Flexibility and phase transitions in zeolite frameworks (Vol. 42, No. 4)

image Detail of a zeolite structure built from corner-sharing tetrahedral units.

The zeolites are a group of minerals whose complex and beautiful atomic structures are formed by different arrangements of a very simple building block- a group of four oxygen atoms forming a tetrahedron, with a silicon or aluminium atom at the centre. Each oxygen atom belongs to two tetrahedra, so the structure can be viewed as a network of tetrahedra linked at the corners.

Zeolites have found widespread applications in chemical industry, particularly as catalysts. Their chemical properties depend on the shape of the pores and channels that run through the structure, containing water molecules, ions and even small organic molecules. More than a hundred different frameworks are known to exist in natural minerals or have been synthesised by chemists.

A fundamental geometric question is whether it is possible for the tetrahedra of the framework to exist in an undistorted, geometrically ideal form, or whether distortions are inevitably caused by the linking together of the tetrahedral units to form the structure. A new study links this question to the compression behaviour of zeolites in the analcime group. Four different structures display a common behaviour: they exist in a high-symmetry form at low pressures when the tetrahedra can exist without distortions, but transform to low-symmetry forms under pressure when distortions become inevitable. A deeper understanding of the rules governing the formation of zeolite structures may one day allow us to synthesise structures with specific properties on demand. New insights into the physics and geometry of frameworks are an important step in this direction.

Flexibility windows and phase transitions of ordered and disordered ANA framework zeolites
S. A. Wells, A. Sartbaeva and G. D. Gatta, EPL, 94, 56001 (2011)
[Abstract]