Microporous organic polymers (MOPs) are porous materials. Owing to their high surface area, tunable pore sizes and high physicochemical stability, they are studied for applications including gas capture and separation and heterogeneous catalysis. In this thesis, a series of imine/azo-linked MOPs were synthesized. The MOPs were examined as potential CO2 sorbents and as supports for heterogeneous catalysis. The MOPs were synthesized by Schiff base polycondensations and oxidative couplings. The porosities of the imine-linked MOPs were tunable and affected by a range of factors, such as the synthesis conditions, monomer lengths, monomer ratios. All the MOPs had ultramicropores and displayed relatively high CO2 uptakes and CO2-over-N2 selectivities at the CO2 concentrations relevant for post-combustion capture of CO2. Moreover, the ketimine-linked MOPs were moderately hydrophobic, which might increase their efficiency for CO2 capture and separation. The diverse synthesis routes and rich functionalities of MOPs allowed further post-modification to improve their performance in CO2 capture. A micro-/mesoporous polymer PP1-2, rich in aldehyde end groups, was post-synthetically modified by the alkyl amine tris(2-aminoethyl)amine (tren). The tethered amine moieties induced chemisorption of CO2 on the polymer, which was confirmed by the study of in situ infrared (IR) and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. As a result, the modified polymer PP1-2-tren had a large CO2 capacity and very high CO2-over-N2 selectivity at low partial pressures of CO2. Pd(II) species were incorporated in the selected MOPs by means of complexation or chemical bonding with the imine or azo groups. The Pd(II)-rich MOPs were tested as heterogeneous catalysts for various organic reactions. The porous Pd(II)-polyimine (Pd2+/PP-1) was an excellent co-catalyst in combination with chiral amine for cooperatively catalyzed and enantioselective cascade reactions. In addition, the cyclopalladated azo-linked MOP (Pd(II)/PP-2) catalyzed Suzuki and Heck coupling reactions highly efficiently. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Accepted. Paper 7: Manuscript.</p>

Global CO2 emissions produced by energy-related processes, mainly power plants, have increased rapidly in recent decades; and are widely accepted as the dominant contributor to the greenhouse gas (GHG) effect and consequent climate changes. Among countermeasures against the emissions, CO2 capture and storage (CCS) is receiving much attention. Capture of CO2 is the core step of CCS as it contributes around 75% of the overall cost, and may increase the production costs of electricity by over 50%. The reduction in capture costs is one of the most challenging issues in application of CCS to the energy industry. Using limestone in CaO-looping cycles is a promising capture technology to provide a cost-effective separation process to remove CO2 content from power plants operations. Limestone has the advantage of being relatively abundant and cheap, and that has already been widely used as a sorbent for sulphur capture. However, this technology suffers from a critical challenge caused by the decay in the sorbent capture capacity during cyclic carbonation/calcination, which results in the need for more sorbent make-up; hence a reduction in cost efficiency of the technology. The performance of sorbent influenced by several operating and reaction conditions. Therefore, much research involves investigation of influencing factors and different methods to reduce the sorbent deactivation. Cont/d.