Theoretical study of modes of adsorption of water dimer on H-ZSM-5 and H-Faujasite zeolites

Modes of adsorption of water dimer on H-ZSM-5 and H-Faujasite (H-FAU) zeolites have been investigated by a quantum embedded cluster approach, using the hybrid B3LYP density functional theory. The results indicate that there are two possible adsorption pathways, namely the stepwise process where only one water binds strongly to the (-O)3-Al-O(H) tetrahedral unit while the other weakly binds to the zeolite framework and the concerted process where both water molecules form a large ring of hydrogen-bonding network with the Br?nsted proton and an oxygen framework. With inclusion of the effects of the Madelung potential from the extended zeolite framework, for adsorption on H-ZSM-5 zeolite, both the neutral and ion-pair complexes exist with adsorption energies of -15.13 and -14.73 kcal/mol, respectively. For adsorption on the H-FAU, only the ion-pair complex exists with the adsorption energy of -14.63 kcal/mol. Our results indicate that adsorption properties depend not only on the acidity of the Br?nsted acidic site but also on the topology of the zeolite framework, such as on the spatial confinement effects which lead to very different adsorption structures for the ion-pair complexes in H-ZSM-5 and H-FAU, even though their adsorption energies are quite similar. Our calculated vibrational spectra for these ion-pair complexes support previous experimental IR interpretations.