Electronic nature of linkers-based conjugated microporous polymers: a sustainable approach to enhance CO2 capture

Conjugated microporous polymers (CMPs) represent a promising class of materials with diverse applications due to their unique chemophysical characteristics. We introduce a novel approach for developing a TPPDA-TPA CMP- and TPPDA-ThZ CMP-based dynamic tetraphenyl-p-phenylenediamine (TPPDA) unit employing the optimum conditions for the Suzuki protocol. These CMPs incorporate triphenylamine (TPA) and 4,7-di(thiophen-2-yl)benzo[c]thiadiazole (ThZ), and exhibit distinct electronic properties. Our CMPs demonstrate high thermal durability (char yield up to 69.5 wt%) and significant surface areas (up to 132 m(2) g(-1)). The TPPDA-TPA CMP shows a notable presence of nucleophilic bonding sites, enhancing the selective uptake of CO2, with around twofold-higher CO2 uptake (27.49 cm(3) g(-1)) compared with TPPDA-ThZ CMP (14.67 cm(3) g(-1)). Additionally, we evaluate the selectivity of CO2 over N-2 gases on TPPDA CMPs. We analyze CO2 uptake based on key thermodynamic and kinetic principles, including the Clausius-Clapeyron equation and Henry's law. This research offers a promising strategy for enhancing CO2-adsorption capacities on CMPs.