Defense Date


Document Type


Degree Name

Doctor of Philosophy



First Advisor

Hani M. El-Kaderi


Porous organic polymers (POPs) with high physicochemical stability have attracted significant attention from the scientific community as promising platforms for small gas separation adsorbents. Although POPs have amorphous morphology in general, with the help of organic chemistry toolbox, ultrahigh surface area materials can be synthesized. In particular, nitrogen-rich POPs have been studied intensively due to their enhanced framework-CO2 interactions. Postsynthetic modification (PSM) of POPs has been instrumental for incorporating different functional groups into the pores of POPs which would increase the CO2 capture properties. We have shown that functionalizing the surface of POPs with nitro and amine groups increases the CO/N2 and CO2/CH4 selectivity significantly due to selective polarization of CO2 molecule. In addition, controlled postsynthetic nitration of NPOF-1, a nanoporous organic framework constructed by nickel(0)-catalyzed Yamamoto coupling of 1,3,5-tris(4-bromophenyl)benzene, has been performed and is proven to be a promising route to introduce nitro groups and to convert mesopores to micropores without compromising surface area. Reduction of the nitro groups yields aniline-like amine-functionalized NPOF-1-NH2. Adequate basicity of the amine functionalities leads to modest isosteric heats of adsorption for CO2, which allow for high regenerability. The unique combination of high surface area, microporous structure, and amine-functionalized pore walls enables NPOF-1-NH2 to have remarkable CO2 working capacity values for removal from landfill gas and flue gas. Benzimidazole-linked polymers have also been shown to have promising CO2 capture properties. Here, an amine functionalized benzimidazole-linked polymer (BILP-6-NH2) was synthesized via a combination of pre- and postsynthetic modification techniques in two steps. Experimental studies confirm enhanced CO2 uptake in BILP-6-NH2 compared to BILP-6, and DFT calculations were used to understand the interaction modes of CO2 with BILP-6-NH2. Using BILP-6-NH2, higher CO2 uptake and CO2/CH4 selectivity was achieved compared to BILP-6 showing that this material has a very promising working capacity and sorbent selection parameter for landfill gas separation under VSA settings. Additionally, the sorbent evaluation criteria of different classes of organic polymers have been compared in order to reveal structure-property relationships in those materials as solid CO2 adsorbents.


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