Les oxydes de manganèse présentent un grand intérêt en raison de leur activité catalytique pour l'ORR (la réaction de réduction de l’oxygène) en milieu alcalin et peuvent être utilisés comme matériaux sans métaux nobles pour la cathode dans les piles à combustible. La présente thèse est consacrée à l’étude de l’activité d'oxydes de manganèse pour l’ORR. Il a été montré que Mn2O3 avec structure bixbyite a une meilleure activité catalytique vers l'ORR en milieu alcalin que les autres oxydes de manganèse étudiés. L'activité spécifique de Mn2O3 est seulement 4 fois inférieure à celle de Pt à une surtension de 0.3 V (ERH). Le lien entre la structure des oxydes de Mn et l'activité ORR est identifié: l'activité spécifique augmente exponentiellement avec le potentiel du couple redox Mn(III)/Mn(IV) de surface. Pour assurer l'activité électrocatalytique élevée de Mn2O3, il est nécessaire d'ajouter du carbone à la composition d'électrode, ainsi que de garder un potentiel supérieur à 0.7 V (ERH). / Manganese oxides are of great interest due to their catalytic activity towards the ORR (the oxygen reduction reaction) in alkaline media and can be used as noble metal-free materials for the cathode in liquid and polymer electrolyte alkaline fuel cells. The present thesis is devoted to the investigation of the ORR activity of manganese oxides. It was shown that Mn2O3 with bixbyite structure has a better catalytic activity toward the ORR in alkaline media than other investigated manganese oxide, the surface activity of Mn2O3 is only 4 times lower than that of Pt at an overvoltage of 0.3 V (RHE). The link between the structure of Mn oxides and the ORR activity is found: the specific ORR activity exponentially increases with the potential of the surface Mn(III)/Mn(IV) red-ox couple. To ensure the high electrocatalytic activity of Mn2O3, it is necessary to add carbon to the electrode composition, as well as to keep potential above 0.7 V (RHE).

Em uma aeronave, dispositivos de hiper-sustentação à altos ângulos de ataque promovem a formação de esteiras. Tais esteiras influenciam o desempenho aerodinâmico. A esteira do eslate, por exemplo, afeta o ponto de transição do elemento principal da asa e é a fonte de ruído mais importante na estrutura do avião. Devido a geração de sustentação estas esteiras são assimétricas. Corpos imersos em escoamento cisalhante também produzem esteiras assimétricas, com importantes aplicações para a indústria petrolífera. Existem aspectos de tais escoamentos que precisam de investigação. Por exemplo, não há consenso sobre se pode ou não a assimetria suprimir desprendimento de vórtice ou como afeta o desprendimento da frequência. Na verdade, existe uma aparente discrepância entre os resultados encontrados na literatura. O objetivo do presente trabalho é contribuir para esta questão. A idéia foi investigar a influência da assimetria em um perfil de esteira bidimensional sob desenvolvimento temporal. O perfil da esteira assimétrica foi obtido por uma combinação entre um perfil de uma esteira gaussiana e um perfil tangente hiperbólico da camada de mistura. Foi desenvolvido uma análise bidimensional (2D) da teoria de estabilidade linear para o perfil. O trabalho também incluiu simulações numéricas diretas (DNS) bidimensionais da evolução da perturbação usando formulação característica das equações compressíveis de Navier-Stokes na forma não-conservativa. Os resultados mostraram que a assimetria reduz o frequência de desprendimento para a faixa investigada do parâmetro de assimetria 0 \'< OU =\' K \'< OU =\' 0,25. Para pequenos valores deste parâmetro os resultados mostraram que a assimetria promove a estabilidade. Efeitos do número de Mach na esteira assimétrica também foram investigados. Os resultados mostraram que o aumento do Ma reduziu a máxima taxa de amplificação e a banda instável. Além disso, os resultados da literatura foram reconciliados, levando-se em conta a variação do coeficiente de arrasto com a assimetria. Portanto, uma possível explicação para a controvérsia foi oferecido. / In an aircraft, high-lift devices operating at high angle of attack promote the formation wakes. Such wakes influence the aerodynamic performance. The slat wake, for example, affects the transition point of the wing main element and is the most important source of noise in the airframe. Owing to the generation of lift these wakes are asymmetries. Bodies immersed in a shear flow also produce asymmetric wakes, with important applications to the oil industry. There are aspects of such flows that need investigation. For instance, there is no consensus about whether or not the asymmetry can suppress vortex shedding or how it affects the shedding frequency. Indeed there is an apparent discrepancy between results found in literature. The aim of the present work was to contribute to this issue. The idea was to investigate the influence of asymmetry on a two-dimensional wake profile under temporal development. The asymmetric wake profile was obtained by a combination between a Gaussian wake profile and a hyperbolic tangent mixing layer profile. The bidimensional (2D) linear stability theory analysis of the profile was performed. The work also included 2D Direct Numerical Simulation (DNS) using the characteristic formulation of the compressible Navier-Stokes equations in non-conservative form. The results showed that the asymmetry reduces the shedding frequency for the range of 0 \'< OU =\' K \'< OU =\' 0,25 investigated. For small values of the asymmetric parameter the results showed that the asymmetry promotes stability. Effects of the number of Mach in asymmetric wake also were investigated. The results showed that the increase of Ma reduced the maximum rate amplification and the band unstable. Moreover, the results from literature were reconciled by taking into account the variation of the drag coefficient with the asymmetry. Therefore, a possible explanation for the controversy was offered.

Em uma aeronave, dispositivos de hiper-sustentação à altos ângulos de ataque promovem a formação de esteiras. Tais esteiras influenciam o desempenho aerodinâmico. A esteira do eslate, por exemplo, afeta o ponto de transição do elemento principal da asa e é a fonte de ruído mais importante na estrutura do avião. Devido a geração de sustentação estas esteiras são assimétricas. Corpos imersos em escoamento cisalhante também produzem esteiras assimétricas, com importantes aplicações para a indústria petrolífera. Existem aspectos de tais escoamentos que precisam de investigação. Por exemplo, não há consenso sobre se pode ou não a assimetria suprimir desprendimento de vórtice ou como afeta o desprendimento da frequência. Na verdade, existe uma aparente discrepância entre os resultados encontrados na literatura. O objetivo do presente trabalho é contribuir para esta questão. A idéia foi investigar a influência da assimetria em um perfil de esteira bidimensional sob desenvolvimento temporal. O perfil da esteira assimétrica foi obtido por uma combinação entre um perfil de uma esteira gaussiana e um perfil tangente hiperbólico da camada de mistura. Foi desenvolvido uma análise bidimensional (2D) da teoria de estabilidade linear para o perfil. O trabalho também incluiu simulações numéricas diretas (DNS) bidimensionais da evolução da perturbação usando formulação característica das equações compressíveis de Navier-Stokes na forma não-conservativa. Os resultados mostraram que a assimetria reduz o frequência de desprendimento para a faixa investigada do parâmetro de assimetria 0 \'< OU =\' K \'< OU =\' 0,25. Para pequenos valores deste parâmetro os resultados mostraram que a assimetria promove a estabilidade. Efeitos do número de Mach na esteira assimétrica também foram investigados. Os resultados mostraram que o aumento do Ma reduziu a máxima taxa de amplificação e a banda instável. Além disso, os resultados da literatura foram reconciliados, levando-se em conta a variação do coeficiente de arrasto com a assimetria. Portanto, uma possível explicação para a controvérsia foi oferecido. / In an aircraft, high-lift devices operating at high angle of attack promote the formation wakes. Such wakes influence the aerodynamic performance. The slat wake, for example, affects the transition point of the wing main element and is the most important source of noise in the airframe. Owing to the generation of lift these wakes are asymmetries. Bodies immersed in a shear flow also produce asymmetric wakes, with important applications to the oil industry. There are aspects of such flows that need investigation. For instance, there is no consensus about whether or not the asymmetry can suppress vortex shedding or how it affects the shedding frequency. Indeed there is an apparent discrepancy between results found in literature. The aim of the present work was to contribute to this issue. The idea was to investigate the influence of asymmetry on a two-dimensional wake profile under temporal development. The asymmetric wake profile was obtained by a combination between a Gaussian wake profile and a hyperbolic tangent mixing layer profile. The bidimensional (2D) linear stability theory analysis of the profile was performed. The work also included 2D Direct Numerical Simulation (DNS) using the characteristic formulation of the compressible Navier-Stokes equations in non-conservative form. The results showed that the asymmetry reduces the shedding frequency for the range of 0 \'< OU =\' K \'< OU =\' 0,25 investigated. For small values of the asymmetric parameter the results showed that the asymmetry promotes stability. Effects of the number of Mach in asymmetric wake also were investigated. The results showed that the increase of Ma reduced the maximum rate amplification and the band unstable. Moreover, the results from literature were reconciled by taking into account the variation of the drag coefficient with the asymmetry. Therefore, a possible explanation for the controversy was offered.

Magister Scientiae - MSc / Fuel cells convert chemical energy from a fuel into electricity through chemical reaction with oxygen. This possesses some challenges like slow oxygen reduction reaction (ORR), overpotential, and methanol fuel cross over in a direct methanol fuel cell (DMFC). These challenges cause inefficiency and use of higher amounts of the expensive platinum catalyst.Several binary catalysts with better ORR activity have been reported. In this study we investigate the best catalyst with better ORR and MOR performances and lower over-potentials for PEMFC and DMFC applications by comparing the in-house catalysts (10%Pt/C, 20%Pt/C,30%Pt15%Ru/C, 40%Pt20%Ru/C, 30%PtCo/C, 20%Pt20%Cu/C and 20%PtSn/C) with the commercial platinum based catalysts (10%Pt/C, 20%Pt/C, 20%Pt10%Ru/C, 20%PtCo/C,20%PtCu/C and 20%PtSn/C) using the cyclic voltammetry and the rotating disk electrode to determine their oxygen reduction reaction and methanol tolerance. HRTEM and XRD techniques were used to determine their particle size, arrangement and the atomic composition. It was observed that the 20%Pt/C in-house catalyst gave the best ORR activity and higher methanol oxidation current peaks compared to others catalysts followed by 20%Pt10%Ru/C commercial catalyst. The 20%PtCo/C commercial, 30%PtCo/C in-house and 20%PtSn/C in-house catalysts were found to be the most methanol tolerant catalysts making them the best catalysts for ORR in DMFC. It was observed that the ORR activity of 20%PtCo/C commercial and 30%PtCo/C inhouse catalysts were enhanced when heat treated at 350 0C. From XRD and HRTEM studies, the particle sizes were between 2.72nm to 5.02nm with little agglomeration but after the heat treatment, the particles were nicely dispersed on the carbon support.

Eletrocatalisadores baseados em Pd/C, PdCu/C, PdNi/C e PdAg/C foram produzidos pelo método de micro-ondas para serem utilizados como cátodo na célula a combustível alcalina na ausência e presença de álcool. Este método se mostrou bastante efetivo para a produção dos materiais, uma vez que as partículas apresentaram boa dispersão no suporte de carbono e produziram eletrocatalisadores com tamanho de partícula em torno de 3,5 nm, de acordo com as análises de DRX e MET. A partir das voltametrias cíclicas observa-se que para os eletrocatalisadores de PdCu/C e PdNi/C quanto maior a quantidade de Cu ou Ni, respectivamente, maior a área ativa do material estudado. Análises de disco anel rotatório foram realizadas nos eletrocatalisadores demonstrando que, independente da composição estudada, a quantidade produzida de peróxido foi de no máximo 4%. Estes dados corroboram com as inclinação das retas nas análises de Koutecky-Levich, uma vez que em ambos os casos a RRO ocorre via 4 elétrons. Análises de estabilidade dos materiais demonstraram que todos eles mantiveram ou melhoraram seu desempenho diante da RRO, quando se compara os dados obtidos antes e depois de 1000 ciclos voltamétricos. Testes de tolerância ao metanol e etanol foram realizados em meia célula com todas as composições de eletrocatalisadores produzidos. Na presença tanto de metanol quanto de etanol as composições atômica de 50:50, para todos os materiais estudados, foram as que demonstraram menor influência da presença do álcool durante a varredura linear da RRO. Nas medidas realizadas em célula unitária, com relação à tolerância ao metanol durante a RRO, o eletrocatalisador que demonstrou melhor desempenho foi o PdAg/C 70:30 enquanto que na presença de etanol o eletrocatalisador que demonstrou melhor desempenho foi o PdNi/C 70:30. / Pd/C, PdCu/C, PdNi/C and PdAg/C electrocatalysts were produced by microwave method to be used as cathode in alkaline fuel cell in the absence and presence of alcohol. This method showed to be effective for the materials production, the particles exhibited good dispersion in carbon support and it produced electrocatalysts with a particle size of about 3.5 nm, according to XRD and TEM analysis. In cyclic voltammetry is observed that PdCu/C and PdNi/C electrocatalysts has higher active area with higher amount of Cu and Ni, respectively. Rotating ring disk analysis in the electrocatalysts showed that the amount of peroxide produced was at most 4%. This data is similar to Koutecky-Levich analysis, once for both the ORR occurs via 4 electrons. Materials stability analysis showed that they kept or improve performance in ORR, comparing the data before and after 1000 voltammetric cycles. Tolerance tests in methanol and ethanol were performed in a half cell in all electrocatalysts compositions. In presence of methanol and ethanol the compositions 50:50, to all materials studied, showed less influence in the presence of alcohol in ORR linear scan. In alkaline fuel cell PdAg/C 70:30 showed better performance for ORR in presence of methanol and PdNi/C 70:30 showed better performance for ORR in ethanol presence.

The science and technology of catalysis is more important today than at any other time in our history due to the grand energy and environment challenges we are facing. With the explosively growth of computation power nowadays, computer simulation can play an increasingly important role in the design of new catalysts, avoiding the costly trail-and-error attempts and facilitating the development cycle. The goal to inverse design of new materials with desired catalytic property was once far off, but now achievable. The major focus of this dissertation is to find the general rules that govern the catalytic performance of a nanoparticle as the function of its structure. Three types of multi-metallic nanoparticles have been investigated in this dissertation, core-shell, random alloy and alloy-core@shell. Significant structural rearrangement was found on Au@Pt and Pd@Pt nanoparticle, which is responsible for a dramatic improvement in catalytic performance. Nonlin- ear binding trends were found and modeled for random alloy nanoparticles, providing a prescription for tuning catalytic activity through alloying. Studies of ORR on Pd/Au random alloy NP and hydrogenation reaction on Rh/Ag random alloy NP revealed that binding on individual ensemble should be in- vestigated when large disparity of adsorbate affinity is presented between two alloying elements. In the alloy-core@shell system, I demostrated a general linear correlations between the adsorbate binding energy to the shell of an alloy-core@shell nanoparticle and the composition of the core. This relation- ship allows for interpolation of the properties of single-core@shell particles and an approach for tuning the catalytic activity of the particle. A series of promising catalysts were then predicted for ORR, HER and CO oxidation. As a first attempt to bridge the material gap, bimetallic nano clus- ter supported on CeO₂(111) was investigated for CO oxidation. A strong support-metal interaction induces a preferential segregation of the more reac- tive element to the NC-CeO₂ perimeter, generating an interface with the Au component. (Au-Cu)/CeO₂ was found to be optimal for catalyzing CO oxida- tion via a bifunctional mechanism. O₂ preferentially binds to the Cu-rich sites whereas CO binds to the Au-rich sites. A method called distributed replica dynamics (DRD) is proposed at last to utilize enormous distributed computing resources for molecular dynamics simulations of rare-event in chemical reac- tions. High efficiency can be achieved with an appropriate choice of N [subscript rep] and t [subscript rep] for long-time MD simulation. / text

Environmentally-concerned parents and educators today are asking, “How do we co-create learning environments that will foster environmental citizenry?” This reflects David Orr's claim: “More of the same kind of education that enabled us to industrialize the earth can only make things worse.” Using autoethnography to explore my decision to deschool my children, I'm placed in the position of a reflexive practitioner, as I serve as both the primary researcher and subject of that research. Upon arriving at the decision to forgo the compulsory education system I discovered the interconnectedness between deschooling, autoethnography, and 21st century theories of environmental education. I examine the rationales of environmental educators such as Orr, Weston and Jickling who call for new systems of environmental education. I expose underlying assumptions and beliefs that shape my decisions to deschool my daughters and create context for broader community discussion about how to educate for an environmentally engaged citizenry.

James Orr (1844-1913) was a Scottish theologian, apologist and polemicist. He was the leading United Presbyterian theologian at the time of the United Free Church of Scotland union of 1900, and beyond his own church and nation he came to exercise a significant influence in North America. This study is an examination of Orris theological contribution, what he believed and how he expressed it, in its historical setting Particular attention is paid to the convictions which undergirded and gave impetus to his activities. The study reveals that while Orr was far from unaffected by the intellectual movements of the late-Victorian period, his contribution may best be described as a call for continuity with the central tenets of evangelical orthodoxy. He was one of the earliest and principal British critics of the Ritschlian theology, and a strong opponent of rationalistic biblical criticism. He emphatically rejected all evolutionary interpretations of man's moral history, and held firmly to orthodox Christological formulations in the face of alternative assessments of the historical Jesus. While factors of temperament affected the tenor of his work, his contribution was most decisively shaped by the convictions that evangelical orthodoxy is ultimately self-authenticating, that truth comprises a unity or interconnected whole, that genuine Christian belief implies a two-story supernaturalist cosmology, and that the rationalism of the times was a temporary malaise. A general lack of support for his views within the scholarly community, combined with his own deep-seated populist instincts and common sense convictions, led Orr in later years to direct his appeals primarily toward the Christian public. The conclusion reached is that Orr deserves to be recognized, not so much as a brilliant or particularly original thinker, but as an able and exceptionally vigorous participant in a period of dramatic theological challenge and change.

Thesis (M.A.)--University of North Texas, Dec., 2009. / Title from title page display. Includes bibliographical references.

A new approach towards the development of electrocatalytic layers for use in high temperature polymer electrolyte membrane fuel cells is reported. Modified carbon nanotubes were used as the support. The aim was to achieve a uniform distribution of polar groups, which can interact with phosphoric acid, on the surface of the modified carbon support. Multi-wall carbon nanotubes were selected due to their unique properties regarding electronic conductivity and specific surface area. They were surface modified introducing pyridine based groups on the side walls which are known to interact with phosphoric acid. The different supports were thoroughly characterized by means of relevant techniques such as RAMAN,XPS and TGA. Platinum was deposited on the new carbon supports resulting in the newly synthesized catalysts,which were also thoroughly characterized by means of XRD,EDX,TEM and H2 Chemisorption. Stable and finely distributed Pt catalysts with nanoparticles size ranging between 2 and 4 nm were obtained using the chemically modified nanotubes as supports. Measurements of the catalytic activity towards oxygen reduction were also performed in order to evaluate the potential use of these materials as catalytic layers in PEMFCs. / -