Les Metal-Organic Frameworks résultent de l'organisation de clusters métalliques et demolécules organiques chélatantes qui forment un réseau cristallin poreux. Leur découverte apermis des avancées majeures dans le domaine du stockage et de la séparation des gaz.Malheureusement la faible stabilité et l'acidité modérée de ces matériaux ne les rendent quepeu compétitifs par rapport aux zéolites dans le domaine du raffinage ou de la dépollution. Ils'agit d'explorer, avec ces matériaux, de nouvelles applications catalytiques en tirant partie deleur principale qualité : leur modularité. En effet le large choix de métaux, de ligands, ainsique la post fonctionnalisation de ces derniers permet la synthèse contrôlée de matériauxpossédant des propriétés de flexibilité, de confinement ainsi qu'un environnement chimiquesimilaire à celui des sites actifs des enzymes. Ce travail s'inspire du procédé catalytique desenzymes pour obtenir des MOFs hautement sélectifs en conditions douces. Nous décrivons ledéveloppement de méthodes pour encapsuler des catalyseurs organométalliques dans despores calibrés afin de modifier la sélectivité d'une réaction d'oxydation et stabiliser lecatalyseur. Quatre MOFs supportant des groupes amino ont été synthétisés afin de permettreleur post fonctionnalisation. Les propriétés de flexibilité ainsi que la distribution des sitespotentiellement actifs du MOF MIL-53 ont également été contrôlés grâce à lafonctionnalisation partielle de la structure. Enfin ces amino MOFs furent post fonctionnalisésen isocyanate en deux étapes afin d'améliorer la réactivité de la structure et de permettre legreffage de diverses amines. Ces outils pourraient permettre à court terme la conception deMOFs dont les pores ont un environnement semblable aux metalloenzymes.

Advances in flexible and functional metal–organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009–2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host–guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal–organic frameworks for separation, catalysis, sensing, and biomedicine.

Two of the hottest areas in porous materials research in the last decade have been in energy storage, mainly hydrogen and methane, and in carbon capture and sequestration (CCS). Although these topics are intricately linked in terms of our future energy landscape, the specific materials needed to solve these problems must have significantly different properties. High pressure gas storage is most often linked with high surface areas and pore volumes, while carbon capture sorbents require high sorption enthalpies to achieve the needed selectivity. The latter typically involves separating CO2 from mixed gas streams of mostly nitrogen via a temperature swing adsorption (TSA) process. Much of the excitement has arisen because of the potential of metal-organic frameworks (MOFs) and porous polymer networks (PPNs). Both classes of materials have extremely high surface areas (upwards of 4000 m2/g) and can be modified to have specific physical properties, thus enabling high performance materials for targeted applications. This dissertation focuses on the synthesis and characterization of these novel materials for both applications by tuning framework topologies, composition, and surface properties. Specifically, two routes to synthesize a single molecule trap (SMT) highlight the flexibility of MOF design and ability to tune a framework to interact with specifically one guest molecule; computational and experimental evidence of the binding mechanism are shown as well. Furthermore, eight PPNs are synthesized and characterized for post-combustion carbon capture and direct air capture applications. In addition a high-throughput model, grounded in thermodynamics, to calculate the energy penalty associated with the carbon capture step is presented in order to evaluate all materials for TSA applications provide a comparison to the state of the art capture technologies. This includes results of working capacity and energy calculations to determine parasitic loads (per ton of CO2 captured) from readily available experimental data of any material (adsorption isotherms and heat capacities) using a few simple equations. Through various systematic investigations, trends are analyzed to form structure property relationships that will aid future material development.

Synthesis of polycrystalline, vs. single-crystalline porous materials, such as metal-organic frameworks (MOFs), is usually beneficial due to shorter synthetic time and higher yields. However, the structural characterization of these materials by X-ray powder diffraction can be complicated. Even more difficult, is to track structural changes of MOFs by in situ experiments. Hence, we designed several successful techniques for the structural investigation of porous MOFs. These methods utilize the Structure Envelope (SE) density maps. SEs are surfaces which describing the pore system with the framework. It was shown that these maps can be easily generated from the structure factors of a few (1 to 10) of the most intense low index reflections. Application of SE in Charge Flipping calculations shortens and simplifies structure determination of MOF materials. This method provides excellent MOF models which can be used as a good starting point for their refinement. However, the most interesting results have been found by using Difference Envelope Density (DED) analysis. DED plots are made by taking the difference between observed and calculated SE densities. This allows us to study guest related issues of MOFs such as, location of guest molecules in the pores, tracking activation of MOFs and gas loading, etc. We also have shown that, DED created from routine powder diffraction patterns might provide very important information about MOF structure itself. In fact DED can be used for study of interpenetration, substituents locations and effects conformational changes in the MOF ligands. Generation and analysis of SEs and DEDs are easy and straightforward. It provides the information needed to explain major deviations in structure-property relationship in MOFs. In our opinion, this method might become one of the important and routine techniques for MOFs structural analysis.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23732号 / 理博第4822号 / 新制||理||1690(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 吉村 一良, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Thesis (Ph. D.)--University of Canterbury, 2010. / Typescript (photocopy). Includes bibliographical references (p. 196-206). Also available via the World Wide Web.

Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xxii, 212 p.; also includes graphics. Includes bibliographical references (p. 203-212). Available online via OhioLINK's ETD Center

Thesis (Ph.D.)--Ohio University, August, 2003. / Title from PDF t.p. Includes bibliographical references (leaves 188-194)

Membrane technology has become a predominant process in providing one of the key components of life (water), either through water and wastewater treatment for water quality purposes or desalination as seen in Ultra-filtration, Nano-filtration, Reverse osmosis, Membrane distillation, Pervaporation, among others. With the ever-increasing demand for portable water due to population increase, constant research has focused on the improvements of the performances of the different water treatment systems including enhancing the performance of the membrane. Among all the different membrane performance enhancement techniques exploited, incorporation of filler has gained much grounds in the last decades. Traditional fillers like silica gel, activated carbon, metal oxides and zeolites are now being challenged by the recent class of mesoporous materials known as Metal Organic Frameworks (MOFs), which are built of metal ions or metal ion clusters linked together by organic ligands giving these materials tunable pore geometries and pore volume, greatly improved surface area with extraordinary adsorptive properties. The membrane incorporating MOFs demonstrate enhance performances more than the other fillers due to the good coordination of the organic moiety and polymers. The overall objective of this project is to develop and study a membrane incorporated MOFs nanofiber system vis-à-vis their applications in heavy metal contaminated water treatment, stability in aqueous media and the advantages and drawbacks of these composite membranes with regards to the quality of the water produced. The developed materials were characterized by SEM, FTIR, TEM, XPS, DSC, and TGA. The heavy metals earmarked for this study include; Lead, Mercury, Cadmium, and Zinc and were studied using flame atomic absorption spectrometry (FAAS). Upon successful fabrication of the nanofiber membranes, detailed adsorption studies were conducted (pristine MOF, pristine nanofibers, enmeshed MOFs) to establish adsorption kinetics and isotherm, which were used further to select the best performing membranes for filtration application. Two different MOFs were used, MOF808; made of Zirconium and Benzene Tricarboxylate) and MOF F300; made of Iron and Benzene Tricarboxylate) The adsorption capacities of the MOFs for the different heavy metal analyzed were; MOF 808 (Pb-170.74 mg g-1, Zn-287 mg g-1, Cd-225.05 mg g-1, Hg-276.96 mg g-1) and MOF F300 (Pb-148.13 mg g-1, Hg-229.66 mg g-1), while the membrane adsorption capacities were; PA808 (MOF 808 embedded within polyacrylonitrile (PA) nanofibers, (Pb-23.98 mg g-1, Hg-50.88 mg g-1), PA300, MOF F300 embedded within polyacrylonitrile nanofibers, (Pb-30.19 mg g-1, Hg-53.09 mg g-1). Upon activation of MOF 808 by water (hydractivation), the removal efficiency of MOF 808 was improved by 10% while the MOF membrane efficiency was increased by 30%. Filtration experiments could produce 577.5 L of treated water with a single layer of PAN/ MOF808 membrane at 0.1 bar using a 50 ppb Pb ion feed solution.

This thesis describes the synthesis, characterisation and catalytic testing of multifunctional immobilised metal nanoparticle in metal-organic framework (MOF) materials. Combining the activity of metal nanoparticles with the porosity and Lewis acidity of metal-organic frameworks provides a single catalytic material which can perform multi-step reactions. Strategies to immobilise the metal nanoparticles within the metal-organic frameworks have been investigated. Immobilisation has been achieved by applying three different methodologies. First, deposition of metal nanoparticle precursors within mesoporous MOFs is discussed. Chapter 3 shows the effectivity of the double solvents deposition technique to achieve dispersed and small nanoparticles of around 2.7 nm. The best system combined Pd nanoparticles with MIL-101(Cr). This system was further investigated in tandem reductive amination catalysis, discussed in Chapter 4, to investigate the activity and selectivity provided by these multifunctional catalysts. Another immobilisation technique was performed by coating Pd decorated SiO2 spheres with a MOF layer. Using this technique, MOF was grown cyclically in solution, providing tuneable shell thicknesses of MOF on the metal nanoparticle decorated oxide spheres. While the homogeneity of the MOF shell needs more optimisation, it was determined that the surface charge on the spheres played an important role in the growth of MOF in the desired location. Finally, the third immobilisation technique is the core-shell growth of MOF on colloidal metal nanoparticles. Polymer-capped metal nanoparticles with well-defined shapes were synthesised and characterised. From here, the optimisation of conditions for core-shell growth of UiO-66 and MIL-100(Sc) were investigated. Conditions which provided the desired core-shell morphology were found for both MOF types. These materials were then subsequently used in tandem reductive amination catalysis and a more straightforward styrene hydrogenation. It was shown that the metal nanoparticles remain active catalysts within either MOF shell and the MOF shell stabilises the metal nanoparticle and acts as a Lewis acid catalyst.