ABSTRACT This study systematically investigates the impact of molecular isomerism on CO capture using hydrophobic deep eutectic solvents composed of DBU and four stereoisomeric terpenes: Geraniol, nerol, linalool, and L‐menthol. Experimental results demonstrate that the linear trans‐configured geraniol‐based DES exhibits superior performance (0.59 mol/mol) and favorable hydrodynamics due to lower viscosity, whereas sterically hindered isomers show reduced capacity. DFT calculations reveal a base‐promoted concerted mechanism strictly governed by steric hindrance. Consequently, activation free energy barriers follow the order: Geraniol < Menthol < Nerol < Linalool. Furthermore, microwave‐assisted regeneration achieved 86% capacity recovery within 30 s, ensuring rapid cyclability. This work establishes a rigorous structure‐activity relationship, highlighting the pivotal role of stereochemical topology in designing efficient, water‐tolerant non‐aqueous absorbents.
Song et al. (Mon,) studied this question.