Solvation effect on binding modes of model lignin dimer compounds on MWW 2D-zeolite

Lignin as a potential renewable source of biofuels, chemicals, and other value-added products has gained much attention. However, the complexity of lignin structure poses a significant challenge for developing efficient valorization techniques. As most processes involve solvothermal conditions to minimize energy cost, lignin depolymerization is governed by reaction conditions (temperature and pressure) and solvents. In this work, binding of β-O-4 linkage consisting lignin dimers on MWW two-dimensional (2D) zeolite is investigated using periodic density functional theory. Furthermore, the effect of different terminated surfaces (H:OH% = 100:0; 50:50; 0:100%), different temperatures (323, 353, 373 K), and different solvents (water and methanol) on the binding modes is quantified. Our work shows that in the gas phase the binding strength increases 10-15 kcal/mol upon increasing the number of hydroxyl groups on the surface. Also, the phenolic dimer binds more strongly than the nonphenolic dimer, and the binding strength of model compounds increases in the presence of the solvent. Analysis of structural changes in the presence of the solvent reveals that the aromatic rings are parallel to the zeolite surface and primary interaction with zeolite is through the hydroxyl groups near the β-O-4 linkage. Furthermore, while the solvation energy decreases with increasing temperature, the opposite trend is observed for the binding energy with the surface.