<p>Catalytic combustion is an environmentally friendlytechnique to combust fuels in e.g. gas turbines. Introducing acatalyst into the combustion chamber of a gas turbine allowscombustion outside the normal flammability limits. Hence, theadiabatic flame temperature may be lowered below the thresholdtemperature for thermal NO_Xformation while maintaining a stable combustion.However, several challenges are connected to the application ofcatalytic combustion in gas turbines. The first part of thisthesis reviews the use of catalytic combustion in gas turbines.The influence of the fuel has been studied and compared overdifferent catalyst materials.</p><p>The material section is divided into two parts. The firstconcerns bimetallic palladium catalysts. These catalysts showeda more stable activity compared to their pure palladiumcounterparts for methane combustion. This was verified both byusing an annular reactor at ambient pressure and a pilot-scalereactor at elevated pressures and flows closely resembling theones found in a gas turbine combustor.</p><p>The second part concerns high-temperature materials, whichmay be used either as active or washcoat materials. A novelgroup of materials for catalysis, i.e. garnets, has beensynthesised and tested in combustion of methane, a low-heatingvalue gas and diesel fuel. The garnets showed some interestingabilities especially for combustion of low-heating value, LHV,gas. Two other materials were also studied, i.e. spinels andhexaaluminates, both showed very promising thermal stabilityand the substituted hexaaluminates also showed a good catalyticactivity.</p><p>Finally, deactivation of the catalyst materials was studied.In this part the sulphur poisoning of palladium, platinum andthe above-mentioned complex metal oxides has been studied forcombustion of a LHV gas. Platinum and surprisingly the garnetwere least deactivated. Palladium was severely affected formethane combustion while the other washcoat materials were mostaffected for carbon monoxide and hydrogen.</p><p><b>Keywords:</b>catalytic combustion, catalyst materials,palladium, platinum, bimetallic, garnet, spinel, hexaaluminate,deactivation, sulphur, poisoning, diesel, methane,hydrocarbons</p>

This thesis is focused on the development of new palladium and copper- mediated reactions for functionalization of alkenes and propargylic alcohol derivatives. The synthetic utility of the 1,2-diborylated butadienes synthesized in one of these processes has also been demonstrated. We have developed an efficient procedure for the synthesis of allenyl boronates from propargylic carbonates and acetates. This was achieved by using a bimetallic system of palladium and copper or silver as co-catalyst. The reactions were performed under mild conditions for the synthesis of a variety of allenyl boronates. Furthermore, the synthesis of 1,2-diborylated butadienes was achieved with high diastereoselectivity from propargylic epoxides. The reactivity of the 1,2-diborylated butadienes with aldehydes was studied. It was found that the initial allylboration reaction proceeds via an allenylboronate intermediate. The allenylboronate reacts readily with an additional aldehyde to construct 2-ethynylbutane-1,4-diols with moderate to high diastereoselectivity. We have also studied the copper-mediated trifluoromethylation of propargylic halides and trifluoroacetates. It was also shown that a transfer of chirality occurred when an enantioenriched starting material was used. In the last part of the thesis, we have described a method for palladium-catalyzed functionalization of allylic C-H bonds for the selective synthesis of allylic silanes. The protocol only works under highly oxidative conditions which suggest a mechanism involving high oxidation state palladium intermediates. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: Accepted.</p>

Alkenes are remarkably versatile motifs as they can be further functionalized by a vast array of addition, reduction, and oxidation reactions. Thus their efficient synthesis is highly desired. Over the past 35 years, the Suzuki-Miyaura cross-coupling reaction has emerged as a powerful synthetic tool for the formation of carbon-carbon bonds. Herein is described the development of a one-pot two-step protocol for the synthesis of (E)-alkenes comprising palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl or heteroaryl halides, including chlorides, with alkenyl pinacolboronates, prepared in situ via solvent-free zirconium-catalyzed hydroboration of terminal alkynes. Avoiding isolation of intermediates saves time and reduces waste. The regio- and stereochemistry of the alkene is set by initial hydrozirconation of the alkyne. Addition of water to the second step deactivates the zirconocene catalyst, which is otherwise deleterious to cross-coupling. Thus this sequence exploits the water tolerance of the Suzuki-Miyaura reaction.

Alkenes are remarkably versatile motifs as they can be further functionalized by a vast array of addition, reduction, and oxidation reactions. Thus their efficient synthesis is highly desired. Over the past 35 years, the Suzuki-Miyaura cross-coupling reaction has emerged as a powerful synthetic tool for the formation of carbon-carbon bonds. Herein is described the development of a one-pot two-step protocol for the synthesis of (E)-alkenes comprising palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl or heteroaryl halides, including chlorides, with alkenyl pinacolboronates, prepared in situ via solvent-free zirconium-catalyzed hydroboration of terminal alkynes. Avoiding isolation of intermediates saves time and reduces waste. The regio- and stereochemistry of the alkene is set by initial hydrozirconation of the alkyne. Addition of water to the second step deactivates the zirconocene catalyst, which is otherwise deleterious to cross-coupling. Thus this sequence exploits the water tolerance of the Suzuki-Miyaura reaction.

No description available.

Zero-valent metals such as bulk iron and zinc are known to dechlorinate toxicorganic compounds. Enhancement in reaction rates has been achieved through bimetallicnanosized particles such as nickel/iron (Ni/Fe) and palladium/iron (Pd/Fe). Batchdegradation of model compounds, trichlroethylene (TCE) and 2,2'-dichlorobiphenyls(DCB), were conducted using bimetallic Ni/Fe and Pd/Fe nanoparticles. Completedegradation of TCE and DCB is achieved at room temperature. Zero-valent iron, as themajor element, undergoes corrosion to provide hydrogen and electrons for the reductivecatalytic hydrodechlorination reaction. The second dopant metals of nickel and palladium(in nanoscale) act as catalyst for hydrogenation through metal hydride formation thatproduces completely dechlorinated final product. Different compositions of bimetallicNi/Fe and Pd/Fe nanoparticles were synthesized and their reactivity was characterized interms of reaction rate constants, hydrogen generation through iron corrosion, andproducts formation. The observed TCE degradation rate constant was two orders ofmagnitude higher than the bulk iron and nanoiron, indicating that the bimetallicnanoparticles are better materials compared to the monometallic iron systems. Longevitystudy through repeated cycle experiments showed minimum loss of activity. The surfacearea-normalized rate constant was found to have a strong correlation with the hydrogengeneration by iron corrosion reaction. A mathematical model was derived thatincorporates the reaction and Langmuirian-type sorption terms to estimate the intrinsicreaction rate constant and rate-limiting step in the degradation process. Bimetallicnanoparticles were also immobilized into the chitosan matrix for the synthesis of ananocomposite membrane reactor to achieve membrane-phase destruction of chlorinatedorganics under convective flow condition. Formation of uniformly distributed nanosizedparticles is confirmed by high resolution transmission electron microscopy. Themembrane-phase degradation results demonstrated similar trends with the previoussolution phase analysis with the observed enhanced reaction rates. The advantage of themembrane system is its ability to prevent the agglomeration of the nanoparticles in themembrane matrix, to minimize the loss of precious metals into the bulk solution phase,and to prevent the formation of precipitated Fe(III) hydroxide. These are due to thechelating effect of the amine and hydroxyl functional groups in the chitosan backbones.

The purpose of this study is to simulate Pt&ndash / IB (IB=Ag, Au, Cu) and PtPd bimetallic catalysts with Monte Carlo method for 201, 586, 1289, and 2406 atom containing clusters in the temperature range between 298&ndash / 1000K. The simulations were based on a coordination-dependent potential model in which binary interaction parameters were used. The binary interaction parameters were determined from the available thermodynamic data and classical thermodynamics mixing rules. The equilibrium structure of the clusters was dictated as a perfect cubo-octohedral shape. In the first part of this study, Pt&ndash / Ib bimetallics were modelled in order to test the Monte Carlo program against the previously published work. In the second part of the study, the surface composition of PtPd bimetallic catalysts as a function of temperature and cluster size were estimated in order to offer further insight to the catalytic activity for CO oxidation reaction. It was found that at low temperatures Pd segregation took place on the catalyst. The Monte Carlo predictions were in good agreement with the published experimental data on the surface compositions.

121 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-12T15:31:22Z No. of bitstreams: 1 Dissertação final-Francisco Xavier Julião.pdf: 1887183 bytes, checksum: 43c99b717d99959d6c766aca8a3e7001 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-13T17:47:56Z (GMT) No. of bitstreams: 1 Dissertação final-Francisco Xavier Julião.pdf: 1887183 bytes, checksum: 43c99b717d99959d6c766aca8a3e7001 (MD5) / Made available in DSpace on 2013-05-13T17:47:56Z (GMT). No. of bitstreams: 1 Dissertação final-Francisco Xavier Julião.pdf: 1887183 bytes, checksum: 43c99b717d99959d6c766aca8a3e7001 (MD5) Previous issue date: 2011 / CAPES / O presente trabalho investigou os efeitos das propriedades eletrônicas em catalisadores a base de Pd e Pt suportados em alumina modificada com o terra rara praseodímio, avaliando sua atividade e tolerância a compostos de enxofre na reação de hidrogenação de aromáticos. Os catalisadores foram preparados pelo método de impregnação difusional, caracterizados por FRX, DRX, DRS-UV-Vis, XPS e TPD de aminas e testados na reação de hidrogenação da tetralina, na presença de tiofeno, além da realização de um estudo termodinâmico da reação. Os testes catalíticos foram realizados em um sistema micro-catalítico pulsado. Os resultados mostraram que o catalisador Pd-Pt/Al2O3-Pr apresentou uma elevada tolerância ao tiofeno, devido a combinação dos seguintes efeitos: (i) a modificação do suporte com praseodímio, que favoreceu uma interação metalsuporte capaz de diminuir a força de ligação metal-adsorvato e favorecer as interação eletrônicas intermetálicas; (ii) o efeito sinérgico a adição de um segundo metal, paládio, em conjunto com a adição do modificador promovendo transferências eletrônicas do tipo Pt→Pd, Pt→Pr e Pd→Pr; (iii) a migração do paládio para superfície catalítica, considerando que o paládio apresenta uma maior resistência ao envenenamento por compostos sulfurados. Através do estudo da seletividade também foi verificado que as propriedades do paládio foram mais efetivas para os catalisadores bimetalicos, o qual favoreceu a formação do isômero trans-decalina. Também pode-se observar, através da relação trans/cis-decalina (estável), que o sistema bimetálico Pt-Pd sofreu pouca influência nas suas propriedades eletrônicas com a adição contínua do veneno. O sistema em estudo mostrou um efeito de conjunto, pois o catalisador Pd-Pt/Al2O3- Pr apresentou pouca sensibilidade ao envenenamento por enxofre e uma atividade moderada, para concentrações do veneno até 2500 ppm de tiofeno, mostrando-se um catalisador robusto para aplicação em processos de hidrotratamento . / Salvador

Recently, the increasing level of atmospheric CO₂ has been widely noticed due to its association with global warming, provoking a growth in environmental concerns toward the continued use of fossil fuels. To mitigate the concentration of atmospheric CO₂, various strategies have been implemented. Among options to turn waste CO₂ into useful fuels and chemicals, carbon capture and utilisation along with renewable hydrogen production as the source materials for methanol production is more preferable. In the 1960s, the highly active and economic Cu/ZnO/Al₂O₃ catalyst was developed for CO₂ hydrogenation reaction to methanol, since then, metal nanoparticles and nanocomposites have been extensively investigated and applied. Especially, bimetallic catalysts have emerged as an important class of catalysts due to their unique properties and superior catalytic performances compared to their monometallic counterparts. This thesis presents the evolution of the catalyst development for CO₂ hydrogenation to methanol: Firstly, we introduced the CuZn-based catalysts with Zn content increased in the bimetallic CuZn system via a heterojunction synthesis approach. Secondly, we increased the active CuZn sites via introducing ultra-thin layered double hydroxide as the catalyst precursor for methanol production from CO₂ and H₂. Thirdly, a new class of Rh-In bimetallic catalysts were studied, which shows high methanol yield and selectivity under thermodynamically unfavourable methanol synthesis conditions owing to the strong synergies of Rh-In bimetallic system. Fourthly, for the renewable methanol production from H₂ and CO₂, the hydrogen source must come from the green production routes. Therefore, an in-depth study of a nanocomposite system, CdS-carbon nanotubes-MoS₂, for photocatalytic hydrogen production from water has been demonstrated. Finally, the conclusion of this thesis is given and an outlook is presented for the future development in this research area.

A oxidação seletiva de alcoóis é importante para a síntese de intermediários e produtos químicos utilizados na fabricação de inúmeros materiais. O interesse em novos métodos catalíticos para a oxidação de moléculas orgânicas tem aumentado juntamente com a busca por processos ecossustentáveis. Neste trabalho foram estudadas diferentes estratégias de deposição de nanopartículas bimetálicas de ouro e paládio sobre um suporte magnético, constituído por nanopartículas de magnetita revestidas por sílica. Dois métodos de síntese de nanopartículas bimetálicas de ouro e paládio foram estudados: (I) a síntese de nanopartículas bimetálicas formadas por ligas de ouro e paládio, seguida pela deposição dessas nanopartículas pré-formadas sobre o suporte catalítico e (II) a síntese de nanopartículas bimetálicas do tipo core-shell, por meio da redução sucessiva de ouro e paládio sobre o suporte catalítico. A morfologia dos catalisadores foi determinada por diferentes técnicas de microscopia eletrônica. O desempenho catalítico das nanopartículas bimetálicas foi estudado na reação modelo de oxidação de álcool benzílico com oxigênio. Os catalisadores mostraram-se ativos e seletivos para benzaldeído sem a necessidade do uso de solvente ou base e, após separação magnética, foram usados em sucessivas reações com desempenho satisfatório / The selective oxidation of alcohols is important for the synthesis of intermediates and chemical products used for the production of many materials. The interest in new catalytic methods for the oxidation of organic molecules has increased along with the search for eco-sustainable processes. In this thesis we studied different deposition strategies of gold and palladium bimetallic nanoparticles on a magnetic support, comprised by silica coated magnetite nanoparticles. Two synthetic methods for the preparation of supported gold and palladium bimetallic nanoparticles were investigated: (I) the synthesis of gold and palladium bimetallic nanoparticles, followed by deposition of the preformed nanoparticles on the catalytic support and (II) the synthesis of core-shell bimetallic nanoparticles, through the sequential reduction of gold and palladium on the catalytic support. The catalysts\' morphology was investigated by electronic microscopy techniques. The catalytic behavior of the bimetallic nanoparticles was investigated in the model reaction of the oxidation of benzyl alcohol with oxygen. The catalysts were active and selective for benzaldehyde without the use of solvent and base and, after magnetic separation, were able to be reused in successive runs and showed a good performance.