The photocatalytic production of H2 from water as well as from a 1:1 methanol:water solution employing pre–treated TiO2 and various Pt–TiO2 photocatalysts was studied by using an Nd:YAG laser as irradiation source. The photocatalysts (0.5–, 1–, 1.5– and 2 wt% Pt–TiO2) were prepared by utilizing a photocatalytic reduction method after which characterisation by various analytical techniques, i.e. XRD, TEM, ICP, SEM, and EDX, were conducted. XRD clearly indicated that platinum was not present in the crystal structure of TiO2, but was rather loaded onto the surface of TiO2. TEM analysis confirmed the presence of Pt on the surface with a particle/cluster size between 11 nm and 22 nm. SEM showed that repeatable results in respect of surface appearance were obtained. ICP and EDX indicated that the loading method was successful with only a slight deviation between the actual amount loaded and the calculated amount loaded. The impact of the loaded Pt on the band gaps of the different photocatalysts was investigated by diffuse reflectance spectroscopy (DRS) and calculated by employing the Kubelka–Munk method. The band gap values shifted sequentially from 3.236eV to 3.100 eV as the loading increased, moving closer to the absorbance region for visible light. The amount of hydrogen produced from the individual photocatalysts dispersed in both pure water and aqueous methanol solutions, was measured manually with a gas chromatograph. As soon as irradiation was initiated, a distinct colour change from shades of grey to dark blue–grey was observed for all the photocatalysts. XRD confirmed that it was due to the anatase phase transforming to produce more rutile phase. No H2 was detected for the various photocatalysts suspended in water, i.e. in the absence of methanol. The amount of hydrogen produced from the various Pt photocatalysts suspended in the aqueous methanol solution was found to be the highest for the 0.5wt%– and 1.5wt% Pt–TiO2 photocatalysts and the lowest for the 2wt% Pt–TiO2. This could be due to loading Pt above the optimum amount to such an extent, preventing sufficient light from reaching the TiO2 surface. Pt particles can also touch and overlap which will decrease Pt contact with TiO2 thus decreasing effective charge transfer. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

No presente trabalho estudou-se uma nova rota para obter nanopartículas de prata e silício aleatoriamente dispersas em uma matriz nanoporosa de nanotubos de óxido de alumínio sobre alumínio. Além disso, estudou-se a aplicação deste novo material como ânodo em células a combustível alcalinas com etanol como combustível, usando a prata como catalisador na eletroxidação do etanol e da produção de H2. O processo proposto consiste na solidificação rápida mediante melt spinner de uma liga de alumínio-prata rica em alumínio (95.25% em peso de alumínio) para obter uma solução sólida supersaturada. Posteriormente foi feita uma anodização porosa em ácido oxálico e estudo eletroquímico em meio alcalino por meia hora. A morfologia da liga obtida foi caracterizada por Microscopia Eletrônica de Varredura, Difração de Raios-X, Microscopia Eletrônica de Transmissão equipado com Espectrometria de Raios X Dispersiva em Energia e avaliado o desempenho como ânodo mediante ensaios de voltametria cíclica Os resultados obtidos confirmam que o desenvolvimento de um novo processo para produzir nanopartículas cristalinas de prata com um tamanho que varia de 4 a 120 nm, com 95% delas entre 4 e 87 nm. A partir dos estudos eletroquímicos concluiu-se que a liga de Al-Ag produzida exibe um comportamento semelhante ao alumínio puro em NaOH 0.1 M e NaOH 0.1 M com 1 M de etanol. A reação entre o alumínio e o meio alcalino produz uma camada de hidrogênio que impede que a prata catalise a eletroxidação do etanol. Portanto, conclui-se que a liga de alumínio-prata produzida não é um material viável como ânodo em células a combustível alcalinas de etanol direto. Portanto, foi avaliado o método de produção de nanopartículas para uma liga Al-Si eutética (14.2% em peso). Esta liga com nanopartículas de silício apresentou um incremento no desempenho na produção de H2 de 17% comparado à liga Al-Si eutética sem o tratamento térmico. / In the present work a new route to obtain silver nanoparticles randomly dispersed in a porous Al2O3 nanotube matrix layer on aluminum was studied. Moreover, the use as an anode in alkaline fuel cells (AFC) with ethanol as combustible was studied, using the prepared surfaces as a catalyzer for the electrooxidation of ethanol. The developed process consists of the rapid solidification (quenching) through melt spinning of an aluminum-silver alloy (92.25 %wt. Al) to obtain a supersaturated solid solution, followed by a porous anodization in oxalic acid and electrochemical treatment in alkaline medium. The morphology of the alloy was characterized by Scanning Electron Microscopy, X-Ray Diffraction, Transmission Electron Microscopy and Energy Dispersive X. Ray Spectrometry and the performance of the ethanol electrooxidation was tested though cyclic voltammetry The obtained results confirm that this process produces crystalline silver nanoparticles with a size varying from 4 to 120 nm with 95% of the particles between 4 and 87 nm. The electrochemical study showed that the produced alloy exhibits a similar behavior to that of pure aluminum in the tested mediums. The reaction between the aluminum and the alkaline medium produces a gaseous hydrogen layer that impedes the catalytic action of silver on the ethanol oxidation. Moreover, it was concluded that the produced alloy is not a viable material for the use as anode for direct ethanol AFCs. Therefore, the nanoparticle production method was tested for an Al-Si near-eutectic alloy (14.2 %wt.). This alloy with silicon nanoparticles showed an increase in the performance of H2 production rate of 17% compared to that of the regular Al-Si near-eutectic alloy.

No presente trabalho estudou-se uma nova rota para obter nanopartículas de prata e silício aleatoriamente dispersas em uma matriz nanoporosa de nanotubos de óxido de alumínio sobre alumínio. Além disso, estudou-se a aplicação deste novo material como ânodo em células a combustível alcalinas com etanol como combustível, usando a prata como catalisador na eletroxidação do etanol e da produção de H2. O processo proposto consiste na solidificação rápida mediante melt spinner de uma liga de alumínio-prata rica em alumínio (95.25% em peso de alumínio) para obter uma solução sólida supersaturada. Posteriormente foi feita uma anodização porosa em ácido oxálico e estudo eletroquímico em meio alcalino por meia hora. A morfologia da liga obtida foi caracterizada por Microscopia Eletrônica de Varredura, Difração de Raios-X, Microscopia Eletrônica de Transmissão equipado com Espectrometria de Raios X Dispersiva em Energia e avaliado o desempenho como ânodo mediante ensaios de voltametria cíclica Os resultados obtidos confirmam que o desenvolvimento de um novo processo para produzir nanopartículas cristalinas de prata com um tamanho que varia de 4 a 120 nm, com 95% delas entre 4 e 87 nm. A partir dos estudos eletroquímicos concluiu-se que a liga de Al-Ag produzida exibe um comportamento semelhante ao alumínio puro em NaOH 0.1 M e NaOH 0.1 M com 1 M de etanol. A reação entre o alumínio e o meio alcalino produz uma camada de hidrogênio que impede que a prata catalise a eletroxidação do etanol. Portanto, conclui-se que a liga de alumínio-prata produzida não é um material viável como ânodo em células a combustível alcalinas de etanol direto. Portanto, foi avaliado o método de produção de nanopartículas para uma liga Al-Si eutética (14.2% em peso). Esta liga com nanopartículas de silício apresentou um incremento no desempenho na produção de H2 de 17% comparado à liga Al-Si eutética sem o tratamento térmico. / In the present work a new route to obtain silver nanoparticles randomly dispersed in a porous Al2O3 nanotube matrix layer on aluminum was studied. Moreover, the use as an anode in alkaline fuel cells (AFC) with ethanol as combustible was studied, using the prepared surfaces as a catalyzer for the electrooxidation of ethanol. The developed process consists of the rapid solidification (quenching) through melt spinning of an aluminum-silver alloy (92.25 %wt. Al) to obtain a supersaturated solid solution, followed by a porous anodization in oxalic acid and electrochemical treatment in alkaline medium. The morphology of the alloy was characterized by Scanning Electron Microscopy, X-Ray Diffraction, Transmission Electron Microscopy and Energy Dispersive X. Ray Spectrometry and the performance of the ethanol electrooxidation was tested though cyclic voltammetry The obtained results confirm that this process produces crystalline silver nanoparticles with a size varying from 4 to 120 nm with 95% of the particles between 4 and 87 nm. The electrochemical study showed that the produced alloy exhibits a similar behavior to that of pure aluminum in the tested mediums. The reaction between the aluminum and the alkaline medium produces a gaseous hydrogen layer that impedes the catalytic action of silver on the ethanol oxidation. Moreover, it was concluded that the produced alloy is not a viable material for the use as anode for direct ethanol AFCs. Therefore, the nanoparticle production method was tested for an Al-Si near-eutectic alloy (14.2 %wt.). This alloy with silicon nanoparticles showed an increase in the performance of H2 production rate of 17% compared to that of the regular Al-Si near-eutectic alloy.

No description available.

No description available.

A produção de energia é um dos grandes desafios deste século, principalmente com a necessidade no desenvolvimento de processos que utilizem preferencialmente fontes renováveis. Nesse contexto, é claro o interesse por pesquisas baseada no hidrogênio. Porém, os ganhos ambientais efetivos estão associados também à matéria-prima usada no processo de geração do hidrogênio, senso assim mais significativo quando do uso de fontes renováveis. No presente trabalho foi estudado o efeito da adição de diferentes teores de CeO2 em catalisadores de NiZnO, preparados pelo método da co-precipitação. Os catalisadores foram estudados frente à reação de reforma a vapor do etanol (RVE) para produção de H2, e no decorrer do trabalho foi pertinente incluir o estudo da reforma a vapor da acetona (RVA), como complemento dos estudos da RVE. Além disso, esta é uma molécula modelo para reforma a vapor do bio-óleo. Nos sistemas catalíticos sintetizados houve a formação da liga NiZn3, o que aparenta proporcionar um efeito sinérgico entre esses elementos. Observou-se um efeito altamente promotor do CeO2 com relação a diminuição do coque formado, devido a uma menor da formação da acetona, durante as etapas de reforma do etanol. O que consequentemente interferiu na produção de H2. O catalisador contendo 20% de CeO2 denominado NiZn20Ce apresentou um desempenho altamente promissor, pois de acordo com as análises de DRIFT, a presença do CeO2 levou a formação de espécies de formiato, o que consequentemente interferiu em uma menor formação de coque e maior produção de H2. Foi comprovado também que a natureza dos depósitos carbonáceos depende tanto do substrato utilizado quanto das etapas precursoras inicias que levarão a formação desse coque, sendo o ponto chave para um melhor desempenho do catalisador. / Energy production is one of the great challenges of this century, especially with the need to develop processes that use preferentially renewable sources. In this context, it´s evident the interest in research based on hydrogen. However, the environmental benefits are also associated with the raw material used on the hydrogen generation process, being more significant when used renewable sources. In the present work, it was studied the effect of CeO2 addition in NiZnO catalysts, prepared by coprecipitation method. The catalysts were studied front of the ethanol steam reforming reaction (ESR) to produce H2, and in the course of this study was relevant include study of acetone steam reforming (ASR), as a complement of ESR studies. Moreover, acetone is a molecule model for steam reforming of bio-oil. In the catalyst systems there has been the NiZn3 alloy formation, which provides a synergistic effect between these elements. It was observed a high CeO2 promoter effect regarding reduction of the formed coke, due to lower formation of acetone in the ethanol reforming steps, and consequently interfere in the H2 production. The catalyst denominated NiZn20Ce showed a high performance, according to DRIFT analyzes, the presence of the CeO2 led to the formation of species formate, which in turn interfere through a lower coke formation and higher H2 production. It was also established that the nature of the carbonaceous deposits depends as the substrate used as the precursors initial steps that led the formation of this coke, and it is the key to a better performance of the catalyst.

The photocatalytic water splitting reaction showed to be a promising process to obtain renewable and clean energy, but the efficiency reached in this process is still low and must be improved to be viable. Considering this, the research on improving the efficiency of photocatalysts has attracted a strong interest in the past last years. Cerium oxide (CeO2−, 0 < x < 0.5) is a material recently investigated as a possible photocatalyst to obtain H2 from H2O. In this work, cerium oxide nanoparticles with high surface area (104 < S < 201 m2/g), high pore volume (32 < V < 132 mm3/g) values, wide range of diameter (2 < d < 90 nm) and O vacancies population (0.05 < x < 0.46) were applied to the H2 production photocatalytic reaction. The nanoparticles presented activity of up to 10 times higher than the commercial cerium oxide standard. UV-Vis, X-ray Diffraction, X-ray Absorption Spectroscopy, X-ray Photoelectron Spectroscopy, Ultraviolet Photoelectron Spectroscopy and Fourier Transform Infrared measurements were performed aiming to elucidate these results and to determine the main structural and electronic properties that can improve the H2 production photocatalytic reaction. It was obtained that the band gap energy depends on the nanoparticle synthesized and can be as low as 2.73 eV. The Ce 4f orbital occupation and the structural disorder presented by the nanoparticles is directly related with the band gap energies obtained. Density Functional Theory (DFT) calculations were performed to obtain the relation between the band structure (DOS) and the O vacancy population in order to explain the dependence of the band gap energy with the Ce 4f orbital occupation. Moreover, the O vacancies population at the surface have a very different effect depending on the presence or absence of mesopores, where a lower O vacancy population at the surface is better (worse) to the photocatalytic activity in the presence (absence) of mesopores. Furthermore O vacancies population at the surface plays a more fundamental role on the photocatalytic activity than the band gap energies for the samples presenting mesopores. The results allowed shedding light on the improvement of the properties of cerium oxide nanoparticles applied to optimize the H2 production photocatalytic activity.

A produ&ccedil;&atilde;o de energia &eacute; um dos grandes desafios deste s&eacute;culo, principalmente com a necessidade no desenvolvimento de processos que utilizem preferencialmente fontes renov&aacute;veis. Nesse contexto, &eacute; claro o interesse por pesquisas baseada no hidrog&ecirc;nio. Por&eacute;m, os ganhos ambientais efetivos est&atilde;o associados tamb&eacute;m &agrave; mat&eacute;ria-prima usada no processo de gera&ccedil;&atilde;o do hidrog&ecirc;nio, senso assim mais significativo quando do uso de fontes renov&aacute;veis. No presente trabalho foi estudado o efeito da adi&ccedil;&atilde;o de diferentes teores de CeO2 em catalisadores de NiZnO, preparados pelo m&eacute;todo da co-precipita&ccedil;&atilde;o. Os catalisadores foram estudados frente &agrave; rea&ccedil;&atilde;o de reforma a vapor do etanol (RVE) para produ&ccedil;&atilde;o de H2, e no decorrer do trabalho foi pertinente incluir o estudo da reforma a vapor da acetona (RVA), como complemento dos estudos da RVE. Al&eacute;m disso, esta &eacute; uma mol&eacute;cula modelo para reforma a vapor do bio-&oacute;leo. Nos sistemas catal&iacute;ticos sintetizados houve a forma&ccedil;&atilde;o da liga NiZn3, o que aparenta proporcionar um efeito sin&eacute;rgico entre esses elementos. Observou-se um efeito altamente promotor do CeO2 com rela&ccedil;&atilde;o a diminui&ccedil;&atilde;o do coque formado, devido a uma menor da forma&ccedil;&atilde;o da acetona, durante as etapas de reforma do etanol. O que consequentemente interferiu na produ&ccedil;&atilde;o de H2. O catalisador contendo 20% de CeO2 denominado NiZn20Ce apresentou um desempenho altamente promissor, pois de acordo com as an&aacute;lises de DRIFT, a presen&ccedil;a do CeO2 levou a forma&ccedil;&atilde;o de esp&eacute;cies de formiato, o que consequentemente interferiu em uma menor forma&ccedil;&atilde;o de coque e maior produ&ccedil;&atilde;o de H2. Foi comprovado tamb&eacute;m que a natureza dos dep&oacute;sitos carbon&aacute;ceos depende tanto do substrato utilizado quanto das etapas precursoras inicias que levar&atilde;o a forma&ccedil;&atilde;o desse coque, sendo o ponto chave para um melhor desempenho do catalisador. / Energy production is one of the great challenges of this century, especially with the need to develop processes that use preferentially renewable sources. In this context, it&acute;s evident the interest in research based on hydrogen. However, the environmental benefits are also associated with the raw material used on the hydrogen generation process, being more significant when used renewable sources. In the present work, it was studied the effect of CeO2 addition in NiZnO catalysts, prepared by coprecipitation method. The catalysts were studied front of the ethanol steam reforming reaction (ESR) to produce H2, and in the course of this study was relevant include study of acetone steam reforming (ASR), as a complement of ESR studies. Moreover, acetone is a molecule model for steam reforming of bio-oil. In the catalyst systems there has been the NiZn3 alloy formation, which provides a synergistic effect between these elements. It was observed a high CeO2 promoter effect regarding reduction of the formed coke, due to lower formation of acetone in the ethanol reforming steps, and consequently interfere in the H2 production. The catalyst denominated NiZn20Ce showed a high performance, according to DRIFT analyzes, the presence of the CeO2 led to the formation of species formate, which in turn interfere through a lower coke formation and higher H2 production. It was also established that the nature of the carbonaceous deposits depends as the substrate used as the precursors initial steps that led the formation of this coke, and it is the key to a better performance of the catalyst.

La liqueur noire, sous-produit de l’industrie papetière, est convertie par un processus hydrothermal. Elle a été choisie pour son contenu élevé en eau (80 wt%), matière organique (14 wt%) et minéraux (6 wt%) qui font d'elle une biomasse à haute valeur ajoutée bien qu'encore peu exploitée. L'étude en batch, balayant une large gamme de température (350°C-600°C), permet d'identifier deux flux sortant : une proportion d'hydrogène élevée dans la phase gazeuse (600°C), ainsi qu'une phase solide, appelée coke, générée quelques soient les conditions opératoires utilisées. La génération de solide modifie la composition du milieu réactionnel en procédé batch et peut poser problème en cas de transposition en réacteur continu. Il est donc important de comprendre sa formation pour pallier ces verrous. L'analyse du résidu montre qu'à 350°C, pour des temps de réaction courts (<2h), de microparticules carbonées se forment. Leur taille est influencée par les vitesses de montée et descente en température. Pour des températures plus hautes, le solide ne présente pas d'intérêt morphologique et sa proportion massique augmente avec la température. Ainsi, une production d'hydrogène significative s'accompagnera d'un dépôt solide dans le réacteur. Une étude catalytique a donc été menée en vue d'augmenter la quantité d'hydrogène et de diminuer la formation de coke tout en travaillant à plus basse température. Cette étude, menée à 350°C et 450°C, montre que les réactions d'hydrogénation et d'oxydation mises en jeu par le catalyseur conduisent aux résultats escomptés. La conversion de molécules modèles de la liqueur noire, menée dans les mêmes conditions d'expériences, a permis d'appréhender les mécanismes majeurs mises en jeu lors de la conversion hydrothermale. Les microparticules à 350°C peuvent être valorisées. Cependant, le changement de taille et de morphologie au cours du temps interroge sur la possibilité de passer en réacteur continu. La formation de solide peut être évitée à partir de 450°C en présence de catalyseur, favorisant en parallèle la production d'hydrogène. De ce fait, ce travail de thèse aborde les verrous scientifiques, techniques et technologiques liés à la conversion hydrothermale de la liqueur noire et notamment de la formation du solide, en présence ou non de catalyseur. / Black liquor, a by-product of paper industry, is converted by hydrothermal process. It was chosen for its high water content (80 wt%), organic material (14 wt%) and minerals (6 wt%) that make it a high-value biomass while still untapped. The study in batch, screening a wide temperature range (350°C-600°C), used to identify two outgoing flows: a high proportion of hydrogen in the gas phase (600°C) and a solid phase, called coke, generated regardless the operating conditions used. The generation of solid changes the composition of the reaction medium in batch process and can be problematic in case of transposition in continuous reactor. Thus it is important to understand its formation to overcome these obstacles. Analysis of the residue shows that at 350°C, for short reaction times (< 2h), carbonaceous micro-particles are formed. Their size is influenced by the temperature rates of rise and fall. For higher temperatures, the solid is of no morphological interest and its weight proportion increased with temperature. Thus, a significant production of hydrogen will be associated with a solid deposit in the reactor. A catalytic study was conducted to increase the amount of hydrogen and reduce the formation of coke while working at lower temperature. This study, conducted at 350°C and 450°C, shows that hydrogenation and oxidation reactions involved with the catalyst, lead to the expected results. Converting models molecules of black liquor, conducted with the same experimental conditions, helped to understand the major mechanisms involved during the hydrothermal conversion. The micro-particles at 350°C can be valorized. However, the change in size and morphology over time wondered about the possibility of implement in continuous reactor. The solid formation can be prevented from 450°C in the presence of catalyst, favoring in parallel hydrogen production. Therefore, this thesis deals with scientific, technical and technological locks related to hydrothermal conversion of black liquor and especially the solid formation, with or without catalyst.

La photocatalyse est une voie de synthèse prometteuse de l’hydrogène comme carburant solaire. La production photocatalytique est un moyen, à la fois de stocker l’énergie solaire sous forme d’énergie chimique et de produire des carburants de manière renouvelables en utilisant l’eau ou des alcools biosourcés comme matière première. L’objectif de cette thèse est d’étudier la déshydrogénation photocatalytique d’alcools à l’aide de sulfures de métaux de transitions, supportés sur TiO2 (MSx/TiO2). Ces sulfures de métaux de transitions ont des propriétés d’activation de l’hydrogène, des propriétés électrochimiques et des propriétés optiques intéressantes. Une série de sept MSx/TiO2 (M = Co, Ni, Cu, Mo, Ru, Ag, Hg) ont été étudiés. La réaction de déshydrogénation photocatalytique du propan-2-ol est utilisée comme réaction modèle. Des corrélations sont établies entre les propriétés intrinsèques de ces MSx/TiO2 et leur activité photocatalytique. De plus, la mesure d’énergie d’activation d’apparente apporte une compréhension supplémentaire sur les mécanismes photocatalytiques. Cette dernière montre que la production photocatalytique d’hydrogène est principalement limitée par les phénomènes de séparation et de transfert de charges dans les photocatalyseurs. Ainsi, une méthodologie combinant la spectroscopie de photoélectrons UV et la spectroscopie d’absorption UV-Visbile a été mis en place pour déterminer la structure électronique des poudre photocatalytiques. Ce travail conclue sur le caractère central de la structure électronique en photocatalyse. Dans le cas du photocatalyseur RuS2/TiO2, le transfert électronique est l’étape cinétiquement déterminante pour la déshydrogénation photocatalytique du propan-2-ol / Photocatalysis is a promising way to synthesize H2 as a solar fuel. On one hand, the photocatalytic H2 production stores solar energy under chemical energy. On the other hand, it produces H2 with a renewable process using water and bio-based alcohols as a feedstock. This Ph.D thesis aims to study the photocatalytic dehydrogenation of alcohols with transition metal sulfides supported on TiO2 (MSx/TiO2). Those transition metal sulfides have versatile and highly tunable properties. They can activate H2, they have promising electrochemical behavior and optical properties. Seven MSx/TiO2 (M = Co, Ni, Cu, Mo, Ru, Ag, Hg) are therefore studied. The photocatalytic dehydrogenation of propan-2-ol is used as a model reaction. Structure-activity relationships are found between the intrinsic properties of the MSx/TiO2 and their photocatalytic activity. Measuring an apparent activation energy provides additional mechanistic insights. It shows that the photocatalytic production of hydrogen is mostly limited by the charge carrier separation and by the electronic transfer. Therefore a method combining the UPS and the UV-Visbile absorption spectroscopies has been develop to establish the electronic structure of photocatalytic powders. This work concludes that the electronic structure plays a crucial role in photocatalysis. With RuS2/TiO2 photocatalyst, the electron transfer is evidenced as the rate-determining step of the photocatalytic dehydrogenation of propan-2-ol