Adsorption and diffusion of benzene in the nanoporous catalysts FAU, ZSM-5 and MCM-22: A molecular dynamics study

Molecular dynamics (MD) simulations of benzene in siliceous zeolites (FAU, ZSM-5, and MCM-22) were performed at loadings of 1, 2, 4, 8, and 16 molecules per supercell. The potential energy functions for these simulations were constructed in a semi-empirical way from existing potentials and experimental energetic data. The MD simulations were employed to analyze the dynamic properties of the benzene–zeolite systems. The adsorption energies of benzene/siliceous zeolite complexes increase with increasing loading number, due to the intermolecular attraction between benzene molecules. The self-diffusion coefficient of benzene in siliceous zeolites decreases with increasing loading due to the steric hindrance between the sorbates passing each other. From the zeolite–benzene radial distribution functions it was found that the benzene molecules are relatively far from each other, about 5.2 Å for siliceous FAU, 5.2 Å for siliceous ZSM-5, and 4.8 Å for siliceous MCM-22. In the case of FAU, the benzene molecules prefer to be adsorbed parallel to the surface of the sodalite cage above the six-membered-ring. In ZSM-5, we found a T-structure of the benzene molecules at loadings 2, 4, and 8 molecules per supercell. At loadings of 16 molecules per supercell, the molecules are lined up along the straight channel and their movement is highly correlated. For MCM-22 we found adjacent benzene molecules at a loading of 4 molecules with an orientation similar to the stacked conformation of benzene dimer in the gas phase.