L’objectif de cette thèse était d’étudier les propriétés de conversion de photons des ions terres rares insérées dans des matrices d’oxydes transparents en vue d’application photovoltaïques. En particulier, le but était de fonctionnaliser des couches minces déjà utilisées dans les cellules solaires comme couches antireflet ou oxydes transparents conducteurs. Nous avons donc sélectionné deux matériaux (ZnO et CeO2) compatibles avec les cellules solaires au silicium.Ce travail a montré que les couches minces dopes aux terres rares peuvent être utilisées pour convertir les photons dans des applications photovoltaïques, mais qu’il n’est pas facile d’obtenir des rendements élevés.Cependant, nous avons obtenu des informations très importantes sur l’influence de la matrice sur les propriétés de conversion des terres rares et sur les mécanismes de transfert d’énergie entre la matrice et la terre rare. / The objective of this thesis was to investigate the photon converting properties of rare earths (RE) ions embedded in transparent oxide hosts in view of potential application on silicon solar cells. In particular, the goal was to functionalize thin films that are already used in solar cells such as anti-Reflection coatings or transparent conductive oxides.Two host materials (ZnO and CeO2) have been selected, which are compatible with silicon solar cells.This work shows that RE-Doped transparent oxide films are a viable low-Cost solution for obtaining photon-Converting layers that can be applied on solar cells, but that achieving high efficiencies is much more difficult than it might appear in theory. Nevertheless, very valuable information has been obtained on the effect of the host material on the photon management properties and on the energy transfer mechanisms in these systems. In particular, the energy level diagram of some of the rare earth ions in the specific matrices has been reconstructed.

Dans ce travail de recherche, des oxydes mixtes dopés par des métaux nobles ont été préparés et mis en œuvre dans la réaction d'oxydation catalytique du chlorure de vinyle (VC). Les catalyseurs d'oxyde composite de Co-Ce ont été préparés par des procédés sol-gel et testés pour l'activité d'oxydation du VC. L'analyse XPS a certifié que l'introduction de Ce favorisait la présence d'espèces de Co2 + et de Ce3 +, ce qui modifie l'environnement de coordination du réseau d'oxygène et génère plus de vacations d'oxygène. Les oxydes de cobalt modifiés par Ru ont été préparés et étudiés pour l'oxydation du VC. L'analyse XPS montre que le Ru4 + et le Co2 + modifie la concentration des espèces oxygènes sur la surface. Une proportion relative élevée de Co2+ et de Ru4+ perturbe également les lacunes en oxygène. Cela impacte l'activité catalytique et diminue la quantité de sous-produits chlorés. Des mousses cellulaires mésostructurées de phosphate de cobalt-SiO2 (CoPO-MCFs) ont été synthétisées avec succès par la méthode de croissance in situ. Les analyses XPS confirment une augmentation d'espèces d'oxygène de surface pour ce système catalytique. L'énergie apparente d'activation confirme cette tendance. L'influence de la morphologie des particules de Co3O4, sur l'activité catalytique du méthyl benzène et du chlorure de vinyle a été étudiée. Le Co3O4 cubique a montré une meilleure activité et une meilleure stabilité que celle de Co3O4 sphérique. La structure cubique, avec Co2 + exposée à la surface, est le site actif de l'oxydation / In this research works, composite oxides, noble metal supported oxides and noble supported MCFs were prepared, and their catalytic performances were investigated for the catalytic oxidation of vinyl chloride (VC). The Co-Ce composite oxide catalysts were prepared by citrate sol-gel methods, and tested for the activity of VC oxidation. The catalyst with high performance is the molar ratio of Co/Ce=7:3. The XPS analyse certified that the Ce introduction favored the presence of Co2+ and Ce3+ species, which changed the coordination environment of the oxygen lattice and generated more oxygen vacancies. At last, this catalyst exhibited a good performance and stability during 110 h of time on stream at 300 oC. Ru-modified cobalt oxides were prepared and studied for the VC oxidation. The XPS analyse certified that the Ru4+ will be in synergy with Co2+ concentration and this would also change the chemical coordination of oxygen on the surface. High relative proportion of Co2+ and Ru4+ will also devote to oxygen defects or vacancies. This would increased the catalytic activity and decrease the amount of chlorinated by-products.A novel heterostructured material, cobalt phosphate-SiO2 mesostructured cellular foams (CoPO-MCFs), was successfully synthesized by the in-situ growth method. The XPS confirmed a higher amount of surface oxygen species. The activation energy calculated from Arrhenius plots showed a lower value for VC oxidation. The influence of Co3O4 morphology, including cube and sphere, on catalytic activity of methylbenzene and vinyl chloride was studied. The Co3O4 cube had shown better activity and stability than that of the Co3O4 sphere. The cube structure, with Co2+ exposed on the surface, acted as the active site of the oxidation

A redução da emissão de compostos nitrogenados tem sido um dos grandes desafios da área de proteção ambiental e o tratamento catalítico pode reduzir significativamente tal emissão. Neste caminho, têm sido testadas várias categorias de catalisadores. Considerando-se o potencial de utilização de catalisadores de cobre e de cobalto nos processos de abatimento de compostos nitrogenados, bem como a necessidade de exploração dos efeitos gerados pelos suportes de óxido de cério e óxido de titânio, este trabalho teve como objetivos a preparação e a caracterização dos sistemas catalíticos CuO e Co3 O4 suportados em TiO2 , CeO2 e CeO2 -TiO3 (1%, 10%, 20% e 50% de CeO2 ), para aplicação no processo de redução de NO com CO na presença e ausência de O2 . Os catalisadores foram obtidos a partir do método de impregnação. Na caracterização das amostras foram utilizadas as técnicas de difração de raios X (DRX), redução à temperatura programada com H2 (RTP-H2 ), espectroscopia Raman, espectroscopia por energia dispersiva de raios X (EDX), fisissorção de nitrogênio e espectroscopia UV-visível próxima a região do infra-vermelho (UV-VIS-NIR). Os resultados da caracterização mostraram que os catalisadores apresentam fases de CuO altamente dispersas, bem como formando cristalitos com os suportes. Mostraram, também, que o cobalto está sobre a forma oxida Co3 O4 . As reações de redução de NO com CO mostraram que os catalisadores de cobre são mais ativos para estas reações e a adição do suporte CeO2 em TiO2 aumenta significativamente esta atividade. A adição de O2 na reação diminuiu a atividade frente à reação de redução de NO, isso porque o oxigênio é adsorvido sobre a superfície do catalisador, diminuindo sua atividade. / The reduction of the nitrogen composites emissions has been one of the great challenges of the ambient protection area and the catalytic treatment can reduce significantly such emissions. In this way, it has been tested some categories of catalysts. Considering the potential of use of copper and cobalt catalysts in the processes of nitrogen composites discouragement, as well as the necessity of exploration of the effect generated for CeO2 and TiO2 supported , this work had as objective the preparation and the characterization of the catalytic systems supported CuO and Co3O4 in TiO2, CeO2 and CeO2-TiO2 (1%, 10%, 20% and 50% of CeO2), for application in the reduction process of NO with CO in presence and absence of O2. The catalysts had been gotten from the impregnation method. In the characterization of the samples the techniques that had been used was: X-ray diffraction had been used, temperature programmed reduction, Raman spectroscopy, energy dispersive X-ray spectroscopy, nitrogen physsisorption and UV-visible spectroscopy next the region to the infra-red ray (UV-VIS-NIR). The results of the characterization had shown that the catalysts present highly dispersed phases of CuO, as well as cristalitts. And, that cobalto meets under the form Co3O4. The reactions of reduction of NO with CO had shown that the copper catalysts are more active than the cobalto and the addition of the CeO2 support in TiO2 increases significantly this activity. The addition of O2 in the reaction diminished the activity front to the reaction of reduction of NO, just because the oxygen is adsorbed on the surface of the catalysts, diminishing its activity

A redução da emissão de compostos nitrogenados tem sido um dos grandes desafios da área de proteção ambiental e o tratamento catalítico pode reduzir significativamente tal emissão. Neste caminho, têm sido testadas várias categorias de catalisadores. Considerando-se o potencial de utilização de catalisadores de cobre e de cobalto nos processos de abatimento de compostos nitrogenados, bem como a necessidade de exploração dos efeitos gerados pelos suportes de óxido de cério e óxido de titânio, este trabalho teve como objetivos a preparação e a caracterização dos sistemas catalíticos CuO e Co3 O4 suportados em TiO2 , CeO2 e CeO2 -TiO3 (1%, 10%, 20% e 50% de CeO2 ), para aplicação no processo de redução de NO com CO na presença e ausência de O2 . Os catalisadores foram obtidos a partir do método de impregnação. Na caracterização das amostras foram utilizadas as técnicas de difração de raios X (DRX), redução à temperatura programada com H2 (RTP-H2 ), espectroscopia Raman, espectroscopia por energia dispersiva de raios X (EDX), fisissorção de nitrogênio e espectroscopia UV-visível próxima a região do infra-vermelho (UV-VIS-NIR). Os resultados da caracterização mostraram que os catalisadores apresentam fases de CuO altamente dispersas, bem como formando cristalitos com os suportes. Mostraram, também, que o cobalto está sobre a forma oxida Co3 O4 . As reações de redução de NO com CO mostraram que os catalisadores de cobre são mais ativos para estas reações e a adição do suporte CeO2 em TiO2 aumenta significativamente esta atividade. A adição de O2 na reação diminuiu a atividade frente à reação de redução de NO, isso porque o oxigênio é adsorvido sobre a superfície do catalisador, diminuindo sua atividade. / The reduction of the nitrogen composites emissions has been one of the great challenges of the ambient protection area and the catalytic treatment can reduce significantly such emissions. In this way, it has been tested some categories of catalysts. Considering the potential of use of copper and cobalt catalysts in the processes of nitrogen composites discouragement, as well as the necessity of exploration of the effect generated for CeO2 and TiO2 supported , this work had as objective the preparation and the characterization of the catalytic systems supported CuO and Co3O4 in TiO2, CeO2 and CeO2-TiO2 (1%, 10%, 20% and 50% of CeO2), for application in the reduction process of NO with CO in presence and absence of O2. The catalysts had been gotten from the impregnation method. In the characterization of the samples the techniques that had been used was: X-ray diffraction had been used, temperature programmed reduction, Raman spectroscopy, energy dispersive X-ray spectroscopy, nitrogen physsisorption and UV-visible spectroscopy next the region to the infra-red ray (UV-VIS-NIR). The results of the characterization had shown that the catalysts present highly dispersed phases of CuO, as well as cristalitts. And, that cobalto meets under the form Co3O4. The reactions of reduction of NO with CO had shown that the copper catalysts are more active than the cobalto and the addition of the CeO2 support in TiO2 increases significantly this activity. The addition of O2 in the reaction diminished the activity front to the reaction of reduction of NO, just because the oxygen is adsorbed on the surface of the catalysts, diminishing its activity

Visando a produção de hidrogênio, como uma fonte renovável de energia, estudaram-se as reações de reforma a vapor e oxidativa do etanol sobre catalisadores de Ru/CeO2-Al2O3. Foi verificado o efeito do suporte e das interações metal/suporte sobre a atividade e seletividade para as reações. Os suportes e catalisadores foram caracterizados por fisissorção de nitrogênio pelo método B.E.T., para avaliar as áreas superficiais específicas, espectroscopia dispersiva de raios-X (EDX), para determinar a distribuição qualitativa da fase metálica sobre os suportes, difração de raios-X (DRX), para identificação das fases óxidas, espectroscopia na região do ultra-violeta e do visível (UV-vis NIR), para avaliar as transições eletrônicas presentes no material, e redução a temperatura programada (RTP), para avaliação do comportamento de redução e das fases redutíveis. Através dos ensaios catalíticos, pode-se verificar que todos os catalisadores foram ativos para ambas as reações de reforma, sob as temperaturas de 400, 600 e 700ºC, onde a conversão do etanol aumentou com o aumento da temperatura e com o aumento da adição de CeO2 ao suporte catalítico. O catalisador 3%Ru/CeO2 foi o mais ativo frente a reação de reforma a vapor e o 3%Ru/25%CeO2-Al2O3 o catalisador mais ativo para a reação de reforma oxidativa do etanol. A maior seletividade para H2 foi obtida a 600ºC para ambas as reações de reforma, com exceção dos catalisadores 3%Ru/20%CeO2-Al2O3, que foi mais seletivo a 700ºC para a reforma a vapor, e 3%Ru/CeO2, que foi mais seletivo a 400ºC para a reforma oxidativa. / Aiming at hydrogen production, as a source of renewable energy, Ru/CeO2-Al2O3 catalysts were studied in ethanol steam reform and ethanol oxidative reforming. The effect of the support and metal/support interaction was verified on the activity and selectivity of the reactions. The supports and catalysts were characterized by x-rays dispersive spectroscopy (XDS), to verify the qualitative distribution of the metallic phase on the supports, x-rays diffraction (XRD), for identification of the crystalline oxide phases, spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR), to evaluate the electronic transitions present in the material, and temperature programmed reduction (TPR), for evaluation of the reductive phases. According to the catalytic tests, all catalysts were active for both reactions under the temperatures of 400, 600 and 700ºC, where the ethanol conversion increased together with the increase of the temperature and, with the addition of CeO2 to the catalytic support. The 3%Ru/CeO2 catalyst was the most active for ethanol steam reforming and the 3%Ru/25%CeO2-Al2O3 catalyst was the most active for ethanol oxidative reforming. The higher selectivity for H2 occurred at 600ºC for both reactions, excluding the 3%Ru/20%CeO2-Al2O3 catalyst, which was more selective at 700ºC for steam reforming, and the 3%Ru/CeO2 catalyst, which was more selective for the oxidative reforming at 400ºC.

The focus of this thesis was on the synthesis, characterization and application of ceria nanocubes. This thesis is divided into two main sections; the first section investigates the electronic properties of ceria nanocubes, and the second explores their catalytic applications towards alcohol oxidation reactions. The first project of this thesis consisted of the X-ray characterization of hydrothermally synthesized ceria nanocubes of various sizes. For the first time, the electronic properties of such nanocubes were systematically studied using high resolution XPS and XANES. It was found that the concentration of Ce3+ present within the nanocubes was independent of the particle size, as well as the Ce precursor used during synthesis. Throughout the analysis of the Ce 3d and 4d XPS spectra, it was observed that the surface of the ceria nanocube samples was undergoing photoreduction/damage over time. This damage was attributed to the samples’ exposure to high intensity X-ray radiation. This was confirmed through examination of the Ce M4,5- and N4,5-edge XANES spectra. From these results, it was clear that the concentration of Ce3+ on the surface of the ceria nanocubes was independent of particle size. This fact may become important when investigating their potential catalytic activity. The second project of this thesis concentrated on the analysis of the catalytic activity of a variety of CeO2, Au and Au/CeO2 catalysts towards the oxidation of benzyl alcohol. The low temperature oxidation reactions were studied using 1H NMR spectroscopy. It was observed that Au NPs, Au/bulk CeO2, and Au/CeO2 nanocubes in water and K2CO3 were active catalysts for this oxidation reaction at 60°C in both air and O2 (g) atmospheres. Surprisingly, however, the Au/bulk CeO2 and Au/CeO2 nanocube catalysts showed very similar activities. It was also found that ceria nanocubes alone, and Au25(SR)18/bulk CeO2 showed no activity for this reaction under similar conditions. It was determined that below a substrate to catalyst ratio of ~ 1500:1, the Au/CeO2 catalysts, which showed the highest activities, were mass-transport limited with respect to the O2 in the system. The turnover frequencies of the supported catalysts were approximately double those of the unsupported NPs. Furthermore, these reactions have indicated that activating Au25(SR)18/CeO2 for catalysis is a non-trivial task, and more work needs to be done to understand the activation of such clusters.

Visando a produção de hidrogênio, como uma fonte renovável de energia, estudaram-se as reações de reforma a vapor e oxidativa do etanol sobre catalisadores de Ru/CeO2-Al2O3. Foi verificado o efeito do suporte e das interações metal/suporte sobre a atividade e seletividade para as reações. Os suportes e catalisadores foram caracterizados por fisissorção de nitrogênio pelo método B.E.T., para avaliar as áreas superficiais específicas, espectroscopia dispersiva de raios-X (EDX), para determinar a distribuição qualitativa da fase metálica sobre os suportes, difração de raios-X (DRX), para identificação das fases óxidas, espectroscopia na região do ultra-violeta e do visível (UV-vis NIR), para avaliar as transições eletrônicas presentes no material, e redução a temperatura programada (RTP), para avaliação do comportamento de redução e das fases redutíveis. Através dos ensaios catalíticos, pode-se verificar que todos os catalisadores foram ativos para ambas as reações de reforma, sob as temperaturas de 400, 600 e 700ºC, onde a conversão do etanol aumentou com o aumento da temperatura e com o aumento da adição de CeO2 ao suporte catalítico. O catalisador 3%Ru/CeO2 foi o mais ativo frente a reação de reforma a vapor e o 3%Ru/25%CeO2-Al2O3 o catalisador mais ativo para a reação de reforma oxidativa do etanol. A maior seletividade para H2 foi obtida a 600ºC para ambas as reações de reforma, com exceção dos catalisadores 3%Ru/20%CeO2-Al2O3, que foi mais seletivo a 700ºC para a reforma a vapor, e 3%Ru/CeO2, que foi mais seletivo a 400ºC para a reforma oxidativa. / Aiming at hydrogen production, as a source of renewable energy, Ru/CeO2-Al2O3 catalysts were studied in ethanol steam reform and ethanol oxidative reforming. The effect of the support and metal/support interaction was verified on the activity and selectivity of the reactions. The supports and catalysts were characterized by x-rays dispersive spectroscopy (XDS), to verify the qualitative distribution of the metallic phase on the supports, x-rays diffraction (XRD), for identification of the crystalline oxide phases, spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR), to evaluate the electronic transitions present in the material, and temperature programmed reduction (TPR), for evaluation of the reductive phases. According to the catalytic tests, all catalysts were active for both reactions under the temperatures of 400, 600 and 700ºC, where the ethanol conversion increased together with the increase of the temperature and, with the addition of CeO2 to the catalytic support. The 3%Ru/CeO2 catalyst was the most active for ethanol steam reforming and the 3%Ru/25%CeO2-Al2O3 catalyst was the most active for ethanol oxidative reforming. The higher selectivity for H2 occurred at 600ºC for both reactions, excluding the 3%Ru/20%CeO2-Al2O3 catalyst, which was more selective at 700ºC for steam reforming, and the 3%Ru/CeO2 catalyst, which was more selective for the oxidative reforming at 400ºC.

Title: Electronics and adsorption properties of model catalytic systems contains cerium Author: Miloš Cabala Department: Department of Surface and Plasma Science, Supervisor: RNDr. Kateřina Veltruská, Department of Surface and Plasma Science, Abstract: The doctoral thesis contains the study of model catalyst systems based on cerium and ceria. The thesis deals with model systems of CeAg, CeO2/Cu(111), Ni- CeO2/Cu(111) a Ni-Sn-CeO2/Cu(111). We have studied these systems using photoelectron spectroscopy, ion scattering spectroscopy and low energy electron diffraction. Model systems were prepared under strictly defined conditions. The strong bimetallic interaction was observed on the CeAg layers. Molecular adsorption of carbon monoxide on CeAg was demonstrated. We also observed intensive reaction of these layers with oxygen. By measurements in different directions of surface Brillouin zone, we managed to reconstruct the band structure of the prepared CeO2/Cu(111) layer. We have shown that the Cu substrate interacts weakly with deposited CeO2 layer. This interaction results in a charge transfer from Cu into CeO2. Overall, in the valence spectrum we have identified three main electron bands corresponding to O 2p state bound in CeO2. It has been proven that the deposition of Ni on CeO2 layers leads to partial...

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第17795号 / エネ博第278号 / 新制||エネ||58(附属図書館) / 30602 / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 石原 慶一, 教授 東野 達, 准教授 奥村 英之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

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