Insight into the role of ion-pairing in the adsorption of imidazolium derivative-based ionic liquids by activated carbon.

The association of the cation and anion of ionic liquids (ILs) dominates the absorbability of ILs by activated carbon (AC). Nevertheless, the mechanism behind the role of ion-pairs is largely unknown. In this study, the adsorption of a series of imidazolium derivative-based ILs by AC was involved in response to the octanol-water partition coefficient (K), hydrogen bonding acidity (α), ion-pair binding constants (K), binding energy of ion-pairs (E) and density functional theory (DFT) calculation of ILs. A significant positive correlation between lg K and K and between K and lg K was observed (p < 0.05). However, both E and α was inversely proportional to K. Hence, the substitution of oxygen-containing functional groups, such as carboxyethyl, 1-methoxyethyl, and 1-(ethoxycarbonyl)methyl, on imidazolium ring enhanced the hydrogen bond interaction with water molecules and then weakened the binding of imidazolium cation and [NTf], thereby reducing the adsorption of ILs to AC. DFT calculation further revealed that the polar substitution improved the electron density and electronegativity of imidazolium skeleton. By contrast, the ILs functionalized with non-polar groups (e.g., butyl, allyl, and benzyl) generally displayed high K values and low α values. Consequently, the formation of hydrogen bond between the oxygen-containing functional groups of IL cation and water would facilitate the dissociation of IL ion-pairs and then decrease the adsorption of ILs on AC.