Defense Date

2015

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Dr. Hani M. El-Kaderi

Abstract

Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO2 capture.

Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 m2 g-1 and have high chemical and thermal stabilities. The nitrogen atoms of the azo group can act as Lewis bases and the carbon atom of CO2 can act as a Lewis acid. Therefore, ALPs show high CO2 uptake capacities due to this Lewis acid-based interaction. The potential applications of ALPs for selective CO2 capture from flue gas, natural gas, and landfill gas under pressure-swing and vacuum swing separation settings were studied. Due to their high CO2 uptake capacity, selectivity, regenerability, and working capacity, ALPs are among the best porous organic frameworks for selective CO2 capture.

In our second project, a new bis(imino)pyridine-linked porous polymer (BIPLP-1) was synthesized and post-synthetically functionalized with Cu(BF4)2 for highly selective CO2 capture. BIPLP-1 was synthesized via a condensation reaction between 2,6-pyridinedicarboxaldehyde and 1,3,5-tris(4-aminophenyl)benzene, wherein the bis(imino)pyridine linkages are formed in-situ during polymerization. The functionalization of the polymer with Cu(BF4)2 was achieved by treatment of the polymer with a solution of Cu(BF4)2 via complexation of copper cations with bis(imino)pyridine moieties of the polymer. BF4- ions can act Lewis base and CO2 can act as a Lewis acid; and therefore, the functionalized polymer shows high binding affinity for CO2 due to this Lewis acid-based interaction. The functionalization of the pores with Cu(BF4)2 resulted in a significant enhancement in CO2 binding energy, CO2 uptake capacity, and CO2 selectivity values. Due to high reactivity of bis(imino)pyridines toward transitions metals, BIPLP-1 can be post-synthetically functionalized with a wide variety of inorganic species for CO2 separation and catalytic applications.

Rights

© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

12-7-2015