Molecular insights into CO ₂ -to-bicarbonate transformation in functionalized anion exchange ionomers for electrochemical separations

Bipolar membrane (BPM) electrochemical processes are a promising platform for carbon dioxide (CO₂) separations, but the molecular level thermodynamic and kinetic understanding of CO₂-to-bicarbonate (HCO₃^-) transformation remain poorly understood. This study employs a multiscale computational approach to systematically explore the adsorption and reactive transformation of CO₂ in five anion exchange ionomer systems. Classical molecular dynamics (MD) simulation results demonstrate that polymers with imidazolium groups significantly reduce CO₂ diffusion and enhance (OH^-)-CO₂ interactions due to stronger electrostatic and π-interactions. Compared to the commonly used quaternary ammonium ionomers, imidazolium-functionalized ionomers show improved CO₂ proximity and interaction strength. <i>Ab initio</i> MD and density functional theory (DFT) calculations reveal that the benzyl-substituted imidazolium (IM-Ben) substantially reduces the energy barrier for HCO₃^- formation (∼72 meV lower) compared to the alkyl-substituted IM-nBu, while also mitigating imidazolium deprotonation under moderate hydration conditions. Transition state analysis shows IM-Ben forms more extensive hydrogen-bonding networks, which stabilize the transition state structure and contribute to a lower energy barrier for bicarbonate formation. These findings highlight the advantage of the adjacent benzyl moiety in enabling efficient CO₂-to-bicarbonate transformation <i>via</i> hydrated hydroxide ion counterions, offering mechanistic insights and clear molecular design principles for optimizing anion exchange ionomers at bipolar membrane interfaces for electrochemical CO₂ separation applications.