Orientadores: Antonio José Gomez Cobo, Antonio Guerrero Ruiz / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T07:20:21Z (GMT). No. of bitstreams: 1 Silva_MarcioWagnerda_D.pdf: 2089172 bytes, checksum: f1cfbcb71bbf10a37c5a4215dbf395c6 (MD5) Previous issue date: 2010 / Resumo: Alguns compostos organoclorados são motivo de grande preocupação, em razão da elevada toxicidade e persistência, tanto no meio ambiente quanto em organismos vivos. Dentre tais compostos, encontra-se o pentaclorofenol, utilizado para a conservação de madeira e na proteção de lavouras. Uma das tecnologias mais promissoras para o tratamento dessa classe de compostos tóxicos é a hidrodescloração catalítica, através da qual é possível recuperar a matéria-prima utilizada na síntese do contaminante. Embora diferentes catalisadores possam ser utilizados nesta reação, destacam-se os sólidos à base de Pd e Ru, notadamente devido à maior atividade catalítica. No entanto, os elevados preços destes metais nobres podem aumentar significativamente os custos do processo. Nesse contexto, o objetivo do presente trabalho é estudar os efeitos da presença dos metais básicos Fe e Ni em catalisadores à base de Pd e Ru, destinados à hidrodescloração do pentaclorofenol em fase líquida. Para tanto, catalisadores monometálicos e bimetálicos, suportados em alumina (Al2O3) ou titânia (TiO2), foram preparados a partir dos precursores clorados, através do método de co-impregnação a seco. Os sólidos obtidos foram caracterizados por meio das técnicas de adsorção de N2 (método BET), microscopia eletrônica de varredura com espectrometria de energia dispersiva de raios-X (MEV-EDX), espectroscopia fotoeletrônica de raios-X (XPS), redução à temperatura programada (TPR) e microscopia eletrônica de transmissão (MET). A hidrodescloração do pentaclorofenol foi conduzida num reator Parr® do tipo "slurry", à temperatura de 383 K e sob pressão de H2 de 0,5 MPa. Na reação de interesse, a adição de Ni ao catalisador de Ru/TiO2 diminui a atividade catalítica, porém mantém a elevada seletividade de cicloexanol, possibilitando, portanto, uma diminuição do custo do catalisador, sem perda de seletividade. Já para o catalisador de Pd/TiO2, a presença de Ni também diminui a atividade catalítica, assim como observado no caso do catalisador de Ru/TiO2, mas verifica-se uma diminuição da seletividade de fenol. Por sua vez, a adição de Fe ao catalisador de Pd/TiO2 tem pouca influência sobre a atividade e a seletividade, possibilitando, assim, uma significativa diminuição do custo do catalisador, sem prejuízo do desempenho catalítico. Os comportamentos catalíticos observados são analisados e interpretados à luz dos resultados obtidos através das caracterizações dos sólidos, assim como das informações disponíveis na literatura / Abstract: Some organic chlorine compounds are of great concern, because of high toxicity and persistence, both the environment and in living organisms. Among these compounds, is the pentachlorophenol, which is used to Wood conservation and for the protection of crops. A very promising technology to treating this class of toxic compounds is the catalytic hydrodechlorination, through which it is possible the recovery of raw material used in the synthesis of the contaminant. Although various catalysts may be used in this reaction, we highlight the solids Pd and Ru, mainly due to higher catalytic activity. However, the high prices of these noble etals can increase significantly the process costs. In this context, the objective of this work is to study the effects of base metals addition, Fe and Ni, in the catalysts based on Pd and Ru, for the pentachlorophenol hydrodechlorination in liquid phase. For this, monometallic and bimetallic catalysts, supported in alumina (Al2O3) or titanium oxide (TiO2), were prepared from chlorinated precursors by the incipient impregnation method. The obtained solids were characterized by techniques of N2 adsorption (BET method), scanning electronic microscopy with X-ray spectrometry analysis (EDX), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR) and transmission electronic microscopy. The pentachlorophenol hydrodechlorination was carried out in a "slurry" Parr® reactor, at the temperature of 373 K under the hydrogen pressure of 0,5 MPa. In the interest reaction, the addition of Ni to the Ru/TiO2 catalysts reduces the catalytic activity, but the high cyclohexanol selectivity is maintained, enabling thus, decrease the catalyst cost, without loss of selectivity. To the Pd/TiO2 catalyst, the i presence reduce the catalytic activity, like to the observed to the Ru/TiO2 case, but is verified the decreasing of phenol selectivity. In turn, the Fe addition to the Pd/TiO2 catalyst has little influence on the activity and selectivity, leading thus to a significant decrease in the catalyst cost, without prejudice to the catalytic performance. The observed catalytic behaviors are analyzed and interpreted based in the results obtained through the characterization of solids, as well as information available in the literature / Doutorado / Sistemas de Processos Quimicos e Informatica / Doutor em Engenharia Química

M.Sc. / This study focused on the synthesis and evaluation of phosphine ligands with multiple functional ities. Polar ligands suitable for use in homogeneous catalysis in aqueous/organic systems were synthesised, as were ligands incorporating a boron atom in an intramolecular Lewis acid-Lewis base interaction with the phosphorus atom. A malonate moiety was readily incorporated into a phosphorus starting material, and derivatives were obtained by reduction of the ester groups. The polar diol products were reacted with 1,4-butanesultone which made them water soluble and thus ideal for biphasic catalysis. Wittig chemistry was employed to introduce alkenes of varying electronic nature into a phosphorus-containing aldehyde starting material. The catalysed hydroboration reaction making use of diboron reagents was used to introduce a boron functionality into the resulting a, n-unsaturated ester phosphine I igands. All of the ligands produced were tested in transition metal-catalysed reactions, namely the Heck reaction, the Suzuki reaction, the Stille reaction, the carboxymethylation reaction and the hydroformylation reaction. The polar and water soluble ligands all showed comparable or improved yields to the standard benchmark triphenylphosphine ligand in organic, biphasic and ionic liquid media. The electronic nature of the alkene ligands largely dictated the activities observed in the Heck, Suzuki and Stille reactions. The electron rich ligands showed improved activities in the Heck reaction, while the electron poor ligands showed improved activities in the Suzuki reaction. In contrast, the Stille reaction seemed to be more affected by the steric demands of the ligands rather than by electronic considerations. It was also found that the boron containing ligands showed an enhanced activity in comparison to the boron free unsaturated and saturated ester ligands. This enhancement was directly ascribable to the Lewis acidic boron atom. This study allowed the synthesis of a range of functionally varying phosphine ligands which where shown to influence transition metal-catalysed reactions based specifically on the functionality present.

D.Phil. / The work that is presented in this thesis describes the numerous detailed investigations that were conducted with a custom-made horizontally aligned, water-cooled, gas-filled DC arc-discharge reactor. A focus of the investigations was the establishment of the effects of high purity graphite electrodes in ultra-high purity (UHP) He, H2 or mixtures thereof, in the absence of a metal catalyst on the reaction. These studies showed that higher yields of MWCNTs were formed in reactions between graphite electrodes in H2 than in He. Additionally, a range of gaseous hydrocarbons were formed in H2 that were not formed in He. After the initial parameters were established, investigations examined the effects on the products that were formed by the addition of high purity Cu to graphite. The data from these studies revealed that H2 played a pivotal role in the reactions and that metallic copper nanoparticles were the active catalysts. In particular, they showed that when the Cu/C mole ratio and particle size ranges were fixed (i.e. 0.20 and < 150 μm respectively), then branched CNTs were exclusively found in a collar deposited around the cathode, with bamboo-shaped CNTs formed in the reaction chamber. Characterisation of these products revealed that the Cu nanoparticles were probably molten during the reactions and thus a growth model was proposed in which it was suggested that dehydrogenation reactions of gaseous hydrocarbon species on the surfaces of unsupported molten copper nanoparticles led to the formation of either bamboo-shaped or branched CNTs.

No description available.

No description available.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2007. / The synthesis of mixed metal oxides, specifically the need and ability to successfully and accurately control the particle size, their stability and the reactivity of these nanoparticles is required, so as to allow the attachment of catalyst nanoparticle to the surface of a substrate or to other particles without leading to coalescence of the catalyst particle and hence to loss of their size induced properties. However, the synthesis of mixed metal oxides is a complex problem. Though various methods of preparing these types of oxides have been reported and applied, such methods they rarely produced pure forms and have often been recorded as having been contaminated with other phases. Often the particle sizes are too large in the micrometer range, and the size distribution is overly wide. Moreover, even if particles of nanometer size are formed, they tend to aggregate or agglomerate. In the current research, microemulsions were used to synthesize the nanoparticles. Such microemulsion consists of water droplets encapsulated by surfactant molecules in a pool of oil, comprising: water in oil (w/o) or reverse micelles. Reverse micelles in the nanometer size range are thermodynamically stable and optically transparent in the solution. They are believed to be highly dynamic structures whose components rearrange themselves over time and space through interaction or collision, coalescing and redispersing. However, the advantage of this method over using the standard method is that the particle size can largely be controlled, and a narrow size distribution obtained. The aim of the research was to investigate the feasibility of using the reverse micelle technique for the synthesis of mixed metal oxides - specifically α-bismuth molybdate (α- Bi2Mo3O12) with a controlled and desirable particle size and a narrow size distribution...

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

The use of supported catalysts to essentially combine the positive traits offered by both homogeneous and heterogeneous catalysis has become a competitive field of research. In particular, hydrotalcite-like catalysts (HTIc) has proven to be valuable for this purpose. Various osmium - containing catalysts were synthesized according to the co-precipitation method viz. Os-Cu-HTIc, Os-Ni-HTlc and the Os-Co-HTlc. Techniques such as SEM, IR, EDS, XRD, ICP, BET and XPS were exploited during catalyst characterisation and these essentially confirm that the hydrotalcite (HT) structure has been obtained. Various olefin substrates, ranging from simple straight-chained alkenes to cyclic, allylic and halogenated olefins, were tested. The results are promising and suggest that the diols are produced both with high selectivity and in good yield. Further experiments suggest: 1) Ofthe various co-oxidants tested, N-methylmorpholine-N-oxide is most suitable 2) The reaction proceeds faster at 60 °C than at room temperature 3) The addition of water to the reaction mixture increases the rate of the reaction for most substrates and 4) The catalyst is thermally stable and produces better results when calcined at 200 0 C prior to use This thesis reports that a new heterogeneous catalytic system for the efficient and selective cisdihydroxylation of olefins has been developed - one which suggests no leaching of metal into the reaction solution and no over-oxidation products. / Thesis (M.Sc.)-University of KwaZulu Natal, 2004.

Development of selective artificial metalloenzymes by combining the biological concepts for selective recognition with those of transition metal catalysis has received much attention during the last decade. Targeting covalent incorporation of organometallic catalysts into proteins, we explored site-selective covalent coupling of phosphane and N–containing ligands. The successful approach for incorporation of phosphane ligands we report herein consists of site-specific covalent coupling of a maleimide functionalized hydrazide into proteins, followed by coupling of aldehyde functionalized phosphanes via a hydrazone linkage. Site selective incorporation of N–containing ligands was obtained by coupling maleimide functionalized N–ligands to proteins via Michael addition to the maleimide double bond. These two methods can be easily applied to virtually any protein displaying a single reactive cysteine and allows a wide range of possibilities in terms of cofactor design. Site-specific covalent incorporation of transition metal complexes of phosphane ligands into proteins was successfully obtained. The success of the approach is influenced by several factors like the metal precursor, the phosphane type and the protein scaffold. Metal complexes of 5–maleimido–1,10–phenanthroline modified proteins were formed in situ, via addition of a metal precursor to the phenanthroline modified proteins or by coupling preformed metal complexes to proteins via Michael addition of the thiol group from a cysteine residue to the maleimide double bond of the N-ligand. These successful coupling methods enable the use of a wide range of protein structures as templates for the preparation of artificial transition metalloenzymes, which opens the way to full exploration of the power of selective molecular recognition of proteins in transition metal catalysis.