Influence of crystallite size on cation conductivity in faujasitic zeolites.

The influence of particle size on the ionic conductivity of ceramic materials is an active area of research, and novel effects are observed as particles approach the nanoscale in size. Zeolites are crystalline aluminosilicates with ion-exchangeable cations that are responsible for ionic conductivity at high temperatures. In this paper, we present systematic results for the first time of ionic conductivity in alkali metal ion-exchanged faujasitic zeolites with morphologies ranging from a zeolite membrane, micrometer-sized, submicrometer, and nanoparticles of zeolite. Using impedance spectroscopy in the range of 10 MHz to 0.1 Hz, we have obtained the activation energy (E(act)) of cation motion with these various morphologies in the temperature range of 525-625 °C. Overall, the E(act) decreases with Si/Al ratio. Surface modification of the zeolite particles was carried out with a silylating agent, which upon high temperature calcination should lead to the formation of a monolayer Si-O-Si film on the particle surface. This surface modification had minimal influence on the E(act) of micrometer-sized zeolites. However, E(act) increased rapidly as the zeolite particle approached the nanoscale. These observations led us to propose that, for the high-temperature, low-frequency (10(4)-10(5) Hz), long-range ionic conduction in zeolites, cation hopping across grain boundaries is relevant to ion transport, especially as the size of the crystallite approaches the nanoscale. Intergrain boundaries are more defective in the nanosized zeolite and contribute to the higher E(act).