This work concerns the functionalisation of a variety of carbon materials for the selective adsorption of carbon dioxide. A key challenge in post-combustion capture from gas fired power plants is related to the low CO2 concentration in the flue gas (4- 8%). Therefore highly selective adsorbents have the potential to improve the efficiency of the separation of carbon dioxide from gas mixtures. The study was performed in conjunction with the EPSRC funded project ‘Adsorption Materials and Processes for Carbon Capture from Gas-Fired Power Plants – AMPGas’. The carbon materials investigated included multi-walled carbon nanotubes, a microporous activated carbon, two types of mesoporous activated carbon and multi-walled carbon nanotube/polyvinyl alcohol composite aerogels. The uptake of carbon dioxide by these materials was enhanced through the addition of basic amine groups to the materials. The adsorption properties of the samples were tested by the zero-length column technique, thermal gravimetric analysis and breakthrough experiments. The materials were generally tested at conditions representative of those found in the flue gas of a fossil fuel power plant: 0.1 bar partial pressure of CO2. Two approaches were adopted for the chemical functionalization of the solid carbon supports. First, amine groups were covalently grafted directly to the surface and secondly amine molecules were physically adsorbed within the porous structure of the material by wet impregnation. It was seen that wet impregnation enabled the incorporation of a greater number of amine groups and the CO2 capacity of the materials was investigated with respect to the carbon support structure, the type of amine and the amount of amine loading. Larger pore volume mesoporous carbon materials were seen to provide a more efficient support for the amine to interact with the CO2. A greater than 12-fold increase in the CO2 capacity was observed when the amine impregnated carbon material was compared to the raw starting material. The extended zero-length column was introduced and fully characterized as a novel breakthrough experiment. It requires a small sample mass (~50 mg) and it allows binary selectivities to be calculated. It was shown, through multiple experiments and simulations that the breakthrough experiments were conducted under close to isothermal conditions which greatly simplifies the analysis of the breakthrough curves. In addition, a new zero-length column model was proposed to account for the reaction between the amine and the CO2 in the adsorbed phase and fitted to experimental data. An interesting double curvature was observed in the concentration profile during the desorption step which was attributed to the kinetics of the amine-CO2 reaction. A brief investigation was carried out into the binary separation of biogas (45% CO2: 55% CH4) by zeolite 13X, activated carbon and an amine impregnated activated carbon. Finally, initial investigations into the properties of low density carbon nanotube aerogels which have a large accessible pore volume, were carried out. Their potential as highly efficient supports for amine impregnation was investigated. It was found that amine functionalized carbons strongly interact with carbon dioxide and have the potential to be integrated as an adsorbent in a rapid temperature swing process that separates carbon dioxide from dilute gas streams.

The Morita-Baylis-Hillman (MBH) reaction is a carbon-carbon (C-C) bond forming reaction between an activated alkene and an aldehyde. It is a synthetically useful reaction due to the high atom economy and retention of multiple functional groups. Unfortunately, harsh reaction conditions are required during the MBH reaction and unpredictable product stereospecificity have hampered the widespread application of this reaction. Catalysis of the MBH reaction by enzymes has the potential to allow the reaction to occur at ambient conditions, while offering scope for improving the stereospecificity. This thesis focussed on the enzyme design of a MBH enzyme using thermostable fructose-1,6- bisphosphate (FBP) aldolases as scaffolds. These enzymes were chosen because there are common features between the aldol and MBH reactions, both making use of an enol intermediate to attack the aldehyde. In addition, aldolases typically accept a wide variety of substrates. Thermostable aldolases were selected for increased temperature tolerance creating a more desirable catalyst for industrial purposes. Thermoproteus tenax FBP aldolase (TtFBPA; WT and W144L, W144Y, K177A variants) and Staphylococcus carnosus FBP aldolase (ScFruA) were expressed and purified from E. coli. While the retro-aldol reaction catalysed by these enzymes could be easily monitored, the reverse reaction (aldol synthesis) is more difficult to quantify. Multiple methodologies for high throughput spectrophotometric detection of aldol activity were developed as a method of monitoring constructs made during directed evolution of the FBP aldolases. However, none of these proved successful in robustly determining aldol activity. The dihydroxyacetone phosphate (DHAP) mimic 1-hydroxy-3-buten-2-one phosphate (HBOP) was used to assay for MBH catalysis. While crystallographic studies with TtFBPA suggest that HBOP is bound to W144L TtFBPA in a manner compatible with the MBH reaction. NMR studies could not detect any corresponding activity. This suggests further protein engineering will be required to evolve this FBP aldolase to an MBH catalyst. In addition, our crystallographic and NMR studies with TtFBPA reveals this enzyme is capable of catalysing the formation of both FBP and tagatose-1,6-bisphosphate (TBP).Additionally, we determined the first structure of ScFruA. Interestingly, NMR experiments suggested ScFruA lacks significant control of the stereospecificity of the aldol condensation reaction and appears to catalyse the formation of FBP, TBP, xyluose-1,6- bisphosphate and psicose-1,6-bisphosphate. We conclude that while FPB aldolases could indeed provide useful scaffolds for the development of an MBH catalyst, the enzymes lack any inherent activity, necessitating the need for future creation of variants. The success of this approach will depend on the ability to screen mutant libraries for MBH product formation.

Formation of carbon–fluorine and carbon–fluoroalkyl bonds via transition metal complexes represents an efficient synthetic route towards a wide array of valuable fluorinated organic compounds and fluorinated metallacycles offer a potentially green and atom economical pathway towards these functionalized fluorocarbons. This thesis is focused on cycloaddition reactions of Ni=CF2 complexes with fluoroalkenes (FAs) and acetylenes. Cycloaddition reactions of the FAs vinylidene fluoride (CF2=CH2) and perfluoro(methyl vinyl ether) [CF2=CF(OCF3)] with the electron-rich Ni(0) fluorocarbene, Ni=CF2[P(OMe)3](dppe) affords stable metallacyclobutane complexes, likely through a 1,4-diradical mechanism previously investigated for analogous reactions using computational chemistry. With CF2=CHF (TrFE), however, the observed products are the C3 alkene E-CHF=CF(CF3) and the metallacyclopentane complex, Ni(C4H2F6)(dppe), derived from oxidative coupling of two additional equivalents of TrFE. It is proposed that the instability of the initially formed metallacyclobutane gives rise to a 2,1-F shift, yielding the C3 alkene complex. Reaction of the latter with excess TrFE then liberates the C3 alkene, forming the TrFE alkene complex followed by the observed metallacyclopentane product. In the reaction of 1a with chlorotrifluoroethylene (CF2=CFCl) a single regioisomer of the metallacyclobutane is observed, but reacts further in THF solvent via α-Cl migration to Ni, affording the tetrafluoroallyl complex, NiCl(CF2CF=CFH), in which one F has been replaced by a hydrogen. Finally, reaction of 1a with hexafluoropropene [CF2=CF(CF3), HFP] takes an unprecedented turn, affording the Ni trifluoromethyl perfluoroalkenyl complex from formal transfer of one F from HFP to the Ni=CF2 moiety. The capability of 1a to perform cycloaddition with a broader substrate scope was investigating by reacting it with terminal aryl-acetylenes of varying electronic parameters. Reaction of 1a with 1.5 equivalents of 4-R-phenylacetylene afforded the expected difluorometallacyclobutenes (R = H, Cl, tBu). Further observation revealed a second acetylene insertion to yield a nickelacyclohexadiene in the first example of a 4- to 6-membered ring expansion of perfluorometallacycles. The six-membered metallacycle then undergoes reductive elimination to furnish a difluorocyclopentadiene. The electronic parameters of the aryl-acetylene substrate play a dramatic role in the selectivity of product formation. The more electron-donating substrates 4-tert-butylphenylacetylene and 1-hexyne stabilize the metallacyclobutene, while the electron-withdrawing 4-chlorophenylacetylene affords a more reactive metallacyclobutene making it more prone to the second acetylene insertion. Phenylacetylene represented a middle-ground between the two systems and proved effective for further characterization studies. The electronic effect of the surrounding ancillary ligand system was also studied by substituting dppe in 1a for P(OMe)3 and dipe to give analogous Ni(0) difluorocarbene complexes 1b and 1c (dipe = 1,2-bis(diisobutylphosphino)ethane). The -acidic phosphite ligands in 1b gave exclusively nickelacyclohexadiene and difluorinated cyclopentadiene due to a reactive metallacyclobutene, whereas the more electron rich 1c formed the metallacyclobutene product almost exclusively. The results presented here will allow for future investigations of fluorinated metallacycle reactivity, increasing our ability to prepare value-added fluorocarbon products for pharma, agrochemicals, and polymer applications.

This thesis attempts to model the returns on Regional Greenhouse Gas Initiative (RGGI) allowances using logged monthly returns from 2011-2018. This asset, shown to be a useful diversifier in portfolios, has been identified by previous literature to behave similarly to commodities. I used auto-regressive, GARCH, and Markov regime switching models to analyze the returns because the returns displayed changing volatility. These models were comparatively analyzed both in and out-of-sample. In this limited data analysis, the Markov model outperformed both alternatives in-sample. The Markov and Garch models displayed similar predictive power out-of-sample, however neither were particularly effective.

Carbon offsetting means to offset those greenhouse gases that are caused by our actions. The purpose of this paper is to examine how companies are working with carbon offsetting. The focus of the research is how travel agencies and companies that provides carbon offsetting. The writers also highlight the problems carbon offsetting is facing. The study was performed with qualitative methods through interviews with three companies working with carbon offsetting. The research shows that carbon offsetting within air travel can vary in price between different companies and they find it more lucrative to work with business customers. The writers have come to the conclusion that it is people's attitudes as well as lack of promotion and information that is the problem that exists for carbon offsetting. The writers have also found out that it is the uncertainty about carbon offsetting that affects the individual's attitude towards the subject. This, as well as the awareness that exists about the subject and the economy which every individual is prepared to spend on the environment.

Agricultural census data have been identified to possess the potential to provide constraints on carbon uptake by croplands at the regional scale. In this study, we build on previous efforts and further assess this potential quantitatively by comparing 1) fractional cropland coverage in southwestern Ontario, Canada derived from agricultural statistics against three different remotely sensed land cover maps; and 2) carbon uptakes determined from agricultural data with simulations generated by a satellite data-driven biospheric model. In addition, we assimilated the census data-derived carbon uptakes with modeled estimates in a Bayesian inverse approach to determine if and by how much constrain the crop data can provide, as exhibited by uncertainty reductions. Uncertainties in census data-derived gross primary production (GPP) estimates are carefully quantified using a Monte Carlo simulation. In general, results from the fractional cropland coverage comparison indicate significant value of the agricultural census data by revealing biases in the spatial distribution of croplands, as found in all three of the satellite land cover products. However, we find that the carbon uptake values derived from crop harvested records are still subject to significant uncertainties that have been underestimated or neglected altogether in past studies. The Monte Carlo simulation suggests that the largest source of uncertainty can be traced to errors in the growth efficiency, followed by harvest production records, and then the harvest index. As result, attention must be paid to such errors when using the agricultural census data for carbon accounting purposes or to provide constraints to simulations of crop carbon uptake.

Thesis (M.S. in Mechanical Engineering)--Naval Postgraduate School, December 2009. / Thesis Advisor: Kwon, Young W. Second Reader: Didoszak, Jarema M. "December 2009." Description based on title screen as viewed on January 26, 2010. Author(s) subject terms: Composite, Carbon, Low Velocity Impact, Fluid Structure Interaction. Includes bibliographical references (p. 49-50). Also available in print.

Thesis (Ph. D.)--University OF MICHIGAN.

Recalcitrant soil carbon is a poorly understood component of total soil organic carbon (SOC). Although the turnover rate of the recalcitrant fraction is slow, warming temperatures are expected to speed the decomposition of recalcitrant SOC resulting in an increase of atmospheric CO₂ in the future. Several studies show that the oldest SOC is associated with the smallest mineral particles (clays), making direct spectroscopic analysis of old carbon difficult. To overcome the difficulty of analyzing natural samples, we created synthetic soils to examine the association between clay surfaces and specific biomolecules based on the hypothesis that clays with higher surface charge will more strongly bond organic molecules, and also that certain molecules will be better stabilized by clay. We used kaolinite, montmorillonite, or quartz (sand) as a synthetic soil inside 12 mL septum-capped vials, added either dissolved glucose or vanillic acid to each mineral, inoculated with soil microbes, and then purged the vials with a CO₂-free atmosphere. We incubated them and measured the concentration and [delta]¹³C of CO₂ that accumulated in the vials. Respiration rates were significantly higher in experiments containing vanillic acid than in those containing glucose. Respiration rates were lowest in experiments containing montmorillonite. We repeated the experiment using dilute H₂O₂ as an oxidant, and adding vanillic acid, glucose, or glycine. Vials with montmorillonite showed lower rates of CO₂ accumulation than kaolinite, and both glycine- and glucose-containing experiments had less CO₂ than vanillic acid-experiments. We conclude that the montmorillonite protected the organic matter from oxidation better than sand or kaolinite. Both clays protected organic matter better than sand. In all experiments with clay, the respired CO₂ had lower [delta]¹³C values than bulk substrate. This carbon isotope fractionation is likely due to preferential desorption, followed by oxidation, of 12C- as opposed to 13C- bearing organic molecules. The mineral-organic interaction is a strong bond that explains the old age of labile organic compounds in soils. These results indicate that the clay fraction of soils must be considered for accurate prediction of future land-atmosphere carbon fluxes. / text

Metal-catalyzed, hydrogenative methods for carbon-carbon bond formation are attractive alternatives to traditional carbonyl addition reactions. Through in situ generation of aldehyde and organometallic species, these redox-triggered reactions circumvent the need for preactivation of reactive partners, thereby providing a more atom economic, efficient approach to carbonyl addition products. Efforts have been focused on the development of ruthenium-catalyzed coupling reactions of primary and secondary alcohols to basic feedstock chemicals and easily accessible and stable unsaturated compounds. To perform highly stereoselective reactions, investigation into the factors that control stereoselectivity in ruthenium catalyzed transfer hydrogenative couplings was undertaken. As a critical tool for the construction of organic molecules, modernizing methods for carbonyl addition can contribute to the evolution of synthetic organic methodology. / text