Molecular and dissociative adsorption of H2O on zeolite Zn/ZSM-5 studied by diffuse-reflectance IR spectroscopy and quantum chemical calculations

Interest in water adsorption on cation-substituted zeolites is due to the possibility of the M n+ (H2O) + [Si-O-Al]−1 → MOH(n − 1)+ + Si-O(H)-Al (M = metal, n = 1–3) reaction taking place. As a result of this reaction, the cation-substituted zeolite can exhibit Bronsted acid activity. The molecular adsorption of water on Zn/ZSM-5 zeolite at room temperature and the subsequent heterolytic dissociation of adsorbed water under heating have been investigated by diffuse-reflectance IR spectroscopy. For theoretical simulation of these processes, three different fragments of the ZSM-5 lattice corresponding to possible variants of the structure of the ionic site of the substituting cation have been examined. Calculations on the molecular and dissociative adsorption of water molecules on substituting Zn2+ cations have been performed by the DFT method. Two pathways of the dissociation of adsorbed H2O molecules-endothermic and exothermic ones-have been discovered, and it has been demonstrated that the spatial separation of two lattice Al ions at the Zn2+ cation site significantly affects the adsorption energy.