A variety of unicellular green algae have the ability to photo-produce molecular hydrogen (H2). Using sunlight to power the production of H2 from water is attractive due to the abundant supply of both resources and the potential for the technology to address global warming and energy supply concerns. Increasing levels of H2 production from those currently achievable with algal systems is a necessity for the technology to become economically feasible. Green unicellular algae are rare amongst organisms in that some have an ability to switch to an H2-producing metabolism when environmental conditions become anaerobic. The process of H2 production is greatly accentuated in the light due to the role of the photosynthetic apparatus directing electron flow to hydrogenase enzymes located in the chloroplast. Difficulties in maintaining continuous systems of H2 production largely result from the O2 sensitivity of hydrogenase enzymes. As O2 is generally produced through photosynthesis, the process of H2 production has always been short-lived. Recently, a process of inducing H2 production for several days was accomplished by depriving the growth medium of sulphur (Melis et al., 2000). Lacking sulphur, photosystem II activity diminishes to a point where any O2 evolved is consumed by respiration; this leads to the culture becoming anaerobic and to the onset of H2 production. The method of sulphur depletion has proven to be very useful for studies of H2 production due to enhanced rates over longer time periods being possible. This work was performed to search for new H2-producing Australian algal species and to shed light upon the molecular and biochemical interactions occurring when algal species move from aerobic photosynthetic growth to an anaerobic H2-producing status. An assay to test new species for an H2-producing ability was developed and implemented; leading to the isolation of new H2-producing species from Australian waters. The assay involved purging algal cultures in the dark with N2, sealing them in bioreactors and then exposing them to light. Metabolic profiling performed during this assay revealed cells to rapidly enter a fermentative metabolism upon the onset of anoxia. Acetate, formate and ethanol were key metabolites produced alongside H2 during this period. Metabolomics was used as a tool to understand the biochemical interactions occurring during 120 h of sulphur depleted H2 production. Extraction protocols were developed that allowed the detection and identification of over 100 metabolites using gas chromatography coupled to mass spectrometry, nuclear magnetic resonance spectroscopy and thin layer chromatography. Shifts in primary energy metabolism when cells switch from O2 production to H2 production were revealed. Indications are that both starch and triacylglyceride accumulate during the first 24 h of sulphur depletion prior to anoxia. Following the onset of anoxia, fermentative metabolism begins, H2 is produced and amino acids generally increase. A build-up of toxic fermentative end products and a lack of sulphur are believed to cause the termination of H2 production, rather than a lack of energy reserves. Key achievements of this work have been: • The establishment of an assay that can be used for future bio-prospecting work aimed at finding H2-producing algal species. • The isolation of new H2-producing green algal species from Australian waters. • The establishment of protocols for the extraction of metabolites from small volumes (1 ml) of Chlamydomonas reinhardtii cultures for analysis on a variety of analytical platforms. • The mapping of changes in metabolism of C. reinhardtii during the switch from an aerobic environment to an anaerobic H2-producing environment. • A range of recommendations for future research that may lead to higher H2 production.

The energy carrier hydrogen is expected to solve some energy challenges. Since its oxidation does not emit greenhouse gases (GHGs), its use does not contribute to climate change, provided that it is derived from clean energy sources. Thermochemical water splitting using a Cu-Cl cycle, linked with a nuclear super-critical water cooled reactor (SCWR), which is being considered as a Generation IV nuclear reactor, is a promising option for hydrogen production. In this thesis, a comparative environmental study is reported of the three-, four- and five-step Cu-Cl thermochemical water splitting cycles with various other hydrogen production methods. The investigation uses life cycle assessment (LCA), which is an analytical tool to identify and quantify environmentally critical phases during the life cycle of a system or a product and/or to evaluate and decrease the overall environmental impact of the system or product. The LCA results for the hydrogen production processes indicate that the four-step Cu-Cl cycle has lower environmental impacts than the three- and five-step Cu-Cl cycles due to its lower thermal energy requirement. Parametric studies show that acidification potentials (APs) and global warming potentials (GWPs) for the four-step Cu-Cl cycle can be reduced from 0.0031 to 0.0028 kg SO2-eq and from 0.63 to 0.55 kg CO2-eq, respectively, if the lifetime of the system increases from 10 to 100 years. Moreover, the comparative study shows that the nuclear-based S-I and the four-step Cu-Cl cycles are the most environmentally benign hydrogen production methods in terms of AP and GWP. GWPs of the S-I and the four-step Cu-Cl cycles are 0.412 and 0.559 kg CO2-eq for reference case which has a lifetime of 60 years. Also, the corresponding APs of these cycles are 0.00241 and 0.00284 kg SO2-eq. It is also found that an increase in hydrogen plant efficiency from 0.36 to 0.65 decreases the GWP from 0.902 to 0.412 kg CO2-eq and the AP from 0.00459 to 0.00209 kg SO2-eq for the four-step Cu-Cl cycle. / UOIT

The world faces problems with depleting energy resources and the harmful impact of present energy consumption patterns on the environment, and consequently on the global climate and humanity. The concerns regarding global climate change are serious and have resulted in extensive research and developments on alternative, clean energy sources. While many of the available natural energy resources are limited due to their reliability, quality, quantity and density; nuclear energy has the potential to contribute a significant share of large scale energy supply without or little contributing to climate change. Hydrogen production via thermochemical water decomposition is one of the key potential processes for direct utilization of nuclear thermal energy. Thermochemical water splitting with a copper-chlorine (Cu-Cl) cycle is a promising process that could be linked with nuclear reactors to decompose water into its constituents, oxygen and hydrogen as a net result, through intermediate copper and chlorine compounds with a net input of water and heat. The process involves a series of closed-loop chemical reactions that does not contribute to any greenhouse gas emissions into the environment. Although some preliminary technical studies of the Cu-Cl cycle have been reported and some small lab scale experiments of individual reactions in the cycle have been carried out, there is still a need to link all the sub-steps of the cycle and build a pilot plant, to facilitate eventual commercialization. Such an experimental set up of overall cycle is lacking, especially to evaluate characteristics of the complete cycle such as energy, exergy and cost effectiveness. Simulation packages, such as Aspen Plus, are useful tools to provide the system designer or operator with design, optimization and operation information before building a pilot plant. In this thesis, process analysis is performed and simulation models are developed using the Aspen Plus simulation package, based on experimental work carried out at the University of Ontario Institute of Technology (UOIT), the Argonne National Laboratory (ANL), the Atomic Energy of Canada Limited (AECL) and other sources. The energy and mass balances, stream flows and properties, the heat exchanger duties and shaft work are calculated. Heat recovery options are assessed to improve thermal management and hence overall efficiency of the Cu-Cl cycle. An integrated heat exchange network is designed to use heat from the process streams efficiently and decrease the external heat demand. The efficiency of the process, based on three, four and five-step cycles, is examined in this thesis. The thermal efficiency of the five-step thermochemical process is calculated as 44%, of the four-step process is 43% and of the three-step process is 41%, based on the lower heating value of hydrogen. Sensitivity analyses are performed to study the effects of various operating parameters on the efficiency, yield, and cost. A parametric study is conducted, and possible efficiency improvements are discussed. The manner is investigated in which exergy-related parameters can be used to minimize the cost of a Cu-Cl thermochemical cycle for hydrogen production. The iterative optimization technique presented requires a minimum of available data and provides effective assistance in optimizing thermal systems, particularly in dealing with complex systems and/or cases where conventional optimization techniques cannot be applied. The principles of thermoeconomics, as embodied in the specific exergy cost (SPECO) and exergy-cost-energy-mass (EXCEM) methods, are used here to determine changes in the design parameters of the cycle that improve the cost effectiveness of the overall system. It is found that the cost rate of exergy destruction varies between $1 and $15 per kilogram of hydrogen produced; and the exergoeconomic factor between 0.5 and 0.02 as the cost of hydrogen rises from $2.8 to $20 per kg of hydrogen produced. The hydrogen cost is inversely related to the exergoeconomic factor, plant capacity and energy/exergy efficiencies. Based on the cycle’s design parameters and conditions the hydrogen production cost is calculated as $3.8/kg hydrogen. Also, an integrated Cu-Cl cycle hydrogen production system, based on nuclear and renewable energy sources, is investigated. Nuclear and renewable energy sources are reviewed to determine the most appropriate option to couple with the Cu-Cl cycle. An environmental impact assessment is conducted and compared to the conventional methods using fossil fuels and other options. Some cost assessment studies of hydrogen production are presented for this integrated system. The results show that hydrogen production cost could drop down to as low as 2.8 $/kg. The results are expected to assist ongoing efforts to increase the economic viability of the Cu-Cl cycle, and to reduce product costs of potential commercial versions of this process. / UOIT

Hydrogen is known as a clean energy carrier which has the potential to play a major role in addressing the climate change and global warming, and thermochemical water splitting via the copper-chlorine cycle is a promising method of hydrogen production. In this research, thermal management of the copper-chlorine cycle for hydrogen production is investigated by performing analytical and experimental analyses of selected heat recovery options. First, the heat requirement of the copper-chlorine cycle is estimated. The pinch analysis is used to determine the maximum recoverable heat within the cycle, and where in the cycle the recovered heat can be used efficiently. It is shown that a major part of the potential heat recovery can be achieved by cooling and solidifying molten copper(I) chloride exiting one step in the cycle: the oxygen reactor. Heat transfer from molten CuCl can be carried out through direct contact or indirect contact methods. Predictive analytical models are developed to analyze a direct contact heat recovery process (i.e. a spray column) and an indirect contact heat recovery process (i.e. a double-pipe heat exchanger). Characteristics of a spray column, in which recovered heat from molten CuCl is used to produce superheated steam, are presented. Decreasing the droplet size may increase the heat transfer rate from the droplet, and hence decreases the required height of the heat exchanger. For a droplet of 1 mm, the height of the heat exchanger is predicted to be about 7 m. The effect of hydrogen production on the heat exchanger diameter was also shown. For a hydrogen production rate of 1000 kg/day, the diameter of the heat exchanger is about 3 m for a droplet size of 1 mm and 2.2 m for a droplet size of 2 mm. The results for axial growth of the solid layer and variations of the coolant temperature and wall temperature of a double-pipe heat exchanger are also presented. It is shown that reducing the inner tube diameter will increase the heat exchanger length and increase the outlet temperature of air significantly. It is shown that the air temperature increases to 190oC in a heat exchanger with a length of 15 cm and inner tube radius of 10 cm. The length of a heat exchanger with the inner tube radius of 12 cm is predicted to be about 53 cm. The outlet temperature of air is about 380oC in this case. The length of a heat exchanger with an inner tube diameter of 24 cm is predicted to be about 53 cm and 91 cm for coolant flow rates of 3 g/s and 4 g/s, respectively. Increasing the mass flow rate of air will increase the total heat flux from the molten salt by increasing the length of the heat exchanger. Experimental studies are performed to validate the proposed methods and to further investigate their feasibility. The hazards involving copper(I) chloride are also investigated, as well as corresponding hazard reduction options. Using the reactant Cu2OCl2 in the oxygen production step to absorb CuCl vapor is the most preferable option compared to the alternatives, which include absorbing CuCl vapor with water or CuCl2 and building additional structures inside the oxygen production reactor. / UOIT

Production of hydrogen is primarily achieved via catalytic steam reforming, partial oxidation,and auto-thermal reforming of natural gas. Although these processes are mature technologies, they are somewhat complex and CO is formed as a by-product, therefore requiring a separation process if a pure or hydrogen-rich stream is needed. As an alternative method, supported metal catalysts can be used to catalytically decompose hydrocarbons to produce hydrogen. The process is known as catalytic cracking of hydrocarbons. Methane, the hydrocarbon containing the highest percentage of hydrogen, can be used in such a process to produce a hydrogen-rich stream. The decomposition of methane occurs on the surface of the active metal to produce hydrogen and filamentous carbon. As a result, only hydrogen is produced as a gaseous product, which eliminates the need of further separation processes to separate CO2 or CO. Nickel is commonly used in research as a catalyst for methane cracking in the 500-700C temperature range. To conduct methane catalytic cracking in a continuous manner, regeneration of the deactivated catalyst is required and circulation of the catalysts between cracking and regeneration cycles must be achieved. Different reactor designs have been successfully used in cyclic operation, such as a set of parallel fixed-bed reactors alternating between cracking and regeneration, but catalyst agglomeration due to carbon deposition may lead to blockage of the reactor and elevated pressure drop through the fixed bed. Also poor heat transfer in the fixed bed may lead to elevated temperature during the regeneration step when carbon is burned in air, which may cause catalyst sintering. A fluidized bed reactor appears as a viable option for methane catalytic cracking, since it would permit cyclic operation by moving the catalyst between a cracker and a regenerator. In addition, there is the possibility of using fine catalyst particles, which improves catalyst effectiveness. The aims of this project were 1) to develop and characterize a suitable nickel-based catalyst and 2) to develop a model for thermal catalytic decomposition of methane in a fluidized bed.

The resources on earth are limited; thus, the demand for energy, goods and materials is surging because of the growth of the advanced technology and population. The issues of using the resources effectively and changing them into a useful energy are then important. Taiwan creates a vast amount of agricultural waste every year. The traditional way of eliminating the agricultural waste would be burned and buried. However, it is not only the agricultural waste cannot be reused and recycled, but also the problem of air pollution occurred. The objectives of this thesis are thus to transfer the agricultural waste into a useful energy. This study contents two parts. The first part changes the agricultural waste into sugar. The agricultural waste is full of wood fiber and can be transformed to sugar by a microorganism method. A cane which is a common agricultural waste is used; the wood fiber in cane will be added to the thermostable cellulolytic bacterial Geobacillus thermoleovorans T4 isolated from sugar refinery wastewater in southern Taiwan. T4 can convert wood fiber into sugar. Experimental results showed that the rate of reducing sugar is 13.77%. The second part studies the biological hydrogen production by Clostridium acetobutylicum ATCC 824, and the sugar will be added into the process. Also, this study uses ultrasonic treatment in the biological hydrogen production and calculates the natural frequency of ATCC 824. The experiment is designed using the Taguchi method for increasing hydrogen production, hydrogen production rate and hydrogen production efficiency by using an ultrasonic treatment to treat C. acetobutylicum ATCC 824. It is showed that the best combination is temperature 37¢XC, ultrasonic frequency 0.5 MHz, ultrasonic intensity 136 mW/cm2, exposure time 10 s, pH 7.5 and bacterial concentration 20%. This study can apply in bio-energy and fermentation food producing.

Hydrogen production by water-splitting using solar energy and nanostructure photocatalysts is very promising as a renewable, efficient, environmentally clean technology. The key is to reduce the cost of hydrogen production as well as increase the solar-to-hydrogen conversion efficiency by searching for cost-effective photocatalytic materials. In this dissertation, energy efficiency calculation was carried out based on hydrogen production observation to evaluate the nanomaterials activity. The results are important to gain better understanding of water-splitting reaction mechanism. Design, synthesis, characterization/properties and application of these nanomaterials was the road-map to achieve the research objectives. The design of TiO2 is selected based on unique photocatalytic and photovoltaic properties and high stability in aqueous solution. Various structures of nanocomposites TiO2 were designed according to their characteristics and potential activity. TiO2 with quantum dots, nanocomposites thin film, nanofibers, nanorods, nanowires (core/shell), nanotubes, nanopowders, nanoparticles, and nanosphere decorated with low cost metals, sensitized with dye, and doped with nitrogen are designed. Green physical and chemical synthesis methods such as sol-gel techniques, autoclave, microwave, electrospinning, wet impregnation, hydrothermal, chemical vapor deposition, template-based fabrication (porous anodic aluminium oxide membrane), drop casting, dip coating, wet coating were used to synthesize and fabricate the nanomaterials and quantum dots.Both bottom-up and top-down synthesis techniques were used. The ability to control and manipulate the size, shape/geometry, crystal structure, chemical compositions, interaction and interface properties of these materials at nano-scale during the synthesis enable to enhance their thermal, optical, chemical, electrical, …etc properties. Several characterization techniques such as XRD, XPS, EDS, SEM, UV-visible spectra, and optical microscopic and digital camera were also obtained to characterize the properties and confirm to achieve the desired design. The application or processing to test the activity of these nanomaterials for hydrogen production by water-splitting was conducted through extensive experimental program. It was carried out in a one photo-single column experimental set-up to detect hydrogen evolution. A high throughput screening process to evaluate single photo reduction catalysts was established here for simplicity, safety, cost-effective and flexibility of testing nanomaterials for water photoreduction reactivity and hydrogen generation. Therefore, methanol as electron donor or oxidation agent was mixed with water in equal volume ratio in order to prevent the oxygen evolution and only measured the time course of hydrogen production. The primary objectives of this study is to investigate the following (1) The structure-properties relationship through testing quantum dots, nanocomposites thin film, nanofibers, nanorods, nanowires (core/shell), nanotubes, nanopowders, nanoparticles, nanospheres of TiO2 decorated with metals, dye sensitization, and nitrogen-doping. (2) The role of adding electron donors/relays to solution and their effect on semiconductor surface-electrolyte interface under constant conditions such as KI, Mv 2, NaCl, NaHCO3, sea and pure water. (3) Band gap and defect engineering by cation and anion doping. (4) Quantum dots and dye sensitization effect. The nanomaterials activity evaluated based on observed hydrogen production rate (μmol/h/g) experimentally and based on the energy efficiency (percent) calculation. Major findings in this dissertation are (1) A high throughput screening process to evaluate single photoreduction catalysts for solar-hydrogen production by water-splitting was established. (2) nanofibers structure of TiO2 doped with nitrogen, sensitized with dye (Rose Bengal Sodium) and quantum dots (CuInS2), and decorated with metals (Ag) showed the high solar-to-hydrogen conversion efficiency and high hydrogen production rate (3) Simple, safe, inexpensive, robust, efficient and green physical and chemical synthesis methods were used to prepare the nanomaterials and quantum dots. (4) Gaining insight and better understanding of water-splitting reaction mechanism by (a) Studying the structure-properties relationship of nanomaterials (b) Studying the role of additives on surface-interface chemistry of semiconductor and electrolyte (c) Knowing how to reduce the electron-hole recombination reactions to enhance quantum efficiency (d) Extending the absorption of nanomaterials to harness the visible light of solar spectrum radiation by doping and defect chemistry.

Photobiological hydrogen production from organic materials occurs with the help of illumination and under aerobic conditions within photobioreactors. Novel designs are needed in order to increase the light conversion efficiency and to improve the biological hydrogen production. In this thesis, purple non sulfur bacteria Rhodobacter sphaeroides O.U. 001 was employed as the hydrogen producing microorganism. Two different types of photobioreactors, namely oscillatory helical photobioreactor and recycling helical bioreactor, were devised and successfully operated for bacterial growth and hydrogen production. Total liquid capacity of the pneumatically driven oscillatory flow helical tubular photobioreactor was 11.5 L, and 4.5 L of which was occupied by the bacterial culture. The bacteria grew very well both in malate-based and acetate-based media under nitrogen atmosphere. The bacteria sustained their vitality 24 days before the system was shut down. The recycling helical tubular photobioreactor, which was developed for hydrogen production, had a fully occupied total volume of 6.5L. The bacteria produced approximately 1.9L of hydrogen in four days on malate-based media. The hydrogen production rate was 0.009LH2/Lculture.h. The effects of molecular nitrogen gas and the sodium glutamate concentration on the growth of hydrogen producing photosynthetic bacteria Rhodobacter sphaeroides O.U.001 in the reactor were also examined in 500ml-bottles. The bacterial growth curves did not show any difference at the control medium containing 15mM of acetate and 10 mM of sodium glutamate. However, other bottles containing a lesser amount of N-source was found to grow earlier under the nitrogen atmosphere. Besides, even a 15/2 acetate/sodium glutamate ratio was observed to be sufficient to grow the bacteria for inoculation, and to spend extra sodium glutamate was not necessary. The novel designs developed in this study aim to improve the biological hydrogen production by photosynthetic bacteria, and to provide new ways in adaptation of photobiological systems to outdoor conditions for large-scale applications.

A steady-state model for the calculation of temperature and pressure distributions, and heat and work balance for the STAR-LM and the STAR-H2 systems was developed. The STAR-LM system is designed for electricity production and consists of the lead cooled reactor on natural circulation and the supercritical carbon dioxide Brayton cycle. The STAR-H2 system uses the same reactor which is coupled to the hydrogen production plant, the Brayton cycle, and the water desalination plant. The Brayton cycle produces electricity for the on-site needs. Realistic modules for each system component were developed. The model also performs design calculations for the turbine and compressors for the CO2 Brayton cycle. The model was used to optimize the performance of the entire system as well as every system component. The size of each component was calculated. For the 400 MWt reactor power the STAR-LM produces 174.4 MWe (44% efficiency) and the STAR-H2 system produces 7450 kg H2/hr. The steady state model was used to conduct quasi-static passive load follow analysis. The control strategy was developed for each system; no control action on the reactor is required. As a main safety criterion, the peak cladding temperature is used. It was demonstrated that this temperature remains below the safety limit during both normal operation and load follow.

Abstract: Hydrogen can be a renewable energy source to replace conventional fossil fuels. Compared to current hydrogen production processes by consuming fossil fuels, biological hydrogen production has the advantage of being environmentally friendly because of the use of renewable and low value biological materials. Some hyperthermophiles, such as Thermotoga species, are capable of producing hydrogen during growth. In this study, Thermotoga maritima, Thermotoga neapolitana DSM 4359 and DSM 5068, were used to investigate their potential in converting selected sugars (glucose and xylose) and complex carbon sources (cellulose, starch, xylan and agricultural residues, such as barley straw, corn stover, soybean straw, wheat straw and corn husk) to hydrogen. In addition, factors which influenced growth and hydrogen production were studied, and optimal conditions for hydrogen production were obtained. All three Thermotoga species could grow in the presence of mono sugars (glucose, xylose) and complex carbohydrates (starch, xylan, milled corn husk). They all could produce hydrogen in the presence of micro-molar level of oxygen without addition of any reducing agents in the growth medium. Compared to the slight inhibition caused by L-lactate accumulation during the growth, gradual pH decreases were the main reasons to inhibit both growth and hydrogen production of T. neapolitana species. Increasing the initial pH of the growth medium to 8.5 and stabilizing the pH by 50 mM Triz buffer resulted in higher growth and hydrogen production of T. neapolitana strains. Adjusting the medium pH at early stationary phase also increased the hydrogen production, and fewer enhancements to the growth. The pH control methods also resulted in higher conversion efficiency (converting glucose to H2) of T. neapolitana strains from 2.2 to 3.6 (H2/glucose), which was approximately 90% of the theoretical efficiency (4 moles H2 produced from 1 mole glucose). The expression of hydrogenases of T. neapolitana strains could also be increased by the pH control methods. Thermotoga species could grow and produce hydrogen using agricultural residues, such as corn husk, achieving 60% growth and hydrogen production as compared to that iii from glucose. With pH control methods, hydrogen production by T. neapolitana strains from corn husk was higher than that from glucose without pH control. These results indicated that the pH was the main factor to affect both hydrogen production and growth of T. neapolitana species, and optimal conditions for hydrogen production could be achieved by using pH control methods. Selected agricultural residues could be utilized for biological hydrogen production by Thermotoga species with minimum pre-treatment, and the pH control methods could result in a higher hydrogen production compared to that from glucose. Further studies on the continuous growth and hydrogenases of Thermotoga species are needed for better understanding of the hydrogen production mechanisms.