The objective of this study was to investigate the transport properties and the microstructure of CMS membranes derived from a carbon-rich intrinsically microporous polyimide precursor. CMS membranes were prepared by a heat treatment of the polyimide precursor using a well-defined heating protocol in a horizontal tube furnace up to 1000 °C. A nitrogen purge was kept inside the furnace to remove all the evolved by-products as the precursor started to decompose and carbonize. The microstructures of the carbon molecular sieve membranes (CMSMs) were examined using wide-angle x-ray diffraction, Raman spectra, N2 adsorption and CO2 adsorption. The average interlayer spacing (d002) between the graphite plates was estimated using the data obtained by the WXRD. The average d002 decreased as a result of increasing the pyrolysis temperature; average d002 distances for CMS prepared at 700 and 1000 °C were estimated to be 0.40 to 0.38 nm, respectively. Raman spectra confirmed the progressive structural ordering as heat-treatment temperature increased. A substantial decrease in the intensity of the D band was observed as a function of pyrolysis temperature, indicating a decrease in the disordered structure. Graphitic structure and turbostratic carbon coexist in the as-prepared carbon membranes, of which the microcrystal size La and the stacking height Lc were increasing as a function of pyrolysis temperature. N2 adsorption showed a remarkable increase in the BET surface area as a function of pyrolysis temperature. BET surface areas for the pristine and CMSs prepared at 700 to 900 °C were in the range of 650 to 680 m2/g with a remarkable shift in the pore size distribution toward the ultra- microporous region. CO2 adsorption was used to estimate the surface area for pores with sizes of less than 1 nm. Surface areas were observed to increase from 350 m2/g at 500 °C to 857 m2/g at 800 °C, and then started dropping slightly from 857 to 650 m2/g at 800 to 1000 °C, respectively. This is believed to be caused by pore shrinkage effect being severe after 800 °C, which caused some pores to be hard to spot by the CO2 adsorption technique. The transport properties of the pristine and CMS membranes were tested using pure gases He, H2, N2, CH4, CO2, and O2. From the pristine to SBFDA-DMN-700°C, the selectivity increased significantly, with a massive loss in the permeability except for He and H2. From SBFDA-DMN- 700 °C to 900 °C, a substantial increase in selectivity with a moderate decline in permeability was observed. Beyond 900 °C, the permeability again decreased moderately, but a tremendous increase in the selectivity for N2/CH4, CO2/CH4, and H2/CH4 was observed.

A series of hybrid inorganic-organic composites were fabricated from a functionalized fluorinated polyimide and tetraethoxysilane (TEOS), tetramethoxysilane, methyltrimethoxysilane (MTMOS), and phenyltrimethoxy-silane (PTMOS) employing the sol-gel process. Polyimides were synthesized from 4,4'-hexafluoroisopropylidene dianiline (6FpDA) and 4,4'-hexafluoroisopropyl-idenediphthalic anhydride (6FDA) utilizing a solution imidization technique. The hybrid materials were synthesized by in-situ sol-gel processing of the aforementioned alkoxides and a fully imidized polyimide that was functionalized with 3-aminopropyltriethoxysilane. The gas permeability, diffusivity, and selectivity were evaluated for He, O2, N2, CH4, and CO2, while the physical properties of these hybrid materials were evaluated using several analytical techniques. The results from this study revealed that gas transport and physical properties were dependent on the type of alkoxide employed in the hybrid inorganic-organic material. Gas permeability was observed to increase with increasing gas penetrant size for MTMOS and PTMOS based hybrids, while TEOS based hybrids decreased gas permeability at all compositions. In general, MTMOS based hybrid materials had the largest increases in permeability, which was attributed to an increase in free volume. The TEOS based hybrid materials had the largest decreases in permeability, while PTMOS based hybrid materials had performance in between these alkoxides. Decreased permeability for the TEOS based hybrids was attributed to the formation of lower permeable material at a particle interface and coupled with increasing tortuosity. Results of PALS studies suggested that there was an increase in free volume and pore size for MTMOS based hybrids, while both TEOS and PTMOS based hybrids had decreases in both average pore size and free volume. The temperature dependence of permeation, diffusivity, and sorption were evaluated from 35oC to 125oC. These results suggested that there was a decrease in solubility for all hybrids employed in this study. Furthermore, increases in permeability for the MTMOS based hybrids were created by increased penetrant diffusion. Physical property studies revealed that the type of inorganic material incorporated into the hybrid influences the degree of swelling, bulk density, Tg, and thermal stability. Hybrid materials were also created employing 3,5-diaminobenzoic acid (DABA) in the synthesis of modified 6FDA-6FpDA polyimides in order to evaluate how improvements in inorganic and polymer compatibility influenced the gas transport properties. From this separate study, it was found that increases in both permeability and selectivity were possible. The mechanism attributed to this simultaneous increase in permeability and selectivity was the formation of a more permeable and selective interphase at the interface of an inorganic particle and the polymer matrix. In addition to these studies, 6FDA-6FpDA polyimide molecular weights were changed from 19.3K to 35.3K to probe its role on gas transport and physical properties. These studies revealed that permeability, diffusivity, and solubility increased with increasing molecular weight, while density decreased with increasing molecular weight. These results suggest that there is an increase in free volume with increasing 6FDA-6FpDA polyimide molecular weight. / Ph. D.

Carbon molecular sieve (CMS) membranes represent the most attractive pure component materials to compete against polymer membranes for high performance gas separations. CMS membranes are formed from the thermal decomposition of polymer precursors and can therefore be formed into continuous defect free membranes with excellent gas separation performance. Over the last 20 years, CMS membranes have been produced in a variety of geometries and have a wide range of separation performance applicable to several important gas separations. Though research into CMS membrane formation is quite extensive, the relationship between synthesis factors and separation performance is still not well understood. The goal of this study was to elucidate the effect of two different synthesis factors on the separation performance of CMS membranes to allow more control over separation performance. The foci of this study were to clarify (1) the effect of pyrolysis atmosphere and (2) the effect of polymer precursor composition. Dense flat CMS membranes were synthesized from 6FDA:BPDA-DAM precursor at 550 oC using several pyrolysis atmospheres including vacuum pyrolysis (<0.05 torr), helium and argon flowing at atmospheric pressure, and helium and argon flowing at reduced pressures. The separation performance of CMS membranes produced under different pyrolysis atmospheres suggests that the amount of oxygen available during pyrolysis has a significant affect on the microstructure of membrane. CMS membranes were produced from 6FDA:BPDA(1:1)-DAM and 6FDA:BPDA(1:1)-DAM under identical pyrolysis conditions to determine the utility of polymer precursor composition as an engineering tool to fine-tune the performance of CMS membranes. In a second study utilizing 6FDA-6FpDA and 6FDA-6FmDA precursors, the separation performance of CMS membranes was shown to be dependent on the intrinsic precursor free volume. These studies have shown that two factors to be considered when choosing a polymer precursor are the intrinsic free volume of the polymer and the composition of the by-products evolved during pyrolysis.

Natural gas feeds often contain contaminants such as CO₂, H₂S, H₂O, and small hydrocarbons. Carbon dioxide is a major contaminant reducing the heating value of the gas and causing pipeline corrosion, so CO₂ level should be lowered to below 2% to meet the United States pipeline specifications. Membrane separation technology can be advantageous over cryogenic distillation and amine adsorption in terms of cost and efficiency. The key hurdle to overcome in polymeric membrane separation technology is improvement in selectivity, productivity, and durability without introducing significant additional cost. The ultimate goal of this study is to analyze effects due to polymerization conditions and imidization methods on properties of 1,3-propanediol monoesterified crosslinkable polyimide (PDMC). Hillock, Omole, Ward, and Ma did work on PDMC synthesis; however, variability of polymer properties remains a challenge that must be overcome for industrial implementation of PDMC material. First, reaction temperature and reaction time of polymerization prior to imidization were considered as key conditions to affect molecular weight, crosslinkability and transport properties of polymer. Batches with controlled reaction temperature and time were prepared, and properties of each dense film were measured and optimized in terms of permeability, selectivity, and plasticization suppression. Second, imidization methods for PDMC were also studied. There are mainly two kinds of Imidization: chemical Imidization and thermal Imidization. Surprisingly, thermally imidized PDMC showed 70% higher permeability than chemically imidized samples with minimal acrifice in selectivity. At high reaction temperature during the thermal imidization, transamidation can occur. It is believed that the transamidation led to more randomized sequence distribution in the thermally imidized samples. We thus hypothesize that the higher permeability of the thermally imidized PDMC results from greater uniformity of the sequence distribution, as compared to the chemically imidized sample that does not experience high temperature during imidization. XRD, DSC, DMA, and permeation instruments checked and supported this hypothesis. FTIR, TGA, and NMR ruled out the possibility of an alternate hypothesis related to side reaction. Finally, effects of aggressive feed conditions on both chemically imidized PDMC and thermally imidized PDMC dense film were examined. The aggressive feed conditions include high CO₂ partial pressure, operating temperatures, and exposure to high feed pressure. Testing aggressive feed conditions for dense film should be pursued before pursuing hollow fiber applications, to decouple effects on the basic material from those on the more complex asymmetric morphology. This study enables understanding of the disparity between various previous researchers’ selectivity and permeability values. The work shows clearly that polymerization conditions and imidization methods must be specified and controlled to achieve consistently desirable polymer properties. In addition, for batch scale-up and development to a hollow fiber, this fundamental study should enable production of high molecular weight PDMC with good fiber spinnability and defect-free structure.

Abstract NEW SYNTHETIC STRATEGIES FOR IMPROVED GAS SEPARATION BY NANOPOROUS ORGANIC POLYMERS Suha S. Altarawneh, Ph.D. The emission of carbon dioxide (CO2) from fossil fuel combustion is a major cause of climate change. Therefore, the efficient separation of CO2 from mixtures of gases such as flue gas and impure sources of CH4 (e.g. natural gas and landfill gas) is an essential step in meeting the ever increasing demands on natural gas and creating a cleaner environment. Carbon capture and storage technology (CCS) is one of the methods employed for gas separation using chemisorption and/or physisorption processes. Several materials such as porous polymers and amine solutions have been used as gas adsorbents. However, the amount of energy required for the adsorbent regeneration is one of the main concerns that needs to be addressed. In this regard, porous organic polymers (POPs) with defined porosity and preferential binding affinity for CO2 over N2 and CH4 are some of the most attractive materials that could fulfill the above requirement and are also applicable for use in gas storage and separation. Suitable POPs that can be used for gas storage applications need to have high porosity and mechanical stability under high pressure conditions (~100 bar). Alternatively, the most effective POPs in gas separation are those that have preferential binding affinity for CO2 over other gases present at low pressure settings. In all cases, the chemical nature of POPs and their textural properties are key parameters, however, the modest surface area of most POPs limits their efficiency. With the above considerations in mind, the aim of our research is to develop benzimidazole–linked polymers (BILPs) that have variable porosity levels and chemical functionality to enhance gas separation (CO2/CH4, CO2/N2). We have established new synthetic routes that utilize polycondensation reactions between aryl-aldehydes and aryl-o-diamine building units to construct new BILPs with improved gas separation properties. Our strategy targeted structural and textural modifications of BILPs. We used longer linkers (building units) to improve porosity; however, the flexible linkers offered only low porosity due to network interpenetration. To overcome this challenge, a more controlled network growth rate was assessed by adjusting imine-bond formation rates through different acid loading. The acid, HCl, was used to catalyze imine-bond formation. The new resulting acid-catalyzed BILPs have shown an improved porosity up to 92% compared to the non-catalyzed BILPs. We also used the “rational ligand design” approach to introduce new functionalities into BILPs (-OR) to alter the hydrophobic nature of their pores. In this regard, we have illustrated the applicability of this strategy to BILPs containing flexible aryl-o-diamine linkers. The bulky alkoxy groups were incorporated into the aryl-aldehyde building unit prior to polymerization. The resulting polymers have proven that the presence of the bulky pendant alkoxy-chains plays a significant role during the polymerization process which allows for increased control over network formation, and in turn, porosity. Sorption measurements, selectivity, and heats of adsorption data have confirmed the positive impact of the alkoxy-groups and shown that varying the pendant groups is a promising method for designing highly porous BILPs. In addition to pore functionalization with alkoxy-chains, we used pi-conjugated and N-rich building units to prepare new BILPs that have semiconducting properties in addition to their porous nature. This class of BILPs has shown that the extended-conjugated system improved BILPs electronic properties. The other studies performed in this research, involved the use of DFT theory to investigate CO2/BILPs interaction sites and binding affinities. The computational outcomes of DFT have shown that (C-H) bond of the aryl system is a possible site for CO2 interaction beside the free-N side and hydrogen bonding. All new polymers were characterized by spectral and analytical characterization methods and their sorption data were collected to evaluate their capability as candidates for gas separation applications.

Porous organic polymers (POPs) received great attention in recent years because of their novel properties such as permanent porosity, adjustable chemical nature, and remarkable thermal and chemical stability. These attractive features make POPs very promising candidates for use in gas separation and storage applications. In particular, CO2 capture and separation from gas mixtures by POPs have been intensively investigated in recent years because of the greenhouse nature of CO2, which is considered a leading cause for global warming. CO2 chemical absorption by amine solutions from the flue gas of coal-fired power plants suffers from several challenges such as high-energy consumption in desorption, chemical instability, volatility, and corrosive nature, limiting the widespread use of this technology. To mitigate these limitations, new adsorbents with improved CO2 capturing properties need to be designed, synthesized, and tested. Alternatively, the use of cleaner fuels such as methane can reduce CO2 release or completely eliminates it in the case of hydrogen. However, the on-board storage of methane and hydrogen for automotive applications remains a great challenge. With these considerations in mind, our research goals in this dissertation focus on the systematic design and synthesis of N-rich POPs and their use in small gas (H2 and CH4) storage as well as selective CO2 capture from gas mixtures. In particular, we have studied the effect of integrating pyrene and triazine building units into benzimidazole-linked polymers (BILPs) and covalent organic frameworks (COFs) on gas storage and separation. We have found that pyrene-based BILPs exhibit remarkable selective CO2 capturing capacities under industrial settings (VAS, PSA). However the methane and hydrogen storage capacities of BILPs were found to be only modest especially at high pressure due to their moderate surface area and pore volume. We addressed these limitations by the synthesis of a highly porous imine-linked COF (ILCOF-1), which has very high surface area and improved hydrogen and methane uptakes when compared to BILPs. We have demonstrated that the use of pyrene in BILPs and COFs can direct frameworks growth through - stacking and improve porosity and pore volume whereas the use of triazine is instrumental in improving the binding affinity of the frameworks towards CO2.

Polymers were synthesised containing the methanoanthracene (MA), methanopentacene (MP) and benzomethanoanthracene (BzMA) units to investigate their properties as gas separation membranes. For each monomer type, polymers were successfully synthesised using Tröger’s base (TB) chemistry and cast as free standing films from low-boiling point solvents. Gas permeability tests revealed high selectivities for most of the technologically significant gas pairs. Most interestingly, MA/dimethylethanoanthracene co-polymer, MP-TB and BzMT-TB polymers all show a high degree of selectivity in the separation of a number of technologically significant gas pairs when compared to other state-of-the-art polymers. In particular MP-TB has very high selectivity for the N2/O2 gas pair. Synthetic routes to MP-TB and BzMA-TB involve fewer steps and are significantly cheaper to implement compared to other state of the art TB polymers and high performance PIMs that provide data above the Robeson upper bounds due to their high permeability and selectivity. Co-polymers of MA were synthesised in 1:1, 4:1 and 9:1 ratios. Gas permeability data demonstrated that properties correlate with the monomer composition. Results indicate that inclusion of methano-bridged units into the polymers increased the rigidity of polymer chains, leading to smaller pore widths and improved selectivities compared to polymers such made from more flexible structural units. The first chapter of this thesis introduces the concepts of microporosity, permeability and membrane separation, and describes a number of polymers that have demonstrated properties of interest for separating gas mixtures. Chapter two describes the synthesis and gas permeability data of MA-TB polymer and a series of copolymers incorporating MA. Chapter 3 describes the synthesis of polymers containing the MP structural unit and describes the performance of MP-TB as a membrane for gas separation. Chapter 4 describes a number of polymers synthesised using the BzMA structural unit and chapter 5 reports the synthesis of a number of larger units derived from BzMA including benzomethanotetracene, benzomethanopentacene and dibenzomethanopentacene. Permeability data for TB polymers synthesised from BzMA-type monomers is reported in these chapters.

Le comportement plastifiant de polymères purs a été bien étudié dans la littérature. Toutefois, il n'y a eu que peu d'études concernant les membranes à matrices mixtes (MMM). Dans le chapitre 2 de cette thèse, le comportement plastifiant de MMM préparés à partir de nanoparticules mésoporeuses Fe(BTC) et du polymère Matrimid® est étudié avec un gaz pur ou en mélange. Les réseaux métaux-organiques (MOF) sous forme particulaires ont présenté une relativement bonne compatibilité avec le polymère. L'incorporation de Fe(BTC) dans du Matrimid® a permis d'augmenter la perméabilité et la sélectivité des membranes. Pour de faibles pressions de 5 bars, les MMM ont une perméabilité au CO2 de 60% plus grande ainsi qu'une sélectivité de 29% plus grande à comparer à la sélectivité idéale de membranes Matrimid®. Il a été observé que la présence de particules Fe(BTC) retardait l'effet plastifiant vers de plus grandes pressions. De plus, cette pression augmente avec le taux de MOF au sein du matériau. Ce retard est attribué à la mobilité réduite des chaînes polymères dans l'entourage des particules Fe(BTC). Egalement, pour des concentrations en MOF plus élevées, les membranes présentent une sélectivité plus ou moins constante sur toute la gamme de pression étudiée. Le chapitre 3 présente ensuite la préparation et le caractère plastifiant des MMMs basées sur trois types de MOFs (MIL-53(Al) (MOF « repirant »), ZIF-8 (MOF « flexible ») and Cu3(BTC)2 (MOF « rigide »)) dispersés dans le Matrimid®. Les performances en gaz pur ou en mélange ont été étudiées en fonction de la quantité de MOF introduite. Parmi les trois systèmes MOF-MMM, les membranes avec le Cu3(BTC)2 ont présenté la plus haute sélectivité alors que les membranes avec du ZIF-8 ont montré une plus grande perméabilité. Ces améliorations sont essentiellement le fait de la structure cristalline du MOF et de son interaction avec les molécules de CO2. Le chapitre 4 décrit la préparation de membranes à base de mélange Matrimid® polyimide (PI)/polysulfone (PSF) contenant des particules de ZIF-8 pour la séparation gazeuse à haute pression. Un mélange optimisé avec un rapport PI/PSF de 3:1 a été utilisé pour une étude sur la stabilité et la performance de ces MMMs incorporant différentes concentration de ZIF-8. PI et PSF étant miscibles, une bonne compatibilité avec les particules de ZIF-8 est observée. Les MMMs PI/PSF-ZIF-8 ont démontré une amélioration significative de la perméabilité en CO2 lors de l'augmentation de la concentration en ZIF-8, ce qui a été attribué à une augmentation modérée de la capacité de sorption et à une diffusion plus rapide au travers des particules de ZIF-8. Lors des mesures en gaz purs, les membranes PI/PSF (3:1) ont présenté une plastification vers 18 bars alors que l'introduction de ZIF-8 repousse cette valeur à 25 bars. En mélange de gaz, les MMMs PI/PSF-ZIF-8 ont abouti à une suppression de la plastification comme l'a confirmé une mesure constante de la perméabilité et de la sélectivité du CH4, et cet effet est plus accentué avec l'augmentation de la concentration en ZIF-8. Les résultats en séparation des gaz avec les MMMs PI/PSF-ZIF-8 montrent une performance supérieure à celle du Matrimid® ce qui laisse augurer un élargissement du spectre d'application de ces membranes, particulièrement pour la séparation du CO2 à haute pression. Dans le chapitre 5, une nouvelle voie de préparation des MMMs via la fusion contrôlée de particules a été introduite. La modification du Matrimid® par du 1-(3-aminopropyl)-imidazole a permis d'améliorer considérablement la compatibilité avec les particules de ZIF-8. Il a ainsi été possible de préparer des MMMs contenant 30% de MOF sans perte de sélectivité. En augmentant la concentration en ZIF-8, les MMMs ont de meilleures performances dans la séparation de mélange CO2/CH4 à comparer au polymère initial. La perméabilité a augmenté de plus de 200% avec une augmentation de 65% de sélectivité pour le mélange CO2/CH4. / The plasticization behavior of pure polymers is well studied in literature. However, there are only few studies on the plasticization behavior of mixed matrix membranes. In Chapter 2 of this thesis, pure and mixed gas plasticization behavior of MMMs prepared from mesoporous Fe(BTC) nanoparticles and the polymer Matrimid® is investigated. All experiments were carried with solution casted dense membranes. Mesoporous Fe(BTC) MOF particles showed reasonably good compatibility with the polymer. Incorporation of Fe(BTC) in Matrimid® resulted in membranes with increased permeability and selectivity. At low pressures of 5 bar the MMMs showed an increase of 60 % in CO2 permeability and a corresponding increase of 29 % in ideal selectivity over pure Matrimid® membranes. It was observed that the presence of Fe(BTC) particles increases the plasticization pressure of Matrimid® based MMMs. Furthermore, this pressure increases more with increasing MOF loading. This delay in plasticization is attributed to the reduced mobility of the polymer chains in the vicinity of the Fe(BTC) particles. Also, at higher Fe(BTC) loadings, the membranes showed more or less constant selectivity over the whole pressure range investigated. Chapter 3 subsequently presented the preparation and plasticization behavior of MMMs based on three distinctively different MOFs (MIL-53(Al) (breathing MOF), ZIF-8 (flexible MOF) and Cu3(BTC)2 (rigid MOF)) dispersed in Matrimid®. The ideal and mixed gas performance of the prepared MMMs was determined and the effect of MOF structure on the plasticization behavior of MMMs was investigated. Among the three MOF-MMMs, membranes based on Cu3(BTC)2 showed highest selectivity while ZIF-8 based membranes showed highest permeability. The respective increase in performance of the MMMs is very much dependent on the MOF crystal structure and its interactions with CO2 molecules. Chapter 4 described the preparation of Matrimid® polyimide (PI)/polysulfone (PSF)-blend membranes containing ZIF-8 particles for high pressure gas separation. An optimized PI/PSF blend ratio (3:1) was used and performance and stability of PI/PSF mixed matrix membranes filled with different concentrations of ZIF-8 were investigated. PI and PSF were miscible and provided good compatibility with the ZIF-8 particles, even at high loadings. The PI/PSF-ZIF-8 MMMs showed significant enhancement in CO2 permeability with increased ZIF-8 loading, which was attributed to a moderate increase in sorption capacity and faster diffusion through the ZIF-8 particles. In pure gas measurements, pure PI/PSF blend (3:1) membranes showed a plasticization pressure of ~18 bar while the ZIF-8 MMMs showed a higher plasticization pressures of ~25 bar. Mixed gas measurements of PI/PSF-ZIF-8 MMMs showed suppression of plasticization as confirmed by a constant mixed gas CH4 permeability and a nearly constant selectivity with pressure but the effect was stronger at high ZIF-8 loadings. Gas separation results of the prepared PI/PSF-ZIF-8 MMMs show an increased commercial viability of Matrimid® based membranes and broadened their applicability, especially for high-pressure CO2 gas separations. In Chapter 5, a novel route for the preparation of mixed matrix membranes via a particle fusion approach was introduced. Surface modification of the polymer with 1-(3-aminopropyl)-imidazole led to an excellent ZIF-8-Matrimid® interfacial compatibility. It was possible to successfully prepare MMMs with MOF loadings as high as 30 wt.% without any non-selective defects. Upon increasing the ZIF-8 loading, MMMs showed significantly better performance in the separation of CO2/CH4 mixtures as compared to the native polymer. The CO2 permeability increased up to 200 % combined with a 65 % increase in CO2/CH4 selectivity, compared to the native Matrimid®. Chapter 6 finally discussed the conclusions and directions for future research based on the findings presented in this thesis.

Metal-organic frameworks (MOFs) are hybrid organic-inorganic micro- or mesoporous materials that exhibit regular crystalline lattices with rigid pore structures. Chemical functionalization of the organic linkers in the structures of MOFs affords facile control over pore size and physical properties, making MOFs attractive materials for application in gas-separating membranes. A wealth of reports exist discussing the synthesis of MOF structures, however relatively few reports exist discussing MOF membranes. This disparity owes to challenges associated with fabricating films of hybrid materials, including poor substrate-film interactions, moisture sensitivity, and thermal instability. Since even nanometer scale cracks and defects can affect the performance of a membrane for gas separation, these challenges are particularly acute for MOF membranes. The focus of this work is the development of novel methods for MOF film and membrane fabrication with a view to overcoming these challenges. The MOF film production methods discussed herein include in situ synthesis using ligand-modified or metal-modified supports and rapid thermal deposition (RTD).

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Koros, William; Committee Member: Beckham, Haskell; Committee Member: Eckert, Charles; Committee Member: Henderson, Cliff; Committee Member: Meredith, Carson. Part of the SMARTech Electronic Thesis and Dissertation Collection.