Structural phase stability of Se clusters in zeolites

The effect of confinement on the structural phase of Se clusters in zeolites (LTA and FAU) has been studied in the temperature range of 300 ～ 550K by Raman scattering and differential scanning calorimetry. It has been found in Raman spectra that the structural unit and phase stability of Se clusters are greatly affected by the geometrical restriction in the zeolites. No clear phase transformation was observed by DSC measurements for Se clusters in LTA zeolites, while Se clusters in FAU zeolites exhibit a distinct endothermic peak which is ascribed to a glass transition. The glass transition temperature of amorphous Se (320 K) is remarkably elevated when Se rings/chains are incorporated in FAU zeolites; the higher glass transition temperature for the smaller window diameter of zeolites. We have also found that the activation energy for the glass transition is decreased drastically in the zeolites; the smaller activation energy for the smaller window size. The observations imply that the kinetics of the structural relaxation at the glass transition of Se is significantly influenced by the absence of inter-cluster interaction and that the thermokinetic dimension becomes lower owing to the geometrical restriction in the zeolites.