Clay catalysts have been shown to contain both Brönsted and Lewis acid sites [4, 5] with the Bronsted sites mainly
associated with the interlamellar region and the Lewis sites mainly associated with edge sites. The acidity of ion-exchanged clays is very much influenced by the quantity of water between the sheets. If the clay is heated (to around
100°C) so as to remove most of the interlamellar water until only 'one layer' of water remains, at about 5% total
water level, the Brönsted acidity increases markedly [6, 7] to that of a very strong acid. Heating to a higher
temperature (at around 200- 300°C) results in the collapse of the clay interlayer structure as the water is driven out,
resulting in a decrease in Bronsted acidity but an increase in Lewis acidity. Further heating (to around 450°C and
above) results eventually in complete dehydroxylation of the aluminosilicate lattice, producing a completely
amorphous solid that retains Lewis acidity. Organicchemists, with synthesis in mind, have so far confined their
interests to expandable montmorillonite clays [8, 9] and almost all of their clay catalysts have been either (a) acid-treated clays such as K-10 [10] or ion-exchanged clays such as Al
3+
, Cr
3+
or H
+
exchanged Wyoming or Texas
bentonites [11]. The acid-treated and cation exchanged clays can be simply regarded as solid acids andact as
heterogeneous catalysts, with all of the advantagesof easy removal of the catalyst from the product. Acid-treated
clays, because of their increased surface area and swelling properties, have also been widely used as solid supports
for inorganic reagents such as potassium permanganate [12], thallium (III) nitrate [13]. The ion-exchanged clays
have mostly Bronsted acidity in the interlamellar zone and so are characterised by promoting acid-catalysed
reactions often of a bimolecular type between protonated and neighbouring unprotonated reactants
Clay catalysts have been shown to contain both Brönsted and Lewis acid sites [4, 5] with the Bronsted sites mainly
associated with the interlamellar region and the Lewis sites mainly associated with edge sites. The acidity of ion-exchanged clays is very much influenced by the quantity of water between the sheets. If the clay is heated (to around
100°C) so as to remove most of the interlamellar water until only 'one layer' of water remains, at about 5% total
water level, the Brönsted acidity increases markedly [6, 7] to that of a very strong acid. Heating to a higher
temperature (at around 200- 300°C) results in the collapse of the clay interlayer structure as the water is driven out,
resulting in a decrease in Bronsted acidity but an increase in Lewis acidity. Further heating (to around 450°C and
above) results eventually in complete dehydroxylation of the aluminosilicate lattice, producing a completely
amorphous solid that retains Lewis acidity. Organicchemists, with synthesis in mind, have so far confined their
interests to expandable montmorillonite clays [8, 9] and almost all of their clay catalysts have been either (a) acid-treated clays such as K-10 [10] or ion-exchanged clays such as Al
3+
, Cr
3+
or H
+
exchanged Wyoming or Texas
bentonites [11]. The acid-treated and cation exchanged clays can be simply regarded as solid acids andact as
heterogeneous catalysts, with all of the advantagesof easy removal of the catalyst from the product. Acid-treated
clays, because of their increased surface area and swelling properties, have also been widely used as solid supports
for inorganic reagents such as potassium permanganate [12], thallium (III) nitrate [13]. The ion-exchanged clays
have mostly Bronsted acidity in the interlamellar zone and so are characterised by promoting acid-catalysed
reactions often of a bimolecular type between protonated and neighbouring unprotonated reactants
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