Pyrene-Derived Porous Organic Polymers: Design, Synthesis, and Application to Gas Storage and Separation

• Main Author: Sekizkardes, Ali Kemal, PhD
• Format: Others
• Published: VCU Scholars Compass 2014
• Subjects: Porous Polymers; Nanoporous Materials; Gas Separation; Gas Storage; CO2 capture
• Online Access: http://scholarscompass.vcu.edu/etd/3649; http://scholarscompass.vcu.edu/cgi/viewcontent.cgi?article=4666&context=etd

Porous organic polymers (POPs) received great attention in recent years because of their novel properties such as permanent porosity, adjustable chemical nature, and remarkable thermal and chemical stability. These attractive features make POPs very promising candidates for use in gas separation and storage applications. In particular, CO2 capture and separation from gas mixtures by POPs have been intensively investigated in recent years because of the greenhouse nature of CO2, which is considered a leading cause for global warming. CO2 chemical absorption by amine solutions from the flue gas of coal-fired power plants suffers from several challenges such as high-energy consumption in desorption, chemical instability, volatility, and corrosive nature, limiting the widespread use of this technology. To mitigate these limitations, new adsorbents with improved CO2 capturing properties need to be designed, synthesized, and tested. Alternatively, the use of cleaner fuels such as methane can reduce CO2 release or completely eliminates it in the case of hydrogen. However, the on-board storage of methane and hydrogen for automotive applications remains a great challenge. With these considerations in mind, our research goals in this dissertation focus on the systematic design and synthesis of N-rich POPs and their use in small gas (H2 and CH4) storage as well as selective CO2 capture from gas mixtures. In particular, we have studied the effect of integrating pyrene and triazine building units into benzimidazole-linked polymers (BILPs) and covalent organic frameworks (COFs) on gas storage and separation. We have found that pyrene-based BILPs exhibit remarkable selective CO2 capturing capacities under industrial settings (VAS, PSA). However the methane and hydrogen storage capacities of BILPs were found to be only modest especially at high pressure due to their moderate surface area and pore volume. We addressed these limitations by the synthesis of a highly porous imine-linked COF (ILCOF-1), which has very high surface area and improved hydrogen and methane uptakes when compared to BILPs. We have demonstrated that the use of pyrene in BILPs and COFs can direct frameworks growth through - stacking and improve porosity and pore volume whereas the use of triazine is instrumental in improving the binding affinity of the frameworks towards CO2.