(641b) Computational Analysis of Monomer and Dimer Adsorption Trends in the MFI Framework

Porous aluminosilicates such as zeolites are ubiquitous catalysts for the production of high-value and industrially relevant commodity chemicals, including the conversion of hydrocarbons, amines, alcohols, and others. Bimolecular reactions are an important subclass of reactions that can occur on Brønsted acid sites of a zeolite catalyst. Kinetic modeling of these systems at the process scale requires the interaction energetics of reactants and the active sites to be described accurately. It is generally known that adsorption is a coverage-dependent phenomenon, with lower heats of adsorption observed for molecules at higher coverage. However, few studies have systematically investigated the co-adsorption of molecules on a single active site, specifically focusing on the strength of interaction of the second adsorbate after the initial adsorption step. In this work, we quantify the unimolecular and bimolecular adsorption energies of varying adsorbates, including paraffins, olefins, alcohols, amines and non-condensible gases in the acidic and siliceous ZSM-5 frameworks. As a special case, olefin adsorption was examined for physisorption and chemisorption regimes, characterized by pi-complex, framework alkoxide and carbenium ion adsorption, respectively. The effect of functional groups and molecular size were quantified, and correlations that relate the adsorption of the second adsorbate identity to that of the first adsorbate are provided.