Carboxyl-Enriched Conjugated Microporous Polymers: Impact of Building Blocks on Porosity and Gas Adsorption

Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m2·g- 1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO2 capture capabilities of 2.17 and 2.63 mmol·g- 1 (at 273 K and 1.05 × 105 Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO2 capture capabilities of 1.66 and 2.28 mmol·g- 1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.