Une pile à combustible microbiennes (PCM) est un dispositif capable de produire de l’énergie électrique à partir d’énergie chimique grâce à l’activité catalytique des bactéries en présence de combustibles organiques. Ces travaux de thèse ont eu pour objectif la synthèse des nouveaux matériaux d’anode et de cathode qui pourraient constituer des alternatives aux matériaux à base de platine. Coté anode, nous avons synthétisé des matériaux par précipitation chimique sur du graphite en poudre à partir de mélanges contenant des ions ferreux et sulfures. Les caractérisations physicochimiques ont montré la formation de composés soufrés (mackinawite, polysulfures et soufre élémentaire) qui se transforment en produits soufrés plus oxydés en présence d’air. La formation de vivianite a été confirmée dans le cas d’un excès d’ions ferreux par rapport aux ions sulfures. Les analyses électrochimiques montrent que ces matériaux ont un comportement réversible avec des densités de courant d’oxydation élevées à bas potentiel. Coté cathode, nous avons choisi la synthèse par voie électrochimique d’un film de MnOx sur substrat d’acier inoxydable. Les caractérisations physicochimiques ont démontré la formation de la birnessite. Les analyses électrochimiques montrent que la réduction de ce matériau conduit à des courants cathodiques significatifs mais avec une réversibilité limitée, même en présence d’air. La réalisation de prototypes de PCM dans lesquels l’anode à base de composés soufrés est immergée dans une solution de terreau et la cathode à base de MnOx est au contact de l’air, a permis d’obtenir des puissances instantanées maximales de l’ordre de 12 W.m-3 et 1,8 W.m-2, et des densités de courant de l’ordre de 25 A.m-3 et 3,8 A.m-2. Un travail d’optimisation du fonctionnement de PCM a été réalisé. Ainsi, l’augmentation de la conductivité de la solution anodique et la diminution de quantité de sédiment dans la solution de terreau a permis d’améliorer la réponse électrochimique du matériau anodique et d’obtenir des puissances instantanées maximales de l’ordre de 17,5 W.m-3 et 2,7 W.m-2, et des densités de courant de l’ordre de 60 A.m-3 et 9,2 A.m-2. Le facteur limitant reste toujours le comportement électrochimique du film de MnOx. / A microbial fuel cell (MFC) is a device allowing the production of electric power from chemical energy thanks to the catalytic activity of bacteria in presence of organic fuel. These works aimed the synthesis of new anode and cathode materials which could be an alternative to platinum materials. On the anode side, we synthesized the materials by chemical precipitation on powder graphite from mixtures containing ferrous and sulfide ions. Physicochemical characterizations showed the formation of sulfur compounds (mackinawite, polysulfide and elementary sulfur) which transform into sulfur products more oxidized in presence of air. Formation of vivianite was confirmed in the case of an excess of ferrous ions in relation to sulfide ions. Electrochemical analysis shows that these materials have a reversible behavior with high current densities at low voltage. On the cathode side, we chose electrochemical synthesis of an MnOx film on stainless steel substrate. Physicochemical characterizations showed birnessite formation. Electrochemical analysis show that the reduction of this material Leeds to significative cathodic currents but with a limited reversibility, even in presence of air. The realization of MFC prototypes in which the sulfur compounds-based anode is submerged in compost solution and the MnOx-based cathode is in contact with air, allowed the getting of maximum instantaneous powers on the order of 12 W.m-3 and 1,8 W.m-2, and current densities on the order of 25 A.m-3 et 3,8 A.m-2. An optimization work of the MFC functioning has been done. So, the conductivity increase of the anodic solution and the decrease of sediment quantity in the compost solution allowed the improvement of the electrochemical response of the anodic material and to obtain maximal instantaneous powers on the order of 17,5 W.m-3 and 2,7 W.m-2, and current densities on the order of 60 A.m-3 et 9,2 A.m-2. The limiting factor remains the electrochemical behavior of the MnOx film.

Water treatment facilities commonly reduce soluble contaminants, such as soluble manganese (Mn2+), in water by oxidation and subsequent filtration. Previous studies have shown that conventional porous filter system removes Mn2+ from drinking water by developing Mn-oxides (MnOx(s)) bearing coating layers on the surface of filter media. Multiple models have been developed to explain this Mn2+ removal process and the formation mechanism of MnOx(s) coatings. Both, experimental and theoretical studies to date have been largely focused on the micrometer to millimeter scale range; whereas, coating layers are composed of nanoscale particles and films. Hence, understanding the nanoscale particle and film formation mechanisms is essential to comprehend the complexity of soluble contaminant removal processes. The primary objective of this study was to understand the initial MnOx(s) coating formation mechanisms and evaluate the influence of filter media characteristics on these processes. We pursued this objective by characterizing at the micro and nanoscale MnOx(s) coatings developed on different filter media by bench-scale column tests with simulating inorganic aqueous chemistry of a typical coagulation fresh water treatment plant, where free chlorine is present across filter bed. Analytical SEM and TEM, powder and synchrotron-based XRD, XPS, and ICPMS were used for characterization of coatings, filter media and water solution elemental chemistry. A secondary objective was to model how surface coating formation occurred and its correlation with experimentally observed physical characteristics. This modeling exercise indicates that surface roughness and morphology of filtering media are the major contributing factors in surface coating formation process. Contrary to previous models that assumed a uniform distribution and growth of surface coating, the experimental results showed that greater amounts of coating were developed in rougher areas. At the very early stage of coating formation, unevenly distributed thin films and/or particle aggregates were observed, which provided active sites for further surface coating growth. The predominant MnOx(s) phase in the surface coatings was identified to be poorly crystalline birnessite having scavenging activity by intercalation and/or sorption. This would explain the enhancement of efficiency in removing soluble manganese and other contaminants during water filtration. Moreover, the increased Mn2+ removal effect of having aluminum (Al) in pre-treated water is explained. These results indicate that the surface roughness and morphology need to be incorporated into particle capture models to more precisely describe the soluble manganese removal process. / Ph. D.

Many treatment facilities remove soluble Mn by an autocatalytic adsorption-oxidation process involving manganese oxide (MnOx(s))-coated filter media and a free chlorine residual known as the natural greensand effect (NGE). In recent years, significant amounts of aluminum (Al) have been found integrated into MnOx(s) coatings on media from drinking water treatment facilities worldwide. The primary objective of this study was to characterize MnOx(s) coatings developed in the presence and absence of Al, and to further define the role played by Al in the coatings' initiation and development. A secondary objective of the study was to examine the potential for pre-filter oxidation of Mn and formation of nano-size MnOx(s) particles, which would be destabilized by Al(OH)3(s) and captured in the filter. This material could act as a seed for coating formation and help explain the integration of Al into MnOx(s) coatings. Bench-scale column tests were conducted to examine Mn removal and backwash composition, while centrifugation and ultrafiltration were utilized to examine the potential for rapid Mn oxidation. Results indicate that the presence of Al augments the initiation and development of MnOx(s) coatings. The backwash solids of columns loaded with Al were composed of a mixture of Mn and Al, suggesting that active adsorption-oxidation sites were present in the Al(OH)3(s) floc captured by the filter. These results suggest at least a small amount of pre-filter MnOx(s) formation by contact with free chlorine; further, that Al(OH)3(s) solids present may destabilize these negatively charged solids into a form that is important to MnOx(s) coating formation. / Master of Science

The Mn oxide (MnOx(s)) surfaces of water treatment filtration media are known to aid in the capture of dissolved Mn species, but the discovery of significant deposits of Al within these coatings raised several questions about the MnOx(s) surface. A series of experiments and analyses were performed to examine the presence of Al within MnOx(s) coatings formed on water treatment filtration media. It was hypothesized that the presence of Al within the MnOx(s) coatings might have an impact on the capture of Mn by the MnOx(s) surface. A 2008 study of oxide coated filtration media found that Mn and Al are present in nearly equimolar quantities within the oxide coatings. This led to questions of how and why the Al became incorporated into the surface. This phenomenon was analyzed by conducting a series of bench-scale column studies, treatment plant data collection, and analysis of the MnOx(s) surface utilizing an electron microscope. The results confirm that Al deposits onto the MnOx(s) media surface by two separate mechanisms; adsorption of dissolved Al species and the deposition of colloidal and particulate Al(OH)3(s) precipitate species onto the surface. Analysis of the MnOx(s) coating with by electron microscopy shows a heterogeneous surface composed of a mix of crystalline Mn oxides existing alongside amorphous Al(OH)3(s) species. The deposition of Al onto the media surface does not have any significant effect on the removal of soluble Mn, but the potential impact that Al might have on the capture of other dissolved species should be explored further. / Master of Science

Soluble manganese (Mn) is a common water contaminant which can cause discoloration of water and staining if not treated properly in a water treatment plant. The "natural greensand effect" is one of the proven methods for efficient removal of Mn from water. Therefore, research is ongoing to develop different ways to effectively create the natural greensand effect in a post-filtration sorptive contactor for application at water treatment facilities. The research reported by Zuravnsky (2007) focused on the use of oxide-coated media in a post-filtration contactor and served as a starting point for the research reported in this thesis. As a part of the work conducted by Zuravnsky (2007), a preliminary model was formulated to predict soluble Mn removal via adsorption and oxidation onto large-size MnOx(s)-coated media. A major part of the current research was to calibrate the proposed model in predicting the soluble Mn removal performance by incorporating a statistical non-linear regression method to estimate a best-fit value for the fitting parameter kr, the rate constant associated with Mn oxidation by free chlorine. The research work included an 18-week pilot-plant study conducted at a water treatment facility in Newport News, VA. A contactor column loaded with 27â of pyrolucite media was operated at varying applied water conditions. Hydraulic loading rate (HLR), temperature, pH and influent free chlorine concentration were the operational parameters that were varied and their effect on the Mn removal performance evaluated. The resulting data were then used in the model to aid in its calibration and to obtain the best-fit kr values corresponding to effective Mn removal for the various operating conditions. Soluble Mn removal in the contactor column was directly dependent on solution pH and initial free chlorine concentration. The applied water temperature and HLR also had a small impact on the Mn removal profiles observed. On analyzing the results obtained from the model, it was noted that the best-fit kr values for the pilot plant data increased with increasing solution pH (When temperature = 200C and the initial Cl levels were below 1.5mg/L). Also, the Mn uptake capacity of the pyrolucite media increased with both an increase in initial Mn concentration and solution temperature. Long-term operation of the contactor also resulted in significant head loss accumulation in the upper portion of the contactor column, most probably due to MnOx(s) deposition on the media and partial blockage of contactor void spaces. Media fluidization was necessary to address this operational issue. / Master of Science

In China, the textile industry is important for the economy. However, the industry contributes to emissions of organic material and other pollutants. This affects the environment and the quality of life for people and animals. All over the world, water scarcity is becoming an increasing problem, which is why the UN has water purification as one of the goals for sustainable development. To achieve these goals and the regulations in countries, wastewater is purified in water treatment plants before it is discharged. One of the methods that can be used to purify water is catalytic ozonation, an oxidation process in which ozone is used as an oxidant to break down organic material. Catalysts, usually metal oxides, are used to increase the selectivity and the reaction rate. However, this is a relatively unexplored area in water purification and several details within the process are unknown, such as optimal conditions for various catalysts and the exact reaction mechanism. In this work, catalytic ozonation treatment with the metal oxide MnOx-CeOx/γ-Al2O3 has been investigated. Firstly, a literature study was carried out to find earlier research in the field. Then experiments were conducted, varying four different factors and the impact these factors had on the catalytic ozonation was analyzed. The factors examined were contact time, ozone dosage, gas flow and amount of catalyst. All factors had three different levels. COD and UV254 were analyzed to find the conditions that gave the highest reduction of organic matter. The highest reduction of COD was 67 % which gave a COD concentration of 23 mg/L and UV254 90 %. Since the regulations on COD emissions in China are 30 mg/L, the catalytic ozonation gave a satisfying result. The result showed that the highest yield was achieved at the highest level for contact time (40 min), ozone dosage (0.3 mg/L) and amount of catalyst (100 % filled reactor), but the second highest for the gas flow (0.3 L/min). However, the contact time was calculated to be the only significant factor for reducing COD in water. The other factors did not have a significant effect on the reduction of COD or UV254. Furthermore, the conditions that were calculated to give the greatest reduction were used to analyse the reduction of impurities in the wastewater with three dimensional fluorescence. Three dimensional fluorescence showed that the wastewater contained organic compounds, mainly aromatic proteins, soluble microbial by-products and humic acids. All of these compounds were reduced during the catalytic ozonation with MnOx-CeOx/ γ-Al2O3. The residual amount of ozone was analyzed in effluent gas flow was measured with different incoming gas flows. The residual ozone after the ozone treatment was approximately 45 % of the ingoing gas flow. / I Kina är textilindustrin viktig för ekonomin. Dock bidrar industrin till utsläpp av organiskt material och andra föroreningar. Detta påverkar miljön och livskvalitén för människor och djur. Världen över börjar vattenbrist bli ett allt större problem, varför FN har med vattenrening som ett av målen för hållbar utveckling. För att nå dessa mål och de regleringar som gäller renas avloppsvatten i vattenreningsanläggningar innan det släpps ut. En av de metoder som kan användas för att rena vattnet är katalytisk ozonbehandling, vilket är en oxidationsprocess där ozon används som oxidationsmedel för att bryta ned organiskt material. För att öka selektiviteten och reaktionshastigheten används katalysatorer, vanligen metalloxider. Detta är dock ett relativt outforskat område inom vattenrening och flera detaljer inom processen är okända, såsom optimala betingelser och reaktionsmekanismen. I detta arbete har därför katalytisk ozonbehandling med metalloxiden MnOx-CeOx/ γ-Al2O3 undersökts. Först utfördes en litteraturstudie för att ta fram tidigare forskning inom området. Därefter utfördes experiment där fyra olika faktorers påverkan på den katalytiska ozonbehandlingen analyserades. De faktorer som undersöktes var uppehållstid, ozondosering, gasflöde och mängd katalysator. Samtliga faktorer hade tre olika nivåer. De faktorer som analyserades var COD och UV254 för att hitta de förhållanden som gav högst reduktion av organiskt material. Den högsta reduktionen av COD var 67 %, vilket gav en COD-koncentration på 23 mg/L och UV254 reducerades upp till 90 %. Eftersom gränsen på COD-utsläpp i Kina är 30 mg / L gav den katalytiska ozonbehandlingen ett tillfredsställande resultat. Det nivåer som gav bäst utbyte var de högsta för uppehållstiden (40 min), ozondoseringen (0.3 mg/L) och mängden katalysator (100 % fylld reaktor), men den näst högsta för gasflödet (0.3 L/min). Den enda faktorn som hade en signifikant påverkan på reduktionen av organiskt material var dock uppehållstiden. Övriga faktorer hade ingen signifikant påverkan på varken reduktionen av COD eller UV254. Vidare användes ändå de nivåer som beräknats ge störst reduktion av organiskt material för att analysera reduktionen av föroreningar i avloppsvattnet med tredimensionell fluorescens. Avloppsvattnet innehåller organiskt material som aromatiska proteiner, lösliga mikrobiella biprodukter och humussyror och dessa föroreningar reducerades vid katalytiska ozonbehandlingen med MnOx-CeOx/ γ-Al2O3. Dessutom analyserades resterande mängd ozon i utgående gasflöde vid olika storlek på ingående gasflöde. Resterande mängd ozon efter ozonbehandlingen var ungefär 45 % av ingående mängd.

Construed bachelor work features into problems hydrogen fuel articles and survey on low-temperature fuell elements with polymeric electrolyte (PEMFC). Basic sight work is study feature catalyzers on base MnOx on real fuel cell type PEMFC. Exit are then measured characteristic this way creation fuel cell.

In the current study, we give a report when oxalic acid was used as an electrolyte to synthesize an AAO template with hexagonal pore array. Optimum parameters were observed as 0.4 M of oxalic acid, anodizing voltage of 45 V, temperature of approximately 8 °C and the period of 120 minutes. Atomic force microscope (AFM) and High resolution scanning electron microscope (HRSEM) showed that template has an average pore diameter of 103 nm. Co and MnOx (x = 1,2) nanostructures were selectively deposited in the pores of the template using a novel atomic layer deposition (ALD) technique. The diameter sizes and the array of the nanostructures and the template were corresponding. Energy dispersive xrays (EDX) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Co and MnOx (x =1,2) on the samples while x-ray diffraction (XRD) provided an indication of their orientations. Magnetic force microscopy as main characterization tool showed the existence of multi-domains on both Co and MnOx (x =1,2) nanostructures.

In the current study, we give a report when oxalic acid was used as an electrolyte to synthesize an AAO template with hexagonal pore array. Optimum parameters were observed as 0.4 M of oxalic acid, anodizing voltage of 45 V, temperature of approximately 8 °C and the period of 120 minutes. Atomic force microscope (AFM) and High resolution scanning electron microscope (HRSEM) showed that template has an average pore diameter of 103 nm. Co and MnOx (x = 1,2) nanostructures were selectively deposited in the pores of the template using a novel atomic layer deposition (ALD) technique. The diameter sizes and the array of the nanostructures and the template were corresponding. Energy dispersive xrays (EDX) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Co and MnOx (x =1,2) on the samples while x-ray diffraction (XRD) provided an indication of their orientations. Magnetic force microscopy as main characterization tool showed the existence of multi-domains on both Co and MnOx (x =1,2) nanostructures.

>Magister Scientiae - MSc / In the current study, we give a report when oxalic acid was used as an electrolyte to synthesize an AAO template with hexagonal pore array. Optimum parameters were observed as 0.4 M of oxalic acid, anodizing voltage of 45 V, temperature of approximately 8 °C and the period of 120 minutes. Atomic force microscope (AFM) and High resolution scanning electron microscope (HRSEM) showed that template has an average pore diameter of 103 nm. Co and MnOx (x = 1,2) nanostructures were selectively deposited in the pores of the template using a novel atomic layer deposition (ALD) technique. The diameter sizes and the array of the nanostructures and the template were corresponding. Energy dispersive xrays (EDX) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Co and MnOx (x =1,2) on the samples while x-ray diffraction (XRD) provided an indication of their orientations. Magnetic force microscopy as main characterization tool showed the existence of multi-domains on both Co and MnOx (x =1,2) nanostructures. / South Africa