The Role of Nonequilibrium Solvent Effects in Enhancing Direct CO₂ Capture at the Air–Aqueous Amino Acid Interface

Direct air capture (DAC) technologies are limited by the poor understanding of the dynamic role of interfaces in modulating the chemisorption of CO₂ from air into solutions. While the reactivity of aqueous amine-based solvents in the bulk environment is strongly inhibited by nonequilibrium solvent effects, promoting DAC at interfaces posits a possibility to reduce the coupling with the solvent and significantly accelerate DAC. Building on an experimentally proven concept to bring an anionic glycine absorbent to the interface through ion-pairing interactions with a positively charged surfactant, we establish the fundamental time scales for key elementary steps involved in DAC with rate theory and enhanced-sampling <i>ab initio</i> molecular dynamics simulations. We elucidate the mechanism by which water influences the free energy barriers and dynamical crossing-recrossing of those barriers, affecting the reaction rates. We find that water reorganizes to partially dehydrate [-NH₂], facilitating S_N2-based CO₂ conversion to a zwitterion, which then releases a proton via overhydration of [-NH₂]. The low-density interfacial water favors dehydration over overhydration, leading to a comparatively higher barrier (slower kinetics) for proton release. The barrier-recrossing events neutralize this effect, letting both steps occur at the same time scale (sub-microseconds) and making the overall DAC process faster at the interface than in the bulk water. Such an understanding of environment-sensitive solvent effects on the reaction kinetics will help design tailored interfaces for enhanced CO₂ capture kinetics via control of solvation and ion paring.