Metal Organic Frameworks (MOFs) are a class of porous materials that are predominantly obtained as powders and have been investigated as a solid sorbent for gas separation or carbon capture applications from combustion exhaust gases. The manufacturing of products with MOFs to use them for real life applications is still a major problem. The most common productization method used is to form pellets of the powder MOFs. This has a limitation on the product shape which makes it difficult for it to be used in gas separation applications. This study focuses on using additive manufacturing technique to give MOFs a lattice (mesh-like) geometry which is useful for gas separation applications as the mixture of gases would be able to pass through the lattice structure and be separated due to the inherent MOF properties and characteristics. Two MOFs based on magnesium and manganese salts have been studied in this project. An extrudable paste developed using alginate gel as a binder with these MOFs. With alterations in paste formulations and 3D printer parameters, lattice structures were printed using the two MOFs. CO2 and N2 gas uptakes were measured showing that the structure adsorbs CO2 gas to a higher extend which results in the separation of N2 gas in both materials. When compared to their pristine powder form, other properties of the MOFs such as crystallinity, microstructure, reusability and surface area remain to be preserved after being 3D printed in both cases.

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

No description available.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23926号 / 工博第5013号 / 新制||工||1782(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 古川 修平, 教授 生越 友樹, 教授 浜地 格 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

Metal-Organic Frameworks (MOFs) are an important class of materials that are gaining increasing relevance for many fields including energy storage, CO2 capture, photovoltaics, and catalysis. MOF mediated synthesis (MOFMS) is the decomposition of a MOF to form an amorphous carbon material decorated with metal nanoparticles. MOF thin films are an area where MOFMS has not been thoroughly explored, yet they are likely to be industrially relevant due to their potential application as highly dispersed, sinter resistant supported catalysts. In this work, we have developed a method for the growth of copper- and zinc-based MOF thin films on silicon- and aluminum- based wafers. A series of decomposition processes have allowed us to determine which variables can be used to design the final nanoparticle decorated product. These variables include oxygen/nitrogen ratios, the impact of water in atmospheric decomposition, substrate composition, and reduction under hydrogen. A high degree of control over the final thin film product is achieved, with the ability to make a carbon supported CuO structure with features between 1-5 nm, or CuO nanoparticles ranging from 10-500 nm, as well as finely tuned carbon/Cu ratios. Partially reduced Cu nanoparticles were obtained and used in the dehydrogenation of ethanol and methanol. Finally, alloyed nanoparticles were obtained through the growth and decomposition of Cu/Zn mixed-metal MOFs. Understanding the growth and decomposition variables as applied to supported MOF-thin films will enable development of next generation nanomaterials for use in catalysis.

The primary focus of this research is to utilize cellular and polymeric membranes for biomedical applications: To date, several organic and inorganic materials have been used to synthesize nanoparticles (NPs). The question arises as to which criteria and design principles should be considered while selecting the best material. Based on the results of testing, three key roles of NPs have been identified. First, NPs need enough circulation time to reach their target. Then these NPs must be able to target diseased tissue while leaving healthy tissue unaffected. Finally, NPs must be biodegradable and easily eliminated from the body. Biomimetic nanoparticles based on cell membranes have been developed as an efficient way to fulfill the needs of drug delivery goals and achieve targeted delivery by actively interacting and communicating with the biological environment. In the first project, genome editing machinery was delivered to particular cells using biomimetic cancer cell coated zeolitic imidazolate frameworks. MCF-7 cells demonstrated the highest uptake of C3-ZIFMCF compared to HeLa, HDFn, and aTC cells. In terms of genome editing, MCF-7 cells transfected with C3-ZIFMCF showed 3-fold EGFP repression compared to C3-ZIFHELA cells transfected with 1-fold EGFP repression. In vivo tests demonstrated C3-ZIFMCF's affinity for MCF-7 tumor cells. This demonstrates the biomimetic approach's ability to target cells specifically, which is definitely the most essential step in future genome editing technology translation. In the second project, multimodal therapeutic nanowires (NWs D-ZIF) MCF-7 cancer cells were developed. D-ZIF coated NWs had higher cellular uptake and photothermal treatment efficiency than non-coated NWs. (NWs D-ZIF) MCF accumulates in MCF-7 tumor cells and enhances photothermal capability. On the other hand, chiral separation of enantiomers is becoming more important, particularly in pharmaceuticals. Because enzyme activities and other biological processes are stereoselective, chiral drugs' enantiomers often have different metabolic effects, pharmacological activity, metabolic rates, and toxicities. In an attempt to address this issue, we decided in the final project to study the capability of chiral polyamide membrane for efficient and energy-free chiral separation. In particular, to separate essential amino acid critical to all living organisms (DL-tryptophan).

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24177号 / 理博第4868号 / 新制||理||1697(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 有賀 哲也, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

No description available.

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.