Abstract
The efficient capture of carbon dioxide (CO2) using polymer, supported ionic liquids (ILs) remains challenging due to limited understanding of atomic-scale interaction mechanisms. Here, a polystyrene (PS) oligomer supported by an amidinium chloride-based IL is proposed as a CO2-absorbing material. Density functional theory (DFT) calculations were employed to investigate the structural, electronic, and intermolecular interaction energy characteristics of the PS oligomer, amidinium chloride ILs, CO2, and their binary and ternary complexes. Molecular electrostatic potential maps (MEPs), reduced density gradient (RDG) plots with non-covalent interaction (NCI) snapshots, quantum theory of atoms in molecules critical point (CP) analysis, and electron localization function (ELF) analysis reveal pronounced hydrogen bonding and dispersion interactions between PS and IL that modulate the electronic environment of the IL anion, which is the primary CO2 binding site. Interaction energy calculations show that the ternary PS–IL–CO2 complex exhibits a significantly enhanced binding energy compared to the isolated IL–CO2 complex, providing quantitative evidence for the cooperative role of the PS support. The results indicate enhanced CO2 binding in the presence of PS supported by ILs, driven by cooperative electrostatic and dispersion interactions. These findings provide molecular-level insights into CO2 capture mechanisms in polymer–IL hybrid systems.