The implementation of polymer membranes in gas separation applications has been investigated to a great extent. Nevertheless, only a few types of polymers are used in commercial applications, disclosing the need for new materials with superior membrane performance to make membrane processes a more competitive technology over the conventional ones. Based on this context, this work focuses on the development of new polymeric membranes. Polyaniline (PANI), a multifaceted polymer that can change its structural properties upon various modification procedures, was chosen as membrane material. PANI membranes possess attractive O2/N2 selectivities, wherefore it is an interesting candidate for the use in gas separation applications, such as generation of oxygen-enriched air or inert gas generation. However, membranes made from neat PANI are suffering from brittleness and thus create leak paths through the membrane. Therefore PANI was blended with polybenzimidazole (PBI), a temperature stable polymer with good film-forming properties facilitating the preparation of thin, stable polymer films. Furthermore, several techniques were investigated including acid-doping, thermal treatment, and addition of titanate nanotubes (TiNTs) to enhance the separation properties. The materials that have been prepared are: 1)...

The objectives of this research were to study the gas transport properties of proton exchange membranes (PEM), namely disulfonated poly(arylene ether sulfone) (BPSH-35), post sulfonated diels-alder poly(phenylene) (SDAPP), and poly(perfluoro sulfonic acid) (Nafion). The O2 gas permeabilities were found to be lower in BPSH and SDAPP as compared to poly(perfluoro sulfonic acid) because of difference in Tg (TgBSPH= 250 oC, TgSDAPP= 330 oC versus TgNafion=150 oC). Higher Tg polymers have a more rigid, inflexible polymer segments causing a reduction in gas permeability. In comparison to SDAPP, BPSH has a lower O2 gas permeability because of the bulky side groups in the SDAPP backbone. O2 sorption measurements were carried out both under non-humidified and humidified conditions as a function of relative humidity and temperature at a normal PEM operating pressure of 1 atm. Under non-humidified conditions, BPSH, SDAPP, and Nafion 112 exhibited Henry's Law sorption, consistent with dilute dissolution of O2 into the polymer matrix. The enthalpies of sorption were calculated to determine the interaction of O2 with each membrane. The sorption enthalpies in BPSH and SDAPP increased with increasing pressure indicating the formation of more O2-O2 interactions. The enthalpies in Nafion 112 were relatively constant with increasing pressure. In the presence of moisture, the sorption behavior changed from Henry's Law to Type IV sorption behavior, which is common in hydrophilic polymers. The SDAPP membrane was found to have the highest percent wet O2 mass uptake because of a higher number of sulfonic acid groups interacting with the water/O2 system. Finally the O2 sorption for various porous catalyst powders, consisting of platinum supported on carbon was measured in the non-humidified and humidified state. The catalysts were found to have Knudsen diffusion in the non-humidified state with 20 wt% Pt-C having the largest O2 sorption. In the humidified state, the highest O2 mass uptake was achieved with 40 wt% Pt-C. These results are explained in terms of the trade-off between catalyst dispersion and catalyst size. Furthermore, O2 sorption measurements were utilized for membrane electrode assemblies containing 40 wt% Pt-C and hot pressed at 210 oC for BPSH-35 (25 and 80K) and Nafion 112 membranes. The same sorption behavior occurred in the MEAs as in the neat membrane, but at a lower capacity. This is because the electrode introduces a more tortuous path to the gas molecules permeating across the membrane. / Ph. D.

Metal–organic materials (MOMs), a type of porous crystalline structure composed of organic ligands jointed with metal ions, have captured the interest of scientists as potentially useful in gas sorption applications. Some of the most crucial avenues of investigation are in H2 storage (for use as a clean burning fuel source) and CO2 capture and sequestration (to remove the greenhouse gas from the environment). A major advantage of MOMs for such applications is their high variability in terms of physical dimensions and chemical moieties, based on composition and synthesis conditions, making them potentially customizable for specific application if necessary structural characteristics are known. Computational experimentation is an important avenue for determining such specifications as it allows examination of gas/MOM interaction at the molecular level. In this dissertation a number of MOM structure are computationally studied in order to elucidate gas sorption mechanisms. These systems were probed by classical simulation using grand canonical Monte Carlo with a carefully chosen set of intermolecular interaction parameters. While the focus of this work is specifically H2 and CO2 sorptive behavior, the insights gained from simulation extend beyond these specific applications. Addressed first are a series of MOMs with rht topology, which possesses asymmetric copper paddle-wheels and easily functionalized linkers. Beginning with a prototypical structure and then branching out into more chemically interesting variants revealed surprising gas sorption behavior about the metal paddle-wheels (with a definite preference for one copper over its counterpart). A synthetic strategy for controlling the preferred open-metal sorption site through the inclusion of electron rich functionality in the linker bodies, was also revealed. An additional MOM with similar composition components, exhibiting zyg topology, also showed this metal preference effect on the asymmetric paddle-wheels. A second class of MOMs, composed of square-pillared grids and known as the SIFSIX series (due to the inclusion of SiF62− as pillaring units) was also examined. These structures have been shown excellent results for CO2 sorption making the elucidation of the sorptive mechanisms of great interest. Six different structures were examined, probing the effects of linker length, metal selection, and interpenitration of unbonded scaffolds. The nature of the CO2-MOM sorption interactions were revealed through simulation and provided insights regarding the synergistic effect of pore dimensions and SiF62− functionality for specifying specific behavior (i.e. high selectivity vs. high uptake). A final MOM, composed of Y3+ ions and chemically complex linkers, was also examined. Disorder in the crystallographic data (e.g. single atoms with multiple positions) indicated the coexistance of notably different unit cells in the same system. Nevertheless, simulations revealed favored sorption sites in conjunction with results from physical experimentation.

The effect of inclusion of explicit polarization is investigated through several theoret- ical studies of crystalline porous materials herein. In addition to the use of Monte Carlo simulation for such studies, a robust molecular dynamics software is presented which is suitable for analyzing time dependent properties of gases or other molecules in porous materials and other condensed phase systems. Metal-organic frameworks (MOFs) are the main focus of the work included here, a relatively young class of materials originally in- troduced in the early 1990s. These are usually three dimensional crystalline nanoporous materials that exhibit unique properties such as gas separation, storage and catalysis. They are synthesized by the combination of a metal ion e.g. Cu2+ with an organic linker e.g. benzene dicarboxylate. They are a very popular topic of scientific research due to the diversity in possible structures and manifold utility – finding applications in electron transfer, sensing, drug release etc. Industrially, MOFs like HKUST-1 and others are on the global market for use in gas storage and separation in fuel cell and raw materials processing. These materials are often ideal candidates for computer simulation owing to their crystalline nature – a very large atomic system (that is, moles of particles) can be under- stood by only evaluating one or a few unit cells of the MOF, usually less than 5,000 atoms, and macroscopic properties such as gas sorption capacity and diffusion coefficients can be calculated through extrapolation of atomistic interactions in a mathematically infinite lattice. The software developed by the space group as of 2005, Massively Parallel Monte Carlo (MPMC), allows for sophisticated calculation of repulsion dispersion, electrostatic and polarization energies. In this work, Monte Carlo Molecular Dynamics (MCMD) is in- troduced, which can hybridize both methods to explore the phase space of a system with ease and better efficiency, as well as explore the effects of MOF flexibility and dynamic properties which to-date are rarely studied. Studies involving primarily CO2, H2 and CH4 will be presented, but other gases investigated include C2 H2 , C2 H4 , C2 H6 , N2 , H2 O and others. Metal-organic materials with a wide variety of composition and structure will also be presented. Finally, features of the software MCMD will be presented for use by future studies.

Nanoporous organic polymers, including hypercrosslinked polymers (HCPs), covalent organic frameworks (COFs), polymers of intrinsic microporosity (PIMs), and conjugated microporous polymers (CMPs) etc., are considered good candidates for potential gas storage and gas separation applications. Porosities and surface areas of a series of semirigid alternating copolymers, which contained tert-butyl carboxylate-functionalized stilbene or tert-butyl carboxylate-functionalized styrene, and maleic anhydride or tert-butyl carboxylate-functionalized phenyl maleimide, were investigated using nitrogen sorption/desorption isotherms at 77 K and molecular simulations. These alternating copolymers were found to have Brunauer-Emmett-Teller (BET) surface areas in the range of 20-40 m2/g. Surface areas of these alternating copolymers increased as the steric crowding of the polymer backbone increased, which was the result of introducing extra phenyl rings and/or N-phenyl substituent maleimide units. Surface areas were found to increase as the persistence length increased. A series of HCPs containing functionalized stilbene and N-substituted phenyl maleimide were synthesized via free radical suspension polymerization. The incorporation of these functionalized, chain stiffening, Tg enhancing comonomers raised the Tgs of precursor polymers before they were crosslinked. Surface areas of these HCPs, obtained from nitrogen adsorption/desorption isotherms at 77 K, were up to 1058 m2/g. However, the surface areas of these HCPs were systematically lower than the controls. The high rigidity of the polymer backbone, which was the result of incorporating Tg enhancing comonomer, likely affected the chain mobility of the precursor polymer, decreased the efficiency of post-crosslinking reactions, and thus resulted in lower surface areas. Amine-functionalized styrene/stilbene polymers were prepared via free radical polymerization or post-modification. Amine-containing silica-based sorbents were prepared using the impregnation method. Sorption of CO2 by these materials was tested using TGA and compared with control samples. Both high amine content and certain levels of surface area were found to be important for a sorbent to achieve high CO2 uptake. Highest CO2 uptake (12 wt%) under our testing condition in these materials was achieved by an amine-containing silica sorbent. / Ph. D.

A flexible Metal–Organic Framework Zn4O(BenzTB)3/2 (DUT-13) was obtained by combination of a tetratopic linker and Zn4O6+ as connector. The material has a corundum topology and shows the highest pore volume among flexible MOFs. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

La conception de nouveaux matériaux fonctionnels a une longue histoire. Durant les deux dernières décennies, le domaine des polymères organiques et inorganiques a attiré l'attention des chercheurs. Plus important encore, les matériaux poreux tels que les Metal Organic Frameworks (MOFs), en anglais, Covalent Organic Frameworks (COFs), en anglais, ainsi que des polymères de coordination poreux sont maintenant étudiés de manière intensive en raison de leurs applications potentielles, comprenant le stockage de gaz, la séparation de gaz, la catalyse et la détection. D'un autre côté, les polymères contenant du Pt ont montré l'application potentielle dans les cellules solaires et les diodes électroluminescentes. Le mémoire est divisé en trois sections principales présentant des résultats nouveaux. Dans la première section, le chapitre 2 traite essentiellement de la formation de polymères de coordination (CP) avec des sels CuX (X = Cl, Br, I) et trans-[p-MeSC6H4C≡C-Pt(PMe3)2-C≡CC6H4SMe] (L1), soit dans le PrCN ou PhCN. Les polymères résultants sont soit 2D (bidimensionel) ou 1D (unidimensionel). Cependant, en presence de PrCN ou de PhCN, le CP 2D obtenu avec le CuBr n'a pas incorporé de solvant dans ses espaces vides. D'autre part, le CP 2D et le reste des CP 1D obtenus avaient soit des molécules de solvant de cristallisation dans leurs cavités ou coordonnés au cuivre sur la chaîne. Les unités cuivre-halogénures étaient soit des rhomboïdes Cu2X2 ou le cubane Cu4I4. Leurs mesures photophysiques en présence et en l'absence de molécules de solvant de cristallisation ont été effectuées. En outre, la porosité du CP a été évaluée par BET (N2 à 77 K). Le vapochromisme du CP 2D sans solvant et des CP 1D ont été étudiés, ainsi que les mesures de sorption du CO2 ont été effectuées. De plus, nous avons utilisé CuCN et L1 dans MeCN pour former de nouveaux CP’s. Ceci est rapporté dans la deuxième section, le chapitre 3. Le CP obtenu était inattendu : L1 s’est rompu et du cyanure CN‾ s’est coordonné sur le Pt. Ceci a conduit à la formation d’un CP 1D zigzag. Généralement, les CP sont formés avec L1 via des liens Cu-S ou/et Cu([éta]2-C≡C), mais pas dans le cas du CuCN qui lui forme une chaîne 1D (CuCN)n où le L1 rompu se lie avec cette chaîne via un lien Cu-N. Les propriétés photophysiques et de stabilité thermique ont été étudiées. La troisième section (Chapitre 4) traite d'une exploration des CP formés par la reaction des sels CuX (X = Cl, Br, I) et le trans-[p-MeSC6H4C≡C-Pt(PMe3)2-C≡CC6H4SMe] (L1) ou le trans-[p-MeSC6H4C≡C-Pt(PEt3)2-C≡CC6H4SMe] (L2) dans du MeCN afin de trouver des tendances. L'utilisation de L1 a donné lieu à un CP 2D ou 1D CPs avec le MeCN piégé à l'intérieur des cavités, il y a de l’espace vide. L2 a conduit uniquement à des CP 1D sans molecules de solvant de cristallisation. Des analyses thermogravimétriques, photophysique et des mesures d’adsorption de gaz (uniquement pour ceux avec du solvant) ont été étudiées. / Abstract: The design of new functional materials has a long history. For the past two decades, the field of organic and inorganic polymers has attracted attention of researchers. More importantly, porous materials such as Metal Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) as well as porous coordination polymers are now being intensively studied due to their potential applications including gas storage, gas separations, catalyst and sensing. On another hand, Pt-containing polymers have shown potential applications in solar cells and light emitting diodes. The masters’ thesis is mainly divided into three main sections presenting new results. In the first section; Chapter 2 mainly discusses the formation of coordination polymers with CuX salts (X= Cl, Br, I) and trans-[p-MeSC6H4C≡C-Pt(PMe3)2-C≡CC6H4SMe] (L1), in either PrCN or PhCN. The resulting polymers obtained were 2D (bidimensional) CPs or 1D (unidimensional) CPs in all cases. However, 2D CPs obtained when CuBr salt is used by either using PrCN or PhCN did not incorporate the solvents in their cavities. On the other hand, the 2D CP and the rest of 1D CPs obtained had either the crystallization molecules in the cavities or coordinated to the copper cluster. The copper-halide clusters were either the rhomboids Cu2X2 fragments or the step cubane Cu4I4. The photophysical measurements in the presence and absence of solvent crystallization molecules were performed. In addition, the porosity of the CPs was evaluated by adsorption isotherms. The vapochromism of the solvent-free 2D and 1D CPs were investigated as well as CO2 sorption measurements were perfomed. Furthermore, we then attempted to use CuCN and L1 in MeCN which is reported in the second section as Chapter 3. The obtained CP was unexpected as L1 broke and a cyanide (CN‾) ion coordinated to the Pt atom leading to the formation of zigzag 1D CP. The coordination bonds Cu-S or/and Cu([eta]2-C≡C) were generally observed with L1, but not in the CuCN case. Instead a 1D chain of (CuCN)n was made and the broken L1 now binds the chain via a Cu-N bond. The photophysical and thermal stability properties were studied. Lastly, the third section, Chapter 4 deals with a potential predictability of CP formation by using CuX salts (X= Cl, Br, I) and either trans-[p-MeSC6H4C≡C-Pt(PMe3)2-C≡CC6H4SMe] (L1) or trans-[p-MeSC6H4C≡C-Pt(PEt3)2-C≡CC6H4SMe] (L2) in MeCN as the solvent. The use of L1 resulted in either 2D or 1D CPs with the MeCN trapped inside of the cavities while L2 resulted in 1D CPs without MeCN being present in their cavities. The thermogravimetric, photophysical as well as gas sorption measurements (only for those with crystalisation molecules) were perfomed.

A flexible Metal–Organic Framework Zn4O(BenzTB)3/2 (DUT-13) was obtained by combination of a tetratopic linker and Zn4O6+ as connector. The material has a corundum topology and shows the highest pore volume among flexible MOFs. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.