Insertion of Oxygen and Nitrogen in the Siliceous Zeolite TON at High Pressure

Abstract

The insertion of oxygen and nitrogen molecules in the one-dimensional (1D) pore system of the zeolite TON was studied at high pressure by vibrational spectroscopy, X-ray diffraction, and Monte Carlo (MC) molecular modeling. Rietveld refinements and MC modeling indicate that, on average, six diatomic molecules per unit cell enter the pores of the zeolite. This induces changes in compressibility and distortion related to theCmc21-to-Pbn21phase transition compared to the empty-pore material. The filling behavior with N2and O2under pressure is similar to that of argon, suggesting that the kinetic diameter, which is very close in these three systems, plays a major role. The orientation of the diatomic molecules appears to have a rather minor effect on filling occurring at a slightly higher pressure for N2, which has a larger kinetic diameter. Both inserted molecules, initially not showing any marked orientation, begin to exhibit a degree of orientational order above 2 GPa.