Applied Clay Science 31 (2006) 185 193

www.elsevier.com/locate/clay

Solid acidity of 2 : 1 type clay minerals

activated by selective leaching
Kiyoshi Okada a,, Naoki Arimitsu a , Yoshikazu Kameshima a , Akira Nakajima a ,
Kenneth J.D. MacKenzie b
a

Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, O-okayama, Meguro, Tokyo 152-8552, Japan
b
School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600 Wellington, New Zealand
Received 24 May 2004; received in revised form 20 October 2005; accepted 25 October 2005
Available online 28 November 2005

Abstract
Various 2 : 1 type clay minerals were activated by H2SO4 treatment and their solid acidities were evaluated by NH3-temperature
programmed desorption (TPD). Clay minerals with various degrees of Al substitution in the tetrahedral sheets were used as the
starting materials. These included montmorillonite (ideally no tetrahedral Al), saponite (low content of tetrahedral Al), vermiculite
(intermediate content of tetrahedral Al) and phlogopite (high tetrahedral Al content). All these samples showed increased solid
acidity after selective leaching, the solid acidities varying in the order phlogopite b montmorillonite b vermiculite b saponite. The
NH3-TPD spectra were deconvoluted into two peaks; the L-peak at b 200 C corresponds to a weak acid site and the H-peak at
N 250 C corresponds to a strong acid site. The temperature of the H-peak was lowest in phlogopite (252 C) and highest in
saponite (305 C). The generation of solid acidity in these samples is found to be related to the evolution of new tetrahedral Al sites
showing a slightly different 27Al MAS NMR chemical shift from the original tetrahedral Al NMR resonance.
2005 Elsevier B.V. All rights reserved.
Keywords: Solid acidity; Selective leaching; Montmorillonite; Saponite; Vermiculite; Phlogopite

1. Introduction
Selective leaching is an important method for preparing porous materials including activated carbon
(Okada et al., 2003) and porous glass (Nakamura,
1994). Acid treatment of various clay minerals constitutes a simple and cost effective method for obtaining
porous silica. Many studies have been reported, using
various clay minerals as the starting materials, i.e.,
chrysotile (Suquet, 1989), antigorite (Kosuge et al.,

Corresponding author. Tel.: +81 3 5734 2524; fax: +81 3 5734

3355.
E-mail address: kokada@ceram.titech.ac.jp (K. Okada).
0169-1317/$ - see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2005.10.014

1995), montmorillonite (Shinoda et al., 1995), kaolinite

(Okada et al., 1998), sepiolite (Balci, 1999), phlogopite
(Okada et al., 2002), vermiculite (Temuujin et al.,
2003), etc. In these cases, all the components except
SiO2 are almost completely leached by strong acid and/
or prolonged treatment at slightly elevated temperatures. The spaces formed by the leaching of these components become pores in the products.
By contrast to the preparation of porous silica by
selective leaching, rather mild chemical treatment is
known to activate various clay minerals, zeolites, etc
developing their solid acidity and adsorption properties.
Many studies have been reported on the preparation of
acid activated materials for applications as catalysts and
adsorbents from kaolinite (Belver et al., 2002),

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K. Okada et al. / Applied Clay Science 31 (2006) 185193

montmorillonite and vermiculite (Ravichandran et al.,

1996), saponite (Prieto et al., 1999) and pillared clays
(Trombetta et al., 2000). For example, Ravichandran et
al. (1996) investigated the catalytic activity of acidactivated montmorillonite and vermiculite and confirmed the presence of Lewis and Brnsted acid sites
in their activated samples by using catalytic reactions.
Acid activation is especially effective for smectites with
many patents being filed on the preparation and catalytic activity of acidic clay derived from these minerals.
The mechanisms for generating solid acidity proposed for zeolites (Barrer, 1978), depend on the presence of small amounts of Al substitution for Si in the
structural framework. On this basis, the degree of Al
substitution for Si in the tetrahedral SiO4 sheets of the
starting clay minerals should be important for the generation of solid acidity in activated clay minerals. It is
therefore interesting to examine the relationship between the degree of Al substitution in the tetrahedral
sheets of the starting clay minerals and their resulting
solid acidity. Since 2 : 1 type clay minerals have varying
degrees of Al substitution for Si in the SiO4 tetrahedral
sheets, these minerals constitute a suitable suite of starting materials.
For this work, the starting clay minerals were selected on this basis and also for their availability as industrial raw materials, an important factor for many
applications. Four starting clay minerals selected are
as follows; (1) montmorillonite, a mineral with no tetrahedral Al (although this mineral contains ideally no
Al, it can contain small amounts of Al in the tetrahedral
sheets) and octahedral Al (ideally Al5 / 3Mg1 / 3), (2)
saponite, containing a small amount of tetrahedral Al
(this mineral contains only 1 / 12 of its Al in the tetrahedral sheets) and octahedral Mg, (3) vermiculite, with
an intermediate amount of tetrahedral Al (this mineral
contains more Al substitution than saponite in the range
6 / 409 / 40), and octahedral Mg, Fe and Al, and (4)
phlogopite, with a high amount of tetrahedral Al (this
ideally contains 1 / 3 of its Al in the tetrahedral sheets)
and octahedral Mg. The clays were activated with
H2SO4 under various reaction conditions and their
solid acidities were evaluated by temperature
programmed desorption (TPD) using NH3 as the
adsorbate.
2. Experimental
2.1. Samples
The four starting clay minerals were as follows; (1)
montmorillonite from Aderazawa, Yamagata, Japan (Kunipia

F, Kunimine Co., Japan), (2) synthetic saponite (Smecton

SA, Kunimine Co., Japan), (3) vermiculite from Transval,
South Africa (Micron (0), Vermitech Co., Japan), and (4)
phlogopite from Suzor, Lac Letondal, Canada (200-HK,
Marietta Resources International, Canada). The clay samples
were used for the activation experiments without further
treatment.
2.2. Activation by selective leaching
Samples were activated using H2SO4 under the following
conditions; acid concentration: 0.15 M, temperature: 70 and
90 C, time: 0.510 h, sample/solution ratio : 1.5 g/75 ml. A
heated stirrer was used with a Teflon beaker covered by a
wrapping film to avoid evaporation of the solution during the
experiments. After activation, the sample was washed once
with dilute H2SO4 to avoid re-precipitation of dissolved ions
by the extreme pH change. It was then washed three times
with distilled water, centrifuged and dried at 110 C
overnight.
2.3. Characterization
Chemical compositions of the as-received and activated
samples were determined by X-ray fluorescence (RIX2000,
Rigaku, Japan). The X-ray diffraction (XRD) patterns were
measured using monochromated Cu K radiation (LabX
XRD-6100, Shimadzu, Japan). Solid-state 29Si and 27Al
MAS NMR spectra were obtained at 11.7 T using a Varian
Unity 500 spectrometer and Doty probe spun at 1012 kHz.
The 29Si spectra were acquired using a 90 pulse of 60 s and
a recycle time of 100 s, and were referenced to tetramethylsilane (TMS). The 27Al spectra were acquired using a 15 pulse
of 1 s and recycle time of 1 s and were referenced to Al
(H2O)3+
6 .
Nitrogen gas adsorptiondesorption isotherms were measured using a Quanta Chrome Autosorb-1 instrument at 77 K.
The measurements were made after degassing under vacuum
at 180 C for 6 h. The specific surface area (SBET) was
calculated by the BET method (Brunauer et al., 1938) and
the pore size distribution was calculated by the BJH method
(Barrett et al., 1951) using the adsorption and desorption
isotherms, respectively. The total pore volume was calculated
from the maximum amount of nitrogen gas adsorption at
partial pressure (P / P0) = 0.999.
The NH3-TPD spectra were measured using a Bel Japan
TPD-65 instrument. The measurements were made under the
conditions previously proposed by The Committee on Reference Catalyst in Japan Catalyst Society (1991). The sample
(about 50 mg) was heat treated in vacuo at 500 C for 1
h then cooled to 100 C before the measurements. NH3 gas
was then introduced to the sample and adsorbed at 100 C
for 10 min. After vacuum evacuation, the sample was heated
at 10 C/min in flowing He carrier gas and the amount of
desorbed NH3 gas was detected by a mass spectrometer from
100 to 600 C.

K. Okada et al. / Applied Clay Science 31 (2006) 185193

3. Results and discussion

3.1. Starting materials
The as-received samples were characterized by XRF,
XRD, NMR and N2 gas adsorption. The XRD patterns
of the montmorillonite, saponite, vermiculite and phlogopite samples are shown in Fig. 1(a)(d), respectively.
The XRD pattern of the montmorillonite sample (Fig. 1
(a)) shows the sharp peaks of montmorillonite and also a
weak peak at 2 = 26.7 assigned to quartz, an accessory
mineral. The XRD pattern of the saponite sample (Fig. 1
(b)) shows rather broad peaks, especially those corresponding to the basal reflections. This indicates a
small crystallite size corresponding to the stacking direction. The XRD pattern of the vermiculite sample (Fig.

187

1(c)) shows several peaks corresponding to the basal

reflection at 2 b 10. Since the XRD pattern of the
Mg-saturated ethylenglycolated sample shows a sharp
peak at 1.44 nm, as reported by Temuujin et al. (2003),
the bulk of this sample is confirmed as vermiculite, with
small amounts of hydrobiotite and illite as accessory
minerals. The XRD pattern of the phlogopite sample
(Fig. 1(d)) shows the sharp peaks of phlogopite, with
small peaks of the accessory minerals chlorite and talc.
The chemical compositions of these samples are
listed in Table 1. Their structural formulae, calculated
neglecting the co-existing accessory minerals, are as
follows:
montmorillonite : (Na0.38Ca0.04K0.01)0.43(Al1.58Mg0.33
Fe0.10)2.01(Si3.85Al0.15)4O10(OH)2

Fig. 1. XRD patterns of the as-received and activated samples. (a) Montmorillonite, (b) saponite, (c) vermiculite and (d) phlogopite.

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K. Okada et al. / Applied Clay Science 31 (2006) 185193

Table 1
Various data of samples
Sample

Montmorillonite
Montmorillonite
Montmorillonite
Montmorillonite
Montmorillonite
K10
Saponite
Saponite
Saponite
Saponite
Saponite
Saponite
Saponite
Vermiculite
Vermiculite
Vermiculite
Vermiculite
Vermiculite
Phlogopite
Phlogopite
Phlogopite
Phlogopite
Phlogopite

Leaching conditions
Conc.(M)

Temp.(C)

Time(h)

5
5
5
5

0.1
0.15
0.2
0.3
0.5
1.0

1
1
1
1

5
5
5
5

90
90
90
90

70
70
70
70
70
70

70
70
70
70

70
70
70
70

1
2
6
10

0.5
0.5
0.5
0.5
0.5
0.5

0.5
1
2
5

1
2
6
10

S*BET
(m2/
g)

Acidity
(mol/
g)

Si / Al
(atm
ratio)

15
138
145
170
136
255
198
327
486
440
561
456
512
1
80
265
470
647
2
52
56
48
42

9.4
63
55
53
48
85
42
300
200
68
21

52
130
56
17
6.3
9.4
11
11
34

2.23
2.81
3.11
7.37
19.6
3.38
8.00
11.2
24.3
60.4
338
552
355
3.42
4.82
16.0
114
704
2.73
5.33
7.57
17.1
27.7

Chemical composition (atm%)

Si

Al

Mg

Fe

Na

Ca

59.8
69.2
71.5
85.5
94.1
70.4
46.9
64.6
78.8
91.2
98.1
99.3
99.5
36.2
46.7
74.9
94.7
98.5
38.0
54.9
63.4
79.4
85.6

26.8
24.6
23.0
11.6
4.80
20.8
5.86
5.76
3.24
1.51
0.29
0.18
0.28
10.6
9.69
4.69
0.83
0.14
13.9
10.3
8.37
4.63
3.09

5.12
4.76
4.12
2.06
0.80
3.34
42.1
29.6
17.9
7.29
1.62
0.51
0.15
36.0
31.4
14.6
2.74
0.50
31.4
22.3
17.7
9.07
5.79

1.58
1.40
1.35
0.74
0.31
2.77

5.46
4.77
2.72
0.91
0.32
4.05
2.96
2.23
1.22
1.23

0.14
tr**
tr
0.05
tr
2.36

6.13
5.51
2.68
0.57
0.12
9.89
7.64
5.85
3.19
2.12

5.98
tr
tr
tr
tr
tr
5.19
tr
tr
tr
tr
tr
tr

0.72
0.68
0.85
0.86
0.93

0.56
tr
tr
tr
tr
0.30

5.52
1.89
0.46
0.29
0.39
2.13
1.23
1.65
1.64
1.59

*: specific surface area, **: trace amount.

saponite : Na0.39Mg3.15(Si3.50Al0.44)3.94O10(OH)2
vermiculite : (K0.48Ca0.43)0.91(Mg2.81Fe0.07)2.88
(Si2.82Al0.83Fe0.35)4O10(OH)2
phlogopite : (K 0.77 Ca 0.17 Na 0.06 ) 1.00 (Mg 2.44 Fe 0.31
Al 0.03 ) 2.78 (Si 2.95 Al 1.05 ) 4 O 10 (OH) 2
As expected, Al substitution for SiO4 in the tetrahedral sheets varies widely, from 0.15 / 4 in montmorillonite to 1.05 / 4 in phlogopite.
The SBET value of vermiculite and phlogopite are
low (1 and 2 m2/g, respectively) but high in montmorillonite (15 m2/g) and highest in saponite (198 m2/g).
The particle sizes of these samples also differ greatly,
i.e., different between the vermiculite and phlogopite
(of the order of nm) and the montmorillonite and saponite (sub m to nm).
3.2. Activating treatment
Activation as initially carried out on the four samples
under the same conditions, using 1 M H2SO4 at 70 C
for 1 h. The resulting changes in chemical compositions
differed considerably according to the starting materials,
the leaching conditions being excessive for saponite but
insufficient for montmorillonite and phlogopite. The
activation treatment was therefore performed with dif-

ferent acid concentrations, reaction times and temperatures as appropriate for each starting material. As listed
in Table 1, the order of leachability of these samples
(defined as the rate of change of the chemical composition) is montmorillonite b phlogopite b vermiculite bb
saponite. The leachability of 2 : 1 clay minerals by
acid is strongly influenced by various factors such
as (1) the surface area (related to the particle size and
crystallinity), (2) the nature of the octahedral cations
(Breen et al., 1995; Madejova et al., 1998; Novak and
Cicel, 1978; Vincente-Rodriguez et al., 1996), (3) the
nature of the tetrahedral cations (Novak and Cicel,
1978), (4) the ratio of the expandable sheets (Komadel
et al., 1996). Novak and Cicel (1978) have reported a
decrease in the leaching rate of smectites with increasing Al in the octahedral sheets and decreasing Al substitution in the tetrahedral sheets. A similar trend was
also reported in relation to the cations of the octahedral
sheets by Breen et al. (1995), Madejova et al. (1998),
and Vincente-Rodriguez et al. (1996). Decreased leachability of 2 : 1 clay minerals with decreasing Al substitution in the tetrahedral sheets was found in talc by
Okada et al. (2005). In the case of the present four
samples, the order of leachability is expected on the
basis of the surface area data to be vermiculite b phlogopite b montmorillonite bb saponite, but on

K. Okada et al. / Applied Clay Science 31 (2006) 185193

the basis of the octahedral cations present, this order

should be montmorillonite bb saponite b vermiculite b
phlogopite, while on the basis of the tetrahedral
cations present, the expected order would be
montmorillonite b saponite b phlogopite b vermiculite.
The Si content of the saponite increased from 46.9
to 99.5 atm%, corresponding to a change in the Si /
Al ratio from 8.0 to 552 even when activated under
the mildest conditions of the four starting materials.
The reasons for this rapid leaching of saponite thus
appear to be related to the very high S BET and the
low crystallinity of this mineral as shown in Fig. 1
(b). By contrast, the Si content of the montmorillonite changed from 59.8 to 94.1 atm% (Si / Al ratio of
2.23 to 19.6) even after the most severe leaching
treatment. This slow selective leaching of montmorillonite is attributed to its lower content of Mg (Fe)
in the octahedral sheets and lower degree of Al
substitution in the SiO 4 tetrahedral sheets, since
the vermiculite and phlogopite samples, with a

189

higher degree of Mg (Fe) in the octahedral sheets

and Al substitution in the tetrahedral sheets leach
faster than montmorillonite even though they are
much more crystalline and of larger particle size.
With progressive leaching, the XRD peak intensities
(Fig. 1) decrease, especially in the phlogopite sample,
and simultaneously become broader in the montmorillonite and saponite samples. These differences in the
XRD patterns after activation also reflect the differences
in particle size. In phlogopite, the XRD peaks of the
accessory mineral chlorite and talc increase with longer
leaching treatment because of their comparatively smaller leachability. All the samples except phlogopite become amorphous after prolonged activation.
3.3. Solid acidity
NH3-TPD spectra of the samples used to evaluate the
solid acidity are shown in Fig. 2. The as-received montmorillonite sample (Fig. 2(a)) shows only a very small

Fig. 2. NH3-TPD spectra of the as-received and activated samples. (a) Montmorillonite, (b) saponite, (c) vermiculite and (d) phlogopite.

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K. Okada et al. / Applied Clay Science 31 (2006) 185193

broad peak at about 180 C. The increase in the TPD

profiles above 500 C is attributed to the dehydroxylation of the octahedral OH in the montmorillonite, since
the mass number of H2O is close to NH3 and difficult to
distinguish. By contrast with the as-received sample,
montmorillonite activated for 1 h clearly shows a peak
at about 200 C. This TPD peak temperature is similar to
K10, a commercial catalyst prepared by acid activation
of montmorillonite (Shinoda et al., 1995) though the
peak intensity of the present sample is somewhat lower
than in K10, possibly due to the difference in the SBET
value (Table 1). The profile shapes of these TPD spectra
resemble aluminosilicate gels (Okada et al., 1999), possibly indicating a similar mechanism for the generation
of solid acidity in both these materials. These experiments confirm that solid acidity is produced in montmorillonite by selective leaching with H2SO4.
The as-received saponite sample in Fig. 2(b) shows a
small peak at about 190 C, is more evident than in the
as-received montmorillonite. After activation with 0.1
M H2SO4, the sample shows a very strong TPD peak at
about 300 C, together with an overlapping peak below
300 C. The profile shapes of these TPD peaks are
clearly different from those of montmorillonite. With
increasing H2SO4 concentration, the TPD peak decreases, almost disappearing in the sample activated
with 0.3 M H2SO4. The sharp decrease in the TPD
peak intensity upon activation at higher acid concentrations is related to the increased leaching of Al from
these samples (Table 1), reflective the important role
played by Al in the generation of solid acidity in activated samples.
The as-received vermiculite sample in Fig. 2(c)
shows no TPD peak, after activation, a peak begins to
appear at about 200 C, increasing in intensity up to an
activation time of 1 h. Longer activation decreases the
intensity of this peak due to the sharp decrease in Al
content at activation time of 12 h. The profile shapes
of the activated vermiculites are similar to those of the
activated montmorillonites, but with smaller maximum
peak intensities.
The as-received phlogopite sample (Fig. 2(d)) shows
no TPD peak. A small peak appears upon activation,
increasing in intensity up to 10 h activation. The profile
shapes are similar to those of activated montmorillonites and vermiculites. The maximum peak intensity of
the activated phlogopite is the smallest of the four
samples.
The profile shapes of all the TPD spectra are asymmetric and are thought to consist of two the overlapping
peaks usually observed in zeolites (The Committee on
Reference Catalyst in Japan Catalyst Society, 1991).

The most intense spectra were deconvoluted into two

peaks by a least-squares method. Fig. 3 shows an example of the profile calculation for the saponite sample
activated with 0.1 M H2SO4. The calculated and observed profiles are in excellent agreement. The deconvoluted low and high temperature peaks are designated
L- and H-peaks, respectively, and are thought to correspond respectively to a weak and strong acid site. The
peak temperatures and intensities of the L- and H-peaks
in the four samples are shown in Fig. 4. The peak
temperatures of all the L-peaks range from 190193
C, while the peak intensities are also similar and
range from 0.015 to 0.062 mmol/g. By contrast, the
peak temperatures and intensities of the H-peaks differ
considerably between the samples (Fig. 4), showing a
clear linear relation between peak intensity and peak
temperature, except for montmorillonite. Thus, activated saponite shows the highest H-peak temperature and
intensity. The degree of solid acidity determined from
the sum of the L- and H-peaks follows the order phlogopite (high tetrahedral Al content) b montmorillonite
(lower tetrahedral Al content) b vermiculite (intermediate tetrahedral Al content) b saponite (low tetrahedral Al
content). This order in the degree of solid acidity in
these samples suggests that there is an optimal degree of
Al substitution in the tetrahedral sheets of the original
clay minerals, i.e., not as low as in montmorillonite but
as high as in phlogopite.
The 29Si and 27Al MAS NMR spectra of the asreceived and activated saponite samples were measured
to elucidate the mechanism by which solid acidity is
generated, by determining the local structure around the

Fig. 3. Observed and calculated peaks of the NH3-TPD spectrum of

the saponite activated by 0.1 M H2SO4.

K. Okada et al. / Applied Clay Science 31 (2006) 185193

191

Fig. 4. Amounts of solid acidity and temperatures of L- and H-peaks

of the activated samples.

Al and Si atoms. The spectra are shown in Fig. 5. In the

ideal saponite structure, all the Al atoms are incorporated into the SiO4 tetrahedral sites and there is no octahedral Al. The 27Al NMR spectrum of the as-received
sample shows a sharp peak at 65 ppm corresponding to
tetrahedral Al, and a small peak at 7 ppm arising from
octahedral Al. The small size of the octahedral peak
suggests that the Al atoms in the present sample are
essentially as expected for ideal saponite. The 29Si
NMR spectrum shows a major peak at 95 ppm with a
shoulder at 100 ppm. The peak at 95 ppm is assigned
to Q3(1 Al) units while the shoulder is due to Q3(0 Al).
After activation, the saponite 27Al NMR spectra show a
new tetrahedral peak at 54 ppm in addition to the original peak at 65 ppm. The different chemical shift of the
new tetrahedral suggests a somewhat different local

Fig. 6. Relationships between amount of tetrahedral Al formed by

activation and solid acidity of saponite and vermiculite.

structure from the original layered structure. A similar

peak is observed in the porous products prepared by
selective leaching of montmorillonite (Shinoda et al.,
1995), vermiculite (Temuujin et al., 2003) and chlorite
(Okada et al., 2005) but not in phlogopite (Okada et al.,
2002), which showed only a small degree of solid acidity (Table 1). With more concentrated leaching solutions, the octahedral Al peak increased the intensity
while the two tetrahedral Al peaks decreased. The 29Si
NMR spectra show new peaks at about 111 and 102
ppm with more concentrated leaching solutions. These
peaks are assigned respectively to Q4 and Q3 structures
in the activated products (MacKenzie and Smith, 2002).

Fig. 5. 29Si and 27Al MAS NMR spectra of the as-received and activated saponite samples.

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K. Okada et al. / Applied Clay Science 31 (2006) 185193

These 29Si and 27Al NMR spectra indicate that the

product formed by activation undergoes a change from
the original layered structure to a more framework-like
structure containing both AlO4 and SiO4. Thus, the
newly formed tetrahedral Al responsible for the peak at
54 ppm appears to be important for the generation of
solid acidity. The atomic ratios of this Al in both activated saponite and vermiculite were determined from
the 27Al NMR spectra and the chemical compositions
determined by XRF. Fig. 6 shows the relationship between the atomic content of tetrahedral Al and the solid
acidity of activated saponites and vermiculites. This
linear relationship is similar to that of solid acidity
with Al content, though of slightly different slope. It is
concluded from these results that the tetrahedral Al
atoms newly formed by the activation of clay minerals
play an important role in the generation of solid acidity
sites. Higher contents of these tetrahedral Al atoms in the
product enhance its solid acidity. Since solid acidity was
higher in saponite (low tetrahedral Al content) and vermiculite (intermediate tetrahedral Al content) than montmorillonite (lower tetrahedral Al content) and
phlogopite (higher tetrahedral Al content), there may
be an optimum degree of Al substitution in the tetrahedral layer of the original structure. Fig. 7 shows the
relationship between the Al in the tetrahedral sheet
of the original clay mineral (Al(IV)/T) and the resulting solid acidity. The maximum observed at a tetrahedral Al content of about 0.13, clay minerals with
about 0.5 Al substituted in the tetrahedral sheets, viz.
(Si3.5Al0.5) appear to constitute the best starting material composition. Another factor considered to strongly influence solid acidity is the specific surface area
of the samples. This is also the reason for the distinc-

tively strong solid acidity of selectively leached saponite, in addition to the above-mentioned Al
substitution in the tetrahedral sheets.
Solid acidity is thought to increase with increasing
amounts of newly-formed tetrahedral Al, achieved by
suppressing the leaching of tetrahedral Al. As is seen
from Fig. 5, leaching of tetrahedral Al occurs preferentially to octahedral Al since the tetrahedral site is located at the outer plane. Selective leaching using Alcontaining acid solutions such as AlCl3, Al(NO3)3 and
Al2(SO4)3 may improve this condition by increasing the
concentration of Al3+ in solution.
4. Conclusion
Four 2 : 1 clay minerals with different degrees of Al
substitution in the tetrahedral sheets were activated by
selective leaching using various concentrations of
H2SO4 at 70 and 90 C for various times. The solid
acidities of the resulting products were investigated by
NH3-TPD method and the factors involved in the development of solid acidity were examined with particular reference to the local structure of the activated
products. Activation caused all the samples to acquire
enhanced solid acidity and became enriched in SiO2.
The NH3-TPD spectra contain two overlapping peaks,
at about 200 C (corresponding to a weak acid site) and
250300 C (corresponding to a strong acid site). The
solid acidity of these samples increased in the
order phlogopite b montmorillonite b vermiculite b saponite. The solid acidities of activated saponite and
vermiculite show a linear relation with the amount of
newly formed tetrahedral Al, characterized by a 27Al
NMR peak at 54 ppm. This peak appears at a slightly
different position from the 65 ppm tetrahedral Al peak in
the original layered structure. These results suggest that a
moderate degree of Al substitution in the original tetrahedral sheets and increasing of its surface area are optimal for generating solid acidity in these clay minerals.

Acknowledgement
We are grateful to Mr. K. Suzuki and Kunimine
Company, Bermitech Company and Mr. S. Koga for
their help in obtaining the montmorillonite, saponite,
vermiculite and phlogopite samples.
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