Solvate-supported proton transport in zeolites.

Solvate-supported proton transport in zeolite H-ZSM-5 was studied by means of complex impedance spectroscopy. The zeolite shows enhanced proton mobility in the presence of NH3 and H2O that depends on the concentration of the solvate molecule, temperature (298-773 K), and the SiO2/Al2O3 ratio of the zeolite (30-1000). In general, proton conductivity in H-ZSM-5 is most effectively supported in the presence of NH3 and H2O at high concentrations, low temperatures, and low SiO2/Al2O3 ratios (< or = 80). For the aluminum-rich samples desorption measurements reflect different transport mechanisms that depend on the respective temperature range. Up to about 393 K a Grotthus-like proton transport mechanism is assumed, whereas at higher temperatures (393-473 K) vehiclelike transport seems to dominate. The activation energies for NH4+ and H3O+ vehicle conductivity depend on the SiO2/Al2O3 ratio, and the values are in the range of 49-59 and 39-49 kJ mol-1, respectively, and thus significantly lower than those for "pure" proton conduction in solvate-free samples.