Thermal energy storage (TES) is one of the most attractive and cost effective solutions to the intermittent generation systems like solar, wind and other renewable sources, compared to alternatives. It creates a bridge between the power supply and demand during peak hours or at times of emergency to ensure the continuous supply of energy. Among all the TES systems, latent heat thermal energy storage (LHTES) draws lots of interests as it has high energy density and can store or retrieve energy isothermally. Two major technical challenges associated with the LHTES are low thermal conductivity of the phase change materials (PCMs), and corrosion tendency of the containment vessel with the PCMs. Macro-encapsulation of the PCM is one of the techniques to encounter the low thermal conductivity issue as it will maximize the heat transfer area for the given volume of the PCM and restrict the PCMs to get in contact with the containment vessel. However, finding a suitable encapsulation technique that can address the volumetric expansion problem and compatible shell material are significant barriers of this approach. In the present work, an innovative technique to encapsulate PCMs that melt in the 100-350 oC temperature range was developed for industrial and private applications. This technique did not require a sacrificial layer to accommodate the volumetric expansion of the PCMs on melting. The encapsulation consisted of coating a non-reactive polymer over the PCM pellet followed by deposition of a metal layer by a novel non-vacuum metal deposition technique. The fabricated spherical capsules were tested in different heat transfer fluid (HTF) environments like air, oil and molten salt (solar salt). Thermophysical properties of the PCMs were investigated by DSC/TGA, IR and weight change analysis before and after the thermal cycling. Also, the constrained melting and solidification of sodium nitrate PCM inside the spherical capsules of different sizes were compared to explore the charging and discharging time. To accomplish this, three thermocouples were installed vertically inside the capsule at three equidistant positions. Low-density graphene was dispersed in the PCM to increase its conductivity and compared with pure PCM capsules. A laboratory scale packed-bed LHTES system was designed and built to investigate the performance of the capsules. Sodium nitrate (m.p. 306oC) was used as the PCM and air was used as the heat transfer fluid (HTF). The storage system was operated between 286oC and 326oC and the volumetric flow rate of the HTF was varied from 110 m3/h to 151 m3/h. The temperature distribution along the bed (radially and axially) and inside the capsules was monitored continuously during charging and discharging of the system. The effect of the HTF mass flow rate on the charging and discharging time and on the pressure drop across the bed was evaluated. Also, the energy and exergy efficiencies were calculated for three different flow rates. Finally, a step-by-step trial manufacturing process was proposed to produce large number of spherical capsules.

In recent decades, climate change has become one of the most crucial challenges for humanity. Climate change has a direct correlation with global warming, caused mainly by the green house gas emissions (GHG). The Environmental Protection Agency in the U.S. (EPA) attributes carbon dioxide to account for approximately 82\% of the GHG emissions. Unfortunately, the energy sector is the main producer of carbon dioxide, with China and the U.S. as the highest emitters. Therefore, there is a strong (positive) correlation between energy production, global warming, and climate change. Stringent carbon emissions reduction targets have been established in order to reduce the impacts of GHG. Achieving these emissions reduction goals will require implementation of policies like as cap-and-trade and carbon taxes, together with transformation of the electricity grid into a smarter system with high green energy penetration. However, the consideration of policies solely in view of carbon emissions reduction may adversely impact other market outcomes such as electricity prices and consumption. In this dissertation, a two-layer mathematical-statistical framework is presented, that serves to develop carbon policies to reduce emissions level while minimizing the negative impacts on other market outcomes. The bottom layer of the two layer model comprises a bi-level optimization problem. The top layer comprises a statistical model and a Pareto analysis. Two related but different problems are studied under this methodology. The first problem looks into the design of cap-and-trade policies for deregulated electricity markets that satisfy the interest of different market constituents. Via the second problem, it is demonstrated how the framework can be used to obtain levels of carbon emissions reduction while minimizing the negative impact on electricity demand and maximizing green penetration from microgrids. In the aforementioned studies, forecasts for electricity prices and production cost are considered. This, this dissertation also presents anew forecast model that can be easily integrated in the two-layer framework. It is demonstrated in this dissertation that the proposed framework can be utilized by policy-makers, power companies, consumers, and market regulators in developing emissions policy decisions, bidding strategies, market regulations, and electricity dispatch strategies.

Solar cell business has been very critical and challenging since more efficient and low costs materials are required to decrease the costs and to increase the production yield for the amount of electrical energy converted from the Sun's energy. The silicon-based solar cell has proven to be the most efficient and cost-effective photovoltaic industrial device. However, the production cost of the solar cell increases due to the presence of cracks (internal as well as external) in the silicon wafer. The cracks of the wafer are monitored while fabricating the solar cell but the present monitoring techniques are not sufficient when trying to improve the manufacturing process of the solar cells. Attempts are made to understand the location of the cracks in single crystal and polycrystalline silicon solar cells, and analyze the impact of such cracks in the performance of the cell through Scanning Acoustic Microscopy (SAM) and Photoluminescence (PL) based techniques. The features of the solar cell based on single crystal and polycrystalline silicon through PL and SAM were investigated with focused ion beam (FIB) cross section and scanning electron microscopy (SEM). The results revealed that SAM could be a reliable method for visualization and understanding of cracks in the solar cells. The efficiency of a solar cell was calculated using the current (I) - voltage (V) characteristics before and after cracking of the cell. The efficiency reduction ranging from 3.69% to 14.73% for single crystal, and polycrystalline samples highlighted the importance of the use of crack monitoring techniques as well as imaging techniques. The aims of the research are to improve the manufacturing process of solar cells by locating and understanding the crack in single crystal and polycrystalline silicon based devices.

As traditional sources of energy become depleted, significant research interest has gone into conversion of biomass into renewable fuels. Biomass-derived synthesis gas typically contains concentrations of approximately 30 to 600 ppm H2S in stream. H2S is a catalyst poison which adversely affects downstream processing of hydrogen for gas to liquid plants. The water-gas shift reaction is an integral part of converting CO and steam to H2 and CO2. Currently, all known water-gas shift catalysts deactivate in sulfur concentrations typical of biomass-derived synthesis gas. Novel catalysts are needed to remain active in the presence of sulfur concentrations in order to boost efficiency and mitigate costs. Previous studies have shown molybdenum to be active in concentrations of sulfur greater than 300 ppm. Cobalt has been shown to be active as a spinel in concentrations of sulfur less than 240 ppm. Ceria has received attention as a WGS catalyst due to its oxygen donating properties. These elements were synthesized via Pechini's method into various blends of spinel metal oxide solutions. Initial activity testing at lower steam to gas ratios produced near equilibrium conversions for a Ce-Co spinel which remained active in 500 ppm H2S over a temperature range of 350 °C to 400 °C. The catalysts became poisoned and deactivated in higher concentrations of sulfur. Addition of molybdenum to the Ce-Co base had little effect on sulfur tolerance, but it did lead to a reduction in selectivity for methanation. Surface area increased due to adsorbed H2S, and X-Ray Diffraction confirmed that bulk sulfiding did not occur. Incorporation of Ce and Co into a Fe spinel hindered conversion at lower temperatures and deactivated in higher levels of sulfur.

This thesis considers economic factors for reducing greenhouse gas emissions from utility-scale electricity generation in California. The statewide Emission Performance Standard and Renewables Portfolio Standard have led to the announced and projected retirement of many coal power facilities serving California electricity load. This reality requires new baseload power sources to meet growing energy demands over the next several decades. The economic and environmental feasibilities of competitive baseload generation technologies are assessed to determine suitable replacements for decommissioning coal power plants. Geothermal is identified as the optimal replacement due to its economic baseload functionality, low greenhouse gas emissions, small environmental impact, and resource abundance in many regions of California. Developing geothermal capacity from the Salton Sea could provide southern California with a reliable energy source for decades while simultaneously reducing adverse environmental impacts and greenhouse gas emissions from electricity generation in California.

The Ocoee Supergroup is a sequence of Neoproterozoic, immature, continental rift facies clastic sediments. Potential source rocks were tested by analyzing modes of detrital framework minerals, detrital mineral chemistry, whole rock geochemistry and detrital zircon U/Pb geochronology by LA-ICP-MS for Ocoee siltstone-sandstone dominated formations. Ocoee units are arkosic to subarkosic siltstones/sandstones, and ternary tectonic discrimination diagrams confirm a continental basement uplift source. Alkali feldspar predominates over plagioclase feldspar. Detrital feldspar compositions of Ocoee sediments as a group are similar to feldspar in local basement granitic rocks except for high-Ca plagioclase grains present locally in basement granitic rocks. The high alkali content of the detrital feldspars in the Ocoee Supergroup is consistent with derivation from an A-type granite source terrane. Normative Q-A-P values, calculated from wholerock chemistry, and trace element diagrams are also supportive of an A-type granite source for these rocks. The siltstones and sandstones of the Snowbird Group contain high abundances of heavy minerals (zircon, titanite, ilmenite, epidote and apatite), which are dispersed among other detrital grains and as concentrations of heavy minerals in discrete laminae. ZTR index and titanite mineral chemistry suggest a granitic source for these sediments. Detrital zircon geochronology in Ocoee sediments indicates a dominantly Grenville (1000 to 1300 Ma) source for these sediments. The youngest zircon age in the basal Ocoee Wading Branch Formation (639±8 Ma) is related to rift magmatism and provides a minimum depositional age for the Ocoee Supergroup.

This research investigated life cycle environmental impacts and benefits of an integrated microalgae system with wastewater treatment system using an integrated process modeling approach combined with experimentation. The overall goal of this research is to understand energy, carbon and nutrient balances in the integrated system and to evaluate the environmental impacts and benefits of the integrated system from a carbon, nutrient, and energy perspective. In this study, four major research tasks were designed to contribute to a comprehensive understanding of the environmental and economic sustainability of the integrated system, which included development of an integrated co-limitation kinetic model for microalgae growth (Chapter 2), kinetic parameter estimation models for anaerobic co-digestion (Chapter 3), development of an integrated process model (Chapter 4), and life cycle environmental and economic assessments of the integrated system (Chapter 5). The integrated co-limitation kinetic model was developed to understand microalgae growth in the centrate from dewatering of anaerobically digested sludge. This growth kinetic model considered four major growth factors, including Nitrogen (N), dissolved carbon dioxide (CO2) concentrations, light intensity, and temperature. The model framework was constructed by combining threshold and multiplicative structures to explain co-limitation among these factors. The model was calibrated and validated using batch studies with anaerobically digested municipal sludge centrate as wastewater source, and the model was shown to have a reasonable growth rate predictor for Chlorella sp. under different nutrient levels of the centrate. Anaerobic co-digestion was used for energy conversion process in the integrated system. To estimate methane production of anaerobic co-digestion, kinetic models commonly applied. To apply the kinetic model, determining kinetic parameters for anaerobic co-digestion of microalgae and waste activated sludge (WAS) is essential, and this research introduced two potential regression-based parameter estimation models to estimate the kinetic parameters. Using the estimation models presented, the kinetic parameters for co-digestion was able to be determined for different ratios of co-substrates with limited experiments. In this research, the integrated process model was developed to simulate the dynamic behavior of the integrated system. The model included the microalgae cultivation, harvesting, and anaerobic co-digestion processes in the integrated system to provide a comprehensive understanding of the integrated system. For cultivation, the integrated co-limitation kinetic model was applied to estimate microalgae productivity, while the regression-based parameter estimation model was used to determine the first order kinetic parameter to estimate methane production rates for anaerobic co-digestion. The simulated microalgae productivity results were comparable to typical microalgae productivity in open pond systems. For the integrated system, removal of NH4-N by microalgae was not efficient. In particular, the NH4-N removal was minimal during the winter season due to low microalgae growth. As the microalgae productivity increased, the CH4 and biosolids production increased as a result of the increased amount of the substrates from the harvested microalgae biomass. The increase of CH4 and biosolids productions, however, was minor because of the small amount of microalgae biomass for the co-digestion. Based on simulated data for integrated process modeling, the life cycle environmental and economic impacts of the integrated system (with different CO2 supply areas) were evaluated and compared to the conventional wastewater treatment system. The integrated systems had a lower carbon footprint, cumulative energy demand, and life cycle cost than the conventional system. The integrated system with 10% CO2 sparging area was able to achieve the lowest carbon footprint. Without CO2 addition during microalgae cultivation, the integrated system had the lowest energy balance and life cycle cost. However, there is no significant difference between the integrated and conventional systems for eutrophication potential because these systems had the same effluent quality. In terms of an energy saving with the integrated systems, the benefit of energy reduction for the wastewater treatment was greater than the energy production from the anaerobic co-digestion, compared to the conventional system. Overall, the integrated system can improve the carbon balance by reducing the life cycle energy required in the conventional system.

With an ever-increasing human population, the importance in having sustainable energy resources is becoming increasingly evident, as the current energy habits have brought about massive atmospheric pollution in the form of CO2 emissions, resulting in a rise in the average global temperature. To battle the effects of climate change, many alternative energy resources have been investigated. Among these, photocatalytic conversion of CO2 to renewable hydrocarbon fuels such as methane and methanol is one of the most desirable, as it provides the opportunity to utilize the sun’s energy to convert CO2 to renewable fuels. The work in this study is primarily focused on developing a batch photoreactor system to improve the integrity of photocatalytic experiments and using that system to test the performance of Er-doped solid solutions of ZnO/GaN (ZG) towards photocatalytic reduction of CO2. To upgrade the abilities from previous photoreactor systems, a novel photoreactor was deigned in SolidWorks and fabricated in-house. The photoreactor was designed to increase surface area at the gas-solid interface, improve utilization of the light source, and promote larger mass transfer rates of reactants to the catalyst surface. These goals were accomplished by immobilizing the catalyst on a transparent porous support, incorporating a threaded mount on top of the photoreactor for mounting an interchangeable LED to illuminate the catalyst bed, and recirculating the gas mixture through a closed loop system with a compressor, respectively. Pure and Er-doped ZG photocatalyst samples were synthesized through the nitridation of Zn/Ga/CO3 layered double hydroxide (LDH) precursors. Erbium was chosen as a dopant to potentially enhance the photocatalyst by utilizing its upconversion photoluminescence properties. The LDH precursors were synthesized using a coprecipitation method. Levels of erbium doping were varied by [Er]/[Zn] = 0, 0.025, 0.05, and 0.10. ZnO/GaN solid solutions were chosen for their low bandgap energy so that visible light, roughly 40% of the solar spectrum [1], can be used to activate the catalyst. Diffuse reflectance spectroscopic data of the pure and Er-doped ZG samples were measured and used to calculate the bandgap energy. Bandgap values of EG = 2.53, 2.52, 2.56, and 2.56 eV were obtained for the [Er]/[Zn] = 0, 0.025, 0.05, and 0.10 samples, respectively. XRD data of the LDH samples indicated the formation of Zn/Ga/CO3 LDH and the Zn(OH)2, β-Ga2O3, α-GaOOH, and ZnGa2O4 impurity phases. Moreover, the broadening of the diffraction peaks in the Er-doped LDH samples suggested Er3+ ions substituted the Ga3+ ions in the LDH structure. XRD data of the pure and Er-doped ZG samples revealed strong peaks at 2θ = 31.86, 34.37, and 36.31°, indicating the formation of a solid solution of ZnO and GaN. Additionally, peaks at 2θ = 29.27, 48.79, and 57.86° indicate the formation of the secondary phase of Er2O3 in the Er-doped samples. Consequently, it was concluded that the Er3+ ions did not go into the crystal structure of the oxynitride solid solution. These findings were supported by the SEM images revealing hexagonal nanoplates and nanoprisms that coincide with the solid solution along with additional nanostructures corresponding to the Er2O3 phase. During photocatalytic experiments with the pure and Er-doped ZG samples, CO2, and UV light (405 nm nominal wavelength), hydrocarbon production was observed to increase with increasing [Er/Zn]. However, results from control experiments with no catalyst while varying the nominal LED wavelength and the o-ring material suggested that hydrocarbon formation was partially or entirely the result of the o-ring photochemically degrading in the presence of UV light. An o-ring comprised of a silicone material yielded zero hydrocarbon formation in the presence of UV light, while this was not the case for o-ring materials of Viton® and Kalrez®. These findings can be applied to other research groups that plan to perform photocatalytic experiments in a photoreactor with o-rings while using a UV light source.

Buildings contribute a significant part to the electricity demand profile and peak demand for the electrical utilities. The addition of renewable energy generation adds additional variability and uncertainty to the power system. Demand side management in the buildings can help improve the demand profile for the utilities by shifting some of the demand from peak to off-peak times. Heating, ventilation and air-conditioning contribute around 45% to the overall demand of a building. This research studies two strategies for reducing the peak as well as shifting some demand from peak to off-peak periods in commercial buildings: 1. Use of gas heat pumps in place of electric heat pumps, and 2. Shifting demand for air conditioning from peak to off-peak by thermal energy storage in chilled water and ice. The first part of this study evaluates the field performance of gas engine-driven heat pumps (GEHP) tested in a commercial building in Florida. Four GEHP units of 8 Tons of Refrigeration (TR) capacity each providing air-conditioning to seven thermal zones in a commercial building, were instrumented for measuring their performance. The operation of these GEHPs was recorded for ten months, analyzed and compared with prior results reported in the literature. The instantaneous COPunit of these systems varied from 0.1 to 1.4 during typical summer week operation. The COP was low because the gas engines for the heat pumps were being used for loads that were much lower than design capacity which resulted in much lower efficiencies than expected. The performance of equivalent electric heat pump was simulated from a building energy model developed to mimic the measured building loads. An economic comparison of GEHPs and conventional electrical heat pumps was done based on the measured and simulated results. The average performance of the GEHP units was estimated to lie between those of EER-9.2 and EER-11.8 systems. The performance of GEHP systems suffers due to lower efficiency at part load operation. The study highlighted the need for optimum system sizing for GEHP/HVAC systems to meet the building load to obtain better performance in buildings. The second part of this study focusses on using chilled water or ice as thermal energy storage for shifting the air conditioning load from peak to off-peak in a commercial building. Thermal energy storage can play a very important role in providing demand-side management for diversifying the utility demand from buildings. Model of a large commercial office building is developed with thermal storage for cooling for peak power shifting. Three variations of the model were developed and analyzed for their performance with 1) ice storage, 2) chilled water storage with mixed storage tank and 3) chilled water storage with stratified tank, using EnergyPlus 8.5 software developed by the US Department of Energy. Operation strategy with tactical control to incorporate peak power schedule was developed using energy management system (EMS). The modeled HVAC system was optimized for minimum cost with the optimal storage capacity and chiller size using JEPlus. Based on the simulation, an optimal storage capacity of 40-45 GJ was estimated for the large office building model along with 40% smaller chiller capacity resulting in higher chiller part-load performance. Additionally, the auxiliary system like pump and condenser were also optimized to smaller capacities and thus resulting in less power demand during operation. The overall annual saving potential was found in the range of 7-10% for cooling electricity use resulting in 10-17% reduction in costs to the consumer. A possible annual peak shifting of 25-78% was found from the simulation results after comparing with the reference models. Adopting TES in commercial buildings and achieving 25% peak shifting could result in a reduction in peak summer demand of 1398 MW in Tampa.

The slow yet steady expansion of the global economies, has led to an increased demand for energy and fuel, which would eventually lead to shortage of fossil fuel resources in the near future. Consequently, researchers have been investigating other fuels like biodiesel. Biodiesel refers to the monoalkyl esters which can be derived from a wide range of sources like vegetable oils, animal fats, algae lipids and waste greases. Currently, biodiesel is largely produced by the conventional route, using an acid, a base or an enzyme catalyst. Drawbacks associated with this route result in higher production costs and longer processing times. Conversely, supercritical transesterification presents several advantages over conventional transesterification, such as, faster reaction rates, catalyst free reaction, less product purification steps and higher yields. This work focused on the supercritical transesterification of cooking oil, soybean in particular. The experimental investigation was conducted using methanol at supercritical conditions. These conditions were milder in terms of pressure than those reported in literature. A batch setup was designed, built and used to carry out the supercritical transesterification reactions. The biodiesel content was analyzed using gas chromatography-mass spectrometry to calculate reaction yields. Methyl ester yield of 90% was achieved within 10 minutes of reaction time using supercritical transesterification. A maximum yield of 97% was achieved with this process in 50 minutes of reaction time. Two key factors, temperature and molar ratio were studied using variance analysis and linear regression and their significance on the biodiesel yield was determined. The kinetic tendency of the reaction was investigated and the values of rate constants, activation energy and the pre-exponential factor were estimated.