Catalyst surroundings may influence adsorption, reaction, and activation free energies, thereby providing additional degrees of freedom for tuning the reaction kinetics. The critical environmental factors include a solvent, an electrical double layer, confinement, an attached polymer, a ligand, and an enzyme pocket. Synergetic effects of combinations of factors provide new opportunities for controlling reaction rates, breaking linear scaling relationships, and ultimately designing novel environmentally benign and energy-efficient catalytic processes.<br/><br/>Herein, we investigate the synergy between the dynamics of mixed solvents and the effects of the confinement on the catalytic activity of Ti-BEA zeolite in alkene epoxidation reactions using computational methods. We develop a multiscale model of a catalytic site and its environment that combines periodic grand-canonical Monte Carlo simulations, cross-validated against Gibbs ensemble Monte Carlo, and the cluster-model, state-of-the-art quantum mechanics/molecular mechanics methodology to describe chemical bonding and polarization effects. The effects of solvent composition and the chain length of alkene-derived epoxides on adsorption of both solvent and substrate are revealed and compared with available experimental calorimetry, NMR, and kinetics data.

Quantitative simulations of confinement-modulated solvent effects in zeolite catalysis

ACS Spring 2022

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