The role of water in the elastic properties of aluminosilicate zeolites: DFT investigation.

The bulk and Young moduli and heats of hydration have been calculated at the DFT level for fully optimized models of all-siliceous and cationic zeolites with and without water, and then compared to the corresponding experimental data. Upon the addition of water, the monovalent alkali ion and divalent alkaline earth ion exchanged zeolites presented opposite trends in the elastic modulus. The main contribution to the decrease in the elastic modulus of the alkali ion exchanged zeolites appeared to be a shift of cations from the framework oxygen atoms upon water addition, with the coordination number often remaining the same. The contrasting increase in elastic modulus observed for the divalent (alkaline earth) ion exchanged zeolites was explained by cation stabilization resulting from increased coordination, which cannot be achieved within a rigid zeolite framework without water.