The main objectives of this project are the synthesis and redox- or photo-active modification and CO2 adsorption studies of metal-organic frameworks (MOFs) based on Cu3-pyrazolate secondary building units (SBUs). Trinuclear copper(II) complexes of the formula [Cu3(µ3-O)(µ-4-R-pz)3X3]z have been studied extensively due to their redox, magnetic and catalytic properties. In earlier work, we have shown that trinuclear copper(II) complexes of the formula [Cu3(µ3-O)(µ-4-R-pz)3X3]z pz = pyrazolato anion; R = H, CH(O), Cl, Br and NO2; X = Cl, NCS, CH3COO, CF3COO and pyridine – can be oxidized to the corresponding z+1, formally CuII2CuIII, species. In this project, fourteen (14) new copper-pyrazolate complexes of varying nuclearities (Cu3, Cu6, Cu7 and Cu12), terminal ligands (-NO2, py, -N3, -Cl) and bridging ligands (4-Cl-pzH and 4-Ph-pzH) have been synthesized. Efforts have been made to prepare MOFs based on the Cu3(µ3-O)-SBUs. While attempting to design the most suitable SBU for redox-active MOF construction, it was found that the one-electron oxidation of the all-CuII complex [Cu3(µ3-O)(µ-pz)3(NO2)3]2–, [8]2-, was achieved at redox potential more cathodic than any other Cu3(µ3-O)-complexes studied in our laboratory. The mixed-valent compound, [Cu3(µ3-O)(µ-pz)3(NO2)3]–, [8]-, the easiest accessible CuII2CuIII species known to date, was characterized spectroscopically. Compound [8] and analogous [11] release NO almost quantitatively upon the addition of PhSH or acetic acid. The system is catalytic in the presence of excess nitrite. Before embarking on the study of photo-active MOFs, a simpler model compound – a dimer of trimer [{Cu3(µ3-OH)(µ-4-Cl-pz)3(py)2}2(µ-abp)](ClO4)4 [21], where abp = 4,4’-azopyridine, was synthesized and its photochemistry was studied. The absorption spectra recorded before and after irradiation indicated a structural change. Two dimensional (2D) and three dimensional (3D) materials with {[Cu3(µ3-OH)(µ-4-R-pz)3]2+}n SBUs where R = Ph or Cl , which can potentially undergo cis/trans-isomerization, have been prepared during this project. A Phenyl substituent at 4-position on the pyrazole ligand leads to the formation of new class of 2D sheets. Three new 3D porous MOFs based on {[Cu3(µ3-OH)(µ-4-Cl-pz)3]2+}n SBUs have interpenetrated- lattice structures and are capable of adsorbing CO2 selectively. Compounds FIU-1 and FIU-3 also exhibit hysteretic sorption-desorption profiles indicating the flexibility of the MOFs upon adsorption. Compound FIU-1 demonstrates the usefulness of a hexanuclear CuII -pyrazolate moiety as an SBU for generating 3-fold interpenetrated 3D polymeric network. Complexes FIU-2 and FIU-3 have novel 3-fold interpenetrating 3D hexagonal framework structures. Compound FIU-2 crystallizes in the monoclinic crystal system with the P21/c space group, whereas FIU-3 crystallizes in triclinic space group P . Both structures contain Cu3-SBUs connected by the linkers through the Cu-termini.

Since late 70’s when conductive polymers were discovered, a new field of science has opened to the research world. Especially during last 30 years, many applications of using these polymers have been revealed in areas such as electrochemical transistors and OLEDs (Organic Light Emitting Diodes). In separation sciences, there are some studies using conjugated polymers for isolating analytes in liquid and gas matrices. Considering the results of these recent efforts, there is a potential to use conjugated polymers to separate the gases from each other. However, to the best of my knowledge, such application has not been demonstrated yet. The objective of this thesis is to measure the differences in adsorption of carbon dioxide and methane on conjugated polymers. The adsorption measurements on polymer films were made using Quartz Crystal Microbalance with Dissipation Monitoring. We believe this separation method may be helpful in biogas plants or even for separating carbon dioxide in carbon sequestration projects and green house gas abatement plants.

The primary objective of this study was to develop a sensitive and cost-effective sorption system to analyze adsorption and diffusion of different gases on micro porous materials and nanotubes. A high pressure Quartz Crystal Microbalance (QCM) based adsorption apparatus for single-component gas was developed. A QCM is an acoustic-wave resonator in which the acoustic wave propagates through the crystal. Therefore, it is highly responsive to addition or removal of small amounts of mass adsorbed or deposited on the surface of the crystal. This mass sensitivity makes the QCM an ideal tool for the study of gas adsorption. The QCM-based adsorption apparatus is advantageous over the commercialized none-gravimetric and gravimetric equipment in a way that it is low-cost, highly sensitive and accurate for mass sorption applications, satisfactorily stable in a controlled environment, and can be used for thin films. The high pressure apparatus was calibrated using Matrimid 5218, whose thermodynamic properties and adsorption parameters are known. The Matrimid was spin-coated onto a 14 mm-diameter QCM, and sorption equilibrium data for were obtained for CO₂ gas at 25, 30, 48, and 52 ºC and partial pressure range between 0 to 4 bar. In order to compare the experimental data with available literature data, the experimental data was fitted into a dual-mode adsorption model. The model results from Henry's law and a Langmuir mechanism. Comparison of the experimental adsorption isotherm of Matrimide for CO₂ gas with literature data showed reasonable agreement between the experimental and literature data. In this study, the adsorption parameters of aluminosilicate nanotubes are observed. Aluminosilicate nanotubes are ideal materials for chemical sensing, molecule separation, and gas storage; hence, there is a need for adsorption and diffusion data on this material. The adsorption of CO₂, N₂, and CH₄ gases on aluminosilicate nanotubes samples has been studied in the temperature range of 20° to 120° Celsius and pressure range of 0 to 8 bar. The experimental results yield the CO₂ and N₂ heat of adsorptions of -32.9 and -28.1 kJ/mol respectively.

Porous, high surface area activated carbon (AC) can be used to remove certain irritating and toxic gases from contaminated air streams. Impregnating AC with carefully selected chemicals can improve ACs adsorption capacity for certain gases and provide adsorption capacity for gases that un-impregnated AC cannot fi lter. Impregnated activated carbons (IACs) and ACs can be used as the active component in respirators. Comparative studies of di fferent commercially available AC samples and of IAC samples, prepared from a wide variety of di fferent chemicals, were performed. The gas adsorption capacity of the samples was tested using sulfur dioxide (SO2), ammonia (NH3), hydrogen cyanide (HCN) and cyclohexane (C6H12) challenge gases and compared to results obtained from a commercially available broad spectrum respirator carbon. The samples were characterized using wide angle x-ray di raction (XRD), small angle x-ray scattering (SAXS), nitrogen adsorption isotherms, thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM). Highlights of this work include the discovery of a IAC sample prepared from zinc nitrate (Zn(NO3)2) and nitric acid (HNO3) that, after heating at 180 C under argon, had overall dry gas adsorption capacity that was greater than the commercially available sample. The importance of pore size on the C6H12 adsorption capacity of AC was demonstrated using SAXS and nitrogen adsorption data. A relationship between decreased humid C6H12 capacity and pre-adsorbed water was shown using SAXS, TGA and gravimetric studies.

Nanoporous molecular sieve materials like metal organic frameworks (MOFs) and metal oxide nanotubes (AlSiNTs) have found a wide range of technological applications in catalysis, separations, and ion exchange due to their salient features over other contemporary sensing materials. As a result, these materials can function as a chemical recognition layer that relies on analyte adsorption and they have shown to selectively adsorb specific gas molecules from mixtures. The characterization of gas adsorption in these materials is performed predominantly by commercial gravimetric equipment, whose capital and operating costs are generally high and require relatively large amounts of sample. Thus, it is desirable to obtain a reliable measure of the gas transport properties of these materials over a substantial range of pressure and temperature by non-gravimetric methods. The objective of this thesis is to investigate the adsorption and diffusion characteristics of recently-identified nanoporous materials through the development and use of a high-pressure/high-temperature quartz crystal microbalance (QCM) device. In this regard, this thesis is divided into four main objectives, viz. (1) Design and development of high temperature/ high pressure QCM device, (2) Measurement and analysis of adsorption characteristics in nanoporous materials, (3) Diffusion measurement and analysis in polymer thin films and (4) Diffusion measurement and analysis in MOF crystals. The results obtained in Objectives 2-4 will allow us to make important recommendations regarding the use of specific nanoporous materials in molecular separation applications and also lead to significant understanding of gas uptake thermodynamics in nanoporous materials via the application of analytical models to the experimental data.

京都大学 / 新制・論文博士 / 博士(理学) / 乙第13396号 / 論理博第1575号 / 新制||理||1678(附属図書館) / (主査)教授 北川 宏, 教授 吉村 一良, 教授 有賀 哲也 / 学位規則第4条第2項該当 / Doctor of Science / Kyoto University / DGAM

No description available.

Metal organic frameworks (MOFs) is a quite recently discovered porous material group which shows potential in many different areas. One of these areas is carbon capture; the framework structure of the porous materials allows gas molecules to adsorb to the surface of the pores. MOFs are conventionally synthesised at high temperatures and with hazardous solvents. The goal of this projectwas to synthesise highly porous MOFs at room temperature with water as the main solvent, using environmentally friendly and non-hazardous precursors. As well as the room temperature synthesis, conventional synthesis methods were used with the same precursors as comparison. The materials were characterised with X-ray diffraction, thermogravimetrical methods and IR-spectroscopy. To assess the porosity of the materials, gas adsorption evaluation was performed with CO2, N2, SF6, and CH4 at 20⁰C. In the end, three novel porous magnesium-based materials and one zirconium-based material were successfully synthesised. One of the magnesium-based materials showed a moderately high CO2 adsorption (2.38mmol/g), and could be synthesised at room temperature. The zirconium-based material showed a remarkably high selectivity (17.7) for SF6 over N2 and a high surface area (550m2/g)

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24439号 / 理博第4938号 / 新制||理||1705(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 武田 和行, 教授 吉村 一良, 教授 北川 宏 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Anthropogenic emission of greenhouse gases has long been suspected to contribute to global warming and climate change. Most greenhouse gases are emitted in a mixture, so efficient methods and materials to separate and capture the gases are in demand in order to reduce emissions. A promising material group for this purpose is metal-organic frameworks (MOFs). This class of material have the ability to selectively adsorb green house gases due to its high porosity and high surface area. Zeolitic imidazolate frameworks (ZIFs) are a subclass of MOFs that are topologically similar to zeolites and are known for their good chemical and thermal stability.   The aim of this project was to investigate if the greenhouse gas (i.e. CO2 and SF6) capture performance of ZIFs could be improved and tuned using a mixed-linker approach with seven different imidazolate-based organic linkers of different sizes or with various functional groups. As well as to investigate the processability of MOFs using 3D printing. ZIFs composed of different ratios of 2-methylimidazolate as base linker and a second linker of imidazolate, benzimidazolate, 2-aminobenzimidazolate, 5,6-dimethylbenzimidazolate, and 4,5-dichloroimidazolate were succesfully made. The materials were all found to be crystalline, however, mixed-linker ZIFs containing 2-aminobenzimidazole, 5,6-dimethylbenzimidazole and dichloroimidazole were observed to contain more than a single phase. All samples showed to be somewhat porous towards CO2 and SF6, and there seem to be a trend where a low % of a bulkier linker (eg. bIm, ambIm) resulted in a higher uptake of SF6 whereas a high % resulted in a higher uptake of CO2. For dcIm it was the other way around, a low % showed a higher uptake for CO2  whereas a high % showed a higher uptake for SF6. For CO2, the ZIF containing 80% benzimidazolate showed the highest uptake of 9.81 wt%. For SF6, the 25% 4,5-dichloroimidazolate showed the highest uptake of 17.73 wt%. Furthermore, direct ink writing (DIW) 3D printing was also successfully utilized to process and structure a Mn-based MOF using carbopol as binder. The printed structure was found to have similar properties to the pristine MOF in regards to crystallinity and porosity.