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Identifier 000460098
Title Development of novel Metal-Organic Frameworks (MOFs) with dynamic behavior and selective gas/vapor sorption properties
Alternative Title Ανάπτυξη καινοτόμων Μέταλλο-Οργανικών Πλεγμάτων (MOFs) με δυναμική συμπεριφορά και ιδιότητες εκλεκτικής προσρόφησης αερίων και ατμών
Author Μανουσάκης, Κυριάκος Ε.
Thesis advisor Τρικαλίτης, Κυριάκος
Reviewer Μήλιος, Κωνσταντίνος
Φρουδάκης, Γεώργιος
Abstract This thesis delves into the study of reticular chemistry, specifically the chemistry of metal-organic frameworks (MOFs). First, we study the complex behavior of the third generation of MOFs, the dynamic/flexible MOFs. We report the synthesis and characterization of a chemically robust, flexible microporous MOF based on a functionalized carboxylate linker, a diamine linker, and nickel. This material has been thoroughly characterized, focusing on its vapor sorption capabilities. Notably, in the case of polar vapors, the material displays a stepwise sorption isotherm associated with framework flexibility. On the other hand, non-polar vapors are not being adsorbed, indicating a high selectivity towards the polar ones. Pre-synthetic and post-synthetic modification procedures using this MOF as a base, with the diamine linker or metal substitution, led to the formation of five more MOF materials of which the flexible behavior, if any, was investigated. Moreover, another flexible MOF was synthesized based on the same functionalized carboxylate linker with manganese. This structure possessed many coordinated solvent molecules, and their substitution by other solvent molecules led to a non-reversible structural transformation. Despite that, this MOF proved to possess a higher affinity toward the sorption of more polar vapors. The flexible behavior of the MOFs investigated in this work proved to be important for industrial-level gas storage and gas separation applications among many other potential applications. In a different study, we utilized the isoreticular expansion technique to explore the creation of MOFs with an extended tetratopic bicarbazole linker as a building block. Our goal was to construct porous structures with larger cavities and more porosity. We experimented with various metal sources but only managed to produce either microcrystalline, microporous MOF structures or interpenetrated ones. This extension of the linker by adding aromatic rings introduces strong π-π interactions between the molecules, and makes them less soluble in most MOF synthesis solvents. Moreover, using this linker favors the formation of interpenetrated frameworks due to the strong π-π interactions and large cavities created. We solved these challenges by adding methyl groups to the extended linker, increasing its solubility in the solvents used in MOF synthesis, and decreasing the probability of forming interpenetrated frameworks. We created two new MOF structures using zirconium and yttrium, with the zirconium-based MOF containing the first in literature 16-connected Zr6 cluster. Our findings show that adding alkyl groups during MOF synthesis can reduce the problems of solubility of the ligand, and formation of interpenetrated frameworks, leading to the discovery of novel MOFs with larger cavities and higher porosity that can address many important energy problems.
Language English, Greek
Subject Coordination polymers
Extended structures
Flexibility
Porous
Εκτεταμένες δομές
Ευκαμψία
Πολυμερή συναρμογής
Πορώδη
Issue date 2023-11-23
Collection   School/Department--School of Sciences and Engineering--Department of Chemistry--Post-graduate theses
  Type of Work--Post-graduate theses
Permanent Link https://elocus.lib.uoc.gr//dlib/0/b/4/metadata-dlib-1698934954-440975-20349.tkl Bookmark and Share
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