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Yes / Catalysts play a vital role in petroleum and chemical reactions. Intensified concerns for cleaner air with strict environmental regulations on sulfur content in addition to meet economic requirements have generated significant interests for the development of more efficient and innovative oxidative catalysts recently. In this study, a novel homemade nano catalyst (manganese oxide (MnO2) over tin (IV) oxide (SnO2)) was used for the first time as an effective catalyst in removing dibenzothiophene (DBT) from kerosene fuel using hydrogen peroxide (H2O2) as oxidant in catalytic oxidative-extractive desulfurization process (OEDS). The catalyst was prepared by impregnation method with various amount of MnO2 loaded on SnO2. The oxidation step was carried out at different operating parameters such as reaction temperature and reaction time in batch reactor. The extractive desulfurization step was performed by using acetonitrile as solvent under several operating conditions (agitation speed and mixing time). The activity of MnO2/SnO2 catalyst in removing various sulfur compounds from kerosene fuel at the best operating conditions was investigated in this work. The results of the catalyst characterization proved that a high dispersion of MnO2 over the SnO2 was obtained. The experiments showed that the highest DBT and various sulfur compounds removal efficiency from kerosene fuel under the best operating conditions (oxidation: 5% MnO2/SnO2, reaction temperature of 75 0C, and reaction time of 100 min, extraction: acetonitrile, agitation speed of 900 rpm, and mixing time of 30 min) via the catalytic oxidative-extractive desulfurization process was 92.4% and 91.2%, respectively. Also, the MnO2/SnO2 catalyst activity was studied after six consecutive oxidation cycles at the best operating conditions, and the catalyst prove satisfactory stability in terms of sulfur compounds removal. After that, the spent catalyst were regenerated by utilizing different solvents (methanol, ethanol and iso-octane), and the experimental data explained that iso-octane achieved highest regeneration efficiency. / This study was supported by College of Petroleum Processes Engineering, Tikrit University, Iraq and Ministry of Oil, Iraq.

A variety of nanostructures of tin (IV) oxide (TO) are synthesized using two fabrication methods: a solution spin-coating method followed by post-annealing in an oxygen flow and a newly developed catalyst-assisted pulsed laser deposition (PLD) technique. The spin-coating method is used to fabricate granular TO films with monodisperse, stable, ultra-small nanocrystallites (4-5 nm in size), the size of which is found to increase exponentially with post-anneal above 500??C. These nanocrystalline films are conductive and highly transparent, and their bandgap shows broadening due to a high carrier concentration. Their resistivity behavior as a function of temperature in the 50-280 K range can be explained by a two-medium transport model, i.e. transport through the crystalline grains and across the grain boundaries, and through the charge-depletion layer, where a potential barrier is found for transport across the grain boundaries. Electronic transport in these films follows a 3D-variable range hopping model, which reveals an increase in the localization length of carriers with increasing the TAnneal above the onset of exponential growth at TAnneal= 500??C. By homogenously doping Eu3+ in these nanocrystalline films up to a high doping level of ~ 8%, optical luminescence and magnetic orderings can be introduced into these nanocrystalline TO films. Both characteristic Eu3+ emission and defect-related TO emissions are observed in the otherwise transparent TO films upon UV-excitation. In spite of the non-magnetic nature of Eu3+ ions, magnetic orderings appear in the highly doped TO films below 50 K upon the emergence of Eu2Sn2O7 phase. In the second part of this work, we employ a layer of gold nanoislands with controlled sizes (10-50 nm) as catalysts for pulsed laser deposition of TO nanostructures. Highly crystalline TO nanobricks, cuboid nanoparticles, nanowires and nanobelts are obtained for the first time through vapour-solid or vapour-liquid-solid (VLS) mechanisms. Of particular interest are the micron long one-dimensional (1D) nanowires and nanobelts, with the smallest square and rectangular cross-sections, respectively, ever reported. These single-crystalline nanostructures are obtained at relatively low temperatures of 600??C, for nanowires, and 500??C, for nanobelts, and their cross-sectional sizes can be easily controlled by the size of the gold nanoislands. The nanobelts are found to grow along the [100] and [101] axes, while the nanowires appear to grow along the [100] axis. The growth evolution of the nanobelts are also investigated in detail revealing their VLS growth mode and their single-crystalline structure throughout the growth, which opens the prospect of controlling their growth axis and consequently their side-surface planes by pinning the base to the substrate at the desired crystalline orientation. Together, the two fabrication methods developed in the present work offer facile approaches to growing two scientifically and technologically important classes of TO nanostructures, i.e., nanocrystalline film and 1D nanostructures. Thorough characterization of the resulted nanostructured materials using advanced microscopic, spectroscopic and other techniques, including Helium Ion Microscopy, has been provided. Modification of structure, morphology and physical properties of these functional nanostructured materials are also illustrated by controlling the growth parameters and by (Eu-)doping, which pave the way for introducing new properties for applications in chemical sensing, (opto)electronics and displays.

The objective of this work is to develop catalysts that are active in simultaneous conversion of triacylglycerides and fatty acids into fatty acid methyl esters. Three Sn(IV) complexes, named butyl stannoic acid (BTA), di-n-butyl-oxo-stannane (DBTO) and dibutyltin dilaurate (DBTDL), were initially tested as catalysts for esterification reaction of fatty acids in the presence of methanol as alcoholysis agent. Parameters like reaction time, temperature, and catalyst amount were systematically evaluated in this work. All complexes were active at relative high reaction temperatures, but BTA displayed the highest activity. Former studies have already demonstrated that these same complexes display good catalytic activity in methanolysis of triacylglycerides (TAGs). These results prompted us to test BTA catalyst also in simultaneous esterification/transesterification reactions from a mixture of free fatty acids (FFAs) and TAGs in the presence of methanol. The BTA was able to convert mixtures of fatty acid methyl esters (FAMEs) with excellent yields of up to 96% during 4 hours with simple isolation procedures. The BTA was also tested in the hydrolysis of TAG and conversions were quite satisfactory, reaching approximately 98% at 160 ° C. From the results obtained it was possible to determine that, in comparison to hydroesterification reactions, the simultaneous esterification/transesterification is the best route to obtain FAMEs using this type of catalyst. The complexes exhibiting general formula R4-xSn(C11H20O2)x, wherein R = C4H9 or CH3 and x= 1 ou 2, were tested in order to evaluate the influence of the nature of different ligands bearing the metal center, on the esterification conversion. The results obtained in this study may suggest the following catalytic activity order: dimetildiundecenoate tin > dibutildiundec-10-enoate tin > tributilundecenoate tin, supporting a significant influence of the stereo effect in esterification reaction. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo deste trabalho foi testar e desenvolver catalisadores que sejam ativos tanto em reações de esterificação quanto transesterificação. Compostos de Sn(IV), denominados n-butil hidroxioxi de estanho (BTA), óxido de dibutil estanho (DBTO) e dibutildilaurato de estanho (DBTDL), foram inicialmente testados como catalisadores para a reação de esterificação de ácidos graxos (AG) na presença de metanol como agente de alcoólise. Parâmetros como o tempo de reação, temperatura e quantidade de catalisador, foram sistematicamente avaliadas. Todos os complexos foram ativos a temperaturas de reação entre 80 e 160 ºC, sendo que o BTA apresentou maior atividade com conversões de aproximadamente 96 % em ésteres metílicos de ácidos graxos (% EMAGs). Estudos anteriores já demonstraram que estes mesmos complexos exibem boa atividade catalítica na metanólise de triacilglicerídeos (TAG). Esse conjunto de resultados nos levou a testar o catalisador BTA também em reações simultâneas de esterificação/transesterificação de uma mistura de AG e TAG, na presença de metanol. O BTA foi capaz de converter as misturas em ésteres metílicos de ácidos graxos (EMAGs) com excelentes rendimentos, de até 96% durante 4 horas, com processos de purificação simples. O BTA também foi testado na hidrólise de TAG e as conversões em AG foram bastante satisfatórias, chegando aproximadamente 100 % a 160 ºC durante 10 horas. A partir dos resultados obtidos pôde-se determinar que, comparativamente à hidroesterificação, a reação de esterificação/transesterificação simultânea é a melhor rota a ser empregada na obtenção de EMAGs em presença de matérias primas de baixo custo, utilizando este tipo de catalisador. Foram sintetizados e testados novos complexos, a fim de avaliar a influência da natureza de diferentes ligantes em torno do centro metálico sobre a conversão em reações de esterificação. Com os resultados obtidos neste estudo pode-se sugerir uma ordem de atividade catalítica: dimetil diundecenoato de estanho > dibutildiundecenoato de estanho > tributilundecenoato de estanho, evidenciando uma influência significativa de efeitos estéreos na reação de esterificação.

Currently organic-inorganic hybrid perovskite solar cells (PSCs) is one kind of promising photovoltaic technology due to low production cost, easy fabrication method and high power conversion efficiency. Charge transport layers are found to be critical for device performance and stability. A traditional electron transport layer (ETL), such as TiO2 (Titanium dioxide), is not very efficient for charge extraction at the interface. Compared with TiO2, SnO2 (Tin (IV) Oxide) possesses several advantages such as higher mobility and better energy level alignment. In addition, PSCs with planar structure can be processed at lower temperature compared to PSCs with other structures. In this thesis, planar-structure perovskite solar cells with SnO2 as the electron transport layer are fabricated. The one-step spin-coating method is employed for the fabrication. Several issues are studied such as annealing the samples in ambient air or glovebox, different concentration of solution used for the samples, the impact of using filter for solutions on samples. Finally, a reproducible fabrication procedure for planer-structure perovskite solar cells with an average power conversion efficiency of 16.8%, and a maximum power conversion efficiency of 18.1% is provided.

In this work we have investigated the catalytic activity of four metal complexes which exhibit Lewis acid character: dibutyltin diacetate, dibutyltin dilaurate, butylstannoic acid and di-n-butyl-oxo-stannane. With the aim to obtain a mixture of fatty acid esters, called biodiesel, these catalysts have been tested in alcoholysis of soybean and castor oils. Transterification experiments of the vegetable oils have been carried out using two types of apparatus. The first was a glass reactor connected to a reflux condenser. The second was a pressurized container (inoxidable steel reactor), containing a manometer and a temperature controller. In all transterification experiments carried out, the use of the steel reactor were more efficient face to the analogous reactions carried out with the glass reactor. The alcoholysis were also carried out in more severe conditions. The reactions were carried out at higher temperatures, from 80 to 150°C. It was observed that the reaction yield increases, increasing the reaction temperature. In a second stage of this work, the transesterification reaction of the soybean oil was carried out employing methylic, ethylic, iso-propylic, n-butylic and iso-butylic alcohols. The effect of the different type of alcohols in the reaction yield were evaluated. It was remarked that higher yields were obtained with long chain alcohols (butanol and isobutanol) which were similar to that observed with conventional ones (methanol and ethanol). Finally, the use of metal complexes of tin(IV) as catalysts for transterification reactions of vegetable oils to obtain biodiesel seems to be very promising. The experimental data, discussions, and conclusions are described on this dissertation. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho investigou-se a atividade catalítica de quatro complexos metálicos exibindo caráter ácido de Lewis: dibutil diacetato de estanho, dibutil dilaurato de estanho, óxido de dibutil estanho e ácido butil estanóico. Estes catalisadores foram testados na alcoólise do óleo de soja e de mamona para a obtenção de uma mistura de ésteres de ácidos graxos, denominada biodiesel. Nos experimentos de transesterificação dos óleos vegetais, as reações foram realizadas em dois tipos de equipamentos. O primeiro equipamento era composto de um reator de vidro acoplado a um condensador de refluxo. O segundo equipamento foi composto de um reator de aço inox, hermeticamente fechado, equipado com um manômetro e um controlador de temperatura. Em todos os experimentos de transesterificação realizados o uso do reator aço inox mostrou-se mais vantajoso frente ao reator de vidro com condensador de refluxo. A alcoólise dos triglicerídeos também foi desenvolvida em condições mais enérgicas de reação. As reações foram realizadas em temperaturas que variaram entre 80 °C e 150 °C. Observou-se que o aumento da temperatura geralmente favorece o aumento no rendimento da reação. Em outra etapa deste trabalho a transesterificação do óleo de soja foi realizada empregando-se os álcoois metílico, etílico, isopropílico, butílico e isobutílico. Os efeitos dos diversos tipos de álcoois no rendimento final da reação foram observados e avaliados. Destacaram-se nesses experimentos os altos rendimentos obtidos com os álcoois de cadeias longas (butanol e isobutanol) quando comparados com os álcoois convencionais (metanol e etanol). Por fim, o uso de complexos metálicos a base de estanho(IV) mostrou-se promissor na reação de transesterificação de óleos vegetais visando a obtenção de biodiesel. Os dados relativos aos experimentos, a discussão dos resultados e as conclusões estão descritas nessa dissertação.

Currently, the oil of easy exploration has become increasingly scarce, and it may promote an increase in the prices of its derivatives and/or a possible shortage of raw materials, chemical products of great importance for the chemical industry. In addition, the reduction of dependence on non-renewable resources, such as the ones on petroleum-based, are firmly linked in the yearning of contemporary society, being the concept of "green" chemistry closely associated with the search for products and/or chemical processes that are linked to the use of clean technologies and sustainable development. Thus, many efforts have been employed in the search for new sources as chemical raw materials and energy through sources like carbohydrates from lignocellulosic biomass. In this context, the aim of this study was to implement and evaluate catalytic systems Sn base (IV) (dibutyltin dilaurate (IV) (DBTDL), Butylstannoic acid (BTA), di-n-butyl-oxo-stannane (DBTO) and tin oxide (SnO2)), in the conversion of carbohydrates such as fructose and glucose and chemical products with high added value (5-hidroximetilfurfal and lactic acid, for example), as compared to conventional systems without using catalyst reactions with the catalyst and sulfuric acid. The activity in terms of conversion, yield and selectivity of these catalytic complexes were evaluated in reactions performed at temperatures of 150 to 190 ° C, in water, at various reaction times. At 150 ° C, the use of catalysts led to low yields and conversions, however, the 190 ° C catalysts BTA, DBTO and DBTDL performed well in the fructose degradation reactions, with complete conversion within 30 min of reaction. The three systems were selective principally to lactic acid: BTA showed lower selectivity (33%) whereas the selectivity to DBTO and DBTDL catalyst was 55% at 30 min. The DBTO was also evaluated at times of 5, 10 and 15 min. The conversion was greater than 90% at 5 and 10 min, and the total in 15 min, with selectivity to lactic acid of 58% already at 15 min. For glucose degradation reactions, the metal complex DBTO was also active in isomerizing glucose to fructose and convert it into products such as 5-hydroxymethylfurfural and lactic acid, but with lower yields when compared with the results obtained with fructose. / Atualmente, o petróleo de fácil exploração vem ficando cada vez mais escasso, podendo promover um aumento nos preços de seus derivados e/ou uma possível escassez das matérias-primas, insumos químicos de grande importância para a indústria química. Além disso, a redução da dependência de recursos não renováveis, como os a base de petróleo, estão firmemente atrelados no anseio da sociedade contemporânea, sendo o conceito de química “verde”, intimamente associado à busca por produtos e/ou processos químicos que estejam vinculados ao uso de tecnologias limpas e ao desenvolvimento sustentável. Com isso, muitos esforços têm sido empregados na busca de novas fontes como insumos químicos e energia através de fontes como carboidratos da biomassa lignocelulósica. Neste contexto, o objetivo deste trabalho foi o de aplicar e avaliar sistemas catalíticos a base de Sn(IV) (Dibutildilaurato de estanho (IV) (DBTDL), Ácido butilestanóico (BTA), Óxido de dibutil estanho (DBTO) e Óxido de estanho (SnO2)), na conversão de carboidratos como frutose e glicose em insumos químicos com alto valor agregado (5-hidroximetilfurfal e ácido lático, por exemplo), comparativamente a sistemas tradicionais como reações sem uso de catalisador e com o catalisador ácido sulfúrico. A atividade em termos de conversão, rendimento e seletividade desses complexos catalíticos foram avaliadas em reações realizadas nas temperaturas de 150 e 190 ºC, em água, em diversos tempos de reação. A 150 ºC, o emprego dos catalisadores conduziram a baixos rendimentos e conversões, porém, a 190 ºC os catalisadores BTA, DBTO e DBTDL apresentaram bom desempenho nas reações de degradação da frutose, havendo conversão total em 30 min de reação. Os três sistemas foram seletivos, principalmente, a ácido lático: o BTA apresentou menor seletividade (33 %) enquanto que a seletividade para os catalisadores DBTO e DBTDL foi de 55 % em 30 min. O DBTO também foi avaliado em tempos de 5, 10 e 15 min. A conversão foi superior a 90 % em 5 e 10 min e total em 15 min, com seletividade a ácido lático de 58 % já em 15 min. Para as reações de degradação da glicose, o complexo metálico DBTO também foi ativo em isomerizar a glicose à frutose, e convertê-la em produtos como o 5-hidroximetilfurfural e ácido lático, porém com menores rendimentos quando se compara com os resultados obtidos com a frutose.

The catalytic activity of metal complex exhibiting Lewis acid character (dibutyltin diacetate, dibutyltin dilaurate, butylstannoic acid and di-n-butyl-oxostannane) was investigated. These catalytic complexes have been tested in the alcoholysis of soybean and castor oils, aiming to obtain a mixture of fatty acid alkyl esters, called biodiesel. In the transesterification experiments of vegetable oils, the reactions were performed using three types of reactors. The first one consisted in a glass reactor connected to a reflux condenser (RVCR). The second device consisted of a stainless steel reactor (RP), hermetically sealed, fitted with a pressure gauge and a temperature controller. The third one was adapted to be used on a microwave system. On the last two reactor systems, the alcoholysis of triglycerides was also developed at vigorous conditions, at temperatures ranging from 80 °C and 150 °C. Comparing all reactions, the results show that the most reactive catalysts using the RVCR on the methanolysis of soybean oil are DBTDA and DBTDL with comparable performances. However, in the same reaction conditions, very low yields were observed using castor oil, and no generalizations could be pointed out. When RP were employed, better yields were obtained. When the temperature raise from 80 to 150 ºC, all catalytic systems display similar performances, indicating that temperature and solubility have significant influences on these type of catalytic systems. Very low reaction yield were observed when the microwave reactor was employed. This observation must be due to the very low rate of stirring performed on this type of reactor. In a second part of this work, it was evaluated the performance of catalysts based on tin oxide (SnO2), sulfated or not, in transesterification or esterification reactions of soybean oil and its fatty acids derivatives, respectively, in the presence of methanol. The low activity verified on these systems must be related to their structural characteristics. / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Neste trabalho foi investigada a atividade catalítica de quatro complexos metálicos exibindo caráter ácido de Lewis: dibutildiacetato de estanho, dibutildilaurato de estanho, óxido de dibutil estanho e ácido butilestanóico. Esses complexos catalíticos foram testados na alcoólise do óleo de soja e de mamona, visando a obtenção de uma mistura de ésteres alquílicos de ácidos graxos, denominada biodiesel. Nos experimentos de transesterificação dos óleos vegetais, as reações foram realizadas em três tipos de reatores. O primeiro equipamento foi composto de um reator de vidro acoplado a um condensador de refluxo (RVCR). O segundo equipamento foi composto de um reator de aço inox (RP), hermeticamente fechado, equipado com um manômetro e um controlador de temperatura. O terceiro reator empregado era adaptado para ser utilizado em um sistema de microondas. Nos dois últimos sistemas de reatores, a alcoólise dos triglicerídeos foi desenvolvida em condições mais enérgicas de reação, em temperaturas que variaram entre 80 °C e 150 °C. Comparando-se todas as reações, os resultados obtidos indicam que o emprego do RVCR na metanólise do óleo de soja, os catalisadores mais ativos são o DBTDA e o DBTDL com desempenhos comparáveis. Por outro lado, empregando-se o óleo de mamona, nessa condição reacional, os rendimentos foram muito baixos, não permitindo obter generalizações. Quando do uso do RP, rendimentos superiores aos observados com o RVCR são obtidos e à medida que a temperatura aumenta de 80 a 150 ºC as reatividades dos sistemas catalíticos tornam se bastante semelhantes, indicando que fatores como temperatura e solubilidade têm influência significativa nesse tipo de sistemas catalíticos. Com o emprego do reator microondas, os rendimentos reacionais foram inferiores, provavelmente devido à baixa velocidade de agitação que tal reator pode realizar. Numa segunda parte do trabalho, foi realizado um estudo do desempenho de catalisadores a base de óxido de estanho (SnO2), sulfatado ou não, em reações de transesterificação ou esterificação de óleo de soja e seus ácidos graxos, respectivamente, na presença de metanol. A baixa atividade dos catalisadores foi relacionada às características texturais dos mesmos.

В магистерской диссертации представлена методология пошагового синтеза композиционного сорбента на основе катионообменника и гидроксида титана (IV). Показаны результаты сорбции меди (II) и других тяжелых металлов синтезированным композиционным сорбентом. Для математического моделирования результатов сорбции были использованы изотермы Ленгмюра, Фрейндлиха и Темкина. Установлено, что модель Ленгмюра наиболее точно описывает сорбционный процесс. Определены константы модели Ленгмюра и площадь удельной поверхности композиционного сорбента. Гранулы композиционного сорбента изучены с помощью методов сканирующей электронной микроскопии (СЭМ) и энергодисперсионного микроанализа (ЭДМА). Вычислены коэффициенты распределения меди (II) в гранулах композиционного сорбента и степень сорбции меди (II) из водных растворов CuSO4 различной концентрации. / The methodology of stepwise synthesis of the composite sorbent based on cation exchanger and tin(IV) hydroxide was demonstrated. The sorption results of copper(II) and other heavy metals onto the composite sorbent are presented. Langmuir, Freundlich and Temkin adsorption isotherms were used in mathematical modeling of the sorption data. The Langmuir model most accurately describes the sorption process. The constants of the Langmuir model and the specific surface area of the composite sorbent were defined. Granules of the composite sorbent were studied by scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDXMA). The distribution coefficients of copper(II) in the composite sorbent and the sorption degree from CuSO4 aqueous solutions of various concentrations were computed.