Thesis (doctoral)--Swedish University of Agricultural Sciences, 2003. / Appendix consists of reprints of three papers and a manuscript, three of which are co-authored with others. Includes bibliographical references. Also partially issued electronically via World Wide Web in PDF format; online version lacks appendix.

Este trabalho tem como objetivo aplicar a teoria de modelos mistos ao estudo do teor de nitrogênio e carbono no solo, em diversas profundidades. Devido a grande quantidade de matéria orgânica no solo, o teor de nitrogênio e carbono apresentam alta variabilidade nas primeiras profundidades, além de apresentar um comportamento não linear. Assim, fez-se necessário utilizar a abordagem de modelos não lineares mistos a dados longitudinais. A utilização desta abordagem proporciona um modelo que permite modelar dados não lineares, com heterogeneidade de variâncias, fornecendo uma curva para cada amostra. / This paper has as an objective to apply the theory of mixed models to the content of nitrogen and carbon in the soil at various depths. Due to the large amount of organic material in the soil, the content of nitrogen and carbon present high variability in the depths of soil surface, and present a nonlinear behavior. Thus, it was necessary to use the approach of nonlinear mixed models to longitudinal data analysis. The use of this approach provides a model that allows to model nonlinear data with heterogeneity of variances by providing a curve for each sample.

L'objectif de ce travail est la synthèse et l'étude des propriétés acido-basiques de nanotubes de carbone (CNT) dopés à l’azote pour les utiliser comme catalyseurs ou supports de catalyseurs. Pour ce faire, trois types de nanotubes de carbone dopés à l'azote ont été synthétisés, caractérisés et testés dans la conversion de l'alcool isopropylique. Les nanotubes de carbone dopés diffèrent par le taux d’azote et la présence ou non d'une section non dopée dans leur structure. Pour les matériaux à faible teneur en azote, la réaction conduit à la formation d'acétone indiquant la présence de sites basiques. À plus forte teneur en azote, les catalyseurs dopés conduisent à la formation d'acétone et de propène, mettant en évidence la présence de sites basiques et acides. La caractérisation par XPS nous a permis de proposer que les sites basiques sont constitués de groupes de surface pyridiniques et les sites acides sont des groupements sulfoniques formés au cours de la purification de ces matériaux avec de l'acide sulfurique. Des catalyseurs au ruthénium et au palladium supportés (2%) sur des nanotubes de carbone non dopés et dopés à l'azote (N-CNT), ont été préparés et évalués dans la réaction de décomposition de l'alcool isopropylique comme réaction test. La présence de fonctionnalités azotées (azote pyridinique, pyrrolique et quaternaire) sur le support dopé à l'azote induit une plus grande dispersion du métal. En ce qui concerne les catalyseurs supportés, ceux de palladium étaient plus actifs et plus sélectifs que ceux au ruthénium. De plus, les catalyseurs au Pd sont sélectifs en acétone, tandis que les catalyseurs au Ru conduisent à la déshydratation et la déshydrogénation. Le dopage des nanotubes de carbone par l’azote conduit aussi à l'apparition de propriétés d'oxydo-réduction. Enfin, nous avons montré que des nanotubes de carbone, constitués de deux sections différentes : une partie non dopée hydrophobe reliée à un segment hydrophile, sont amphiphiles. Nous les avons utilisés comme supports tensioactif de catalyseur au palladium. Ces nouveaux catalyseurs à base de Pd supporté ont été testés dans la réaction d'oxydation de plusieurs alcools en utilisant l'oxygène moléculaire en phase liquide. L'oxydation du 2- heptanol produit sélectivement la cétone correspondante, alors que l'oxydation de l'alcool benzylique est très sélective vis-à-vis de l'aldéhyde. Par ailleurs, l'oxydation de l'éthanol produit de l'acide acétique de manière sélective. / The objective of this work is the synthesis and the investigation of the acid and basicproperties of nitrogen doped carbon nanotubes (CNTs) able to be used as catalysts or catalystsupports. For this, three types of purified nitrogen doped CNTs were synthesized,characterized and tested for isopropyl alcohol conversion under nitrogen or air atmosphere,and compared to undoped CNTs. The N-doped CNTs differ from their nitrogen content andfrom the presence or not of undoped section in their structure. The reaction lead to theformation of acetone as the sole product on catalysts presenting no nitrogen or low nitrogencontent (< 2.8% w/w), pointing to the presence of basic sites. At higher nitrogen content, Ndopedcatalysts lead to the formation of acetone and propene, highlighting the presence ofboth basic and acids sites on such material. XPS characterization allow us to propose that thebasic sites consist in pyridinic surface groups and the acidic sites in sulfonic surface groupsformed during the purification of these material with sulfuric acid. Ruthenium and palladiumsupported catalysts (2% w/w) were prepared on nitrogen-doped and non-doped carbonnanotubes (N-CNT), and evaluated for the reaction of decomposition of isopropyl alcohol asprobe reaction. The presence of nitrogen functionalities (pyridinic, pyrrolic and quaternarynitrogen) on the nitrogen doped support induces a higher metal dispersion: 1.8 nm (Pd/NCNT)< 4.9 nm (Pd/CNT), and 2.4 nm (Ru/N-CNT) < 3.0 nm (Ru/CNT). As far as thesupported catalysts are concerned, the palladium ones were more active and more selectivethan the ruthenium ones. The Pd catalysts were selective towards acetone, whereas Rucatalysts lead to dehydration and dehydrogenation products. The nitrogen doping induces theappearance of redox properties, which appear when oxygen is present in the reaction mixture.Finally, we have shown that unique amphiphilic magnetic hybrid carbon nanotubes thatcontain on the same nanotube two different sections: a hydrophobic undoped part connectedto a hydrophilic N-doped segment are synthesized and used as tensioactive supports forpalladium catalysts. These new Pd-supported catalysts have been used in the alcoholoxidation reaction using molecular oxygen in the liquid phase. The oxidation of 2-heptanolproduces selectively the ketone, the oxidation of benzyl alcohol is very selective towards thealdehyde, and ethanol oxidation produces selectively acetic acid.

CARBON AND NITROGEN POOLS AND FLUXES OF TWO FOREST ECOSYSTEMS IN THE ORE MOUNTAINS With increasing atmospheric CO2 concentrations, forest ecosystems are considered for their sequestration ability. However, there are differences between coniferous and deciduous tree species in their impact on the carbon (C) and nitrogen (N) fluxes within forest ecosystems, which influence soil carbon and nitrogen pools. In natural beech and monoculture spruce stands on research sites of Czech Geological Survey in the Ore Mountains, C and N fluxes and pools were investigated. There were investigated ecosystem inputs (C, N, in throughfall, litterfall) as well as outputs (soil respiration, concentrations of C, N in seepage water discharge). Further, C and N pools of living biomass and soils were determined. Throughfall DOC was significantly higher in the spruce stand, on the other hand litterfall C flux showed the opposite relationship. At output, DOC, DON and NH4 + discharge fluxes from O horizon were significantly higher in the spruce stand whereas in the beech stand higher NO3 - flux from mineral soil was recorded. Soil respiration was quite similar in the both stands, however different parts of original sources of respiration among tree species were different. Beech stand has larger pools of carbon and nitrogen in...

Nitrogen-doped carbon materials have garnered much interest due to their electrocatalytic activity towards important reactions such as the reduction of hydrogen peroxide. N-doped carbon materials are typically prepared and deposited on solid conductive supports, which can sometimes involve time-consuming, complex, and/or costly procedures. Here, nitrogen-doped screen-printed carbon electrodes (N-SPCEs) were fabricated directly from a lab-formulated ink composed of graphite that was modified with surface nitrogen groups by a simple soft nitriding technique. N-SPCEs prepared from inexpensive starting materials (graphite powder and urea) demonstrated good electrocatalytic activity towards hydrogen peroxide reduction. Amperometric detection of H2O2 using N-SPCEs with an applied potential of −0.4 V (vs. Ag/AgCl) exhibited good reproducibility and stability as well as a reasonable limit of detection (2.5 µM) and wide linear range (0.020 to 5.3 mM).

Studies of single, isolated nanoparticles provide better understanding of the structure-function relationship of nanoparticles since they avoid complications like interparticle distance and nanoparticle loading that are typically associated with collections of nanoparticles distributed on electrode supports. However, interpretation of results obtained from single nanoparticle immobilization studies can be difficult to interpret since the underlying nanoelectrode platform can contribute to the measured current, or the immobilization technique can adversely affect electron transfer. Here, we immobilized ligand-free gold nanoparticles on relatively electrocatalytically inert nitrogen-doped carbon ultramicroelectrodes that were prepared via a soft nitriding method. Sizes of the particles were estimated by a recently reported electrochemical method and were found to vary linearly with deposition time. The particles also exhibited electrocatalytic activity toward methanol oxidation. This immobilization strategy shows promise and may be translated to smaller nanoelectrodes in order to study electrocatalytic properties of single nanoparticles.

Understanding the quality of the air we breathe is critical in quantifying the impact that atmospheric chemistry has on health. Poor air quality increases the risk of heart and lung diseases as well as having a detrimental effect on climate, ecology and the built environment. The burning of fossil fuels and plant matter (biomass burning) creates large quantities of gases and particulate matter that impact air quality and the air we breathe. Biomass burning is estimated to contribute 400 Tg of non-methane organic compounds, 40 Tg of methane and 7.1 Tg of nitrogen oxides to the atmosphere each year. This thesis aims to better understand the role of biomass burning on air quality and tropospheric chemistry. The in depth analysis presented here addresses of the impact of boreal biomass burning in North America on air quality, in particular, carbon monoxide (CO) and ozone (O3). By using a number of different modelling techniques along with data collected from a field campaign and satellites the transport and chemistry of biomass burning emissions were analysed and quantified. The first research chapter of the thesis used the GEOS-Chem atmospheric chemistry transport model to interpret aircraft measurements of CO in biomass burning outflow taken during the 2011 BORTAS-B campaign over Canada. The model has some skill reproducing the observed variability, but has a positive bias for observations < 100 ppb and a negative bias for observations > 300 ppb. It was found that observed CO variations are largely due to fires over Ontario, with smaller and less variable contributions from fossil fuel combustion from eastern Asia and NE North America. To help interpret observed variations of CO an effective physical age of emissions (¯A) metric was developed. It was found that during BORTAS-B the age of emissions intercepted over Halifax, Nova Scotia is typically 4–11 days, and on occasion as young as two days. The analysis shows that ¯A is typically 1–5 days older than the associated photochemical ages inferred from co-located measurements of different hydrocarbons. It is argued that a robust observed relationship between CO and black carbon aerosol during BORTAS-B (r² > 0.7), form the basis of indirect evidence that aerosols co-emitted with gases during pyrolysis markedly slowed down the plume photochemistry during BORTAS-B with respect to photochemistry at the same latitude and altitude in clear skies. The second research chapter focuses on O3 production downwind from boreal biomass burning. Using the GEOS-Chem model, the O3 chemistry within a biomass burning plume from a fire on 17 July 2011 in mid-Canada was examined. The model shows a significant positive bias (~20 ppb) in reproducingO3 mixing ratios over North America for July 2011 when compared to observations. Reducing NO emissions from lightning and fossil fuel by 50% and 54% respectively reduced this bias to ~10 ppb. The cause of the remaining bias is uncertain. Using a novel technique with the model, the centre of the biomass burning plume was tracked and O3 concentrations and chemistry was extracted from the centre of the plume. The biomass burning enhanced O3 concentrations throughout the plume by between 1 – 20 ppb when compared with the same plume path with no biomass burning. The plume was characterised as being NOx-rich for the initial four days of transport. The sensitivity of the O3 chemistry to different emissions was calculated and it was found that the O3 is initially highly sensitive to NO emissions from biomass burning and then to NO emissions from fossil fuels as it travels across an urban area surrounding Quebec City. The O3 net production was found to initially decrease with an increase in NO but increase further downwind. The final research chapter of the thesis uses long-term satellite observations to evaluate natural variability in CO concentrations over the North Atlantic. 15 years of MOPITT CO column observations were used along with modelled CO from the GEOS-Chem model. The model was evaluated against the MOPITT overpass and shows a negative bias of between -8% and -24% over the northern mid-latitudes with the largest bias seen in spring. The model has a large positive bias (8% – 40%) over the Amazon,West Africa and Indonesia through all seasons. Using Empirical Orthogonal Function (EOF) analysis on the MOPITT and GEOS-Chem CO columns shows the largest mode of variability seen in the North Atlantic to be the oxidation of methane for winter and spring, biomass burning during summer and fossil fuel combustion from East Asia during autumn.

O objetivo deste trabalho foi o de avaliar o desempenho de um reator de leito estruturado submetido à aeração intermitente (LEAI) na remoção de matéria orgânica e nitrogênio de esgoto sanitário. O reator apresentava um volume total de 11,6 L, com uma porosidade do leito de 52%. O leito estruturado era composto de 13 estruturas cilíndricas (diâmetro igual a 3 cm) de espuma de poliuretano, dispostas verticalmente no interior do reator. A alimentação do reator era feita continuamente com esgoto sanitário, sendo este proveniente de um interceptor de esgoto que passava próximo ao laboratório onde o sistema foi montado. O reator era provido de sistema de recirculação interna, com razão de recirculação igual a 3, valor este adotado após a realização de ensaios hidrodinâmicos. Foram testadas 4 condições operacionais diferentes, variando-se o tempo de detenção hidráulica (TDH) e os períodos de aeração e não aeração. Para cada condição operacional, foram feitos os seguintes estudos: avaliação da eficiência de remoção de matéria orgânica e nitrogênio, determinação da atividade nitrificante e desnitrificante, determinação do número mais provável (NMP) da comunidade nitrificante e desnitrificante, perfis temporais e análise da comunidade microbiana. O sistema apresentou elevada remoção de N-total, com valores médios de 80% para valores de TDH de 12 e 10 horas, sob 2 horas de aeração e 1 hora sem aeração. Com a diminuição do TDH para 8 horas, houve queda na eficiência do sistema para 70% (mantendo-se os períodos de aeração de 2 horas e não aeração de 1 hora). Alterando-se o período de aeração para 3 horas, mantendo-se em 1 hora o período sem aeração, o reator apresentou eficiência média de remoção de N-total de 79% com o TDH de 8 horas. A remoção de DQO foi elevada em todas as fases, com valores médios em torno de 90%. Os resultados da atividade nitrificante e desnitrificante foram condizentes com valores encontrados na literatura para sistemas que operam com remoção simultânea de matéria orgânica e nitrogênio. Os perfis temporais mostraram que não houve variação nas formas de nitrogênio (N-NH4+, N-NO2- e N-NO3-) no efluente, apesar da operação sob a aeração intermitente devido ao grau de mistura imposto pela recirculação interna. A concentração de sólidos no efluente foi relativamente baixa quando comparada à concentração de efluentes de reatores de biomassa suspensa, com valor máximo de SSV igual a 108mgSSV.L-1. A presença do Metazoário Aelosomas sp no efluente do reator indica um possível consumo do lodo excedente no reator por esses microrganismos. As análises microbiológicas mostraram uma elevada abundância relativa de gêneros aeróbios facultativos, capazes de utilizar N-NO3- e N-NO2- como receptor de elétrons na ausência de oxigênio. Também se verificou a presença do gênero Comamonas sp em elevada abundância relativa. Esse gênero apresenta microrganismos capazes de realizar a nitrificação heterotrófica e a desnitrificação aeróbia. No entanto, os ensaios realizados não permitem inferir sobre a ocorrência desses processos. Desse modo, os processos convencionais de nitrificação e desnitrificação, tanto pela estratificação do biofilme devido à formação de gradiente de concentração de oxigênio dissolvido, quanto devido à aeração intermitente, certamente tiveram papel preponderante na remoção de nitrogênio. Os resultados obtidos permitem considerar o reator LEAI como uma alternativa tecnicamente viável para a remoção simultânea de matéria orgânica e nitrogênio de esgotos sanitários. / This study aimed at evaluating the organic matter and nitrogen removal from sewage in a structured bed reactor subjected to intermittent aeration. The reactor had a total volume of 11.6 L and bed porosity of 52%. Thirteen polyurethane foam cylinders of 3 cm diameter and 60 cm height were fixed vertically inside the reactor using PVC rods. The reactor was continuously fed with sewage collected from a sanitary sewer passing near the laboratory where the system was assembled. The reactor was provided with internal recirculation system with a recirculation ratio at 3, a value adopted after conducting hydrodynamic tests. Four different operating conditions were tested, varying the hydraulic retention time (HRT) and aeration and non-aeration periods. Nitrogen and organic matter removal efficiencies, nitrifying and denitrifying activities, and the most probable number (MPN) of nitrifying and denitrifying communities were evaluated for each operational condition. The reactor presented a Total-N removal efficiency of 80%, at HRT of 12 hours and 10 hours and aerated and non-aerated periods of 2 hours and 1 hour, respectively. With decreasing the HRT to 8 hours, the Total-N removal efficiency decreased to 70% for the same aeration and non-aeration periods. After increasing the aerated period to 3 hours and keeping the non-aerated periods of 1 hour and HRT of 8 hours, the system attained the Total-N removal efficiency of 79%. COD removal efficiencies were about 90% in all operational condition. Nitrifying and denitrifying activities were similar to those found in the literature for systems presenting simultaneous nitrification and denitrification, and carbon removal. No variation in nitrogen forms (NO3--N, NO2--N and NH4+-N) was observed during a cycle of intermittent aeration. The solids concentration in effluent was relatively low compared to the concentration of suspended-growth biomass reactors, with a maximum value of VSS of 108 mgVSS.L-1. The presence of the metazoan Aelosomas sp in the effluent in all operational conditions indicated a possible use of the excess sludge in the reactor by these microorganisms. Microbiological analysis showed a high relative abundance of aerobic/facultative microorganisms, capable to use NO3--N and NO2--N as electron acceptor in the absence of oxygen. It was also verified the presence of the genus Comamonas sp with high relative abundance. This genus presents microorganisms able to perform heterotrophic nitrification and aerobic denitrification. However, the assays do not allow us to infer the occurrence of these processes. Thus, the conventional processes of nitrification and denitrification certainly played a preponderant role in nitrogen removal both by the stratification of the biofilm due to the formation of a concentration gradient of dissolved oxygen, as due to the intermittent aeration. The results allow considering the reactor as a viable technological alternative for the simultaneous removal of organic matter and nitrogen of sewage.

O lançamento de águas residuárias contendo compostos nitrogenados tem um importante impacto sobre a saúde e o meio ambiente, tornando necessária a incorporação de processos de remoção desses compostos nos sistemas de tratamento de águas residuárias. Neste trabalho, foram estudadas as condições de operação para promover a remoção conjunta de nitrogênio e matéria orgânica em reator biológico de leito móvel, contínuo, operado sob aeração intermitente, alimentado com água residuária sintética contendo nitrogênio amoniacal (90 a 110 mg/L) e melaço como matéria orgânica (DQO de 450 a 550 mg/L). Foram utilizados dois reatores em escala de bancada, cada um com dois litros de volume útil, contendo diferentes meios suportes para a imobilização da biomassa: matrizes de espuma de poliuretano e anéis plásticos. Na primeira etapa experimental, o reator contendo anéis plásticos apresentou eficiências de remoção de nitrogênio muito baixas. Na segunda etapa, trocou-se o material suporte por matrizes de espuma de poliuretano inoculadas com lodo aeróbio de estação de tratamento de águas residuárias. A partir de então, trabalhou-se com dois reatores de mesma configuração, exceto pelas origens, idades e características dos lodos de inóculo. Inicialmente, a alimentação foi realizada utilizando-se apenas os micronutrientes contidos no melaço. Posteriormente, a composição da água residuária foi alterada, introduzindo-se solução de micronutrientes, pois se concluiu que a instabilidade no processo de nitrificação devia-se ao fato de o melaço comercial apresentar deficiências nutricionais. Como resultado, em condições de estabilidade operacional, foram obtidas eficiências de remoção de DQO superiores a 85%, oxidação total do nitrogênio amoniacal e eficiências de remoção de nitrogênio de aproximadamente 55%. Variações posteriores nas condições de operação, como o aumento do período anóxico (de 1h para 1h15min) e redução do tempo de detenção hidráulica (para valores inferiores a 12 horas), resultaram em melhora no desempenho dos reatores. Os resultados obtidos permitem admitir que as melhores condições de operação não foram atingidas durante o experimento, abrindo a possibilidade para a otimização do processo em pesquisas futuras. Constatou-se que o desenvolvimento das populações microbianas imobilizadas no meio suporte foi diferente do observado na biomassa em suspensão. Verificou-se, também, que a biomassa responsável pela nitrificação e desnitrificação ocorreu predominantemente no meio suporte, enquanto que a biomassa heterotrófica predominou no lodo em suspensão. / The operating conditions for the combined removal of nitrogen and organic matter in moving- bed biological reactor were investigated. Two bench-scale reactors, two liters each, were operated under intermittent aeration and continuously fed with synthetic wastewater containing ammonia nitrogen (90 to 110 mg/L) and molasses as organic carbon source (COD of 450 to 550 mg/L). Each reactor received different moving-bed materials: polyurethane foam matrices and plastic rings, respectively. During the first experimental period, the reactor containing plastic rings maintained very low nitrogen removal efficiencies during large period. For this reason, the moving-bed was replaced by polyurethane foam matrices and the reactor was re-inoculated with aerobic wastewater plant sludge. Thereafter, the two reactors were similar except for the origin, age and characteristics of the inoculum sludge. First, the wastewater micronutrients were just those contained in the carbon source (molasses). After, the synthetic wastewater composition was changed by adding a solution of micronutrients. This procedure was adopted to achieve a stable nitrification process, because commercial molasses is a very poor regarding its micronutrient composition. As a result of the stable conditions prevalence just after adding micronutrients, organic matter (as COD) removal efficiencies were higher than 85% and complete nitrogen ammonia oxidation was achieved. In nitrogen removal efficiencies were approximately 55%. The performance of the reactors improved after the increase of the anoxic period from1h to 1h15min, and reduction of the hydraulic detention time to less than 12 h. The results obtained in the last operating period indicated the optimum operating conditions was not achieved in this experiment, thus opening the possibility of process improvement in further researches. Microbial populations with different characteristics were developed in suspended growth and attached biomass. Nitrification and denitrification bacteria predominated as attached biomass whereas heterotrophic bacteria predominated as suspended growth biomass.

Neste trabalho foi desenvolvido um procedimento experimental para a fabricação de estruturas 3D de nanotubos de carbono crescidos sobre substrato de cobre e decorados com partículas de óxido de titânio. Foram relacionados os três tipos diferentes de NTCs nesta estrutura (simples, dopados com nitrogênio e tratados com plasma) com a deposição do TiO2 por ALD. Foram igualmente propostas três aplicações para esta estrutura. A síntese dos NTCs verticalmente orientados, dopados e não dopados, foi otimizada dentre alguns parâmetros de síntese como temperatura, agente oxidante e principalmente, o filme catalisador. A introdução de defeitos nos NTCP através do tratamento a plasma oxidativo foi avaliada frente a variáveis como pressão, potência e tempo de exposição. A relação entre os defeitos destes três tipos de NTCs e a deposição de TiO2 por ALD foi avaliada por microscopia eletrônica de transmissão, Raman, XPS e TGA. O procedimento experimental para confecção da estrutura 3D foi desenvolvido etapa por etapa via diversas técnicas experimentais, desde caracterização química, imagem, até testes empíricos. Na estrutura final, foram avaliadas as propriedades fotocatalíticas pela decomposição de corante orgânico em meio aquoso, propriedades capacitivas por voltametria cíclica e propriedades de emissão por campo através de curvas de campo elétrico por corrente de emissão e diagramas F-N. Foram obtidas florestas de NTCs de boa qualidade com até 0.5mm de altura, de diâmetros e número de paredes regulares. Nestes foi possível introduzir defeitos de maneira controlável, mantendo o arranjo da floresta. As florestas de NTCNx alcançam uma altura de até 0,3mm com concentração de nitrogênio de 2% tendo os nanotubos uma estrutura típica “bamboo-like”. Os resultados mostram a relação entre o tipo de defeito e a deposição de TiO2 por ALD, obtendo-se partículas cristalinas para os NTCP e NTCNx, sendo neste ultimo as partículas homogeneamente distribuídas e com tamanho uniforme, enquanto nos NTCOx forma-se uma densa camada de TiO2 composta por grandes grãos monocristalinos A partir de processo como tratamentos térmicos e transferência dos NTC de substrato foi possível obter uma estrutura 3D composta de uma camada carbono grafítico e NTC-VAs sobre um substrato de cobre, sem alterar o arranjo inicial das florestas. As amostras mostraram efeito de emissão de elétrons por campo elétrico, porém estas requerem uma análise mais quantitativa. Os ensaios de fotocatálise mostraram que a imobilização do TiO2 em um suporte denso inviabiliza a degradação do corante em meio aquoso. Os NTCNx apresentaram maior capacitância que as mostras de NTCP, e o TiO2 foi aparentemente ineficaz para a melhoria desta propriedade. / In this work, we propose an experimental procedure for fabrication of 3D carbon nanotubes structures anchored with titanium oxide particles, on a copper substrate. We correlate three different types of CNTs from this structure (pristine, doped with nitrogen and treated with plasma) with the deposition of TiO2 by ALD. It was yet suggested, three applications for this structure. The synthesis of vertically aligned CNTs, doped and undoped, was optimized among several synthesis parameters such as temperature, oxidizing agent and specially, the catalyst film. The introduction of defects in NTCP by oxidative plasma treatment was evaluated against variables such as pressure, power and exposure time. The association between the defects from these three types of CNTs and the deposition of TiO2 by ALD was assessed by transmission microscopy, Raman, XPS and TGA. The experimental procedure for assembling the 3D structure had been studied step by step by various techniques, from chemical and imaging, up to empirical testing. In the final structure, the photocatalytic properties were evaluated by the organic dye decomposition in an aqueous medium, capacitive properties by cyclic voltammetry and field emission properties through electric field versus emission current curves and F-N diagram. Was obtained high quality NTCs with a height up to 0.5mm with regular diameters and number of walls. On these, it was introduced, in a controllable way, a high amount of defects without jeopardizing the forest structure. The NTCNx forest reach a 0,3nm height with a 2% nitrogen concentration in its typical structure “bamboo-like”. The results show the relation between the type of defect and the deposition of TiO2 by ALD, forming crystalline particles over the NTCP and NTCNx, in this last evenly distributed with uniform size, while on the NTCOx is is formed a dense TiO2 layer shaped by large monocrystalline grains. By process such as heat treatments and CNT transferring was achieved a 3d structure composed by a graphitic carbon layer and VACNTs over a cupper substrate, without disturb the forest assembly. The samples showed electron field emission effect, but its assessment for quantitative analysis was limited to technical issues. The photocatalysis tests showed that immobilization of TiO2 on a dense support prevents the dye degradation in an aqueous medium. The NTCNx shown higher capacitance than NTCP, and the TiO2 was apparently ineffective for improvement of this property.