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ZEOLITE STRUCTURES

R.M. Barrer
Chemistry Department
Imperial College of Science and Technology
London SW7 2AY
England

ABSTRACT

An account has been given of silicate anions from topological


and configurational aspects, with special reference to zeolites.
Different ways of constructing zeolite anions are described which
lead to known frameworks and to a large number of novel ones.
Brief consideration is also given to resultant channel systems
and to AI, Si order and disorder.

1. INTRODUCTION: SILICATE ANIONS

The structural side of zeolite chemistry is concerned with


their three-dimensional giant anions and the associated intra-
zeolite cations and water molecules. Much the most accurate
structural information relates to the anionic frameworks which
have geometrical elegance, provide numerous honeycomb structures
and determine important zeolite properties. However zeolite
anions are a part only of a remarkable array of silicate anions
in which many sub-units found in zeolites are also present. It
is therefore of considerable interest to give examples of these
anions in a build up to the main topic of zeolite anions. Zeolites
are usually synthesised from gels or from other silicates.
Because nucleation can be influenced by the starting materials
examples of the diverse silicate anions which could be chosen as
sources of silica acquire an additional significance.

Two aspects of the structure of silicate anions are their


topology and their configuration. By topology we will mean the

F. R. Ribeiro et al. (eds.), Zeolites: Science and Technology


© Martinus Nijhoff Publishers, The Hague 1984
36

Table 1: Silicates grouped according to anion types

Type Sub-types

Fini te anions Ortho- and pyro-silicates. Short


("Island" anions) unbranched chains. Single ring
anions. Branched single rings.
Double ring prisms. Structures
with two or more island anions.

Infinite chain anions Unbranched single chains. Open-


branched single chains. Loop-
branched single chains (linked
rings). Multiple chains (two,
three, four or five cross-linked
chains). Hybrid chains. Tubular
chains.

Infinite sheet anions Unbranched single sheets. Branched


single sheets. Double sheets.
Hybrid triple sheets.

Infinite three-dimensional Non-porous and porous tecto-


anions silicates.

pattern of the Si-O-T bonds (T = Al or Si) and by configuration we


will mean the spatial disposition of the bond pattern. For example,
Si0 4 tetrahedra can join with other Si0 4 tetrahedra to give un-
branched linear chains. These can, as we shall see, be variously
puckered. These anions all have the same topology in terms of the
bond pattern, but they have different configurations. Silicates
can be grouped according to their topologies as in Table 1. In the
following sections examples of the various categories of Table 1
will be given, leading up to and with emphasis on zeolites.

2. FINITE ANIONS

Some island anions are as follows (1):-

Single tetrahedron Siot- Orthosi li cates


Two linked tetrahedra Si20~­ Disilicates
Chain of' three tetrahedra S· 0 8 - Trisilicates
~3 10