Indiana University-Purdue University Indianapolis (IUPUI) / Extrusion-based 3D printing is one of the emerging additive manufacturing technologies used for printing a range of materials from metal to ceramics. In this process, the required material is extruded from the extruder in the form of a slurry. Zeolite and MOFs are mainly used for CO2 adsorption in the form of pellets and beads due to their good adsorptive property. Researchers are developing monoliths of Zeolite and MOFs and fabricate them using traditional extrusion and implement them in the gas adsorption applications as an option for beads and pellets by developing a monolithic structure. Previous research on Zeolite 13X and 5A have shown good structural and physical properties in monolith form. In this study, we developed slurry of two molecular sieve Zeolite 3A and 4A monoliths powders, mixing it with bentonite clay, methyl cellulose, and PVA as a binder. The slurry preparation was carried out at room temperature. Once the 3D printed samples are dried at room temperature, a sintering process was performed to increase mechanical strength. To be used in real-time applications, the 3D printed Zeolite sample need to have sufficient mechanical strength. The BET surface area test showed good results for Zeolite 13X compared to available literature. The surface area calculated for 3D printed Zeolite 13X was 767m2/g and available literature showed 498 m2/g for 3D printed Zeolite 13X. The microhardness values of 3D printed Zeolite samples were measured using a Vicker hardness tester. The hardness value of the 3D - printed Zeolite samples increased from 8.3 ± 2 to 12.5 ± 3 HV0.05 for Zeolite 13X, 3.3 ± 1 to 7.3 ± 1 HV0.05 for Zeolite 3A, 4.3 ± 2 to 7.5 ± 2 HV0.05 for Zeolite 4A, 7.4 ± 1 to 14.0 ± 0.5 HV0.05 for Zeolite 5A respectively. The SEM, EDS and XRD analysis was performed for 3D printed samples before and after sintering to evaluate their structural properties. The SEM analysis reveals that all 3D printed Zeolite samples retained their microstructure after slurry preparation and also after the sintering process. The porous nature of 3D printed Zeolite walls was retained after the sintering process. The EDS analysis showed that the composition of 3D printed Zeolite samples remained somewhat similar with minor variation for before and after sintering. The framework structure of Zeolite Type X for Zeolite 13X and Zeolite Type A for Zeolite 3A, 4A, 5A were in good shape after sintering as standard peak intensity points were retained. Zn-MOF74 was synthesized using solvothermal synthesis which is a well-established synthesis process used for the synthesis of MOFs. We also developed slurry for Zn-MOF-74 using bentonite clay and PVA as binders and printed small parts using hand printing.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18641号 / 理博第4020号 / 新制||理||1579(附属図書館) / 31555 / 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 吉村 一良, 准教授 前里 光彦 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19916号 / 理博第4216号 / 新制||理||1605(附属図書館) / 33002 / 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 島川 祐一, 教授 有賀 哲也 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20603号 / 理博第4318号 / 新制||理||1620(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 竹腰 清乃理, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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Metal-Organic Frameworks (MOFs), a class of porous materials realized via reticular construction of a plethora of organic linkers and metal nodes, have emerged as excellent candidates for light-harvesting compositions (LHC), photo or electrocatalysis. This is due to their ability to organize chromophores and metal nodes with desired functionalities, and remarkable porosity that allows efficient mass transfer of reactants and electrolytes. Recent studies have shown intriguing delocalized excited state of the orderly organized pigments in MOFs. Furthermore, the accessible pores/channels allow it to host complementary optical/redox active species within the frameworks by means of de novo or postsynthetic functionalization, as a manner for MOF compositions to integrate functionalities beyond photosensitizer, such as photo/electrocatalytic sites. In such multi-component assemblies, profound understanding of charge transfer and separation process is crucial to make the designed LHC efficient. Therefore, we could adopt chromophoric MOFs as a scaffold to systematically investigate photoinduced charge transfer by installing judiciously selected redox moieties into MOFs, whose unique electronic properties could define distinct electronic interplay with MOFs. From an aspect of further applications, photo-generated electrons can be utilized more efficiently by an external electric field applied on MOF films, which prolongs the charge-separation lifetime. For this purpose, sufficient electrical conductivity is necessary to allow charges delivered across the MOF film. Considering a large energy mismatch between the majority of traditional metal nodes including metal oxo clusters and carboxylic based struts, charge transport is defined by a slow hopping process, which hinders the harvesting of relatively short-lived separated charges. Hence, developing neoteric linkage chemistry is critically needed to overcome the charge-transport challenge.Keeping these points in mind, the scope of this dissertation mainly focuses on unraveling the fundamental principles of photoinduced charge transfer and separation, ground-state charge transport boosted by nontraditional coordination chemistry and incorporation of complementary redox species, and their substantial correlation with MOF-based photocatalysis, electrocatalysis and photoelectrocatalysis. The first chapter lays the foundational knowledge regarding generic properties (chemical and physical) of MOFs, and adopted typical postsynthetic functionalization method, namely, solvent-assisted ligand incorporation (SALI), and other physical processes including photoinduced charge and energy transfer among components within MOFs, and mechanism of electron transport, that has so far been understood, in MOFs driven by an external electric field and commonly used approaches to measure that. Chapter two and three reveal the rule to control photoinduced charge transfer in MOF compositions prepared by the installation of a series of zinc porphyrins possessing gradient excited-state and frontier-orbital energy that can define distinct charge-transfer driving force into the mesopore of a photosensitizing MOF, NU-1000. These compositions show potential for their utilization as artificial light-harvesting assemblies. Chapter four highlights new design for solid porous CO2 reduction catalysts realized by introducing cobalt phthalocyanine into NU-1000. Importantly, we interpreted the catalytic activity from the aspect of charge transport efficiency, by comparing with catalysts constituted by NU-1000 and different molecular catalysts. To harvest the photo-generated electrons, an external electric field can be applied on MOF films deposited on transparent electrodes under photoexcitation, for which sufficient electrical conductivity is a must. Therefore, in chapter five, a new semiconducting coordination polymer framework was developed by employing a novel carbodithioate group for the linkage with nickel(II) that extends in three dimensions, which shows enhanced, electrical conductivity (i.e. 10-6 – 10-7 S cm-1) in contrast to traditional carboxylate-based MOFs due to a more delocalized electronic feature of the carbodithioate-nickel cluster. More importantly, its unique electronic properties, especially a long-lived charge-separation state captured by transient-absorption technique, could alleviate the compromise between electrical conductivity and charge separation (resulted from bandgap) of light-harvesting material. We then extend this binding group to chromium(III), as introduced in chapter 6, leading to a paramagnetic 3D coordination polymer with metallic conductivity as opposed to its nickel counterpart.

Thesis advisor: Dunwei Wang / Metal organic frameworks (MOFs) are a class of compounds that show promising potential for a variety of applications due to their uniformity, highly porous structure, lack of dead volume, and fine-tunability. One of these significant applications is in selective ion transport, which makes MOF films a uniquely good separatory material for dual-electrolyte setups, such as those being investigated with Mg-Br batteries. This research has important environmental and industrial ramifications, considering the various drawbacks associated with commercially available batteries such as the lithium-ion battery. The MOF investigated was Mg-MOF-74, which showed promising selective Mg2+ transport abilities. Both Mg-MOF-74 powder and films were synthesized via a vapor-assisted conversion process to maximize efficiency. To characterize the MOF, XRD and SEM imaging was used. This allowed us to gain a nuanced understanding of the material and its properties for further applications. / Thesis (BA) — Boston College, 2022. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Departmental Honors. / Discipline: Chemistry.