The reactions between aqueous radiolysis products and oxide surfaces are important in nuclear technology in many ways. In solid-liquid systems, they affect (and at the same time are dependent on) both the solution chemistry and the stability of materials under the influence of ionizing radiation. The stability of surface oxides is a factor that determines the longevity of the materials where such oxides are formed. Additionally, the aqueous radiolysis products are responsible for corrosion and erosion of the materials.   In this study, the reactions between radiolysis products of water – mainly H2O2 and HO radicals – with metal, lanthanide and actinide oxides are investigated. For this, experimental and computational chemistry methods are employed. For the experimental study of these systems it was necessary to implement new methodologies especially for the study of the reactive species – the HO radicals. Similarly, the computational study also required the development of models and benchmarking of methods. The experiments combined with the computational chemistry studies produced valuable kinetic, energetic and mechanistic data.   It is demonstrated here that the HO radicals are a primary product of the decomposition of H2O2. For all the materials, the catalytic decomposition of H2O2 consists first of molecular adsorption onto the surfaces of the oxides. This step is followed by the cleavage of the O-O bond in H2O2 to form HO radicals. The HO radicals are able to react further with the hydroxylated surfaces of the oxides to form water and a surface bound HO• center. The dynamics of formation of HO• vary widely for the different materials studied. These differences are also observed in the activation energies and kinetics for decomposition of H2O2. It is found further that the removal of HO• from the system where H2O2 undergoes decomposition, by means of a scavenger, leads to the spontaneous formation of H2.   The combined theoretical-experimental methodology led to mechanistic understanding of the reactivity of the oxide materials towards H2O2 and HO radicals. This reactivity can be expressed in terms of fundamental properties of the cations present in the oxides. Correlations were found between several properties of the metal cations present in the oxides and adsorption energies of H2O, adsorption energies of HO radicals and energy barriers for H2O2 decomposition. This knowledge can aid in improving materials and processes important for nuclear technological systems, catalysis, and energy storage, and also help to better understand geochemical processes. / <p>QC 20130322</p>

This research investigates an alternative approach to the use of two wastes from agricultural and livestock activities developed in Colombia. Swinemanure and coffee mucilage were used to evaluatean anaerobic co-digestion process focused on hydrogen production. In addition, the aims covered a further stage in order to close the cycle of the both wastes. The thesis was conducted in three phases : 1. Evaluation of hydrogen production from the co-digestion of coffee mucilage and swine manure during dark fermentation ; 2. Trends over retention time through the monitoring of microorganisms by quantitative PCR and other parameters incluiding pH, oxidation reduction potential, and hydrogen partial pressure ; 3. Treatment of the effluent from hydrogen production process by anaerobic digestion with methane production. The experimental results showed that mixtures of both wastes are able to produce hydrogen. A substrate ratio of 5:5, which was associated with a C/N ratio of 53, was suitable for hydrogen production. Moreover, the stability and optimization of the process were evaluated by increasing the influent organic load rate. This wasthe best experimental condition in terms of average cumulative hydrogen volume, production rate and yield which were 2661 NmL, 760 NmLH2/Lwd and 43 NmL H2/gCOD, respectively. This performance was preserved over time, which was verified through the repetitive batch cultivation during 43 days. Two trends were identified over retention time associated with similar cumulative hydrogen, but with differences in lag-phase time and hydrogen production rate. T.thermosaccharolyticum was the dominating genus during the short trend related to the shortest lag phase time and highest hydrogen production rate. The long trends were associated with a decrease of Bacillus sp. concentration at the beginning of the experiments and with the possible competition for soluble substrates between T.thermosaccharolyticum and Clostridium sp. The third phase showed that the use of a second stage to produce methane was useful enhancing the treatment of both wastes. Finally, the overall energy produced for both biofuels (Hydrogen andmethane) showed similar levels with other process. However, hydrogen was around the 10% of the overall energy produced in the process. In addition, both gases could be mixed to produce biohythane which improves the properties of biogas.

Nuclear-based hydrogen production via thermochemical water decomposition using a copper-chlorine cycle consists of a series of chemical reactions that split water into hydrogen and oxygen. This is accomplished through reactions involving intermediate copper and chlorine compounds, which act as catalysts that are recycled in the process. In this thesis, analytical and numerical solutions are developed to predict the behaviour of aqueous cupric chloride droplets in a solution undergoing spray-drying in the Cu-Cl cycle. The aqueous CuCl2 is present as a slurry within the cycle, which will later generate oxygen and hydrogen as a net result. The efficiency of the cycle can be increased by utilizing low-grade waste heat from any industrial source or nuclear power plant to assist in the drying process. There are many different methods employed in industry for drying of solutions. Each method has its own advantages and disadvantages, depending on the application and conditions. In this thesis, analytical correlations of heat and mass transfer are developed for the aqueous solution, subject to various drying conditions. The analysis is performed for moist air in contact with a sprayed aqueous solution of CuCl2(2H2O). Validation of the model is performed by comparisons with experimental results obtained from a Niro-spray dryer for CuCl2 and previous experimental and theoretical data for different fluids, on the basis of non-dimensional analysis. / UOIT

In this thesis, a number of clean-energy materials for hydrogen generation, hydrogen storage, and Li-ion battery energy storage applications have been investigated through state-of-the-art density functional theory. As an alternative fuel, hydrogen has been regarded as one of the promising clean energies with the advantage of abundance (generated through water splitting) and pollution-free emission if used in fuel cell systems. However, some key problems such as finding efficient ways to produce and store hydrogen have been hindering the realization of the hydrogen economy. Here from the scientific perspective, various materials including the nanostructures and the bulk hydrides have been examined in terms of their crystal and electronic structures, energetics, and different properties for hydrogen generation or hydrogen storage applications. In the study of chemisorbed graphene-based nanostructures, the N, O-N and N-N decorated ones are designed to work as promising electron mediators in Z-scheme photocatalytic hydrogen production. Graphene nanofibres (especially the helical type) are found to be good catalysts for hydrogen desorption from NaAlH4. The milestone nanomaterial, C60, is found to be able to significantly improve the hydrogen release from the (LiH+NH3) mixture. In addition, the energetics analysis of hydrazine borane and its derivative solid have revealed the underlying reasons for their excellent hydrogen storage properties.  As the other technical trend of replacing fossil fuels in electrical vehicles, the Li-ion battery technology for energy storage depends greatly on the development of electrode materials. In this thesis, the pure NiTiH and its various metal-doped hydrides have been studied as Li-ion battery anode materials. The Li-doped NiTiH is found to be the best candidate and the Fe, Mn, or Cr-doped material follows. / <p>QC 20130925</p>

As reserves of conventional crude oil are depleted, there is a growing need to develop unconventional oils such as heavy oil and bitumen from oil sands. In terms of recoverable oil, Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than the conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas. With the future expansion of oil sands operations, the demand of H₂ for oil sand operations is likely to quadruple in the next decade. As natural gas reforming involves significant carbon dioxide (CO₂) emissions, this sector is likely to be one of the largest emitters of CO₂ in Canada. <br> <br>In the current H₂ plants, CO₂ emissions originate from two sources, the combustion flue gases from the steam reformer furnace and the off-gas from the process (steam reforming and water-gas shift) reactions. The objective of this study is to develop a process that captures CO₂ at minimum energy penalty in typical H₂ plants. <br> <br>The approach is to look at the best operating conditions when considering the H₂ and steam production, CO₂ production and external fuel requirements. The simulation in this study incorporates the kinetics of the steam methane reforming (SMR) and the water gas shift (WGS) reactions. It also includes the integration of CO₂ capture technologies to typical H₂ plants using pressure swing adsorption (PSA) to purify the H₂ product. These typical H₂ plants are the world standard of producing H₂ and are then considered as the base case for this study. The base case is modified to account for the implementation of CO₂ capture technologies. Two capture schemes are tested in this study. The first process scheme is the integration of a monoethanolamine (MEA) CO₂ scrubbing process. The other scheme is the introduction of a cardo polyimide hollow fibre membrane capture process. Both schemes are designed to capture 80% of the CO₂ from the H₂ process at a purity of 98%. <br> <br>The simulation results show that the H₂ plant with the integration of CO₂ capture has to be operated at the lowest steam to carbon (S/C) ratio, highest inlet temperature of the SMR and lowest inlet temperatures for the WGS converters to attain lowest energy penalty. H₂ plant with membrane separation technology requires higher electricity requirement. However, it produces better quality of steam than the H₂ plant with MEA-CO₂ capture process which is used to supply the electricity requirement of the process. Fuel (highvale coal) is burned to supply the additional electricity requirement. The membrane based H₂ plant requires higher additional electricity requirement for most of the operating conditions tested. However, it requires comparable energy penalty than the H₂ plant with MEA-CO₂ capture process when operated at the lowest energy operating conditions at 80% CO₂ recovery. <br> <br>This thesis also investigates the sensitivity of the energy penalty as function of the percent CO₂ recovery. The break-even point is determined at a certain amount of CO₂ recovery where the amount of energy produced is equal to the amount of energy required. This point, where no additional energy is required, is approximately 73% CO₂ recovery for the MEA based capture plant and 57% CO₂ recovery for the membrane based capture plant. <br> <br>The amount of CO₂ emissions at various CO₂ recoveries using the best operating conditions is also presented. The results show that MEA plant has comparable CO₂ emissions to that of the membrane plant at 80% CO₂ recovery. MEA plant is more attractive than membrane plant at lower CO₂ recoveries.

The main objective of this study is exploring the parameters affecting photobiological hydrogen production and developing anaerobic photobioreactor for efficient photofermentative hydrogen production from organic acids in outdoor conditions. Rhodobacter capsulatus and Rhodobacter sphaeroides strains were used as microorganisms. EU project &ldquo / Hyvolution&rdquo / targets to combine thermophilic fermentation with photofermentation for the conversion of biomass to hydrogen. In this study, the effluent obtained by dark fermentation of Miscanthus hydrolysate by T. neapolitana was fed to photobioreactor for photofermentation by R. capsulatus. Hydrogen yield was 1.4 L/Lculture showing that the integration of dark and photofermentation is possible. Innovative elements were introduced to the photobioreactor design such as removal of argon flushing. An online gas monitoring system was developed which became a commercial product. It was found that the light intensity should be at least 270 W/m2 on the bioreactor surface for the highest hydrogen productivity and the hydrogen production decreased by 43 % if infrared light was not provided to the bioreactor. Scale-up of photofermentation process to 25L was achieved yielding 27L hydrogen in 11 days by R. capsulatus on acetate/lactate/glutamate (40/7.5/2 mM) medium. The outdoor application of the system was made. Shading and water spraying were adapted as cooling methods for controlling the temperature of the outdoor bioreactor. It was found that uptake hydrogenase deleted mutant of R. capsulatus show better hydrogen productivity (0.52 mg/L.h) compared to the wild type parent (0.27 mg/L.h) in outdoor conditions. It was also shown that the hydrogen production depended on the sunlight intensity received.

photosynthetic bacteria is attractive field as production is fueled by solar energy. Hydrogen production potential of two photosynthetic bacteria R.capsulatus (DSM1710 wild type and R.capsulatus YO3 Hup- uptake hydrogenase deleted mutant strain) were examined in agar immobilized systems. In the present work agar and glutamate concentrations were optimized for immobilization of bacteria while feeding bacteria with 40/2-4 mM acetate/ glutamate. Immobilized bacteria produced hydrogen for 420-1428 hours covering 5-7 rounds. Optimizing of acetate concentration indicated that 60 mM produced the highest observed yield around 90-95%. Results shown that 2.5 mg dry cell weight/mL is the optimum cell concentration for wild type strain while 5 mg dry cell weight/mL was optimum for YO3 strain. Using either glycerol or sodium dithionite caused decrease in hydrogen production capacity of immobilized bacteria. It was observed that agar provided protection against inhibition effect of ammonium. Co- v immobilization of bacteria with packed cells of H. salinarium increased total hydrogen production capacity by about 1.14-1.41 folds. Hydrogen production by immobilized bacteria in panel photobioreactor was achieved by a novel system which allowed long term hydrogen production. Immobilized R. capsulatus DSM 1710 in panel reactor worked for about 67-82 days covering 4-5 rounds while immobilized R. capsulatus YO3 worked for 69-72 days covering seven rounds.

The main aim of this study was to investigate biological hydrogen production from sucrose and molasses by purple non-sulphur bacteria (PNS). The hydrogen production capacities of four different PNS bacteria (Rhodobacter capsulatus (DSM 1710), Rhodobacter capsulatus YO3 (Hup-), Rhodopseudomonas palustris (DSM 127) and Rhodobacter sphaeroides O.U.001 (DSM 5864)) were tested on sucrose and molasses. The photobiological hydrogen production were performed in 50 ml and 150 ml small scale photobioreactors, in batch mode. The produced hydrogen quantities, bacterial growth profiles and pH of the media were recorded through the photobiological hydrogen production processes. Organic acids and sucrose consumption rates were determined by HPLC during the experiments. The maximum hydrogen productivitiy of 0.78 (mmol/lc.h) and 0.55 (mmol/lc.h) was obtained by R. palustris (DSM 127) on sucrose and molasses, respectively. Secondly, co-cultivation of these bacterial strains was studied. The maximum hydrogen productivity by co-cultivation of R. sphaeroides O.U.001 (DSM 5864) and R. palustris (DSM 127) was found as 1.0 (mmol/lc.h).

The synthesis of diiron thiolate complexes was carried out using two ligands that were expected to furnish improved catalytic activity, solubility in water, and stability to the metal complexes. The water-soluble phosphine 1,3,5-triaza-7- phosphaadamantane, PTA, coordinates to the Fe centers forming the disubstituted complex (m-pdt)[Fe(CO)2PTA]2, which presents one PTA in each iron in a transoid arrangement. Substitution of one CO ligand in the (m-pdt)[Fe(CO)3]2 parent complex forms the asymmetric (m-pdt)[Fe(CO)3][Fe(CO)2PTA]. Enhanced water solubility was achieved through reactions with electrophiles, H+ and CH3 +, which reacted with the N on the PTA ligand forming the protonated and methylated derivatives, respectively. The 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), IMes, was reacted with (m-pdt)[Fe(CO)3]2 yielding the asymmetric (m-pdt)[Fe(CO)3][Fe(CO)2IMes], an electron rich, air stable complex that does not show reactivity with H+. Electrocatalytic production of hydrogen was studied for the all-CO, bis-PMe3, mono- and di-PTA FeIFeI complexes, as well as the PTA-protonated and -methylated derivatives. The all-CO species produce H2, in the presence of the weak HOAc, at their second reduction event, FeIFe0 ?? Fe0Fe0, that occurs at ca. ??1.9 V, through an EECC mechanism. The mono- and di-substituted phosphine complexes present electrocatalytic production of H2 from the Fe0FeI redox state; this reduction takes place at ??1.54 V for (m-pdt)[Fe(CO)3][Fe(CO)2PTA], and at ca. ??1.8 for the disubstituted PMe3 and PTA derivatives. A positive charge on the starting complex does not have an effect on the production of H2. It was found that the protonated and methylated derivatives are not the catalytic species for H2 production. At their first reduction event the neutral precursor forms, and catalysis occurs from the FeIFeI complex in all cases. The possibility of enhanced catalytic activity in the presence of H2 O was explored by conducting electrochemical experiments in the mixed CH3CN:H2O solvent system for the PTA-substituted complexes. The reduction potential of the catalytic peak is shifted to more positive values by the presence of H2 O. The cyclic voltammogram of {(m-pdt)[Fe(CO)2(PTA?? H)]2}2+ in CH3CN:H2O 3:1 shows the reduction of a more easily reduced species in the return scan. This curve-crossing event provides evidence for the (h2-H2)FeII intermediate proposed in the ECCE mechanism.

<p>This thesis encompasses CO₂ mitigation using three different processes: i) natural gas-fired combined cycle with chemical looping combustion (CLC), ii) trigeneration of electrical power, hydrogen and district heating with extended CLC, iii) steam-based gasification of biomass integrated in an advanced power cycle. </p><p>In CLC, a solid oxygen carrier circulates between two fluidised-bed reactors and transports oxygen from the combustion air to the fuel; thus, the fuel is not mixed with air and an inherent CO₂ separation occurs. In this thesis, CLC has been studied as an alternative process for CO₂ capture in a natural gas-fired combined cycle (NGCC). The potential efficiency of such a process using a turbine inlet temperature of 1200 °C and a pressure ratio of 13 is between 52 and 53 % when including the penalty for CO₂compression to 110 bar. It is shown that this efficiency cannot be further improved by including an additional CO₂ turbine. Two conceivable reactor designs for CLC in an NGCC are presented. Top-firing has been studied as an option to overcome a temperature limitation in the CLC reactor system. The degree of CO₂ capture is shown versus the temperature in the CLC reactor and its combustion efficiency. CLC has the potential to reach both a higher efficiency and a higher degree of CO₂capture than conventional post combustion CO₂ capture technique. However, further research is needed to solve technical problems as, for example, temperature limitations in the reactor to reach this potential. </p><p>Extended CLC (exCLC) is introduced, in which hydrogen is not only produced but also inherently purified. The potential efficiency of a novel tri-generation process for hydrogen, electricity and district heating using exCLC for CO₂capture is investigated. The results show that a thermal efficiency of about 54% might be achieved. </p><p>A novel power process named evaporative biomass air turbine (EvGT-BAT) for biomass feedstock is presented. This process contains a steam-based gasification of biomass, which is integrated in an externally fired gas turbine cycle with top-firing. In the EvGT-BAT process, the steam-based gasification is conducted in an entrained-flow tubular reactor that is installed in the SFC as a heat exchanger. The EvGT-BAT process has the potential to generate electrical power from biomass with an efficiency of 41 %.</p>