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.

Titanium dioxide(TiO2) is a stable, effective and well-known photocatalyst for degradation of pollutants. However, its practical applications are limited due to the need for energy higher than 3.2 eV, or a wavelength lower than 390 nm (high frequency waves, ultraviolet and above) hindering its ability to effectively work in the visible light region (about 400 nm to 700 nm). Nitrogen-doped TiO2 (N-TiO2) has garnered some attention as a photocatalyst as it appears to work even in the visible light region. This could allow the utilization of a larger part of the solar spectrum. This thesis presents the results of photocatalytic degradation of methylene blue (MB) carried out under simulated visible light by using TiO2 and N-TiO2(doped in the lab) to evaluate and compare their efficiencies under similar conditions.

abstract: Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel cell cost is mostly due to the expensive noble catalyst Pt. Alkaline fuel cell (AFC) systems, have potential to make use of non-noble catalysts and thus, provides with a solution of overall lower cost. Therefore, this issue has been addressed in this thesis work. Hydrogen-oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm-2 using H22 and O2 gases. This thesis also includes work on synthesizing nitrogen doped MWCNTs using post-doping and In-Situ methods. Post-doped N-MWNCTs were prepared through heat treatment with NH4OH as nitrogen source. Characterization was done through fuel cell testing, which gave peak power density ~40mW.cm-2. For In-Situ N-MWCT, pyridine was used as nitrogen source. The sample characterization was done using Raman spectroscopy and RBS, which showed the presence ~3 at.% of nitrogen on the carbon surface. / Dissertation/Thesis / M.S.Tech Technology 2012

In this thesis, we focused on understanding the synthesis of titanium dioxide (TiO2) films and nitrogen doped TiO2 films using an atmospheric pressure Dielectric Barrier Discharge (DBD). The first part of the work was dedicated to the deposition of TiO2 films by cold plasma DBD with titanium tetraisopropoxide as precursor in a single-step process at room temperature. The deposition rate was about 70 nm·min-1. The photocatalytic degradation rate for the degradation of methylene blue (MB) under ultra violet (UV) irradiation of the TiO2 film after annealing was close to a reference anatase TiO2 spin coated film. Moreover, the TiO2 films showed a good photocatalytic stability. The second part of the study focused on the optimization and the understanding of the effect of the plasma parameters (gas flow rate and power) on the morphology of the TiO2 films and on the investigation of the deposition mechanisms. The morphology of the film changed from granular to compact film by either increasing the total flow rate or decreasing the plasma power. In other words, adapting the energy density in the plasma allowed the control of the morphology of the TiO2 films. To our knowledge, it was the first time that the energy density parameters of the plasma were used to control the morphology of TiO2 films. The photocatalytic degradation rate for the degradation of MB under UV irradiation of the annealed TiO2 film turned out to be about 2 and 15 times higher than the one of the commercial TiO2 film and the as-deposited TiO2 films, respectively. In order to extend the light utilization to the visible light range, TiO2 films were doped with nitrogen using a room temperature argon/ammonia plasma discharge. XPS and SIMS results confirmed that the nitrogen has been incorporated in the TiO2 lattice mostly in Ti-N state. This was further confirmed by Raman spectroscopy and XRD. The plasma properties and the doping mechanism were studied by Optical Emission Spectroscopy. It is suggested that the NH radicals played a key role in the doping of TiO2. The concentration of nitrogen in the N-TiO2 coatings could be tuned by adapting the ratio of NH3 in the plasma or the plasma power. The band gap of our N-TiO2 coatings is lower than the one of undoped TiO2 coating. The photocatalytic degradation rate for N-TiO2 coating was more than 4 times higher than the one of the undoped TiO2 coating. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Nitrogen-doped (N-doped) porous carbons have drawn increasing attention due to their high activity for electrochemical catalysis, and high capacity for lithium-ion (Li-ion) batteries and supercapacitors. So far, the controlled synthesis of N-enriched ordered mesoporous carbons (N-OMCs) for Li-ion batteries is rarely reported due to the lack of a reliable nitrogen-doping protocol that maintains the ordered mesoporous structure. In order to realize this, in this work, ordered mesoporous carbons with controllable N contents were successfully prepared by using melamine, F127 and phenolic resin as the N-source, template and carbon-source respectively via a solvent-free ball-milling method. The as-prepared N-OMCs which showed a high N content up to 31.7 wt% were used as anodes for Li-ion batteries. Remarkably, the N-OMCs with an N content of 24.4 wt% exhibit the highest reversible capacity (506 mA h g−1) even after 300 cycles at 300 mA g−1 and a capacity retention of 103.3%. N-OMCs were also used as electrode materials in supercapacitors and a capacity of 150 F g−1 at 0.2 A g−1 with stable cycling up to 2500 times at 1 A g−1 was achieved. These attractive results encourage the design and synthesis of high heteroatom content ordered porous carbons for applications in the field of energy storage and conversion.

No description available.

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.

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active biomolecules such as DNA bases and neurotransmitters. The results highlight a simplified surface modification procedure for producing efficient and highly selective electrocatalysts. The next four chapters focus on evaluating nitrogen-doped carbon nano-onions (𝑛-CNOs) as electrocatalysts for oxygen reduction and CO2 reduction. 𝑛-CNOs exhibit excellent electrocatalytic performance toward O2 to H2O reduction, which is a pivotal process in fuel cells. 𝑛-CNOs demonstrate excellent resistance against CO poisoning and long-term stability compared to state-of-the-art Pt/C catalysts. In CO2 electrochemical conversion, 𝑛-CNOs demonstrate significant improvement in catalytic performance toward reduction of CO2 to CO with a low overpotential and high selectivity. The outstanding catalytic performance of 𝑛-CNOs originates from the asymmetric charge distribution and creation of catalytic sites during incorporation of nitrogen atoms. High contents of pyridinic and graphitic N are critical for high catalytic performance. This work suggests that carbon-based materials can be outstanding alternatives to traditional metal-based electrocatalysts when their microstructures and surface chemistries are properly tailored.

Carbon nanotubes (CNTs) are well known as excellent electrical conductors. However, their transport properties are limited by electrical breakdown in ambient. Moreover, the electronic properties can further be modulated by doping. Devices such as Schottky diodes, transistors and logic gates based on un-doped and doped CNT junctions have been realized. Recently, nitrogen doped CNTs show potential application in replacing platinum cathode catalyst in fuel cell technology. We synthesize pristine, nitrogen-doped and nitrogen-doped:pristine CNT intratubular junctions by one-step co-pyrolysis and explore them for different applications. We show that the position of electrical breakdown can be predicted which is essential to know for high current applications. Among other applications, we show that individual CNT intratubular junction exhibits rectifying characteristics. Further investigation indicates the intratubular junction behaves like Schottky diode. Lastly, the potential replacement of platinum by nitrogen doped CNTs in direct methanol fuel cell has been explored.