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A novel polymeric acid catalyst immobilized on a membrane substrate was found to possess superior catalytic activity and selectivity for biomass hydrolysis. The catalyst consists of two polymer chains, a poly(styrene sulfonic acid) (PSSA) polymer chain for catalyzing carbohydrate substrate, and a neighboring poly(vinyl imidazolium chloride) ionic liquid (PIL) polymer chain for promoting the solvation of the PSSA chain to enhance the catalytic activity. In order to elucidate the mechanism and determine the energetics of biomass catalytic processing using this unique catalyst, classical molecular dynamics (MD) coupled with metadynamics (MTD) simulations were conducted to determine the free energy surfaces (FES) of cellulose hydrolysis. The critical role that PIL plays in the catalytic conversion is elucidated. The solvation free energy and the interactions between PSSA, PIL, and cellulose chains are found to be significantly affected by the solvent.

Elucidating the Energetics and Effects of Solvents on Cellulose Hydrolysis Using a Polymeric Acid Catalyst