Agile Construction of Bioinspired Porous Ionic Hyper-Crosslinked Polymers for Enhanced CO ₂ Capture and Conversion

Hydrogen bond interactions between alkaloids in deoxyribonucleic acid (DNA) maintain the stability of the double helix structure. Inspired by this principle, in this work, we present a one-pot synthesis of ionic hyper-cross-linked polymers (iHCPs) via simultaneous quaternization and Friedel–Crafts alkylation reactions of alkaloids and biphenyl dichloride (BP). These iHCPs exhibited hydrogen bonding capabilities, abundant alkaline and ionic active sites, as well as hierarchically porous structures with ultrahigh surface areas (up to 1480 m 2 ·g –1 ). The optimized iHCPs, AN-BP(1:3), demonstrated exceptional CO 2 adsorption (154.4 mg·g –1 at 273 K and 1 bar) and served as a recyclable catalyst for the solvent-free conversion of CO 2 and epoxides into cyclic carbonates without requiring additional cocatalysts. In situ FTIR spectroscopy and density functional theory (DFT) calculations revealed that basic groups enhanced the CO 2 adsorption and facilitated chloride ions in promoting the epoxide ring-opening reaction via hydrogen bonding, thereby reducing the relative Gibbs free energy barrier. This work establishes a bioinspired design paradigm for ionic polymers by integrating pore engineering with hydrogen-bond catalysis, thus advancing both CO 2 capture and conversion.