Transport diffusion of gases is rapid in flexible carbon nanotu

Molecular dynamics simulations of rigid, defect-free single-walled carbon nanotubes have previously suggested that the transport diffusivity of gases adsorbed in these materials can be orders of magnitude higher than any other nanoporous material (A. I. Skoulidas et al., Phys. Rev. Lett. 2002, 89, 185901). These simulations must overestimate the molecular diffusion coefficients because they neglect energy exhange between the diffusing molecules and the nanotube. Recently, Jakobtorweihen et al. have reported careful simulations of molecular self-diffusion that allow nanotube flexibility (Phys. Rev. Lett. 2005, 95, 044501). We have used the efficient thermostat developed by Jakobtorweihen et al. to examine the influence of nanotube flexibility on the transport diffusion of CH4 in (20,0) and (15,0) nanotubes. The inclusion of nanotube flexibility reduces the transport diffusion relative to the rigid nanotube by roughly an order of magnitude close to zero pressure, but at pressures above about I bar the transport diffusivities for flexible and rigid nanotubes are very similar, differing by less than a factor or two on average. Hence, the transport diffusivities are still extremely large compared to other known materials when flexibility is taken into account.

Physicochemical properties of WOx/ZrO2 catalysts for palmitic acid esterification

A series of WOx/ZrO2 with various tungsten loadings was prepared via incipient-wetness impregnation of zirconium hydroxide. The resulting thermally processed materials were characterised by XRD, XPS, porosimetry, NH3-TPD and pyridine FTIR spectroscopy to elucidate their composition, morphology and acidity, and subsequently tested in the esterification of palmitic acid with methanol. Catalytic performance was strongly dependent upon calcination temperature and W surface density. Esterification activity increased with increasing surface W density, reaching a maximum at 8.9Wnm-2 corresponding to near monolayer coverage. Subsequent growth of crystalline WO3 lowered activity, consistent with a decrease in the density of active surface sites. Calcination temperatures as high as 800°C increased surface acidity and hence catalytic activity. The formation of polymeric tungstate species on zirconia is necessary to generate the Brönsted acid sites responsible for palmitic acid esterification under mild conditions. © 2014 Elsevier B.V.

A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X -band electron paramagnetic resonance spectroscopy. © 2010 American Institute of Physics.

Polymerisations in mesoporous environments

The solid acid supported aluminium chloride is an effective cationic initiator for the polymerisation of hydrocarbons. Reactions are highly dependent on the nature of the active sites and the Lewis/Bronsted acid balance in particular.

Multimode Analysis of Nanoscale Biomolecular Interactions

Biomolecular interactions, including protein-protein, protein-DNA, and protein-ligand interactions, are of special importance in all biological systems. These interactions may occer during the loading of biomolecules to interfaces, the translocation of biomolecules through transmembrane protein pores, and the movement of biomolecules in a crowded intracellular environment. The molecular interaction of a protein with its binding partners is crucial in fundamental biological processes such as electron transfer, intracellular signal transmission and regulation, neuroprotective mechanisms, and regulation of DNA topology. In this dissertation, a customized surface plasmon resonance (SPR) has been optimized and new theoretical and label free experimental methods with related analytical calculations have been developed for the analysis of biomolecular interactions. Human neuroglobin (hNgb) and cytochrome c from equine heart (Cyt c) proteins have been used to optimize the customized SPR instrument. The obtained Kd value (~13 µM), from SPR results, for Cyt c-hNgb molecular interactions is in general agreement with a previously published result. The SPR results also confirmed no significant impact of the internal disulfide bridge between Cys 46 and Cys 55 on hNgb binding to Cyt c. Using SPR, E. coli topoisomerase I enzyme turnover during plasmid DNA relaxation was found to be enhanced in the presence of Mg2+. In addition, a new theoretical approach of analyzing biphasic SPR data has been introduced based on analytical solutions of the biphasic rate equations. In order to develop a new label free method to quantitatively study protein-protein interactions, quartz nanopipettes were chemically modified. The derived Kd (~20 µM) value for the Cyt c-hNgb complex formations matched very well with SPR measurements (Kd ~16 µM). The finite element numerical simulation results were similar to the nanopipette experimental results. These results demonstrate that nanopipettes can potentially be used as a new class of a label-free analytical method to quantitatively characterize protein-protein interactions in attoliter sensing volumes, based on a charge sensing mechanism. Moreover, the molecule-based selective nature of hydrophobic and nanometer sized carbon nanotube (CNT) pores was observed. This result might be helpful to understand the selective nature of cellular transport through transmembrane protein pores.

An investigation by AFM and TEM of the mechanism of anodic formation of nanoporosity in n-InP in KOH

The early stages of nanoporous layer formation, under anodic conditions in the absence of light, were investigated for n-type InP with a carrier concentration of ∼3× 1018 cm-3 in 5 mol dm-3 KOH and a mechanism for the process is proposed. At potentials less than ∼0.35 V, spectroscopic ellipsometry and transmission electron microscopy (TEM) showed a thin oxide film on the surface. Atomic force microscopy (AFM) of electrode surfaces showed no pitting below ∼0.35 V but clearly showed etch pit formation in the range 0.4-0.53 V. The density of surface pits increased with time in both linear potential sweep and constant potential reaching a constant value at a time corresponding approximately to the current peak in linear sweep voltammograms and current-time curves at constant potential. TEM clearly showed individual nanoporous domains separated from the surface by a dense ∼40 nm InP layer. It is concluded that each domain develops as a result of directionally preferential pore propagation from an individual surface pit which forms a channel through this near-surface layer. As they grow larger, domains meet, and the merging of multiple domains eventually leads to a continuous nanoporous sub-surface region.

Fabrication et caractérisation de cellules solaires organiques nanostructurées par la méthode de nanoimpression thermique

La morphologie des couches actives des cellules solaires organiques joue un rôle important sur l’efficacité de conversion de l’énergie solaire en énergie électrique de ces dispositifs. Les hétérojonctions planaires et les hétérojonctions en volume sont les plus communément utilisées. Cependant, la morphologie idéale pour l’efficacité se situerait à mis chemin entre celles-ci. Il s’agit de l’hétérojonction nanostructurée qui augmenterait la surface entre les couches actives de matériaux tout en favorisant le transport des porteurs de charge. L’objectif de ce projet de maîtrise est d’étudier l’impact de l’implantation de nanostructures dans les cellules solaires organiques sur leurs performances photovoltaïques. Pour ce faire, on utilise la méthode de nanoimpression thermique sur le matériau donneur, le P3HT, afin que celui-ci forme une interface nanostructurée avec le matériau accepteur, le PCBM. Pour effectuer les nanoimpressions, des moules en alumine nanoporeuse ont été fabriqués à l’aide du procédé d’anodisation en deux temps développé par Masuda et al. Ces moules ont subi un traitement afin de faciliter leur séparation du P3HT. Les agents antiadhésifs PDMS et FTDS ont été utilisés à cette fin. Les résultats obtenus témoignent de la complexité d’exécution du procédé de nanoimpression. Il a été démontré que la pression appliquée durant le procédé, la tension superficielle des éléments en contact et les dimensions des nanopores des moules sont des paramètres critiques pour le succès des nanoimpressions. Ceux-ci ont donc dû être optimisés de manière à réussir cette opération. Ainsi, des cellules à interface nanostructurée à 25% avec des nanobâtonnets de 35 nm de hauteur ont pu être fabriquées. Les cellules nanostructurées ont démontré une efficacité 2,3 ± 0,6 fois supérieure aux cellules sans nanostructures, dites planaires. D’autre part, un solvant a été proposé pour diminuer l’interdiffusion entre les couches de P3HT et de PCBM pouvant altérer les nanostructures. Ce phénomène bien connu survient lors du dépot de la couche de PCBM avec le dichlorométhane, un solvant orthogonal avec ces matériaux. Des mesures au TOF-SIMS ont démontré que le limonène permet de diminuer l’interdiffusion entre les couches de P3HT et de PCBM, ce qui en fait un meilleur solvant orthogonal que le dichlorométhane.

Développement d'un matériau photocatalytique pour l'oxydation de méthanol dans l'eau

La photocatalyse est un procédé d’oxydation avancé très intéressant puisqu’il ne nécessite l’ajout d’aucun réactif chimique. Beaucoup de compagnies souhaitent utiliser ce procédé pour le traitement des gaz et des eaux. Les services Exp inc. est une compagnie qui s’intéresse à la dégradation des composés organiques volatils en milieu aqueux. Ils ont comme objectif d’améliorer leurs technologies et d’en développer de nouvelles comme la photocatalyse. L’objectif ce de projet de maîtrise est de développer un matériau capable d‘oxyder le méthanol en phase aqueuse. Le développement d’un tel photocatalyseur permet d’évaluer systématiquement l’impact de toutes les modifications apportées à un matériau de base et d’en comprendre les bénéfices. Le matériau préparé est basé sur des nanotiges de WO3 synthétisées par voie hydrothermale où l’on ajoute des nanoparticules de TiO2 pour former un composé mixte. Un co-catalyseur de réduction, le platine, est ajouté par photodéposition sur le composé TiO2/WO3. Le produit est finalement traité à l’hydrogène pour en augmenter l’activité catalytique. Pour tester les matériaux, un réacteur photocatalytique a été conçu. Le réacteur possède deux configurations, soit une avec une lampe ultraviolette plongée dans l’eau et une avec une bande de diodes électroluminescentes bleues autour du réacteur. Les modifications, telles que le traitement sous hydrogène et l’ajout de platine, augmentent considérablement l’activité des photocatalyseurs. Les nanotiges de WO3 possèdent une faible surface spécifique offrant donc une activité inférieure à un autre composé avec plus de surface. L’activité des photocatalyseurs est plus faible que celles desprocédés utilisant du peroxyde. Cependant, plusieurs avantages sont remarqués. La photocatalyse se fait à pH neutre et il est possible d’utiliser de la lumière visible. Un matériau photocatalytique basé sur des nanoparticules de WO3 à haute surface spécifique avec du TiO2, du platine et traité à l’hydrogène pourrait offrir une avenue intéressante pour Exp inc.

Nonlinear Optics and Carrier Dynamics in Nanostructured and Two-Dimensional Materials

Understanding and measuring the interaction of light with sub-wavelength structures and atomically thin materials is of critical importance for the development of next generation photonic devices.  One approach to achieve the desired optical properties in a material is to manipulate its mesoscopic structure or its composition in order to affect the properties of the light-matter interaction.  There has been tremendous recent interest in so called two-dimensional materials, consisting of only a single to a few layers of atoms arranged in a planar sheet.  These materials have demonstrated great promise as a platform for studying unique phenomena arising from the low-dimensionality of the material and for developing new types of devices based on these effects.  A thorough investigation of the optical and electronic properties of these new materials is essential to realizing their potential.  In this work we present studies that explore the nonlinear optical properties and carrier dynamics in nanoporous silicon waveguides, two-dimensional graphite (graphene), and atomically thin black phosphorus. We first present an investigation of the nonlinear response of nanoporous silicon optical waveguides using a novel pump-probe method. A two-frequency heterodyne technique is developed in order to measure the pump-induced transient change in phase and intensity in a single measurement. The experimental data reveal a characteristic material response time and temporally resolved intensity and phase behavior matching a physical model dominated by free-carrier effects that are significantly stronger and faster than those observed in traditional silicon-based waveguides.  These results shed light on the large optical nonlinearity observed in nanoporous silicon and demonstrate a new measurement technique for heterodyne pump-probe spectroscopy. Next we explore the optical properties of low-doped graphene in the terahertz spectral regime, where both intraband and interband effects play a significant role. Probing the graphene at intermediate photon energies enables the investigation of the nonlinear optical properties in the graphene as its electron system is heated by the intense pump pulse. By simultaneously measuring the reflected and transmitted terahertz light, a precise determination of the pump-induced change in absorption can be made. We observe that as the intensity of the terahertz radiation is increased, the optical properties of the graphene change from interband, semiconductor-like absorption, to a more metallic behavior with increased intraband processes. This transition reveals itself in our measurements as an increase in the terahertz transmission through the graphene at low fluence, followed by a decrease in transmission and the onset of a large, photo-induced reflection as fluence is increased.  A hybrid optical-thermodynamic model successfully describes our observations and predicts this transition will persist across mid- and far-infrared frequencies.  This study further demonstrates the important role that reflection plays since the absorption saturation intensity (an important figure of merit for graphene-based saturable absorbers) can be underestimated if only the transmitted light is considered. These findings are expected to contribute to the development of new optoelectronic devices designed to operate in the mid- and far-infrared frequency range.  Lastly we discuss recent work with black phosphorus, a two-dimensional material that has recently attracted interest due to its high mobility and direct, configurable band gap (300 meV to 2eV), depending on the number of atomic layers comprising the sample. In this work we examine the pump-induced change in optical transmission of mechanically exfoliated black phosphorus flakes using a two-color optical pump-probe measurement. The time-resolved data reveal a fast pump-induced transparency accompanied by a slower absorption that we attribute to Pauli blocking and free-carrier absorption, respectively. Polarization studies show that these effects are also highly anisotropic - underscoring the importance of crystal orientation in the design of optical devices based on this material. We conclude our discussion of black phosphorus with a study that employs this material as the active element in a photoconductive detector capable of gigahertz class detection at room temperature for mid-infrared frequencies.

Fabrication et caractérisation de cellules solaires organiques nanostructurées par la méthode de nanoimpression thermique

La morphologie des couches actives des cellules solaires organiques joue un rôle important sur l’efficacité de conversion de l’énergie solaire en énergie électrique de ces dispositifs. Les hétérojonctions planaires et les hétérojonctions en volume sont les plus communément utilisées. Cependant, la morphologie idéale pour l’efficacité se situerait à mis chemin entre celles-ci. Il s’agit de l’hétérojonction nanostructurée qui augmenterait la surface entre les couches actives de matériaux tout en favorisant le transport des porteurs de charge. L’objectif de ce projet de maîtrise est d’étudier l’impact de l’implantation de nanostructures dans les cellules solaires organiques sur leurs performances photovoltaïques. Pour ce faire, on utilise la méthode de nanoimpression thermique sur le matériau donneur, le P3HT, afin que celui-ci forme une interface nanostructurée avec le matériau accepteur, le PCBM. Pour effectuer les nanoimpressions, des moules en alumine nanoporeuse ont été fabriqués à l’aide du procédé d’anodisation en deux temps développé par Masuda et al. Ces moules ont subi un traitement afin de faciliter leur séparation du P3HT. Les agents antiadhésifs PDMS et FTDS ont été utilisés à cette fin. Les résultats obtenus témoignent de la complexité d’exécution du procédé de nanoimpression. Il a été démontré que la pression appliquée durant le procédé, la tension superficielle des éléments en contact et les dimensions des nanopores des moules sont des paramètres critiques pour le succès des nanoimpressions. Ceux-ci ont donc dû être optimisés de manière à réussir cette opération. Ainsi, des cellules à interface nanostructurée à 25% avec des nanobâtonnets de 35 nm de hauteur ont pu être fabriquées. Les cellules nanostructurées ont démontré une efficacité 2,3 ± 0,6 fois supérieure aux cellules sans nanostructures, dites planaires. D’autre part, un solvant a été proposé pour diminuer l’interdiffusion entre les couches de P3HT et de PCBM pouvant altérer les nanostructures. Ce phénomène bien connu survient lors du dépot de la couche de PCBM avec le dichlorométhane, un solvant orthogonal avec ces matériaux. Des mesures au TOF-SIMS ont démontré que le limonène permet de diminuer l’interdiffusion entre les couches de P3HT et de PCBM, ce qui en fait un meilleur solvant orthogonal que le dichlorométhane.

Purificación de aire mediante oxidación fotocatalítica de gases contaminantes NOₓ: estudio de los fotocatalizadores TiO₂ y ZnO

Los óxidos de nitrógeno (NOx) son gases contaminantes que afectan al medio ambiente al ser responsables de la formación de smog fotoquímico, lluvia ácida, ozono troposférico, reducción de la capa de ozono, además de participar en el efecto invernadero en la forma de N2O. Adicionalmente, la exposición a estos gases provoca daños a la salud de los seres humanos. Una propuesta tecnológica para abordar esta problemática ambiental es su eliminación mediante un proceso fotooxidativo, lo cual requiere del empleo de óxidos semiconductores con alta actividad fotocatalítica. En el presente trabajo de investigación se valoró el alcance de la tecnología de fotocatálisis heterogénea para la purificación de aire por eliminación de gases tipo NOx. Para este propósito, en una primera parte del trabajo se construyó un reactor fotocatalítico de acuerdo a la norma internacional ISO 22197-1 con el fin de realizar las pruebas fotocatalíticas en condiciones estándar a las establecidas por la regulación internacional y dar así consistencia a los resultados obtenidos. La segunda parte del trabajo consistió en la síntesis y caracterización de los óxidos semiconductores TiO2 y ZnO por el método sol-gel para lo cual en cada caso se aplicó un diseño de experimentos con el fin de encontrar las condiciones experimentales que permitieran la obtención del mejor fotocatalizador de cada sistema en base a sus propiedades fisicoquímicas. La actividad fotocatalítica de las muestras de TiO2 y ZnO se determinó en la reacción de fotooxidación de óxido nítrico (NO) en aire bajo radiación UV. Los mejores fotocatalizadores fueron seleccionados para pruebas de desempeño variando las condiciones experimentales de la reacción fotocatalítica como el caudal volumétrico que entró al reactor, la irradiancia y la cantidad de humedad presente en el medio de reacción, evaluando además el efecto de diversas variables experimentales de la reacción fotocatalítica en sus respectivos valores. Asimismo, el seguimiento de los productos de reacción confirmó la presencia iones nitrato (NO3-) como producto mayoritario de la fotooxidación de NO, lo que dota al proceso de eliminación de NO de un carácter sustentable. En una tercera parte del trabajo se probó la actividad fotocatalítica del fotocatalizador TiO2 cuando fue incorporado en un prototipo de material de construcción. El desempeño fue probado bajo condiciones simuladas y reales de exposición a la intemperie. Los resultados obtenidos indicaron la potencial aplicación de los materiales para el desarrollo comercial de productos fotocatalíticos. En la parte final del trabajo se presentan resultados obtenidos con óxidos semiconductores alternos a los convencionales como Bi2Mo3O12 y TiO2/WO3 cuyo principal propósito fue el de desarrollar fotocatalizadores cuya activación fuera mediante absorción en la porción visible del espectro solar.

Mesoscale Optoelectronic Design of Wire-Based Photovoltaic and Photoelectrochemical Devices

The overarching theme of this thesis is mesoscale optical and optoelectronic design of photovoltaic and photoelectrochemical devices. In a photovoltaic device, light absorption and charge carrier transport are coupled together on the mesoscale, and in a photoelectrochemical device, light absorption, charge carrier transport, catalysis, and solution species transport are all coupled together on the mesoscale. The work discussed herein demonstrates that simulation-based mesoscale optical and optoelectronic modeling can lead to detailed understanding of the operation and performance of these complex mesostructured devices, serve as a powerful tool for device optimization, and efficiently guide device design and experimental fabrication efforts. In-depth studies of two mesoscale wire-based device designs illustrate these principles—(i) an optoelectronic study of a tandem Si|WO3 microwire photoelectrochemical device, and (ii) an optical study of III-V nanowire arrays.

The study of the monolithic, tandem, Si|WO3 microwire photoelectrochemical device begins with development and validation of an optoelectronic model with experiment. This study capitalizes on synergy between experiment and simulation to demonstrate the model’s predictive power for extractable device voltage and light-limited current density. The developed model is then used to understand the limiting factors of the device and optimize its optoelectronic performance. The results of this work reveal that high fidelity modeling can facilitate unequivocal identification of limiting phenomena, such as parasitic absorption via excitation of a surface plasmon-polariton mode, and quick design optimization, achieving over a 300% enhancement in optoelectronic performance over a nominal design for this device architecture, which would be time-consuming and challenging to do via experiment.

The work on III-V nanowire arrays also starts as a collaboration of experiment and simulation aimed at gaining understanding of unprecedented, experimentally observed absorption enhancements in sparse arrays of vertically-oriented GaAs nanowires. To explain this resonant absorption in periodic arrays of high index semiconductor nanowires, a unified framework that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes is developed in the context of silicon, using both analytic theory and electromagnetic simulations. This detailed theoretical understanding is then applied to a simulation-based optimization of light absorption in sparse arrays of GaAs nanowires. Near-unity absorption in sparse, 5% fill fraction arrays is demonstrated via tapering of nanowires and multiple wire radii in a single array. Finally, experimental efforts are presented towards fabrication of the optimized array geometries. A hybrid self-catalyzed and selective area MOCVD growth method is used to establish morphology control of GaP nanowire arrays. Similarly, morphology and pattern control of nanowires is demonstrated with ICP-RIE of InP. Optical characterization of the InP nanowire arrays gives proof of principle that tapering and multiple wire radii can lead to near-unity absorption in sparse arrays of InP nanowires.

Development of advanced catalytic systems for the selective hydrogenolysis of biomass-derived polyols

195 p.

Membrana de alumina anódica: comportamento da microestrutura e estudo das propriedades ópticas após tratamento térmico

Thin commercial aluminum electrolytic and passed through reactions was obtained with anodic alumina membranes nanopores. These materials have applications in areas recognized electronic, biomedical, chemical and biological weapons, especially in obtaining nanostructures using these membranes as a substrate or template for processing nanowires, nanodots and nanofibers for applications noble. Previous studies showed that the membranes that have undergone heat treatment temperature to 1300° C underwent changes in morphology, crystal structure and optical properties. This aim, this thesis, a study of the heat treatment of porous anodic alumina membranes, in order to obtain and to characterize the behavior changes structures during the crystallization process of the membranes, at temperatures ranging between 300 and 1700° C. It was therefore necessary to mount a system formed by a tubular furnace resistive alumina tube and controlled environment, applying flux with special blend of Ag-87% and 13% N2, in which argon had the role of carrying out the oxygen nitrogen system and induce the closing of the pores during the densification of the membrane. The duration of heat treatment ranged from 60 to 15 minutes, at temperatures from 300 to 1700° C respectively. With the heat treatment occurred: a drastic reduction of porosity, grain growth and increased translucency of the membrane. For the characterization of the membranes were analyzed properties: Physical - thermogravimetric, X-ray diffraction, BET surface area; morphological - SEM, EDS through compositional and, optical absorbance, and transmittance in the UV-VIS, and FTIR. The results using the SEM showed that crystallization has occurred, densification and significant changes in membrane structure, as well as obtaining microtube, the BET analysis showed a decrease in specific surface area of the membranes has to 44.381 m2.g-1 to less than 1.8 m2.g-1 and in the analysis of transmittance and absorbance was found a value of 16.5% in the range of 800 nm, characteristic of the near infrared and FTIR have confirmed the molecular groups of the material. Thus, one can say that the membranes were mixed characteristics and properties which qualify for use in gas filtration system, as well as applications in the range of optical wavelength of the infra-red, and as a substrate of nanomaterials. This requires the continuation and deepening of additional study

Synthesis of Ordered Mesoporous Carbon Materials by Dry Etching

A novel synthesis method for ordered mesoporous carbons is presented. The inverse replication of a silica template was achieved using the carbonization of sucrose within mesoporous KIT-6. Instead of liquid acid etching, as in classical nanocasting, a novel dry chlorine etching procedure for template removal is presented for the first time. The resultant ordered mesostructured carbon material outperforms carbons obtained by conventional hard templating with respect to high specific micro- and mesopore volumes (0.6 and 1.6 cm3 g−1, respectively), due to the presence of a hierarchical pore system. A high specific surface area of 1671 m2 g−1 was achieved, rendering this synthesis route a highly convenient method to produce ordered mesoporous carbons.