (1 %). The numerous hydroconversion products have been identified using comprehensive two-dimensional chromatography for various levels of reactant conversions, which allowed us to gain insight into the reaction mechanisms. The presence, loading and nature of the TMS, and the nature of the support, have been investigated. With respect to the bare HY zeolite, RuSx/HY (which served as our reference) is more stable and ten times more active, with a ring-opening selectivity of up to 30 % at 240 °C. The most abundant products are skeletal-isomerization ones, which suggests that the acidic support dominates the reaction scheme. The TMS role is to activate hydrogen, catalyze hydrogenation/ dehydrogenation and prevent the coking of acidic sites. NiSx/HY performs similarly to Ru, Ir and Rh-based catalysts, and a synergetic promoting effect is observed for Ni-Ru and Ni-Rh combinations. However, with respect to noble metals such as Ir and Ru under H2S-free conditions, the sulfide counterparts appear much less (if not) hydrogenolytic. As compared to HY, the H-Beta support shows similar performance but promotes cracking