Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1994. / Vita. Abstract. Includes bibliographical references (leaves 76-78). Also available via the Internet.

Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xii, 115 p.; also includes graphics. Includes bibliographical references (p. 107-115). Available online via OhioLINK's ETD Center

<div> <p>Metal-organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands in porous structure forms. MOFs have been proposed in use for gas adsorption, purification, and separation applications. This work combines MOFs with 3D printing technologies, in which 3D printed plastics serve as a mechanical structural support for MOFs powder, in order to realize a component design for gas adsorption. The objective of the thesis is to understand the gas adsorption behavior of MIL-101 (Cr) MOF coated on 3D printed PETG, a glycol modified version of polyethylene terephthalate, through a combined experimental and modeling study. The specific goals are: (1) synthesis of MIL-101 (Cr) MOFs; (2) nitrogen gas adsorption measurements and microstructure and phase characterization of the MOFs; (3) design and 3D printing of porous PETG substrate structures; (4) deposition of MOFs coating on the PETG substrates; and (5) Monte Carlo (MC) modeling of sorption isotherms of nitrogen and carbon dioxide in the MOFs.</p><p>The results show that pure MIL-101 (Cr) MOFs were successfully synthesized, as confirmed by the scanning electron microscopy (SEM) images and X-ray diffrac- tion (XRD), which are consistent with literature data. The Brunauer-Emmett-Teller (BET) surface area measurement shows that the MOFs samples have a high cover- age of nitrogen. The specific surface area of a typical MIL-101 (Cr) MOFs sample is 2716.83 m2/g. MIL-101 (Cr) also shows good uptake at low pressures in experimental tests for nitrogen adsorption. For the PETG substrate, disk-shape plastic samples with a controlled pore morphology were designed and fabricated using the fused de-</p><p> </p><p>position modeling (FDM) process. MOFs were coated on the PETG substrates using a layer-by-layer (LbL) assembly approach, up to 30 layers. The MOFs coating layer thicknesses increase with the number of deposition layers. The computational model illustrates that the MOFs show increased outputs in adsorption of nitrogen as pres- sure increases, similar to the trend observed in the adsorption experiment. The model also shows promising results for carbon dioxide uptake at low pressures, and hence the developed MOFs based components would serve as a viable candidate in gas adsorption applications.</p><div><br></div></div>

Indiana University-Purdue University Indianapolis (IUPUI) / Metal-organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands in porous structure forms. MOFs have been proposed in use for gas adsorption, purification, and separation applications. This work combines MOFs with 3D printing technologies, in which 3D printed plastics serve as a mechanical structural support for MOFs powder, in order to realize a component design for gas adsorption. The objective of the thesis is to understand the gas adsorption behavior of MIL-101 (Cr) MOF coated on 3D printed PETG, a glycol modified version of polyethylene terephthalate, through a combined experimental and modeling study. The specific goals are: (1) synthesis of MIL-101 (Cr) MOFs; (2) nitrogen gas adsorption measurements and microstructure and phase characterization of the MOFs; (3) design and 3D printing of porous PETG substrate structures; (4) deposition of MOFs coating on the PETG substrates; and (5) Monte Carlo (MC) modeling of sorption isotherms of nitrogen and carbon dioxide in the MOFs. The results show that pure MIL-101 (Cr) MOFs were successfully synthesized, as confirmed by the scanning electron microscopy (SEM) images and X-ray diffraction (XRD), which are consistent with literature data. The Brunauer-Emmett-Teller (BET) surface area measurement shows that the MOFs samples have a high cover- age of nitrogen. The specific surface area of a typical MIL-101 (Cr) MOFs sample is 2716.83 m2/g. MIL-101 (Cr) also shows good uptake at low pressures in experimental tests for nitrogen adsorption. For the PETG substrate, disk-shape plastic samples with a controlled pore morphology were designed and fabricated using the fused deposition modeling (FDM) process. MOFs were coated on the PETG substrates using a layer-by-layer (LbL) assembly approach, up to 30 layers. The MOFs coating layer thicknesses increase with the number of deposition layers. The computational model illustrates that the MOFs show increased outputs in adsorption of nitrogen as pressure increases, similar to the trend observed in the adsorption experiment. The model also shows promising results for carbon dioxide uptake at low pressures, and hence the developed MOFs based components would serve as a viable candidate in gas adsorption applications.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico / The significant increase of carbon dioxide emissions in the atmosphere comes intensifying the global warming. The search for energetic source that turn emission down is of great importance, as well as the use of complementary actions like dioxide carbon capture process of the main emissions sources. From among some processes already very well-known industrially highlights chemical absorption with alkanolamine, which shows some disadvantages in being costly and generate waste derived from recovery. The use gas-solid selective in carbon dioxide adsorption has very advantages over absorption liquid amine such as easy handling without risks to the environment and recovering of adsorbent material, being possible to use industries plants with continuous flux. In this context were synthesized through hydrothermal method two materials of family M41S of type MCM-41 and MCM-48. Then the materials were impregnated with ethylenediamine by wet impregnation method. These materials were used for the carbon dioxide adsorption process and were characterized by several physic-chemical techniques. The powder X-ray diffraction patterns of the samples showed all peaks characteristics of MCM-41 and MCM-48 before and after impregnation with amines. The absorption spectrum in the infrared region showed bands due to Si-O and O-Si-O bonds in all materials and N-H bonds due to presence of amine in the supports after impregnation process. The thermogravimetric curves showed that stability of material containing amines is up to 100 °C. The materials showed N2 adsorption isotherms type IV, some with hysteresis type H1 and high surfaces areas (over 1000 m2 g-1). Carbon dioxide capture tests in flux system and atmosphere pressure showed significant drawbacks in the capture capacities of carbon dioxide for the materials impregnated with ethylenediamine in comparison to the values obtained with the MCM-41 and MCM-48 supports alone. Tests with closed system and pressure variation in the range of 0.5 to 30 bar allowed the construction of the isotherms to prepared materials of which were fitted using the Langmuir model. The results showed that the samples of MCM-41 and MCM-48 without impregnation are favorable for applications where high pressures are required. / O aumento significativo das emissões de dióxido de carbono na atmosfera vem acentuando o efeito do aquecimento global. A busca por fontes energéticas que minimizem as emissões é de grande importância, como também o uso de ações complementares como processos para captura deste gás das principais fontes emissoras. Dentre alguns processos já bem conhecidos industrialmente, destaca-se a absorção química com alcanolaminas, a qual apresenta algumas desvantagens por ser dispendiosa e gerar rejeitos da sua recuperação. O uso da adsorção gás-sólido seletiva de dióxido de carbono tem muitas vantagens sobre a absorção com aminas líquidas, tais como: fácil manipulação sem riscos ao ambiente, e recuperação do material adsorvente, podendo-se utilizar plantas industriais com fluxo contínuo. Neste contexto, foram sintetizados através do método hidrotérmico dois materiais da família M41S do tipo MCM-41 e MCM-48. Em seguida os materiais foram impregnados com etilenodiamina, através do método de impregnação por via úmida. Estes materiais foram utilizados para o processo de adsorção de dióxido de carbono e foram caracterizados por diversas técnicas físico-químicas. Os difratogramas de raios-X das amostras sintetizadas apresentaram os picos característicos do MCM-41 e do MCM-48 antes e após a impregnação com aminas. Os espectros de absorção na região do infravermelho mostraram bandas devido às ligações Si-O e O-Si-O em todos os materiais e de ligações N-H devido à presença da amina nos suportes após a impregnação. As curvas termogravimétricas mostraram que a estabilidade do material contendo aminas é de até 100 °C. Todos os materiais apresentaram isotermas de adsorção de N2 do tipo IV, alguns com histerese do tipo H1 e elevadas áreas superficiais (acima de 1000 m2 g-1). Os testes de captura de dióxido de carbono em sistema com fluxo e pressão atmosférica mostraram significativas reduções nas capacidades de captura para os materiais impregnados em comparação com os valores obtidos com os suportes MCM-41 e MCM-48. Testes com sistema fechado e variação de pressão na faixa de 0,5-30 bar permitiram o levantamento de isotermas de equilíbrio para os materiais preparados as quais foram ajustadas através do modelo de Langmuir. Os resultados mostraram que as amostras de MCM-41 e MCM-48 são favoráveis para aplicações onde altas pressões são requeridas.

With the benefits of an ever increasing advance of industrialization around the globe come formidable environmental CO2 . Three environmental problems that have relevance to the research described in this thesis are the 1) buildup of atmospheric CO2 gas through the burning of fossil fuels, 2) eutrophication of aquatic systems, and 3) the acidification of environments from acid mine drainage (AMD) resulting from coal-mining activities. In particular research is presented in this thesis that investigated the surface chemistry of CO2 and phosphate (PO43-) on a suite of environmentally relevant iron oxyhydroxide materials and the chemistry of phospholipid molecules on environmentally relevant iron sulfide surfaces to suppress AMD. To develop a microscopic understanding of the surface chemistry of the different systems, an array of experimental and computational techniques were used in the research. Techniques included X-ray photoelectron spectroscopy, atomic adsorption, X-ray diffraction, scanning transmission microscopy with electron dispersive X-ray spectroscopy (STEM/EDS), ion chromatography (IC), and attenuated total reflectance Fourier transform Infrared (ATR-FTIR). Results from the latter technique were interpreted with the aid of density function theory (DFT) calculations. Iron oxyhydroxides, which consisted of ferrihydrite (FeOOH), goethite α-FeOOH), ferrimagnetic ferrihydrite (FerriFh), and aluminum-doped iron oxyhydroxide (content from 0-100 mol%) were synthesized and studied before and after exposure to gaseous CO2 , CO32-, and PO43- species. FeOOH and mixed Al/Fe oxyhydroxide surfaces showed high affinities for the formation of carbonate and bicarbonate species upon exposure to gaseous CO2 . Within the Al/Fe oxyhydroxide circumstance, a low Al level of incorporation in the iron oxyhydroxide structure caused a slight increase in surface area and increase in the amount of oxyanion (e.g., CO32- or PO43-) adsorption up to an Al level of 30 mol%. Significant changes were observed in the binding geometry of the adsorbed complexes on the Al/Fe mineral compared to single phase α-FeOOH, AlOOH, and FeOOH surfaces. ATR-FTIR results combined with vibrational frequency (DFT) calculations suggested the formation of multiple phosphate surface complexes via a variety of configurations such as inner-sphere/outer-sphere bidentate, monodentate depending on the solution pH and the Al mol% substituted into the Fe-oxyhydroxide. Studies investigated the adsorption of CO2 on FerriFh and compared those results to CO2 on ferrihydrite. The CO2 pressures used in these particular studies ranged from 1 to 57.8 bars. It is found that citrate bound species, resulting from the synthesis conditions used to make FerriFh, blocked surface sites for the formation of carbonate and bicarbonate species on the magnetic FerriFh and ferrihydrite oxyhydroxide minerals upon CO2 (gas) exposure. A bicarbonate or bent-CO2 like species (~1220 cm-1) formed at lower CO2 pressures (≤ 3.5 bars) but was absent at the higher pressures. Additional studies investigated the adsorption of various phospholipid molecules on pyrite, and iron sulfide with FeS2 stoichiometry. These studies were focused on suppressing the oxidative decomposition of pyrite to sulfuric acid, the root cause of AMD. Batch and column studies were employed to investigate the ability of phospholipids to reduce AMD over an extended period of time (up to 3 years). In studies that used actual coal mining refuse, which contained significant amount of pyrite, it was shown that the rate of acid production from pyrite decomposition could be reduced by as much as 70% due to the presence of surface bound phospholipid. Assembly of the phospholipid into a bilayer motif on the sulfide surface was hypothesized to form a hydrophobic barrier that kept dissolved O2 and bacteria from facilitating the oxidation of FeS2. Column experiments showed that when water at pH 7 was flowed over the coal mining waste, the effluent had a pH close to 3. In contrast when water at pH 7 was flowed over the pyrite containing waste, which was pretreated with lipid, the effluent had a pH closer to 7, and the total amount of Fe (Fe2+/Fe3+) and SO42- in the effluent waters was also reduced relative to the untreated pyrite containing waste circumstance. These studies showed that the application of phospholipid to pyrite containing coal mining waste could potentially be an environmentally friendly remediation technique. / Chemistry