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• Water markedly affected phase change behaviors of anhydrous biphasic absorbents. • The presence of water was negative for CO 2 absorption but beneficial to desorption. • The main CO 2 -product was HCO 3 - in the presence of water rather than carbamate. • Effect of water on CO 2 absorption mechanism of [N 1111 ][Gly]/ethanol was clarified. The ionic liquids (ILs)-based biphasic absorbents are viewed as promising substitutes for CO 2 capture due to their remarkable CO 2 absorption performance, excellent stability and low energy requirement for regeneration. Further decreasing the regeneration heat requirement can be achieved by utilizing ILs-based anhydrous biphasic absorbents, whose solid CO 2 -rich phase contained small volume and low specific heat capacity. Given the high hygroscopicity of ILs and the water present in the flue gas, comprehending the effect of water is crucial for post-combustion carbon capture using ILs-based anhydrous biphasic absorbents. In this work, the effect of water on CO 2 absorption by an anhydrous biphasic absorbent, tetramethylammonium glycinate ([N 1111 ][Gly])/ethanol, was studied. The experimental results demonstrated that the CO 2 loading and absorption rate were decreased in the presence of water, but the CO 2 desorption efficiency was enhanced. Besides, the presence of water slightly reduced the reaction heat of CO 2 absorption by [N 1111 ][Gly]/ethanol to 69.48 kJ/mol CO 2 , which was 20% lower than that of monoethanolamine (MEA) absorbent. Furthermore, the 13C NMR results indicated that the primary CO 2 -product was bicarbonate in the presence of water rather than carbamate. There were three possible pathways for bicarbonate generation: zwitterion hydrolysis, carbamate hydrolysis, and base-catalyzed CO 2 hydration. Water and ethanol competed to react with carbamate. When a large amount of water was present (≥70 wt%), the reaction of ethanol with the carbamate hardly occurred. [ABSTRACT FROM AUTHOR]

• Three possible pathways for bicarbonate generation were investigated based on DFT. • Base-catalyzed CO 2 hydration is dominant in [N 1111 ][Gly]/EtOH aqueous system. • Water effect on phase change behavior is analyzed from hydrogen bonding view. • Water content of 5 wt% promotes products aggregation in favor of phase change. Ionic liquids-based anhydrous biphasic absorbents have the potential to lower the energy consumption for CO 2 capture. Recent experimental studies have revealed that the presence of water in [N 1111 ][Gly]/EtOH system leads to generation of a new CO 2 -product – bicarbonate and affects the phase change behavior. However, the reaction pathway for bicarbonate formation remains unclear. In this work, the reaction pathways were investigated in depth through quantum chemical calculations employing density functional theory, with reaction rate constants determined via transition state theory. Among the three possible reaction pathways, the base-catalyzed CO 2 hydration reaction prevailed, i.e. a one-step reaction involving [Gly]-, H 2 O, and CO 2. An H atom in H 2 O was transferred to [Gly]-'s amino group, forming protonated [Gly]-, and hydroxide combined with CO 2 to generate bicarbonate. Additionally, molecular dynamics simulations were conducted to understand the phase change behaviors with varying water content. When water content exceeded 5 wt%, an increased water content led to reduced hydrogen bonding among products and enhanced hydrogen bonding of products-solvent with the solvent, diminishing product self-aggregation. No phase change behavior were observed at water contents up to 80 wt%. This study could well explain the experimental phenomena of water effect on CO 2 absorption in [N 1111 ][Gly]/EtOH, providing theoretical references for application of ILs-based anhydrous biphasic absorbent. [ABSTRACT FROM AUTHOR]