Deeper insight into hydrolysis mechanisms of polyester/cotton blended fabrics for separation by explicit solvent models

Aiming to get a deeper and accurate understanding on separation of polyester/cotton blended fabrics in subcritical water, the hydrolysis mechanisms of cellulose and polyester were studied using dispersion-corrected density functional theory (DFT-D) method with and without explicit H2O under the conductor-like screening model (COSMO) set. The number and locations of explicit H2O were determined by their likely functions including being dissociation and solvent and catalyst. The calculations disclosed that explicit H2O provide inductive activation on glycosidic bond of cellulose and ester groups at the center of polyester and the assistance on the transfer of proton as proton-carrier and as catalyst of proton shuttle, affecting the reaction and activation energies in a realistic manner. In addition, the number of explicit H2O molecules functioning as catalyst of proton shuttle may also has a strong influence on catalytic activity. Based on the improved explicit solvation models, the overall activation energies of proposed hydrolysis mechanisms for cellulose and polyester are 14.81 and 21.46 kcal/mol respectively, which explains the preferential hydrolysis of cellulose from experimental results.