O objetivo deste estudo foi avaliar o efeito da adição de alcalinidade, da concentração da glicose e da taxa de carregamento orgânico na produção de hidrogênio e ácidos orgânicos em reator anaeróbio de leito fluidificado (RALF), contendo argila expandida (2,8 - 3,35 mm) como material suporte para adesão microbiana. Foram utilizados oito reatores idênticos, sendo quatro deles operados sem adição de alcalinidade, e com concentração de glicose de 2000, 4000, 10000 e 25000 mg/L, respectivamente. Outros quatro reatores operados com adição de alcalinidade, e com as mesmas concentrações de glicose cada um. Os reatores foram inoculados com lodo anaeróbio pré-tratado termicamente, operado com tempo de detenção hidráulica (TDH) decrescente de 8 h a 1 h à temperatura controlada de 30°C. Foi constatada produção volumétrica de hidrogênio máxima de 1,58 L/h.L, para o reator operado com 10000 mg/L de glicose com adição de alcalinidade (R10CA) e um rendimento máximo de 2,52 mol \'H IND.2\'/mol glicose, para o reator operado com 4000 mg/L de glicose com adição de alcalinidade (R4CA). O biogás produzido foi composto de \'H IND.2\' e \'CO IND.2\'. Em ambos os reatores, o conteúdo de hidrogênio aumentou com a redução do TDH de 8 h para 1 h, alcançando valor máximo de 77%, para o reator operado com 4000 mg/L sem adição de alcalinidade (R4SA). Os reatores operados com altas concentrações de glicose produção de hidrogênio, o qual predominou o ácido acético e butírico. Neste mesmo reator, o rendimento da produção de hidrogênio foi superior aos outros reatores. As análises de clonagem e sequenciamento do consórcio bacteriano revelaram semelhanças com Clostridium, Klebsiella, Enterobacter e bactérias não cultivadas. / This study evaluated the effect alkalinity addition, glucose concentration and organic loading rate in the hydrogen production and organic acids in an anaerobic fluidized bed reactor (AFBR), containing expanded clay (2.8 - 3,35 mm) as support material for microbial adhesion. We used eight identical reactors, four of them operated without the addition of alkalinity, and concentration of glucose in 2000, 4000, 10000 and 25000 mg/L, respectively. Another four reactors operated with the addition of alkalinity, and with the same concentrations of glucose each. The reactors were operated with hydraulic retention times (HRT) ranging from 8 h at 1 h, and temperature of 30°C. It has been found for hydrogen production rate maximum 1.58 L/h.L for the reactor operated with 10000 mg/L glucose with the addition of alkalinity (R10CA) and a maximum yield of 2.52 mol \'H IND.2\'/mol glucose to the reactor operated with 4000 mg/L glucose with the addition of alkalinity (R4CA). The biogas produced was composed of \'H IND.2\' and \'CO IND.2\'. In both reactors, the hydrogen content increased with the reduction of HRT of 8 h at 1 h, reaching a maximum of 77% for the reactor operated from 4000 mg/L without added alkalinity (R4SA). The reactors operated with high glucose concentrations (10000 mg/L and 25000 mg/L) had higher proportions of solvents such as soluble metabolites. There was a linear correlation between the hydrogen production rate and organic loading rate in all reactors. The yield, the hydrogen production rate and distribution of soluble metabolites in both reactors, were influenced by the glucose concentration. The reactor operated with 4000 mg/L and addition of alkalinity, presented the most favorable distribution of soluble metabolites to hydrogen production, which was predominant acetic and butyric acid. In the same reactor, the hydrogen yield was higher than other reactors. The cloning and sequencing analysis bacterial consortium revealed the presence of Clostridium, Klebsiella, Enterobacter and uncultivated bacteria.

[pt] Partículas que apresentam dois lados com propriedades químicas distintas são chamadas de Janus, como uma referência ao deus de duas faces da mitologia Romana. A combinação de propriedades diferentes em um mesmo sistema vem se demonstrando interessante para inúmeras aplicações. Neste trabalho, nanopartículas de ouro anfifílicas foram sintetizadas através do recobrimento seletivo dos hemisférios do núcleo metálico, por dois polímeros, sendo um hidrofóbico e outro hidrofílico. Em seguida, foi realizado o crescimento preferencial de dióxido de titânio apenas na face com recobrimento hidrofílico. Os resultados obtidos pela caracterização estrutural e físico-química confirmaram a formação de nanopartículas de ouro com um hemisfério recoberto por dióxido de titânio de baixa cristalinidade e alta porosidade, provando seu caráter Janus. As nanopartículas Janus obtidas foram testadas como fotocatalisadores para produção de gás hidrogênio a partir da água. Os resultados mostraram sua atividade superior em relação a nanopartículas formadas apenas por titânia. Portanto, este estudo descreve uma nova estratégia para obtenção de nanopartículas Janus, que podem ser utilizadas para diferentes aplicações, e ainda demonstra sua importância nas áreas de catálise e de produção de gás hidrogênio como combustível renovável. / [en] Particles possessing two sides with different chemical properties are named Janus, as a reference to the double-faced god of Roman mythology. The combination of two different properties in the same system has been showing interesting for numerous applications. In this work, amphiphilic gold nanoparticles were synthesized by selectively coating the metallic nucleus hemispheres with two polymers, one hydrophobic and one hydrophilic. Then, a preferential growth of titanium dioxide over the hydrophilic face was performed. The results obtained by structural and physicochemical characterization confirmed the formation of gold nanoparticles with one hemisphere coated by titanium dioxide with low crystallinity and high porosity, proving the Janus character. The obtained Janus nanoparticles were tested as photocatalysts for hydrogen production from water. Results showed the superior activity in comparison to nanoparticles comprised only by titania. Thus, this study describes a new strategy to obtain Janus nanoparticles, which can be used for different applications and also demonstrates their importance in the fields of catalysis and production of hydrogen gas as renewable fuel.

O desenvolvimento de novas tecnologias para produção de combustíveis é assunto de vital importância, principalmente quando se trata de combustíveis de fontes limpas e renováveis. Nesse aspecto, surge o hidrogênio (H2), tecnologia limpa, vindo de fontes renováveis, como o etanol. Para a obtenção do H2 a partir do etanol, destaca-se a reforma a vapor. No entanto, a reforma a vapor apresenta alguns desafios como maximização da conversão e seletividade em H2, além da minimização na formação de carbono e dos seus precursores (acetaldeído e acetona), uma vez que a formação de carbono pode levar a perda da atividade do catalisador. Nesse contenxto, a ideia deste trabalho é desenvolver catalisadore a base de níquel (Ni) suportados em céria (CeO2) dopados com os lantanídeos gadolínio (Gd), samario (Sm) e neodímio (Nd) para aplicação na reforma a vapor do etanol de modo a aumentar a conversão do etanol e a seletividade em H2, bem como minimizar a formação de carbono e de seus percursores. Para isso, fixou-se o teor de Ni em 5% e variou-se os teores do dopantes em 1%, 5% e 10%, também sintetizou-se o catalisador sem presença de dopante para comparação. A partir desses catalisadores, fez-se a caracterização e os testes catalíticos a 400, 500 e 600 °C. Percebeu-se a formação de solução sólida para todos os dopantes (Gd, Sm e Nd), por meio da expansão dos parâmetros de rede, na qual a expansão de rede aumentou com o aumento do teor de dopante e com o aumento do raio iônico do dopante. A adição de 1% de dopante para os catalisadores dopados com Sm e Nd levaram a um aumento significativo da área superficial, bem como a diminuição do tamanho do cristalito do suporte. A temperatura de reação na qual se observa os melhores resultados catalíticos é a 600 °C de modo que houve uma conversão máxima de etanol, seletividades em H2 acima de 2,80 molprod.molEtOHconv-1 e minimização na formação de espécies líquidas como a acetona e acetaldeído, bem como na formação de coque. A conversão do etanol nessa temperatura foi similar para todos os catalisadores, mas os catalisadores 5Ni_5GdCeO2 e 5Ni_5NdCeO2 apresentaram a maior seletividade a H2. No entanto, os catalisadores com a presença de Nd apresentaram as menores taxas de formação de coque. / The development of new technologies for fuel production is a vital issue, especially clean and renewable fuels. In this apect, hydrogen (H2), a clean technology, is highlighted when it comes from renewable sources, such as ethanol. To obtain H2 from ethanol, the steam reform is pointed out. However, steam reforming presents some challenges, such as maximizing conversion and H2 selectivity, as well as minimizing the formation of carbon and its precursors (acetaldehyde and acetone), since carbon formation can lead to catalytic activity loss. In this context, the idea of this work is the development of nickel (Ni) based catalysts supported in ceria (CeO2), doped with the lanthanides gadolinium (Gd), samarium (Sm) and neodymium (Nd), for ethanol steam reforming application in order to increase ethanol conversion and H2 selectivity, as well as to minimize the formation of carbon and its precursors. For this, the Ni content was set at 5% and the dopant contents varied in 1%, 5% and 10%, the catalyst was also synthesized without presence of dopant for comparison. From these catalysts, the characterization and the catalytic tests were carried out at 400, 500 and 600 °C. The formation of a solid solution for all dopants (Gd, Sm and Nd) was observed by means of the network parameters expansion , in which the network expansion increased with increasing dopant content and with increasing dopant ionic radius. The addition of 1% dopant, to the Sm and Nd doped catalysts, led to a significant increase in surface area as well as a decrease in the support crystallite size. The reaction temperature at which the best catalytic results are observed is at 600 °C, so that there was a maximum conversion of ethanol, H2 selectivity 2.80 molprod.molEtOHconv-1, and minimization of liquid species formation, such as acetone and acetaldehyde, as well as the coke formation. Ethanol conversion at this temperature was similar for all catalysts, but the catalysts 5Ni_5GdCeO2 and 5Ni_5NdCeO2 showed the highest selectivity to H2. However, the catalysts with the presence of Nd presented the lowest rates of coke formation.

O presente trabalho avaliou o efeito da relação \'C\'/\'N\' na produção biológica de hidrogênio a partir de água residuária sintética a base de sacarose. Reatores de leito fixo e fluxo ascendente, com polietileno de baixa densidade reciclado para adesão da biomassa, foram operados a 25°C e com um tempo de detenção hidráulica (TDH) de 2 horas. Analisaram-se diferentes relações \'C\'/\'N\' (40, 90, 140 e 190), usando a sacarose e a uréia como fontes de carbono e nitrogênio, respectivamente. Os valores médios de produtividade de \'H IND.2\' foram de 0,6 mol-\'H IND.2\'/mol-sac, 1,3 mol-\'H IND.2\'/mol-sac, 2,2 mol-\'H IND.2\'/mol-sac e 1,7 mol-\'H IND.2\'/mol-sac quando operados os reatores com relações \'C\'/\'N\' iguais a 40, 90, 140 e 190, respectivamente. Encontrou-se um valor ótimo para \'C\'/\'N\' de 137, que resultaria em produtividade de \'H IND.2\' de 3,5 mol-\'H IND.2\'/mol-sac, valor igual ao alcançado na relação \'C\'/\'N\' de 140. O biogás produzido foi composto de \'H IND.2\' e \'CO IND.2\', com valores médios porcentuais para o \'H IND.2\' de 53%, 49%, 61% e 52% para as relações \'C\'/\'N\' de 40, 90, 140 e 190, respectivamente. Os principais produtos intermediários produzidos durante a produção de \'H IND.2\' foram similares em todas as relações \'C\'/\'N\', sendo principalmente detectados ácido acético, ácido butírico e etanol. Sob excesso de nitrogênio, o crescimento da biomassa foi maior com efeitos negativos sobre a produção de hidrogênio, enquanto carência de nitrogênio permitiu o controle do crescimento da biomassa e resultou em maiores produtividades de hidrogênio. Durante os experimentos observou-se queda na produção do biogás provavelmente por atuação de bactérias hidrogênio-oxidantes. / This study evaluated the effect of the carbon/nitrogen (\'C\'/\'N\') ratio on the hydrogen production from a sucrose-based synthetic wastewater. Up-flow fixed-bed anaerobic reactors with recycled low-density polyethylene for biomass attachment, were operated at 25ºC and with a 2 hours time of hydraulic detention. Several \'C\'/\'N\' relationship were studied (40, 90, 140 and 190), using sucrose and urea as carbon and nitrogen sources, respectively. The average value of the hydrogen productivity were 0,6 mol-\'H IND.2\'/mol-suc, 1,3 mol-\'H IND.2\'/mol-suc, 2,7 mol-\'H IND.2\'/mol-suc e 1,7 mol-\'H IND.2\'/mol-suc they were reached when the reactors were operated with \'C\'/\'N\' of 40, 90, 140 and 190, respectively. It was found an optimal value for \'C\'/\'N\' of 137, which would result in productivity of 3,5 mol-\'H IND.2\'/mol-suc, an amount equal to that achieved in the \'C\'/\'N\' relationship of 140. Biogas produced was composed of \'H IND.2\' and \'CO IND.2\', with average \'H IND.2\' content 53%, 49%, 61% and 52% for \'C\'/\'N\' of 40, 90, 140 e 190, respectively. The mainly intermediary products during \'H IND.2\' fermentation were similar for all the \'C\'/\'N\' ratios, being specially detected acetic acid, butyric acid and ethanol. Under excess of nitrogen the biomass growth is higher with negative effects on hydrogen production while deprivation of nitrogen permits the control of biomass growth and results in higher hydrogen productivity. During the experiments it was been observed decline in the biogas production, probably because of the action of the hydrogen-oxidizing bacteria.

Concerns over both environmental issues and about the depletion of fossil fuels have acted as twin driving forces to the development of renewable energy and its integration into existing electricity grids. The variable nature of RE generators assessment affects the ability to balance supply and demand across electricity networks; however, the use of energy storage and demand-side response techniques is expected to help relieve this situation. One possibility in this regard might be the use of water electrolysis to produce hydrogen while producing industrial-scale DSR services. This would be facilitated by the use of tariff structures that incentive the operation of electrolysers as dispatchable loads. This research has been carried out to answer the following question: What is the feasibility of using electrolysers to provide industrial-scale of Demand-side Response for grid balancing while producing hydrogen at a competitive price? The hydrogen thus produced can then be used, and indeed sold, as a clean automotive fuel. To these ends, two common types of electrolyser, alkaline and PEM, are examined in considerable detail. In particular, two cost scenarios for system components are considered, namely those for 2015 and 2030. The coastal city of Darnah in Libya was chosen as the basis for this case study, where renewable energy can be produced via wind turbines and photovoltaics (PVs), and where there are currently six petrol stations serving the city that can be converted to hydrogen refuelling stations (HRSs). In 2015 all scenarios for both PEM and alkaline electrolysers were considered and were found to be able to partly meet the project aims but with high cost of hydrogen due to the high cost of system capital costs, low price of social carbon cost and less government support. However, by 2030 the price of hydrogen price will make it a good option as energy storage and clean fuel for many reasons such as the expected drop in capital cost, improvement in the efficiency of the equipment, and the expectation of high price of social carbon cost. Penetration of hydrogen into the energy sector requires strong governmental support by either establishing or modifying policies and energy laws to increasingly support renewable energy usage. Government support could effectively bring forward the date at which hydrogen becomes techno-economically viable (i.e. sooner than 2030).

Neste trabalho investigou-se a influência do cobre em diferentes catalisadores a base de níquel na decomposição catalítica do metano. Foram avaliados desde aspectos relacionados ao tratamento térmico das amostras até o desempenho catalítico nos testes de atividade. As amostras foram preparadas a partir de dois métodos diferentes. Um grupo foi preparado pelo método de impregnação úmida utilizando sílica como suporte, enquanto o segundo foi preparado pelo método de coprecipitação contínua, utilizando nitratos de cobre, níquel e alumínio em diferentes composições molares. Os ensaios foram realizados em reator tubular de leito fixo acoplado a um forno com controle de temperatura e conectado em linha com cromatógrafo gasoso. Utilizou-se 100 mg de amostra, numa faixa de temperatura de 500 a 750°C, utilizando como alimentação uma mistura reacional de N2:CH4 na proporção de 9:1. A caracterização das amostras foi realizada através das análises de SBET, TGA, TPR, TPO, DRX e Espectroscopia Raman. Os resultados mostraram uma significativa influência do cobre na atividade das amostras em temperaturas superiores a 500°C. A presença de cobre influenciou a área específica e a temperatura de redução das amostras calcinadas. Pequenas quantidades de cobre contribuem ao evitar a desativação do catalisador por sinterização em temperaturas superiores a 500°C. Para os catalisadores coprecipitados, além da influência do cobre, avaliou-se também a influência do gás utilizado no tratamento térmico das amostras. Foram utilizadas amostras não calcinadas, amostras calcinadas em ar por seis horas e calcinadas em N2 pelo mesmo período. Os resultados indicaram que a presença de cobre contribui para uma maior estabilidade e atividade nos ensaios realizados nas temperaturas de 600 e 650°C, principalmente para as amostras calcinadas em ar. As amostras com 11% de cobre na composição apresentaram elevada estabilidade na temperatura de 600°C, mesmo quando não calcinadas, indicando que a etapa de tratamento térmico pode ser evitada para este tipo de amostra. As análises de DRX, TPO e Espectroscopia Raman sugerem que o carbono formado, tanto para os catalisadores suportados quanto para os coprecipitados, depositou-se na forma de nanotubos de paredes múltiplas. / The effect of copper in different nickel-based catalysts in the catalytic decomposition of methane was investigated. Were evaluated aspects from the heat treatment of the samples to the catalytic performance in activity tests. Samples were prepared using two different methods. One group was prepared by the wet impregnation method using silica as the support and the second group was prepared by continuous coprecipitation method using copper nitrate, nickel and aluminum in different molar compositions. Catalytic activity runs were carried out in a tubular fixed-bed reactor coupled to an oven with temperature control and connected in line with a gas chromatograph. Samples of 100 mg were used in a temperature range of 500 to 750°C applying a reaction mixture of N2:CH4 at a ratio 9:1 as feed supply. The characterization of the samples was performed through the analysis of SBET, TGA, TPR, TPO, XRD and Raman spectroscopy. The results showed a significant effect of copper on the activity of the samples at temperatures above 500°C. The presence of copper influenced the specific area and the reduction temperature of the calcined samples. Small amounts of copper contributed to avoid catalyst deactivation by sintering at temperatures above 500°C. For the coprecipitated catalysts in addition to the influence of copper, the effect of the gas used for the thermal treatment of samples was also evaluated. Uncalcined samples and samples calcined in air and in N2 for six hours were used. The results indicated that the presence of copper contributed to a superior stability and activity in runs performed at temperatures of 600 to 650°C, especially for samples calcined in air. Samples with 11% of copper showed high stability at 600°C, even if not calcined, indicating that the thermal treatment step can be avoided for this type of sample. The XRD, TPO and Raman spectroscopy results suggest that the carbon deposited on the spent catalysts was in the form of multi-walled nanotubes, for both the supported and the coprecipitated catalysts.

L’économie actuelle repose sur l’utilisation d’énergies fossiles dont les réserves sont limitées. En plus, l’utilisation de ces ressources a un impact négatif sur l’environnement dû à l’émission des gaz polluants et du CO2. Il est donc nécessaire de remplacer les ressources fossiles par les énergies renouvelables. Les énergies renouvelables peuvent être facilement converties en électricité pour une utilisation directe, mais l’électricité ne peut pas être stockée en grande quantité. Dans ce contexte, l’hydrogène pourrait servir de vecteur énergétique. Il est possible de produire de l’hydrogène par électrolyse de l’eau. L’hydrogène sera ensuite utilisé via une pile à combustible pour fournir de l’électricité et de la chaleur. Ce procédé ne produit que de l’eau qui va être re-consommé ensuite par l’électrolyse.Ce travail de thèse est axé sur la production d’hydrogène par électrolyse de l’eau en milieu acide par la technologie PEM (proton exchange membrane). L’objectif est de remplacer le platine, catalyseur de la réduction à la cathode par des complexes de cobalt de type cobalt-oxime.Le premier chapitre traite différents aspects de l’électrolyse de l’eau et différents catalyseurs étudiés dans la littérature.Le second chapitre décrit différentes techniques expérimentales utilisées pour caractériser les complexes étudiés.Le chapitre trois décrit la synthèse et l’activité catalytique des complexes de cobalt-oxime en solution dans l’acétonitrile vis-à-vis de la réduction des protons en hydrogène.Le chapitre quatre présente les premiers travaux obtenus en utilisant les complexes de cobalt-oxime à la place du platine dans les électrolyseurs PEM. / Today's economy is base on the use of fossil fuels, whose reserves are limited. In addition, the use of these resources has a negative impact on the environment due to the emission of polluting gases and CO2. Therefore it is necessary to replace fossil fuels by renewable energy. Renewable energy can be easily converted to electricity to direct use, but electricity can not be stored in large quantities. In this context, hydrogen could be used as an energy carrier. It is possible to produce hydrogen by electrolysis of water. Hydrogen is then used via a fuel cell to supply electricity and heat. This process produces only water which will then be re-used by the electrolysis.This thesis focuses on hydrogen production by water electrolysis in acidic medium by the PEM (proton exchange membrane) technology. The goal is to replace the platinum, catalyst for proton reduction at the cathode by cobalt-oxime complexes.The first chapter describes various aspects of water electrolysis and different catalyst studied in the literature.The second chapter describes different characterization techniquesChapter three describes the synthesis and catalytic activity of the complexes of cobalt-oxime in solution in acetonitrile towards proton reduction into hydrogen.Chapter four presents the early work obtained using cobalt complexes oxime instead of platinum in PEM electrolyzers.

Sellafield is home to the UK's largest repository of nuclear waste, including reprocessed uranium and plutonium, as well as a backlog of unprocessed used fuel and waste kept in outdated storage facilities; commonly referred to as "legacy waste". For this reason, Sellafield has often been called the most hazardous place in Western Europe and as such, is currently undergoing a multi-billion pound decommissioning and clean-up operation. Each on-site facility has unique challenges associated with it, many of them presenting situations where the radiation chemistry aspects of the material degradation are not well understood. The key factors that can affect water radiolysis processes in the Sellafield challenges are a high pH environment, the presence of magnesium hydroxide, the presence of iron oxide, and the presence of organic materials. This work examines the effect each of these factors has on H2 and H2O2 production in water radiolysis as well as developing a computational model to offer some understanding to the kinetic behaviour of water radiolysis under such conditions. The computational model was able to replicate experimental measurements of radiolytic H2 and H2O2 production in both aerated and deaerated water at neutral pH, and provide a further understanding of the role of dissolved oxygen in water radiolysis. Measurements of H2O2 from solutions containing NaOH have shown that an increase in pH generally results in a higher steady state of H2O2, while measurements of H2 show a similar increase with a maximum production rate at pH ~11. The model was also able to closely replicate these experimental measurements with some over prediction, which highlights a gap in our understanding of high pH radiolysis and also brings into question the validity of the estimated rate constant for the reaction: O- + O2- → 2OH- + O2 k= 6.0×10^8 M^-1 s^-1 which was originally determined from kinetic model calculations designed to describe the decay of ozonide (O3ˉ) during pulse-radiolysis studies of high pH solutions conducted byK. Sehested et al in 1982.The radiolysis of magnesium hydroxide slurry also resulted in an increased yield of hydrogen gas but had little effect on the yield of hydrogen peroxide. The hydrogen yield was 0.52 molecules per 100eV while a NaOH solution of equivalent pH gave a yield of 0.27, however interference from carbonate may be the cause of the increased yield. A surface effect was also estimated to contribute 0.05 molecules per 100 eV to the hydrogen gas yield. Hydrogen gas and hydrogen peroxide was measured from the radiolysis of aqueous methanol. This was modelled with a near agreement, but modifications to the model were necessary; highlighting areas of the model that need improvement, as well as providing a reaction scheme from which a more comprehensive model for aqueous methanol radiolysis could be developed.

Neste trabalho, foi estudada a decomposição catalítica do metano sobre catalisadores coprecipitados, à base de Co-Al, para produção de hidrogênio e nanotubos de carbono. Foram testados catalisadores com diferentes proporções de cobalto e alumínio, bem como o efeito da adição de outros metais bivalentes (Mg, Ni, Zn ou Cu) ao sistema Co-Al. Os catalisadores foram caracterizados por TGA-DTA, DRX, TPR, TPO e imagens de MEV. As reações foram conduzidas em uma termobalança operando como reator diferencial, com 10 mg de catalisador. A faixa de temperatura analisada foi de 500-750°C. Os melhores resultados em termos de atividade e estabilidade foram obtidos com o catalisador Co66Al33. A adição de outros metais bivalentes não melhorou o desempenho do catalisador, principalmente porque esses metais afetaram a redutibilidade do catalisador. Para o catalisador que apresentou os melhores resultados (Co66Al33), foram realizados testes em diferentes temperaturas e condições reacionais. Os resultados mostraram que a forma de ativação afeta o desempenho deste catalisador, de forma que o catalisador pré-ativado produziu maiores quantidades de hidrogênio, nas reações a 550, 600 e 700°C. No entanto, a 650°C, a amostra autoativada teve desempenho semelhante à pré-ativada, inclusive mostrando-se mais ativa após certo tempo de reação. A caracterização do carbono depositado mostrou que todos os catalisadores produziram nanotubos de carbono. As imagens de microscopia eletrônica por varredura (MEV) mostraram a presença de filamentos mais longos e abundantes na amostra Co50Al50. As análises de oxidação a temperatura programada (TPO) indicaram que os nanotubos de carbono são de parede simples (SWNT). Para o catalisador Co66Al33, as análises de TPO indicaram maior produção de SWNT por parte das amostras pré-ativadas. / In this work, we studied the catalytic decomposition of methane over coprecipitated Co-Al based catalysts, for production of hydrogen and carbon nanotubes. Tests were performed with catalysts containing different Co-Al molar ratios, as well as with addition of other divalent metals (Mg, Ni, Zn, or Cu) to Co-Al system. The samples were characterized by TGA-DTA, XRD, TPR, TPO and SEM images. Activity tests were carried out in a thermobalance, operating as a differential reactor, with 10 mg of catalyst. The temperature range studied was 500-750°C. The best results in terms of activity and stability were obtained with the catalyst Co66Al33. Addition of other divalent metals did not improve the catalyst performance, mainly because these metals affected the catalyst reducibility. For the best results sample (Co66Al33), additional tests were performed at different temperatures and reaction conditions. Results showed that the activation method affects the catalyst performance, so as pre-activated sample produced more hydrogen than auto-activated sample, at 550, 600 and 700°C of reaction temperature. Nevertheless, at 650°C, auto-activated sample had performance almost similar to the pre-activated sample, even showing higher activity after a period of reaction. Characterization of deposited carbon showed that all catalysts produced carbon nanotubes. The images of scanning electron microscopy (SEM) showed formation of longer and abundant filaments in the sample Co50Al50. Temperature programmed oxidation analyses indicated that filaments are single walled carbon nanotubes (SWNT). For the catalyst Co66Al33, TPO analyses indicated a higher production of SWNT by pre-activated samples.

The thesis, entitled 'Investigation of the conversion of fuels in the presence of solid oxygen carriers and the development of a plasma-assisted chemical looping system for H2 production', presents the work of Yaoyao Zheng in the Department of Engineering, University of Cambridge, for the degree of Doctor of Philosophy. The thesis focused on chemical looping conversion of fuels, which employ oxygen carriers to supply oxygen, followed by the regeneration of the reduced oxygen carriers in air. Combustion of a Polish coal-derived char was first carried out in a fluidised bed reactor in the presence of Fe2O3 or ZrO2-supported Fe2O3. CO2 was introduced to the fluidised bed, to allow the char to be gasified in situ, prior to the reaction with the oxygen carriers. The presence of Fe2O3 did not alter the gasification step, given that the gasification of the char was free of external mass transfer limitation. A numerical model was developed to describe the gasification behaviour, as well as predicting the effect of CO on gasification. The inhibition effect of CO on char gasification was found more significant than expected. Combustion of biomass (wood pellets), by Fe2O3 or mayenite-supported CuO was studied in a fluidised bed. This was to understand how efficient the wood pellets were combusted by the oxygen carriers, as well as the distribution of the products. A tar measurement system, based on a plasma reactor, was first developed. With the developed measuring system, it was found that both Fe2O3 and mayenite-supported CuO were efficient for combusting wood pellets. Particularly, the CLOU nature of CuO makes mayenite-supported CuO a promising candidate for direct combustion, without introducing any reactive gaseous oxidant. The final part of the dissertation was focused on developing a plasma-assisted chemical looping system for H2-rich gas production (PCLH) from CH4 at mild temperatures (~ 673 K). SrFeO3-, Fe2O3, and Ni-doped SrFeO3- and Fe2O3 were investigated as the packing material. Total combustion of CH4 was observed in SrFeO3-. The addition of Ni onto SrFeO3- significantly improved the selectivity towards H2; whilst it was only active in the fresh cycle. Fe2O3 was found to be inert for converting CH4; however, the addition of Ni to form NiO/Fe2O3 dramatically improved H2 production and the reactivity maintained high for three redox cycles. The energy cost of such PCLH was comparable to that of water electrolysis.