Conselho Nacional de Desenvolvimento Científico e Tecnológico / Calcination variables, temperature, time and heating rate, used in obtaining different transition aluminas were simultaneously investigated using statistical experimental design. Empirical models correlating catalyst final properties and calcination conditions were employed. It was found that all calcination variables play fundamental roles on acidity of alumina catalyst. Furthermore, interaction effects among these variables and non-linear effects also are of fundamental importance for the final properties catalyst. Therefore, the use of simultaneous variation of calcination conditions through experimental design is of great importance in detecting such interactions. It was observed that the use of high heating rates favor the formation of pore with larger diameters and with high pore volume and, for short calcination time, high heating rate also contributes to the formation of higher concentration of acid sites. The acid sites characterization of transition aluminas were performed by temperature programmed desorption of ammonia (NH3-DTP), which showed that there are two distinct acid sites on the surface these materials. The desorption dates were adjusted by a model in which the catalyst bed was considered as single continuously stirred tank reactor and the intrinsic kinetic was chosen to be of first order for adsorption and desorption. The ethanol conversion was higher for the alumina with higher acid sites concentration, suggesting a relationship between the activity of the alumina for the ethanol conversion and its acidity. The selectivity for the ethylene formation also was higher for the more acid aluminas, while the selectivity to ether presented opposite behavior. Therefore, a successful control of all calcination conditions can be an effective method to adjust the final physical and chemical properties of transition alumina catalyst, aiming the highest yield of ethylene from ethanol dehydration. / Foram preparadas aluminas de transição investigando-se simultaneamente o efeito das variáveis de calcinação: temperatura, tempo e taxa de aquecimento, usando planejamento estatístico de experimentos. Modelos empíricos foram empregados para correlacionar as propriedades finais dos catalisadores às variáveis de calcinação. Foi observado que todas as variáveis de calcinação influenciam a concentração de sítios ácidos das aluminas. Além disso, efeitos de interação entre estas variáveis, bem como efeitos não lineares também são de fundamental importância para as propriedades finais deste catalisador. Estes efeitos só podem ser identificados com a variação simultânea das condições de calcinação através do uso do planejamento de experimentos. Foi observado que o uso de elevada taxa de aquecimento favorece a formação de aluminas com maior volume e tamanho de poros e, para curtos períodos de tempo de calcinação, elevada taxa de aquecimento também contribui para a formação de maior concentração de sítios ácidos. A caracterização dos sítios ácidos das aluminas foi realizada pela técnica de dessorção de amônia à temperatura programada (DTPNH3). Esta caracterização indicou a presença de dois tipos de sítios ácidos na superfície destes materiais. Os dados de dessorção foram ajustados por um modelo que considera a cinética de dessorção e readsorção como reações de primeira ordem em um modelo de reator de mistura perfeita. A conversão de etanol foi maior para as aluminas com maior concentração de sítios ácidos, indicando uma relação entre a atividade das aluminas para a conversão de etanol e sua acidez. A seletividade para a formação de eteno também foi maior para as aluminas mais ácidas, enquanto que a seletividade para éter exibiu comportamento inverso. Portanto, o controle adequado de todas as condições de calcinação pode ser um método eficiente para ajustar as propriedades físicas e químicas finais de aluminas de transição, visando obter maior rendimento na produção de eteno a partir da desidratação de etanol.

MENVSC / Department of Ecology and Resource Management / Some boreholes in South Africa which serve as a source of drinking water for rural communities are reported to have high fluoride concentration, much above the WHO guideline of 1.5 mg/L. This study aimed at activating aluminosilicate clay soil mechanochemically, modifying aluminosilicate clay soil with Al-oxide and fabricating porous ceramic granules using Al-oxide modified mechanochemically activated aluminosilicate clay soil/ mechanochemically activated clay soil/ corn starch and evaluating their performances in defluoridation of groundwater. The raw clay materials were mechanochemically activated for 5, 10, 15 and 30 minutes for physicochemical transformation of the solid aggregate. The morphology of the samples showed the honeycomb structure. The surface area analyses of samples using Brunauer–Emmett–Teller (BET) gave the highest surface area of 50.5228 m2/g at 30 min activation time. Hence, the optimum activation time was 30 min. The Fourier Transform Infrared (FT-IR) analysis showed increase in the absorbance of FT-IR by Si-O-H groups at 510 cm-1 with increasing milling time. This is evidence that more surface Si-O-H groups were available at higher particle surface area that would be necessary to interact with fluoride. X-ray diffraction (XRD) analyses revealed that, at 30 minutes milling time, the peak broadening is intensified whereas the reflection peak intensities decreased. The X-ray fluorescence spectrometry (XRF) results for 30 minutes milling time showed that silica and alumina were the highest components in the clay soil. Using the activated clay in batch defluoridation of fluoride-spiked water, a maximum fluoride removal of 41% was achieved at a pHe of 2.41. The initial fluoride concentration was 9 mg/L while the sorbent dosage was 0.6 g/100 mL and the contact time being 30 minutes. The adsorption data fitted to both Langmuir and Freundlich isotherms. The adsorption data fitted only the pseudo-second-order kinetic, showing chemisorption. Optimization of Al3+ concentration for modification was carried out by modifying the mechanochemical activated aluminosilicate clay soil with different concentrations of Al3+ from which the optimum modification was achieved with 1.5 M. Characterisation studies on the Al-oxide modified mechanochemically activated aluminosilicate clay soil by SEM, BET, FT-IR, XRD and XRF, analyses were carried out to determine the resultant changes in physicochemical properties of the adsorbent owing to modification. The SEM image of Al-oxide modified mechanochemically activated clay soil showed many small pores and honey-comb structure on the surface of different images. The BET surface area and the BDH adsorption cumulative area of the Al-oxide modified mechanochemically activated v aluminosilicate clay soil were more than double those for the raw clay soil. There was also an increase in pore volume of the Al-oxide modified mechanochemically activated aluminosilicate clay soil. The FT-IR spectra showed that there was increase in the absorbance by the Si-OH, H-O-H, Al-O-H and Si-O-Al. The equilibrium pH of solution was higher than the point-of-zero charge (pHpzc) implying that fluoride removal occurred at solution pH > pHpzc where the net surface charge of the mechanochemically activated clay aluminosilicate soil was negative.The efficiency of 1.5 M Al-oxide modified aluminosilicate clay soil to remove fluoride from water was studied and found to be 96.5 % at pHe 6.86, contact time of 30 minutes and dosage of 0.3 g/100 mL for 10 mg/L fluoride solution at 200 rpm shaking speed. The result shows that Al-oxide modified mechanochemically activated aluminosilicate clay soil is effective for defluoridation. The adsorption data fitted to both Langmuir and Freundlich isotherms. The adsorption data fitted only the pseudo-second-order kinetic, showing chemisorption. Al-oxide modified mechanochemically activated aluminosilicate clay soil was tested for fluoride removal on field water and the percentage fluoride removal was 96.5 % at the dosage of 0.6 g/100 mL with the pHe of 6.48. The optimum Al-oxide modified mechanochemically activated aluminosilicate clay soil/ mechanochemically activated clay soil/ corn starch mixing ratio for fabrication of porous ceramic granules was determined by varying ratios and temperature. The optimum ratio found was 20:5:1.The porous ceramic granules were characterised using SEM, BET, FT-IR, XRD and XRF. SEM analysis showed that the porous ceramic granules have the porous structure of the organic foam template. The porous ceramic granule showed an increase in pore surface area and volume as compared to mechanochemically activated aluminosilicate clay soil. The FT-IR showed the presence of a strong broad bending and stretching vibrations band at about 993 cm-1 which shows the presence of Si–O–Si bonds. Mineralogical characterisation showed the presence of quartz, albite, horneblende and microcline as the main minerals of the calcined porous ceramic granules. The major oxides of the porous ceramic granules as shown by XRF analysis were SiO2, Al2O3, MnO and Na2O. The porous ceramic granules reduced the concentrations of fluoride in the water from 10 to 3.31 mg/L. The optimum adsorption capacity was 0.6648 mg/g at a pHe of 6.32 and the percentage fluoride removal was 66.9 % at an adsorbent dosage of 1.0063 g/100 mL and a temperature of 600 ⁰C. The porous ceramic granules were tested for fluoride removal on field water and the percentage fluoride removal was 45.4 % at the dosage of 1.0009 g/100 mL with the pHe of 7.87. Mechanochemically activated aluminosilicate clay soil showed higher adsorption capacity at acidic pH, therefore it is recommended that future work should focus on improving their adsorption capacity at wider range of pH. The porous ceramic granules can also be evaluated in column dynamic flow experiments.

Aufkonversions-Nanokristalle (UCNC) zeichnen sich als einzigartige Lumineszenzreporter aus, die Nah-infrarotes Anregungslicht in Photonen höherer Energie umwandeln. Für die gezielte Anpassung von Eigenschaften, bedarf es ein tiefes Verständnis der Prozesse der Aufwärtskonversionslumineszenz (UCL) und deren Abhängigkeit von Material und Partikeldesign. Diese Doktorarbeit untersucht die UCL-Prozesse von Yb3+,Er3+ dotierten SrF2-UCNC und zielt darauf ab, die UCL-Eigenschaften der bisher unterschätzten kubischen Wirtsgitter zu verstehen und zu steigern. Hierbei wird die fluorolytische Sol-Gel-Synthese als neuartige Syntheseroute für UCNC vorgestellt. Vorteile wie ausgezeichnete Reproduzierbarkeit, viele Freiheitsgrade bei der Temperaturbehandlung und Partikelgestaltung werden anhand von SrF2 UCNC demonstriert. Die UCNC wurden mittels UCL-Spektren, UCL-Quantenausbeuten, leistungsdichte-abhängiger relativer spektraler Verteilung sowie der Lumineszenzabklingkinetiken unter Einbeziehung kristalliner Eigenschaften wie der Kristallphase, der Kristallitgröße, der Gitterparameter und der Teilchengröße untersucht. Die Abhängigkeit der UCL-Eigenschaften von der Dotierungsmenge wurde mit einer umfassenden Dotierungsreihe beschrieben und der optimale Dotierungsbereich (Yb3+,Er3+) von kleinen, ungeschalten SrF2-UCNC eingegrenzt. Bei der Studie dotierter Kerne mit passivierenden Schalen wurde der Einfluss von Temperaturbehandlung auf die UCL-Mechanismen und die Kern-Schale-Vermischung untersucht. Anhand von unterschiedlich kalzinierten UCNC Pulvern wurde die Empfindlichkeit der UCL gegenüber der Änderung kristalliner Eigenschaften, wie Kristallphase, Kristallinität, und Kristallitgröße betrachtet. Zusammen liefern die Dotierungs-, die Kern-Schale- und die Kalzinierungsstudie wertvolle Einblicke in das gitterspezifische Verhalten der UCL-Eigenschaften als Funktion der Energiemigration und der Kristalleigenschaften. / Upconversion nanocrystals (UCNC) represent a unique type of luminescence reporters that convert near-infrared excitation light into higher energy photons. Tailoring UCNC with specific luminescence properties requires an in-depth understanding of upconversion luminescence (UCL) processes and their dependence on material and particle design. This Ph.D. thesis focuses on the UCL processes of Yb3+,Er3+ doped SrF2-UCNC and aims to understand and enhance the UCL properties of the previously underestimated cubic host lattices. Herein, fluorolytic sol-gel synthesis is introduced as a novel synthetic route for UCNC. Advantages such as excellent reproducibility, high flexibility in temperature treatment and particle design are demonstrated using SrF2 UCNC. The UCNC were characterized by UCL spectra, UCL quantum yields, excitation power density-dependent relative spectral distribution, and luminescence decay kinetics involving crystalline properties such as crystal phase, crystallite size, lattice parameters, and particle size. The dependence of UCL properties on doping amount was described in a comprehensive doping study, and the optimal doping range (Yb3+,Er3+) of small, unshelled SrF2-UCNC was identified. In a core-shell study of doped core UCNC with passivating shells, the influence of temperature treatment on UCL mechanisms and core-shell mixing was investigated. Further, using different calcined UCNC powders, the sensitivity of UCL to the change of crystalline properties, such as crystal phase, crystallinity, and crystallite size, was assessed. Together, the doping, core-shell, and calcination studies provide valuable insight into the lattice-specific behavior of UCL properties as a function of energy migration and crystal properties.