Thermal behaviour of siliceous faujasite: further structural interpretation of negative thermal expansion

The high-temperature behaviour of siliceous faujasite (Si-Y) was investigated by in situ synchrotron Xray powder diffraction from room temperature up to 1123 K. This porous phase is remarkably stable
when heated, and no phase transitions or changes in symmetry are observed. A marked negative thermal expansion (NTE), already reported in literature for a heating range from 25 to 573 K, was confirmed up to
about 923 K. Above this temperature a positive thermal expansion was observed. Si-Y’s thermal behaviour was interpreted on the basis of the transverse thermal vibrations of the oxygen atoms involved in
the T–O–T linkages and a series of other structural features characterizing the faujasite structure, namely the T–T distances between adjacent tetrahedral sites, the thickness of the double 6-membered rings, and
the ditrigonal index of the 6-membered rings. Moreover, the thermal behaviour of several other anhydrous porous materials with NTE behaviour is discussed and compared to that of Si-Y.