Intermolecular interactions upon carbon dioxide capture in deep-eutectic solvents

Abstract

Herein we report the CO₂ uptake in potential deep-eutectic solvents (DESs) formed between hydrogen bond acceptors (HBAs) such as monoethanolammonium chloride ([MEA·Cl]), 1-methylimidazolium chloride ([HMIM·Cl]) and tetra-n-butylammonium bromide ([TBAB]) and hydrogen bond donors (HBDs) like ethylenediamine ([EDA]), diethylenetriamine ([DETA]), tetraethylenepentamine ([TEPA]), pentaethylenehexamine ([PEHA]), 3-amino-1-propanol ([AP]) and aminomethoxypropanol ([AMP]) and analyzed the outcome in terms of the specific polarity parameters. Among various combinations of HBAs and HBDs, [MEA·Cl][EDA]-, [MEA·Cl][AP]-, [HMIM·Cl][EDA]- and [HMIM·Cl][AP] showed excellent CO₂ uptake which was further improved upon increasing the mole ratio of HBA : HBD from 1 : 1 to 1 : 4. The lowest CO₂ uptake in [MEA·Cl][PEHA] (12.7 wt%) and [HMIM·Cl][PEHA] (8.4 wt%) despite the highest basicity of [PEHA] infers that the basicity is not the sole criteria for guiding the CO₂ uptake but, in reality, CO₂ capture in a DES relies on the interplay of H-bonding interactions between each HBA and HBD. The role of HBAs in guiding CO₂ uptake was more prominent with weak HBDs such as [TEPA] and [PEHA]. The speciation of absorbed CO₂ into carbamate, carbonate, and bicarbonate was favorable in DES characterized by comparable hydrogen bond donor acidity (α) and hydrogen bond acceptor basicity (β) values, whereas the conversion of carbamate to carbonate/bicarbonate was observed to depend on α. The addition of water in DES resulted in lower CO₂ uptake due to the decreased basicity (β).