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Novel Pathways to Synthesize Organic-Inorganic Polymers with Controlled Characteristics

Elham Tavakoli, University of Nebraska - Lincoln


Emerging two-dimensional (2D) materials have been recognized as a platform to design and synthesize materials with superior properties. Recently, 2D Covalent Organic Frameworks (COFs) consisting of pure organic building blocks, regarded as “organic zeolites” have been arisen. They represent a new class of crystalline porous materials constructed with predictable and tunable structures, porosity, and functionality. Having promising properties, such as high surface area, well-defined pore geometry, high thermal and chemical stability, COFs have found widespread applications in energy storage, catalysis, separations, and photoelectronic applications. Conventional methods reported for COFs synthesis suffer from long reaction time and solvent sensitivity. More importantly, low solubility and hard-to-processability hampered further developments. In this thesis, we focus on novel approaches for in-situ synthesis of COFs on arbitrary substrates. We also investigate the operational and chemical parameters that influence the physical and chemical properties of the deposited materials. In the second chapter, we report an electrochemical approach for poly(5,10,15,20-tetrakis(4-aminophenyl) porphyrin)-covalent organic frameworks (POR-COFs) via phenazine linkages. The importance of operational parameters such as potential scan rate, temperature, and substrate, as well as the role of pyridine as a co-crystallization agent, is revealed. The structure-to-function relationship of deposited material toward Oxygen Reduction Reaction (ORR) catalysis isalso shown. In Chapter 3, the parameters involved in the electropolymerization of TAPP were optimized to achieve free-standing poly(TAPP) (PTAPP) film. The performance of the fabricated PTAPP membranes is evaluated towards organic solvent nanofiltration and gas separation. Finally, in Chapter 4, we designed and assembled a state-of-art vapor deposition reactor to deposit POR-COFs via a solvent-free approach on various substrates. The crystalline growth of POR-COFs is carefully studied.

Subject Area

Materials science|Inorganic chemistry|Chemical engineering|Organic chemistry|Polymer chemistry|Morphology|Chemistry

Recommended Citation

Tavakoli, Elham, "Novel Pathways to Synthesize Organic-Inorganic Polymers with Controlled Characteristics" (2021). ETD collection for University of Nebraska-Lincoln. AAI28645164.