Neste trabalho foram preparados e caracterizados catalisadores de platina suportados em g-alumina (g-Al2O3), óxido de zircônio (ZrO2) e em suportes mistos de óxido de zircônio e g-alumina. Os suportes bi-componente contendo (15%) ZrO2/g-Al2O3 foram preparados por dois métodos distintos: no primeiro, utilizou-se uma suspensão ácida de óxido de zircônio comercial e no segundo, óxido de zircônio precipitado a partir do acetato. Os catalisadores foram submetidos a ensaios catalíticos de reforma a vapor de etanol a fim de verificar o efeito do suporte sobre a distribuição dos produtos. As técnicas de caracterização utilizadas foram área superficial específica (B.E.T), redução a temperatura programada (RTP), difração de raios-X (DRX) e espectroscopia de absorção molecular na região UV-VI, que identificou a espécie [PtOxCly]s2-. A conversão do etanol e a distribuição dos produtos variaram para cada suporte testado e para os diferentes tempos de contatos (W/F) utilizados. O catalisador (1%) Pt/g-Al2O3 apresentou a melhor seletividade para a produção de hidrogênio e a menor conversão para o etanol. Os catalisadores que utilizaram o suporte bi-componente (15%) ZrO2/g-Al2O3 e ZrO2 pura apresentaram alta conversão de etanol e baixa seletividade para hidrogênio, além de alta tendência à formação de bio-produtos. / In this work catalysts of platinum supported on g-alumina (g-Al2O3), oxide of zirconium (ZrO2) and mixed oxide of zirconium and g-alumina had been prepared and characterized. The bi-component supports containing ( 15%) ZrO2/g-Al2O3 had been prepared by two different methods : in the first, an acid suspension of comercial oxide of zirconium was used and in the second, oxide of zirconium was precipitated from acetate. The catalysts were tested in ethanol steam reforming reaction to verify the effect of the support on the distribution of the products. For the characterization, the following techniques were used. Superficial specific area (B.E.T,), temperature programmed reduction (TPR.), X-ray powder diffraction (XRD) and spectroscopy of molecular absorption in the UV-vis, for identification of [PtOxCly]s 2- species. The ethanol conversion and product distribution were different for each support tested and for different time of contact (W/F) used. The catalyst (1%) Pt/g-Al2O3 presented the best selectivity for the hydrogen production and the lower conversion for ethanol. The catalysts with bi-component support (15%) ZrO2/ g-Al2O3 and pure ZrO2 presented high ethanol conversion and lower selectivity for hydrogen production with high selectivity and formation of bio-products.

No description available.

No description available.

Neste trabalho foram preparados e caracterizados catalisadores de platina suportados em g-alumina (g-Al2O3), óxido de zircônio (ZrO2) e em suportes mistos de óxido de zircônio e g-alumina. Os suportes bi-componente contendo (15%) ZrO2/g-Al2O3 foram preparados por dois métodos distintos: no primeiro, utilizou-se uma suspensão ácida de óxido de zircônio comercial e no segundo, óxido de zircônio precipitado a partir do acetato. Os catalisadores foram submetidos a ensaios catalíticos de reforma a vapor de etanol a fim de verificar o efeito do suporte sobre a distribuição dos produtos. As técnicas de caracterização utilizadas foram área superficial específica (B.E.T), redução a temperatura programada (RTP), difração de raios-X (DRX) e espectroscopia de absorção molecular na região UV-VI, que identificou a espécie [PtOxCly]s2-. A conversão do etanol e a distribuição dos produtos variaram para cada suporte testado e para os diferentes tempos de contatos (W/F) utilizados. O catalisador (1%) Pt/g-Al2O3 apresentou a melhor seletividade para a produção de hidrogênio e a menor conversão para o etanol. Os catalisadores que utilizaram o suporte bi-componente (15%) ZrO2/g-Al2O3 e ZrO2 pura apresentaram alta conversão de etanol e baixa seletividade para hidrogênio, além de alta tendência à formação de bio-produtos. / In this work catalysts of platinum supported on g-alumina (g-Al2O3), oxide of zirconium (ZrO2) and mixed oxide of zirconium and g-alumina had been prepared and characterized. The bi-component supports containing ( 15%) ZrO2/g-Al2O3 had been prepared by two different methods : in the first, an acid suspension of comercial oxide of zirconium was used and in the second, oxide of zirconium was precipitated from acetate. The catalysts were tested in ethanol steam reforming reaction to verify the effect of the support on the distribution of the products. For the characterization, the following techniques were used. Superficial specific area (B.E.T,), temperature programmed reduction (TPR.), X-ray powder diffraction (XRD) and spectroscopy of molecular absorption in the UV-vis, for identification of [PtOxCly]s 2- species. The ethanol conversion and product distribution were different for each support tested and for different time of contact (W/F) used. The catalyst (1%) Pt/g-Al2O3 presented the best selectivity for the hydrogen production and the lower conversion for ethanol. The catalysts with bi-component support (15%) ZrO2/ g-Al2O3 and pure ZrO2 presented high ethanol conversion and lower selectivity for hydrogen production with high selectivity and formation of bio-products.

Durability of carbon-supported platinum nanoparticle is one of the limiting factors for PEM fuel cell commercial applications. In our research work, we applied both experimental and mathematical simulative tools to study the mechanisms of Pt/C catalyst degradation. An accelerated catalyst degradation protocol by cycling the cathode potential in a square-wave profile was applied to study the losses of cell performances, catalyst ORR activity, and Pt active surface areas. Post-mortem analyses of cathode Pt particle size by X-ray diffraction and platinum distributions in CCMs by SEM/EDS were also conducted. Increased cell temperature and relative humidity was found to accelerate the cathode catalyst degradation. High membrane water contents or abundant water/ionic channels within the polymer electrolyte were believed to accelerate Pt ion transport and cathode degradation. After degradation tests, significant amount of Pt loss into the membrane forming a Pt "band" was observed through cathode platinum dissolution and chemical reduction of soluble Pt ions by permeated hydrogen from the anode. Platinum deposition was confirmed at a location where the permeated hydrogen and oxygen had the complete catalytic combustion over the deposited Pt clusters/particles as the catalyst. A cathode degradation model was built including the processes of platinum oxidation, dissolution/replating, diffusion of Pt ions and Pt band formation in electrolyte. A simplified bi-modal particle size distribution was applied with equal numbers of small and large type particles uniformly distributed in the cathode initially. Processes of Pt mass exchange between two types of particles were demonstrated to cause the overall particle growth. This was due to the particle size effect that platinum dissolution from the small type particles and replating of Pt ions onto the large particles was favored. Parametric study found the increased upper cycling potential was the dominated factor to accelerate the catalyst degradation. Also high frequency of potential cycle and low surface oxide coverage accelerated the degradation rate. Pt dissolution and oxidation processes in perchloric acid were preliminary investigated, and both chemical and electrochemical processes of oxidation and dissolution were believed to be involved under closed-circuit fuel cell conditions with oxygen presence at cathode.

No description available.

Thematic interrelation is an underdeveloped field of inquiry in Lukan studies. The design and elegance of Lukan theology begs for guided investigation into a possible system of organisation that governs history and theology, that is, narrative and theme. Based on the Greimasian Actantial Model, morpho–syntactical structural–critical analysis of Luke and Acts reveals that the covenant concept in its operative aspect of service functions as an organising principle, structuring the narratives and facilitating thematic interrelation. A survey of representative Lukan research consisting of five methodologically determined approaches shows a commonality regarding Lukan purpose. These all share the “plan of God” as a fundamental concept, thus intimating its plausibility as a common organisational principle in the text. This observation encourages further analysis of Lukan narrative and meta–narrative as relevant subject matter. Investigation into the purpose and goals of Ancient Jewish and Ancient Greek literature suggests that the concepts of piety/holiness and justness combined with a notion of divine order and expectation demonstrates organisational capacity. Under the terms and conditions of the Old Covenant three non–exclusive themes/concepts hold organisational functionality and ability to facilitate thematic interrelation: Exodus typology, the covenant concept and the eschaton idea. Exodus typology connects narrative with theme, developing Israel’s story. The covenant idea frames stories using parallelism and gives the meta–story progression. The eschaton idea presents the Day of YHWH as an organisational principle guiding the story of judgment to restoration. It is observed that the covenant concept is the most prevalent of these themes/ideas. Assuming the conceptual unity of Luke and Acts and adopting a morpho–syntactical structuralist approach, it was observed that the covenant concept in its operative aspect of service occurred as Helper at ten places, determining the development and structure of the meta–narrative. According to the Greimasian Actantial Model, Israel failed to fulfil its covenant–based mandate to serve God and shine God’s light of mercy to the nations. Jesus, Israel’s new Helper, becomes the Subject and by his covenant–based ministry, characterised as the greatest service, resolves the problem that prevents Israel from carrying out its divine mandate and sets the stage for its fulfilment. In Jesus Israel is given new leaders, an ethical platform of discipleship and the Holy Spirit. The apostle Paul as the epitomised and exemplary witness and servant of Jesus fulfils what Israel could not. He is vindicated in righteousness and shares in the Isaianic ministry of Jesus, to bear witness to leaders and to shine God’s light to the nations. Paul is unhindered in this ministry. Additionally, in thematic–critical terms, the key placement of the covenant concept in its operative aspect of service at plot–defining junctures features its catalytic dynamic as a “template” concept advancing the re–conceptualising of themes and providing a platform for meaningful relation. The evidence thus suggests that the covenant concept in its operative aspect structures the conjoined narratives of Luke and Acts. It also provides a basis for relation between the divine and humans in the context of the history of God’s salvation, linking history and theology, and makes possible a discernible means to thematic interrelation. The SO2 electrolysis was performed by supplying the anode of the cell with SO2 gas, while the water was fed to the cathode using graphite plates as flow fields. Initial experimental work was done at ambient pressures on the anode (SO2 gas–fed) and cathode (water–fed) after which the water pressure was increased from ambient to 1 bar. Various parameters were evaluated for SO2 electrolysis at ambient conditions, including operating temperature, membrane thickness and catalyst loading. The operating temperature was increased from 50oC to 80oC which resulted in a significant voltage improvement from 0.78V to 0.64V at 300mA/cm2. Operating the cell with thinner membranes (86 vs 170um) also resulted in an improved overall cell performance, while the catalyst loading (1 vs 0.5mgPt/cm2) had a negligible effect on the operating voltage. SEM images and EDX analysis were performed on the best performing MEA (N1135) which showed that no degradation of the MEA had occurred. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011.

Thematic interrelation is an underdeveloped field of inquiry in Lukan studies. The design and elegance of Lukan theology begs for guided investigation into a possible system of organisation that governs history and theology, that is, narrative and theme. Based on the Greimasian Actantial Model, morpho–syntactical structural–critical analysis of Luke and Acts reveals that the covenant concept in its operative aspect of service functions as an organising principle, structuring the narratives and facilitating thematic interrelation. A survey of representative Lukan research consisting of five methodologically determined approaches shows a commonality regarding Lukan purpose. These all share the “plan of God” as a fundamental concept, thus intimating its plausibility as a common organisational principle in the text. This observation encourages further analysis of Lukan narrative and meta–narrative as relevant subject matter. Investigation into the purpose and goals of Ancient Jewish and Ancient Greek literature suggests that the concepts of piety/holiness and justness combined with a notion of divine order and expectation demonstrates organisational capacity. Under the terms and conditions of the Old Covenant three non–exclusive themes/concepts hold organisational functionality and ability to facilitate thematic interrelation: Exodus typology, the covenant concept and the eschaton idea. Exodus typology connects narrative with theme, developing Israel’s story. The covenant idea frames stories using parallelism and gives the meta–story progression. The eschaton idea presents the Day of YHWH as an organisational principle guiding the story of judgment to restoration. It is observed that the covenant concept is the most prevalent of these themes/ideas. Assuming the conceptual unity of Luke and Acts and adopting a morpho–syntactical structuralist approach, it was observed that the covenant concept in its operative aspect of service occurred as Helper at ten places, determining the development and structure of the meta–narrative. According to the Greimasian Actantial Model, Israel failed to fulfil its covenant–based mandate to serve God and shine God’s light of mercy to the nations. Jesus, Israel’s new Helper, becomes the Subject and by his covenant–based ministry, characterised as the greatest service, resolves the problem that prevents Israel from carrying out its divine mandate and sets the stage for its fulfilment. In Jesus Israel is given new leaders, an ethical platform of discipleship and the Holy Spirit. The apostle Paul as the epitomised and exemplary witness and servant of Jesus fulfils what Israel could not. He is vindicated in righteousness and shares in the Isaianic ministry of Jesus, to bear witness to leaders and to shine God’s light to the nations. Paul is unhindered in this ministry. Additionally, in thematic–critical terms, the key placement of the covenant concept in its operative aspect of service at plot–defining junctures features its catalytic dynamic as a “template” concept advancing the re–conceptualising of themes and providing a platform for meaningful relation. The evidence thus suggests that the covenant concept in its operative aspect structures the conjoined narratives of Luke and Acts. It also provides a basis for relation between the divine and humans in the context of the history of God’s salvation, linking history and theology, and makes possible a discernible means to thematic interrelation. The SO2 electrolysis was performed by supplying the anode of the cell with SO2 gas, while the water was fed to the cathode using graphite plates as flow fields. Initial experimental work was done at ambient pressures on the anode (SO2 gas–fed) and cathode (water–fed) after which the water pressure was increased from ambient to 1 bar. Various parameters were evaluated for SO2 electrolysis at ambient conditions, including operating temperature, membrane thickness and catalyst loading. The operating temperature was increased from 50oC to 80oC which resulted in a significant voltage improvement from 0.78V to 0.64V at 300mA/cm2. Operating the cell with thinner membranes (86 vs 170um) also resulted in an improved overall cell performance, while the catalyst loading (1 vs 0.5mgPt/cm2) had a negligible effect on the operating voltage. SEM images and EDX analysis were performed on the best performing MEA (N1135) which showed that no degradation of the MEA had occurred. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011.