M.Tech. (Chemistry, Faculty of Applied and Computer Science), Vaal University of Technology. / Complexes of alkyldithiocarbamate and thiuram have been extensively explored for various applications in the medical field. Thiuram and dithiocarbamate ligands were used to prepared complexes of cobalt and copper. The high abundance of sulfur in these ligands has resulted to be the preferred complexes for the synthesis of metal sulfide nanoparticles. All the prepared complexes were characterized using techniques such as IR and 1HNMR spectroscopy, elemental analysis, and thermogravimetric analysis. All the spectra data obtained were consistent with the coordination of the ligands through sulfur atom to the metal ion. The thermogravimetric analysis of all complexes decomposed to form metal sulfide, which really confirmed that all the complexes could be used to metal sulfide nanoparticles. All the prepared complexes were used to synthesize MxSy nanoparticles. The metal sulfide nanoparticles were successful prepared by thermal decomposition of the single-source precursor in hexadecylamine solution. The reaction parameter such as the concentration (1.0, 0.5, 0.25 and 0.125 g), reaction temperature (80, 130, 200, 250 °C) and the time (5, 10, 15, 20, 25 and 30) of the reactionwere varied to see their effect on the preparation of the nanoparticles. The prepared metal sulfide nanoparticles were characterized using techniques such as UV spectroscopy, photoluminescence spectroscopy, X-ray diffraction analysis and transmission electron microscopy. The concentration was found to have a profound effect in size and shape of the prepared nanoparticles. The nanoparticles prepared at various concentrations were dominated by sphere with an average size of 2-30 nm. The XRD pattern confirmed that the composition is not affected by the temperature. Thetemperature has a dramatic effect in size, shape and the stoichiometry of the reaction. This was confirmed by an increase in size as the temperature was increased, with the exception of cobalt sulfide nanoparticles that decrease in size while temperature was increase. The XRD pattern showed different composition as the temperature was varied. Time of the reaction was found to affect the particles size of the nanoparticle. The sizes of the nanoparticles were increase as the time of the reaction was prolonged.

Metal sulfide thin films are important class of materials which have applications in photovoltaics, microelectronics and displays. Chemical vapour deposition (CVD) is well known method for the deposition of high quality thin films. Very few classes of single source precursors (eg: dithiocarbamates, xanthates) were successful for the deposition of good quality metal sulfide films by MOCVD. This limited choice was due to the difficulties of finding precursors with suitable physico-chemical properties. Hence, it is important to develop precursors with suitable volatility, solubility and being able to deposit films with little or no contamination. This work describes the synthesis of a series of metal (Fe, Co, Ni, Zn, Cd) complexes of thio- and dithio-biuret ligands, their structural and spectroscopic characterization and thermal decomposition. The complexes were used as single source precursors for the deposition of iron, cobalt, nickel, zinc, cadmium and zinc cadmium sulfide thin films by AACVD. The effect of alkyl groups, coordinating atoms, deposition temperatures on phases and morphology of the films were studied. The deposited films were characterised by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and atomic force microscopy (AFM). The complex [Fe(SON(CNiPr2)2)3] gave hexagonal troilite FeS films with small amount of tetragonal pyrrhotites Fe1-xS at 300 °C, whereas only troilite FeS was deposited at 350, 400 or 450 °C. Complexes [Fe2(µ-OMe)2 (SON(CNEt2)2)2] and [Fe(SON(CNEt2)2)3] deposited a mixture of hexagonal troilite FeS and cubic pyrite FeS2 films at all temperatures. [Fe(SON(CNMe2)2)3] deposited very thin films of FeS at all temperatures as troilite. Complexes [Co(N(SCNMe2)2)3] and [Co(N(SCNEt2)2)3] deposited hexagonal Co1-xS films at all temperatures of 350-500 °C, whereas [Co(SON(CNiPr2)2)2] gave mixture of cubic and hexagonal Co4S3 films at 280-400 °C. Thiobiuret complex [Ni(SON(CNMe2)2)2] gave orthorhombic Ni7S6. Complexes [Ni(SON(CNMe2CNEt2))2] and [Ni(SON(CNEt2)2)2] gave mixtures of hexagonal Ni17S18 and orthorhombic Ni7S6. In contrast, [Ni(SON(CNiPr2)2)2] gave orthorhombic Ni9S8. Dithiobiuret complexes [Ni(N(SCNMe2SCNEt2))2] and [Ni(N(SCNEt2)2)2] gave hexagonal NiS1.03 at 360 and 400 °C, orthorhombic Ni7S6 phase at 440 and 480 °C. The zinc complexes [Zn(N(SCNMe2)2)2] and [Zn(SON(CNiPr2)2)2] deposited cubic ZnS at 300 and 350 °C, whereas at 400 and 450 °C hexagonal ZnS were apparent [Zn(N(SCNEt2)2)2] gave hexagonal ZnS films at all deposition temperatures. Cadmium complexes [Cd(N(SCNMe2)2)2], [Cd(N(SCNEt2)2)2] and [Cd(SON(CNiPr2)2)2] gave hexagonal CdS films at all deposition temperatures.

In this thesis, a facile methodology for the synthesis of CdS and PbS particles using novel thiobisphthalimide (D1) and dithiobisphthalimide (D2) organic sulfur precursors is proposed. A slightly different approach was followed for the synthesis of CuS particles. The effect on the size and morphology of the particles of a variety of reaction parameters such as the nature of sulfur precursor, the reducing agent concentration, the metal-to-sulfur ratio and the reaction temperature was investigated. The phase and composition identifications of the CdS and PbS particles were done by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques were employed to determine the morphologies of the particles. The optical properties of the CdS, PbS and CuS particles were examined by UV-Vis and fluorescence spectroscopy techniques. The phase identification results showed that pure cubic CdS and PbS, and hexagonal CuS particles were successfully synthesized with both D1 and D2 precursors. The synthesized CdS and PbS particles possess various morphologies depending on the precursor type and the reaction parameters mentioned previously. Control of the size of the PbS particles in one dimension in a quantum confinement regime was possible, whereas the CdS particles exhibited faster growth and 3D morphologies. The CuS particles, on the other hand, were produced with high monodispersity in a surfactantless environment.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2014-10-21T15:52:48Z No. of bitstreams: 1 Dissertação de mestrado Paula Lopes.pdf: 3114896 bytes, checksum: 64c14138aec1c0f19b0f9445d7a07625 (MD5) / Approved for entry into archive by Ana Hilda Fonseca (anahilda@ufba.br) on 2014-10-29T17:29:36Z (GMT) No. of bitstreams: 1 Dissertação de mestrado Paula Lopes.pdf: 3114896 bytes, checksum: 64c14138aec1c0f19b0f9445d7a07625 (MD5) / Made available in DSpace on 2014-10-29T17:29:36Z (GMT). No. of bitstreams: 1 Dissertação de mestrado Paula Lopes.pdf: 3114896 bytes, checksum: 64c14138aec1c0f19b0f9445d7a07625 (MD5) / Energia e Ambiente ocupam posições de destaque dentre os grandes desafios da hu manidade e a produção de hidrogênio a partir da reforma foto - induzida de solução aquosa de glicerol é uma investigação de grande interesse científico e importância para a sociedade e o meio ambiente , pelo fato de gerar energia limpa a partir de fontes reno váveis e com baixo custo. Neste sentido, o presente trabalho propõe desenvolver semicondutores do tipo sulfetos metálicos e soluções sólidas do tipo Cd (1 - x) Zn x S capazes de absorver luz visível e assim conduzir a reação de decomposição da água e glicerol le vando à produção de hidrogênio assistida por um simulador de luz solar . Para tanto, foi desenvolvido um método sonoquímico de síntese de nanopartículas dos sulfetos com diferentes proporções Cd:Zn:S nas soluções de partida. As análises de difração de raios X confirmaram a obtenção das fases dos sulfetos puros e soluções sólidas. As micrografias obtidas por microscopia eletrônica de varredura revelam diferentes morfologias a depender do teor de zinco nas soluções sólidas e a formação de nanoesferas de CdS pu ro em fase hexagonal. Os materiais ainda foram caracterizados por EDX, DRS e análise textural por adsorção de N 2 . A avaliação da atividade fotocatalítica na produção de hidrogênio revelou que todas as amostras contendo Cd em sua composição foram ativas, co m exceção da amostra S 8 ( Cd:S 1:8). O fotocatalisador que apresentou melhor atividade foi a solução sólida obtida com a proporção 1:8:4 (Cd:Zn:S), com uma taxa de produção de hidrogênio de 239  mol g - 1 h - 1 . Os resultados demonstraram que a introdução de zinco na matriz wurtzita de CdS aumenta a atividade fotocatalítica e a estab ilidade do fotocatalisador em me io aquoso. / Energy and Environment are ones of the great challenges of humanity and the production of hydrogen from photo - induced reforming of glycerol aqueous solution is an investigation of great scientific interest and importan t fo r the society and the environment . This process can generate clean e nergy from renewable sources with low cost. In this sense, the present work proposes to develop semiconductor s, metal sulfide type and solid solutions type, Cd (1 - x) Zn x S , able to absorb vis ible light and decompos e water and glycerol leading to hydrogen production assisted by a simulator sunlight. Thus , it was developed a sonochemical method to synthesi ze semiconductor nanopar ticles with different Cd:Zn:S ratios in starting solutions. X - ray d iffraction analysi s confirmed the formation of pure sulfides and solid solutions phase s . The micrographs obtained by scanning electron microscopy reveal different morphologies depending on the zinc content in the solid solutions and the formation of CdS na no - spheres in hexagonal pure phase. The material s w ere also ch aracterized by EDX, DRS and textural analysi s by N 2 adsorption . The assessment of photocatalytic activity in hydrogen production showed that all samples containing Cd were active with respect to hydrogen production , exception S 8 sample ( Cd:S 1:8). The photocatalyst that showed the best activity was the solid solution obtained with the ratio 1:8:4 (Cd:Zn:S), with a hydrogen production rate of 239 μmol g - 1 h - 1 . The results demonstrated that the int roduction of zinc in CdS wurtzite matrix increases the photocatalyt ic activity and stability of the photocatalyst in aqueous medium

Ph. D. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / The study based on thiourea derivatives has received significant interest from several disciplines due to their variable bonding modes, promising biological implications and their complexation capacity. Thiosemicarbazones are a stimulating type of ligands that reveals a diverse range of biological activities. They are effectual intermediates for the production of pharmaceutical and bioactive materials which makes them very useful in the field of medicinal chemistry. The FTIR spectral variations in the stretching frequencies of C=N, C–N and C=S that appeared at 1663, 1327 and 726 cm-1, respectively confirmed the formation of the ligand. The present study describes the preparation of (Z)-2-(pyrrolidin-2-ylidene)thiourea ligand for the synthesis of ZnS, CdS and Ag2S nanoparticles via homogeneous/chemical precipitation technique. The effect of different capping agents such as starch, PVP, PEG, PVA, and the role of ammonium hydroxide solution during the synthetic processes was investigated and distinguished. The study based on the effect of capping molecule on the formation of nanoparticles proved that the capping agent has a great influence on the formation of nanoparticles. The FTIR spectra of the capped nanoparticles revealed the shift toward the higher frequencies compared with the uncapped metal sulfide nanoparticles. The metal sulfide nanoparticles also showed an increased in energy band gaps which were different from the bulk materials. The 2-hydroxy-1-naphthaldehyde is regarded as a low-cost ligand which has also been widely used in biological synthesis to determine free amino acid groups. The metal complexes of this ligand are easily prepared and can be used to synthesize metal oxide nanomaterials at low cost which are environmentally friendly that can be expended in bio-applications. The preparation of the Zn, Cd and Ag complexes based on the bis(2- hydroxy-1-naphthaldehydate ligand through the reaction desired metal acetate are reported and confirmed by FTIR spectroscopy, elemental analysis and thermogravimetric analysis (TGA). There has been a great research significance for the synthesis of metal oxide since such materials have high specific surface area and a high fraction of surface atoms. The synthesis of ZnO, CdO and Ag2O nanoparticles through thermal decomposition of the Zn(II), Cd(II) and Ag(I) complexes into trioctylphosphene oxide (TOPO) and/or hexadecylamine (HDA) at different decomposition temperatures is reported. The study proved that the combination of oleylamine as a solvent and TOPO as a capping molecule produced controlled shaped and reasonably dispersed particles. The XRD patterns of all the metal oxide nanoparticles synthesized with TOPO were showing face-centred cubic structures. These metal oxide based complexes were also used as single source precursors to prepare metal oxide thin films at different annealing temperatures on the glass substrate using different methods such as annealing, thermal decomposition, aerosol assisted chemical vapour deposition (AACVD) methods. The optical absorption and size distribution of the synthesized nanoparticles and thin films have been explored using XRD, SEM, AFM, FTIR, PL and UV-Vis spectroscopy techniques. The results show that the decomposition temperature has a huge effect on the formation of the nanomaterials. The SEM images of the as synthesized nanoparticles revealed different shapes of the particles as the decomposition temperature is increased. A change in X-ray diffraction parttern was observed when the decomposition temperatures were increased. The capped metal sulphides and metal oxide nanoparticles were then allowed to react with polydadmac or chitosan to form the polymer nanocomposites. The optical absorption, luminescence properties, size distribution and the bonds distribution of the polymer nanocomposites were characterized with UV-Vis, PL and FTIR spectroscopy. The structural and morphological properties have been studied by XRD, TEM and SEM. The absorption analysis of the prepared nanocomposites revealed the properties of both nanoparticles and polymers. Chitosan and polydadmac are biopolymers that have been proven as the best adsorbents to remove the heavy metal ions from wastewater.In this study, polydadmac and chitosan based metal sulphide and metal oxide nanocopmposites were used as adsorbents for the removal of Fe(III) from the wastewater. The batch experiments were conducted to achieve the optimum conditions. The effect of pH, contact time, and initial metal ion concentration were also determined. The pH = 8 was found to be the optimum pH for the removal of Fe(II) ions from the water sample by utilizing pure chitosan and chitosan nanocomposites as adsorbents.

No description available.

In this study some of the first row transition metal oxides were transformed to metal sulfides by new solid gas reaction system. Transition metal sulfides have wide application area in industry and technology. Several techniques are known for the production of metal sulfides. Such as reactions between metal or metal oxide with H2S, precipitation in several liquid medium, reaction between metal and sulfur in closed vessel, chemical vapor deposition (CVD) technique. These techniques will have some disadvantages / for example, reactants are rarely available or expensive materials, their production systems are complicated and hard to set up these systems, products contain oxygen or hydrogen or corresponding metal sulfate as impurities. In our new sulfidizing system the reactants are metal oxides, carbon and SO2. These materials can be found easily. Especially, SO2 usage in this system is a big advantage of giving possibility of usage the hazardous waste product of SO2 in industry. The sulfidizing gas mixture was obtained by passing SO2 over activated carbon at 750 OC in a vertical tubular furnace. The obtained gas contains, mainly, CS2, CO and COS. The sulfidizing reactions took place in the horizontal tubular furnace at 450OC-1250 OC. The duration of the reaction, (three hours), and flow rate (60ml/min) of the SO2 gas were kept constant. The products were examined by X-ray powder diffraction and Raman scattering spectroscopy. All examined metal oxides were transformed to metal sulfides by sulfidizing gas mixture successfully. Ti3S5 was obtained from TiO2. Cr2S3 was obtained from Cr2O3. MnS (Alabandite) was obtained from MnO2. FeS and Fe1-xS (Pyrrhotite) were obtained from Fe2O3. Co9S8 (Cobaltpentlandite) and CoS (Jaipurite) were obtained from Co3O4. NiS was obtained from NiO. Cu7.2S, Cu1.6S (Calcocite-Q), Cu1.81S, Cu7S4 (Anilite) Cu9S5 (Digenite), Cu8S5 (Geerite) were obtained from CuO, ZnS was obtained from ZnO. The electrical conductivity character of each product obtained by sulfidizing reaction was analyzed in the temperature range of 77 K-300 K. Titanium sulfide, cobalt sulfide and nickel sulfide showed metallic conductivity, cupper sulfide and iron sulfide showed semiconductor behavior in this temperature range.

Photoelectron spectroscopy is an experimental method to study the electronic structure in matter. In this thesis, a combination of soft and hard X-ray based photoelectron spectroscopy has been used to obtain atomic level understanding of electronic structures and energy level alignments in mesoscopic solar cells. The thesis describes how the method can be varied between being surface and bulk sensitive and how to follow the structure linked to particular elements. The results were discussed with respect to the material function in mesoscopic solar cell configurations. The heart of a solar cell is the charge separation of photoexcited electrons and holes, and in a mesoscopic solar cell, this occurs at interfaces between different materials. Understanding the energy level alignment between the materials is important for developing the function of the device. In this work, it is shown that photoelectron spectroscopy can be used to experimentally follow the energy level alignment at interfaces such as TiO2/metal sulfide/polymer, as well as TiO2/perovskite. The electronic structures of two perovskite materials, CH3NH3PbI3 and CH3NH3PbBr3 were characterized by photoelectron spectroscopy and the results were discussed with support from quantum chemical calculations. The outermost levels consisted mainly of lead and halide orbitals and due to a relatively higher cross section for heavier elements, hard X-ray excitation was shown useful to study the position as well as the orbital character of the valence band edge. Modifications of the energy level positions can be followed by core level shifts. Such studies showed that a commonly used additive in mesoscopic solar cells, Li-TFSI, affected molecular hole conductors in the same way as a p-dopant. A more controlled doping can also be achieved by redox active dopants such as Co(+III) complexes and can be studied quantitatively with photoelectron spectroscopy methods. Hard X-rays allow studies of hidden interfaces, which were used to follow the oxidation of Ti in stacks of thin films for conducting glass. By the use of soft X-rays, the interface structure and bonding of dye molecules to mesoporous TiO2 or ZnO could be studied in detail. A combination of the two methods can be used to obtain a depth profiling of the sample.

In this thesis, geometry is used as a basis for conducting experiments aimed at growing and arranging inorganic minerals on curved interfaces. Mineralisation is directed using crystalline and liquid-crystalline metallic soaps and surfactant/water systems as templates.¶ A review of the history, syntheses, structure and liquid crystallinity of metallic soaps and other amphiphiles is presented as a foundation to understanding the interfacial architectures in mesostructured template systems in general.¶ In this study, a range of metallic soaps of varying chain length and cation type are synthesised and characterised to find potentially useful templates for mineral growth. These include alkaline-earth, transition metal, heavy metal and lanthanide soaps. These are systematically characterised using a variety of analytical techniques, including chemical analyses, x-ray diffraction (XRD) infrared spectroscopy (IR) and differential scanning calorimetry (DSC). Their molecular and crystal structures are studied using transmission electron microscopy (TEM), cryo-TEM, electron diffraction (ED), electron paramagnetic spin resonance (EPR), absorption spectroscopy (UV-VIS), high resolution laser spectroscopy, atomic force microscopy (AFM), nuclear magnetic resonance spectroscopy, scanning electron microscopy (SEM), electron dispersive x-ray analysis (EDXA), thermal gravimetric analysis (TGA) and magnetic measurements. Models for the molecular and crystal structures of metallic soaps are proposed. The soaps are predominantly lamellar crystalline or liquid crystalline lamellar rotor phases with tilted and/or untilted molecular constituents. These display evidence of varying degrees of headgroup organisation, including superstructuring and polymerisation. A single crystal structure is presented for a complex of pyridine with cobalt soap. Simple models for their structure are discussed in terms of their swelling properties in water and oils. Experiments are also presented to demonstrate the sorbent properties of aluminium soaps on oil spills.¶ The thermotropic liquid crystallinity of alkaline earth, transition metal, heavy metal and lanthanide soaps is investigated in detail. This is done to assess their suitability as templates, and to document their novel thermotropic behaviour, particularly the relatively unknown lanthanide soaps. Liquid crystalline behaviours are studied using high-temperature XRD (HTXRD), hot-stage optical microscopy and DSC. Models for a liquid crystalline phase progression from crystals to anisotropic liquids are discussed in terms of theories of self-assembly and interfacial curvature. The terminology required for this is drawn from various nomenclature systems for amphiphilic crystals and liquid crystals. General agreement with previous studies is reported for known soaps, while liquid crystallinity is demonstrated in the lanthanide and some non-lanthanide soaps for the first time. A general phase progression of crystalline lamellar through liquid crystalline lamellar to non-lamellar liquid crystalline is discussed in terms of models concerned with the molecular and crystal structures of the soaps and their phase transitions via headgroup and chain re-arrangements.¶ Experiments aimed at guiding growth of metal sulfides using metallic soaps as templates are described, and a model for this growth is discussed. Metal sulfides have been successfully grown by reacting crystalline and liquid crystalline transition metal and heavy metal soaps with H2S gas at room temperature and at elevated temperature. These have been characterised using XRD, TEM, ED and IR. Sulfide growth is demonstrated to be restricted and guided by the reacting soap template architecture. Zinc, cadmium, indium and lead soaps formed confined nanoparticles within the matrix of their reacting soap template. In contrast, curved and flat sheet-like structures, some resembling sponges were found in the products of sulfided iron, cobalt, nickel, copper, tin and bismuth soaps. A model to explain this behaviour is developed in terms of the crystal and liquid crystal structures of the soaps and the crystal structures of the metal sulfide particles.¶ Liquid crystalline iron soaps have been subjected to controlled thermal degradation yielding magnetic iron oxide nanoparticles. Some XRD and TEM evidence has been found for formation of magnetic mesostructures in heat-treated iron soaps. Models for the molecular and liquid crystalline structure of iron soaps, their thermotropic phase progression and eventual conversion to these magnetic products are discussed. Systematic syntheses of mesoporous silicates from sheeted clays are discussed.¶The templates that have been used are cationic surfactants and small, organic molecular salts. Experiments are reported where a cooperative self-assembly of surfactant/water/kanemite plus or minus salt and oils yields 'folded sheet materials' (FSM'S). Templating of kanemite has also been achieved using cobalt cage surfactants. A theoretical prediction of the specific surface areas and specific volumes of homologous sets of FSM's gave excellent agreement with measured values. The geometry and topology of the mesostructures are discussed. A theoretical model is also discussed regarding the curvature found in the sheets of natural clays , and results of templating clays and silica using metallic soaps are presented. Experiments and a model for low temperature nucleation and growth of microporous silicalite-1 are described in terms of silica templating by water clathrates.¶ Finally, the problem of finding minimal surface descriptions of crystal networks is addressed. Combinatoric methods are used to disprove the existence of possible embeddings of type I and II clathrate networks in non-self intersecting periodic minimal surfaces. The crystal network of the clathrate silicate, melanophlogite is successfully embedded in the WI-10 self-intersecting surface. Details of a previously unreported, genus-25 periodic surface with symmetry Im3m are discussed.