A new photocatalytic material was synthesized to investigate its performance for the photoreduction of carbon dioxide (CO2) in the presence of water vapor (H2O) to valuable products such as carbon monoxide (CO) and methane (CH4). The performance was studied using a gas chromatograph (GC) with a flame ionization detector (FID) and a thermal conductivity detector (TCD). The new photocatalytic material was an ionic liquid functionalized reduced graphite oxide (IL-RGO (high conductive surface))-TiO2 (photocatalyst) nanocomposite. Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and UV-vis absorption spectroscopy techniques were employed to characterize the new catalyst. In the series of experiments performed, the nanocomposite material was confined in a UV-quartz batch reactor, exposed to CO2 and H2O and illuminated by UV light. The primary product formed was CO with a maximum production ranging from 0.18-1.02 µmol(gcatalyst-hour)-1 for TiO2 and 0.41-1.41 µmol(gcatalyst-hour)-1 for IL-RGO-TiO2. A trace amount of CH4 was also formed with its maximum ranging from 0.009-0.01 µmol(gcatalyst-hour)-1 for TiO2 and 0.01-0.04 µmol(gcatalyst-hour)-1 for IL-RGO-TiO2. A series of background experiments were conducted and results showed that; (a) the use of a ionic liquid functionalized reduced graphite oxide -TiO2 produced more products as compared to commercial TiO2, (b) the addition of methanol as a hole scavenger boosted the production of CO but not CH4, (c) a higher and lower reduction time of IL-RGO as compared to the usual 24 hours of reduction presented basically the same production of CO and CH4, (d) the positive effect of having an ionic liquid was demonstrated by the double production of CO obtained for IL-RGO-TiO2 as compared to RGO-TiO2 and (e) a change in the amount of IL-RGO in the IL-RGO-TiO2 represented a small difference in the CO production but not in the CH4 production. This work ultimately demonstrated the huge potential of the utility of a UV-responsive ionic liquid functionalized reduced graphite oxide-TiO2 nano-composite for the reduction of CO2 in the presence of H2O for the production of fuels.

The accurate and fast determination of carbon dioxide (CO2) levels is critical for many health and environmental applications. For example, the analysis of CO2 levels in exhaled breath allows for the evaluation of systemic metabolism, perfusion, and ventilation, and provides the doctors and patients with a non-invasive and simple method to predict the presence and severity of asthma, and Chronic Obstructive Pulmonary Disease (COPD). Similarly, the monitoring of CO2 levels in the atmosphere allows for assessment of indoor air quality (IAQ) as the indoor CO2 levels have been proved to be associated with increased prevalence of certain mucous membrane and respiratory sick building syndrome (SBS) symptoms. A pocket-sized CO2 analyzer has been developed for real-time analysis of breath CO2 and environmental CO2. This CO2 analyzer is designed to comprise two key components including a fluidic system for efficient gas sample delivery and a colorimetric detection unit integrated into the fluidic system. The CO2 levels in the gas samples are determined by a disposable colorimetric sensor chip. The sensor chip is a novel composite based sensor that has been optimized to provide fast and reversible response to CO2 over a wide concentration range, covering the needs of both environmental and health applications. The sensor is immune to the presence of various interfering gases in ambient or expired air. The performance of the sensor in real-time breath-by-breath analysis has also been validated by a commercial CO2 detector. Furthermore, a 3D model was created to simulate fluid dynamics of breath and chemical reactions for CO2 assessment to achieve overall understanding of the breath CO2 detection process and further optimization of the device.

Metabolic engineering is an extremely useful tool enabling the biosynthetic production of commodity chemicals (typically derived from petroleum) from renewable resources. In this work, a pathway for the biosynthesis of styrene (a plastics monomer) has been engineered in Escherichia coli from glucose by utilizing the pathway for the naturally occurring amino acid phenylalanine, the precursor to styrene. Styrene production was accomplished using an E. coli phenylalanine overproducer, E. coli NST74, and over-expression of PAL2 from Arabidopsis thaliana and FDC1 from Saccharomyces cerevisiae. The styrene pathway was then extended by just one enzyme to either (S)-styrene oxide (StyAB from Pseudomonas putida S12) or (R)-1,2-phenylethanediol (NahAaAbAcAd from Pseudomonas sp. NCIB 9816-4) which are both used in pharmaceutical production. Overall, these pathways suffered from limitations due to product toxicity as well as limited precursor availability. In an effort to overcome the toxicity threshold, the styrene pathway was transferred to a yeast host with a higher toxicity limit. First, Saccharomyces cerevisiae BY4741 was engineered to overproduce phenylalanine. Next, PAL2 (the only enzyme needed to complete the styrene pathway) was then expressed in the BY4741 phenylalanine overproducer. Further strain improvements included the deletion of the phenylpyruvate decarboxylase (ARO10) and expression of a feedback-resistant choristmate mutase (ARO4K229L). These works have successfully demonstrated the possibility of utilizing microorganisms as cellular factories for the production styrene, (S)-styrene oxide, and (R)-1,2-phenylethanediol.

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.

Some cyanobacteria can generate hydrogen (H2) under certain physiological conditions and are considered potential agents for biohydrogen production. However, they also present low amounts of H2 production, a reaction reversal towards H2 consumption, and O2 sensitivity. Most attempts to improve H2 production have involved genetic or metabolic engineering approaches. I used a bio-prospecting approach instead to find novel strains that are naturally more apt for biohydrogen production. A set of 36, phylogenetically diverse strains isolated from terrestrial, freshwater and marine environments were probed for their potential to produce H2 from excess reductant. Two distinct patterns in H2 production were detected. Strains displaying Pattern 1, as previously known from Synechocystis sp. PCC 6803, produced H2 only temporarily, reverting to H2 consumption within a short time and after reaching only moderately high H2 concentrations. By contrast, Pattern 2 cyanobacteria, in the genera Lyngbya and Microcoleus, displayed high production rates, did not reverse the direction of the reaction and reached much higher steady-state H2 concentrations. L. aestuarii BL J, an isolate from marine intertidal mats, had the fastest production rates and reached the highest steady-state concentrations, 15-fold higher than that observed in Synechocystis sp. PCC 6803. Because all Pattern 2 strains originated in intertidal microbial mats that become anoxic in dark, it was hypothesized that their strong hydrogenogenic capacity may have evolved to aid in fermentation of the photosynthate. When forced to ferment, these cyanobacteria display similarly desirable characteristics of physiological H2 production. Again, L. aestuarii BL J had the fastest specific rates and attained the highest H2 concentrations during fermentation, which proceeded via a mixed-acid pathway to yield acetate, ethanol, lactate, H2, CO2 and pyruvate. The genome of L. aestuarii BL J was sequenced and bioinformatically compared to other cyanobacterial genomes to ascertain any potential genetic or structural basis for powerful H2 production. The association hcp exclusively in Pattern 2 strains suggests its possible role in increased H2 production. This study demonstrates the value of bioprospecting approaches to biotechnology, pointing to the strain L. aestuarii BL J as a source of useful genetic information or as a potential platform for biohydrogen production.

To further the efforts producing energy from more renewable sources, microbial electrochemical cells (MXCs) can utilize anode respiring bacteria (ARB) to couple the oxidation of an organic substrate to the delivery of electrons to the anode. Although ARB such as Geobacter and Shewanella have been well-studied in terms of their microbiology and electrochemistry, much is still unknown about the mechanism of electron transfer to the anode. To this end, this thesis seeks to elucidate the complexities of electron transfer existing in Geobacter sulfurreducens biofilms by employing Electrochemical Impedance Spectroscopy (EIS) as the tool of choice. Experiments measuring EIS resistances as a function of growth were used to uncover the potential gradients that emerge in biofilms as they grow and become thicker. While a better understanding of this model ARB is sought, electrochemical characterization of a halophile, Geoalkalibacter subterraneus (Glk. subterraneus), revealed that this organism can function as an ARB and produce seemingly high current densities while consuming different organic substrates, including acetate, butyrate, and glycerol. The importance of identifying and studying novel ARB for broader MXC applications was stressed in this thesis as a potential avenue for tackling some of human energy problems.

The diversity of industrially important chemicals that can be produced biocatalytically from renewable resources continues to expand with the aid of metabolic and pathway engineering. In addition to biofuels, these chemicals also include a number of monomers with utility in conventional and novel plastic materials production. Monomers used for polyamide production are no exception, as evidenced by the recent engineering of microbial biocatalysts to produce cadaverine, putrescine, and succinate. In this thesis the repertoire and depth of these renewable polyamide precursors is expanded upon through the engineering of a novel pathway that enables Escherichia coli to produce, as individual products, both δ-aminovaleric acid (AMV) and glutaric acid when grown in glucose mineral salt medium. δ-Aminovaleric acid is the monomeric subunit of nylon-5 homopolymer, whereas glutaric acid is a dicarboxylic acid used to produce copolymers such as nylon-5,5. These feats were achieved by increasing endogenous production of the required pathway precursor, L-lysine. E. coli was engineered for L-lysine over-production through the introduction and expression of metabolically deregulated pathway genes, namely aspartate kinase III and dihydrodipicolinate synthase, encoded by the feedback resistant mutants lysCfbr and dapAfbr, respectively. After deleting a natural L-lysine decarboxylase, up to 1.6 g/L L-lysine could be produced from glucose in shake flasks as a result. The natural L-lysine degradation pathway of numerous Pseudomonas sp., which passes from L-lysine through both δ-aminovaleric acid and glutaric acid, was then functionally reconstructed in a piecewise manner in the E. coli L-lysine over-producer. Expression of davBA alone resulted in the production of over 0.86 g/L AMV in 48 h. Expression of davBADT resulted in the production of over 0.82 g/L glutaric acid under the same conditions. These production titers were achieved with yields of 69.5 and 68.4 mmol/mol of AMV and glutarate, respectively. Future improvements to the ability to synthesize both products will likely come from the ability to eliminate cadaverine by-product formation through the deletion of cadA and ldcC, genes involved in E. coli's native lysine degradation pathway. Nevertheless, through metabolic and pathway engineering, it is now possible produce the polyamide monomers of δ-aminovaleric acid and glutaric acid from renewable resources.

Due to depletion of oil resources, increasing fuel prices and environmental issues associated with burning of fossil fuels, extensive research has been performed in biofuel production and dramatic progress has been made. But still problems exist in economically production of biofuels. One major problem is recovery of biofuels from fermentation broth with the relatively low product titer achieved. A lot of in situ product recovery techniques including liquid-liquid extraction, membrane extraction, pervaporation, gas stripping and adsorption have been developed and adsorption is shown to be the most promising one compared to other methods. Yet adsorption is not perfect due to defect in adsorbents and operation method used. So laurate adsorption using polymer resins was first investigated by doing adsorption isotherm, kinetic, breakthrough curve experiment and column adsorption of laurate from culture. The results indicate that polymer resins have good capacity for laurate with the highest capacity of 430 g/kg achieved by IRA-402 and can successfully recover laurate from culture without causing problem to Synechocystis sp.. Another research of this paper focused on a novel adsorbent: magnetic particles by doing adsorption equilibrium, kinetic and toxicity experiment. Preliminary results showed excellent performance on both adsorption capacity and kinetics. But further experiment revealed that magnetic particles were toxicity and inhibited growth of all kinds of cell tested severely, toxicity probably comes from Co (III) in magnetic particles. This problem might be solved by either using biocompatible coatings or immobilization of cells, which needs more investigation.