Colloids and Surfaces

A: Physicochemical and Engineering Aspects 203 (2002) 185 193

www.elsevier.com/locate/colsurfa

Thermal stability and hydrophobicity of mesoporous silica

FSM-16
Akihiko Matsumoto *, Tatsuo Sasaki, Nobuyuki Nishimiya, Kazuo Tsutsumi
Department of Materials Science, Faculty of Engineering, Toyohashi Uni6ersity of Technology, Tempaku-cho,
Toyohashi 441 -8580, Japan
Received 5 January 2001; accepted 15 October 2001

Abstract
Thermal stability and hydrophobic property of mesoporous silica, FSM-16, has been studied. The mesoporous
structure of FSM-16 was stable against calcination up to 1073 K in vacuo, but collapsed at 1273 K. Adsorption
isotherm and differential heat of adsorption measurements showed that the calcination temperature affected the
hydrophobic nature of FSM-16, and that the surface changed to hydrophilic by hydroxylation of surface siloxane
during water adsorption. Once the surface became hydrophilic, the hydrophobic character was never restored even
after evacuation at 823 K. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Adsorption; Calorimetry; FSM-16; Heat of adsorption; Mesoporous silica

1. Introduction
Mesoporous silica with highly ordered pores,
such as FSM-16 and MCM-41, have attracted
considerable interests in the field of adsorption
science and catalysis chemistry [1 5]. FSM-16 is
prepared by an intercalation of quarterly ammonium surfactant as a template in a layered sodium
silicate, kanemite, followed by calcination to remove the template [1 3]. Because of its highly
ordered mesoporous structure with unidimensional and hexagonal arrays like MCM-41, FSM16 is expected for the application such as catalytic
reaction and adsorbent of large size molecules.
* Corresponding author. Tel.: + 81-532-44-6811; fax: + 81532-48-5833.
E-mail address: aki@tutms.tut.ac.jp (A. Matsumoto).

In molecular adsorption on a solid surface,

chemical nature of the solid surface plays an
important role. Especially, hydrophile hydrophobe properties are important ones to control
the adsorptivity for polar/non-polar molecules.
The hydrophilic property of silica surface depends
on the concentration of silanol groups, because
they are able to bind water molecules by hydrogen
bonding [6]. It was reported that the surfaces of
MCM-41 and FSM-16 showed hydrophobic nature owing to a low concentrations of surface
silanol groups [711]. However, the surface of
FSM-16 becomes hydrophobic by repetition of
water adsorption [10 12]. Because the concentration of silanol groups on silica surface varies with
heating temperatures 13a, 14, the calcination temperature would affect the hydrophobic nature of
FSM-16.

0927-7757/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 0 1 ) 0 1 1 0 5 - 0

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A. Matsumoto et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 185193

In this study, the stability of FSM-16 against

different calcination temperatures was examined
by X-ray diffraction (XRD) and nitrogen adsorption measurements. Effect of the calcination temperature
on
the
hydrophile hydrophobe
properties of FSM-16 was investigated by aid of
in situ IR spectroscopy and adsorption calorimetry of water.

2. Experimental

2.1. Synthesis of FSM-16

FSM-16 was prepared as follows according to
the published method by using hexadecyltrimethylammonium chloride as a template [9].
A 120 mm of 0.27 mol l 1 sodium hydroxide
aqueous solution was added to 60 g of sodium
silicate solution (SiO2/Na2O =2.12, Kishida
Chemical) to adjust SiO2/Na2O =ca. 2. The mixture was stirred at 300 K for 3 h followed by
drying at 373 K in a vacuum drying oven to
remove water. The dried sodium silicate was calcined at 973 K for 6 h in air to obtain a layered
sodium silicate, kanemite (d-Na2Si2O5). Kanemite
was obtained as a white lump. The kanemite
lump was crushed by use of a mortar. This kanemite powder was deliquescent and used for further treatment immediately. Thirty grams of
kanemite was dispersed in 300 ml of water and
then stirred for 3 h at 300 K. Then the suspension was filtered out to obtain wet kanemite
paste. All of the kanemite paste was dispersed in
480 ml of an aqueous solution of n-hexadecyltrimethylammonium chloride (0.125 mol l 1)
and then stirred at 343 K for 3 h. The pH value
of the suspension was 11.5 12.5 at this stage.
Afterwards, the pH value was adjusted carefully
to 8.5 by adding 2 mol l 1 hydrochloric acid
with stirring. The suspension was kept stirring at
343 K for 3 h with keeping the pH value at 8 9.
After cooling to room temperature, the solid
product was filtered out, washed with 1 l of
water and dried in air to yield mesoporous silicate, FSM-16, with retaining the template. The
FSM-16 was calcined at an appropriate temperature from 823 to 1273 K to burn off the surfac-

tant and immediately used for characterization

and adsorption experiments. The FSM-16 sample
is designated FSM-16-nK, where n stands for the
calcination temperature in degree Kelvin.

2.2. Characterization
The XRD pattern of freshly calcined sample
was recorded by use of an automatic powder
diffractometer (Rigaku, RINT2000) using CuKa
radiation. The nitrogen adsorption isotherm was
measured volumetrically at 77 K by use of a
laboratory-made adsorption apparatus. Freshly
calcined sample was immediately preevacuated at
298 K for 6 h in vacuo (1 mPa) before the
adsorption measurement.
IR spectra of FSM-16 were measured in situ
with a resolution of 2 cm 1 over a spectral range
of 30004000 cm 1 at 298 K by FTIR spectrometer (JASCO, FT/IR420) attached with an in
situ diffuse reflectance cell (SR-800) and an MCT
detector, and 1500 consecutive scans were
summed. An appropriate amount of freshly calcined sample was diluted in diamond powder and
placed in the diffuse reflectance cell. The sample
was preevacuated at 423 K for 12 h under 1 mPa
before the measurement. IR spectra of FSM-16
were measured before water adsorption and after
water adsorption at a relative pressure (P/P0)=
ca. 0.8 followed by evacuation at 423 K for 2 h
and optionally at 823 K.

2.3. Characterization of hydrophobichydrophile

properties
Heats of adsorption of water were measured at
298 K by a twin conduction type microcalorimeter (Tokyo Riko Co.) equipped with a volumetric
adsorption apparatus. Adsorption isotherm of
water was consecutively measured with the
calorimetric measurements. The sample that was
freshly calcined at 823 or 1073 K was immediately placed in the sample cell and evacuated at
298 K under 1 mPa for 12 h prior to the measurements. After the first measurements, the sample was evacuated under 1 mPa at 823 K for 12
h and used for the second measurements.

A. Matsumoto et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 185193

187

Fig. 1. Nitrogen adsorption isotherms on FSM-16 calcined at

different temperatures.

3. Results and discussion

Fig. 2. XRD patterns of FSM-16-823 K and -1073 K.

3.1. Effect of calcination temperature on porosity

of FSM-16
The nitrogen adsorption isotherms of FSM-16823 and -1073 K are of Type IV in the IUPAC
classification, as shown in Fig. 1, which are characteristic for mesoporous materials [15]. These
results show that FSM-16 retains its mesoporous
structure even after the heat treatment at 823 or
1073 K. Specific surface areas, as,BET, and apparent pore diameters of FSM-16-823 and -1073 K
were estimated by the BET plot and the BJH
method, respectively, and shown in Table 1. Here
it should be noted that the apparent pore diameters are underestimated because a thickness of
adsorbed layer is not taken into account in the
BJH method [16,17]. The XRD pattern of FSM-

16-823 K shown in Fig. 2 exhibits clear Bragg

peaks attributable to the (100), (110) and (200)
reflections of the hexagonal mesostructure at
2q= 2.48 (d= 3.56 nm), 4.22 and 4.84, respectively. These clear peaks evidenced the formation
of the long-range-order structure. FSM-16-1073
K also showed the XRD pattern attributable the
hexagonal mesostructure (Fig. 2), the (100) reflection appeared at 2q= 2.52 (d= 3.50 nm), however, other peaks overlapped and decreased in
intensity. Inaki et al. reported that FSM-16 is
more thermally stable than MCM-41 and the
hexagonal pore structure of FSM-16 was retained
after evacuation at 1073 K [18]. In the present
study, the result of XRD as well as nitrogen
adsorption measurements for FSM-16-1073 K co-

Table 1
Characteristics of FSM-16 prepared in this study
Sample

Specific surface areaa (m2 g1)

FMS-16-823 K 940
FSM-16-1073 K 920
FSM-16-1273 K 260
a

Determined
Determined
c
The median
d
Determined
b

Specific pore volumeb (ml g1)

Apparent pore diameter (nm)

0.58
0.54
0.09

2.7c
2.4c
0.6d

by the BET plot.

by the hs plot shown in Fig. 3.
of pore size distribution curve determined by BJH method.
by the inflection point in the hs plot shown in Fig. 3.

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A. Matsumoto et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 185193

incides with their report although the hexagonal

structure became less ordered comparing to FSM16-873 K.
On the other hand, the nitrogen isotherm of
FSM-16-1273 K is not of Type IV, as shown in
Fig. 1. Because the hs method revealed that FSM16-1273 K has micropores as mentioned below,
the nitrogen adsorption isotherm of FSM-16-1273
K would be regarded as a combination of Type I
and II isotherms resulting from adsorption in the
micropores and on the external surface, respectively. The change in the isotherm type suggests
that the mesoporous structure was not retained
through calcination at 1273 K. The as,BET of
FSM-16-1273 K was 260 m2 g 1, which also
indicates decreasing the porosity. The structure of
FSM-16 is retained after calcination at 1173 K [3],
but becomes amorphous by heating at 1273 K
[11]. In the present case, the mesoporous structure
of FSM-16 would be collapsed by heating at 1273
K.
The hs method is useful to analyze isotherm on
porous materials [19]. The adsorption isotherms
in Fig. 1 are transformed into the corresponding
hs plots shown in Fig. 3. Standard data for the
adsorption of nitrogen at 77 K on non-porous
silica prepared by crushed quartz were used to
obtain the hs plots [20], because the surface of
FSM-16 is rather hydrophobic like crushed quartz
than hydroxylated silica. In fact, regardless of
different surface nature between these silica materials, the standard data for the nitrogen adsorp-

tion at 77 K on crushed quartz coincides well with

that on non-porous hydroxylated silica in the
P/P0 range between 0 and 0.9 [20]. The hs plots of
FSM-16-823 K and -1073 K showed a linear
relationship passing through the origin at hs B
0.84 and bent upward at hs = ca. 0.84, and then
moderately increased at hs \ 1.0. The linear relationship at hs B 0.84 corresponds to monolayer
multilayer adsorption on both internal and
external surfaces. The steep rise between 0.84B
hs B 1 is due to capillary condensation in mesopores, and the moderate increasing at hs \ 1.0 is
due to multilayer adsorption on external surface.
These hs plots indicate that FSM-16-823 K and
-1073 K have mesoporous structures. On the
other hand, the hs plot of FSM-16-1273 K was
linear and passed through the origin at hs B 0.6
and then moderately increased above hs = 0.6,
which suggests that FSM-16-1273 K is microporous rather than mesoporous. The approximate
pore size of FSM-16-1273 K was estimated as 0.6
nm from the inflection point of hs plot at hs = 0.6
considering the mean thickness of an adsorbed
nitrogen layer. Calcination at 1273 K would bring
about collapse of the mesoporous structure and
formation of micropores. An apparent pore volume of each sample was estimated from the intercept of back-extrapolation of the linear part
above hs = 1 to the ordinate, and shown in Table
1. FSM-16-823 K and -1073 K have higher pore
volume than FSM-16-1273 K. Because FSM-16823 K and -1073 K retained the mesoporous
structure, they were characterized through further
experiments.

3.2. Characterization of surface by IR

measurements

Fig. 3. hs plots of nitrogen adsorption isotherms on FSM-16

calcined at different temperatures.

As shown in Fig. 4(a), the IR spectrum of the

freshly calcined FSM-16-823 K exhibited a strong
absorption band at 3746 cm 1 which was slightly
asymmetric toward the lower wavenumber side
[12]. The band at 3746 cm 1 is attributable to the
OH stretching vibrations of isolated (single)
silanol groups, and the asymmetry would be due
to either isolated or geminal silanol groups
[13b,21,22]. Upon water adsorption followed by
evacuation at 423 K, a shoulder band at 3720

A. Matsumoto et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 185193

Fig. 4. IR spectral change of FSM-16-823 K by water adsorption and evacuation at different temperatures: (a) before water
adsorption; (b) after water adsorption at P/P0 = 0.8 and subsequent evacuation at 423 K; (c) further evacuated at 823 K.

cm 1 and a wide band centered at 3600 cm 1

appeared (Fig. 4(b)). At this stage, physisorbed
water molecules would be desorbed [6,21]. Therefore, it is likely that siloxane bonds cleaved by
hydroxylation in the following steps even at room
temperature: physical adsorption of water
molecules on hydrophilic silanol sites and hydrolysis of siloxane near the silanol sites, to yield a
pair of new silanol groups [6,13a]. Such silanol
groups interact with each other and show the
absorption bands of the OH stretching vibrations of hydrogen-bonded silanols at hydrogen
and oxygen atoms at 3520 and 3720 cm 1, respectively [21]. Therefore, the shoulder at 3720
cm 1 would be due to the variations of hydrogenbonded silanol groups at oxygen atoms. The wide
bands centered at 3600 cm 1 would be due to
overlapping of the bands attributable to the OH
stretching vibrations of hydrogen-bonded silanols
at hydrogen atoms and those from perturbed
silanol groups at points of interparticle contact
centered at 3650 cm 1 [21].
The IR spectrum did not restore the initial
appearance before water loading by evacuation at
823 K as shown in Fig. 4(c): the broad band

189

around 3500 cm 1 disappeared, but the band at

3650 cm 1 assigned to the OH stretching vibrations of the perturbed silanol groups was observed. Furthermore, the strong band at 3746
cm 1 became more asymmetric towards the lower
wavenumber side. These results suggest that the
silanol groups that formed by hydroxylation of
siloxane were not completely removed by evacuation at 823 K.
The IR spectral changes of FSM-16-1073 K by
water adsorption and desorption were similar to
those of FSM-16-823 K as shown in Fig. 5,
however, some differences were observed. The
3746 cm 1-band in the spectrum before water
loading was narrower than that of FSM-16-823 K
(Fig. 5(a)). This result suggests that the concentration of isolated or geminal silanol groups on
FSM-16-1073 K was lower than that on FSM-16823 K. Since the concentration of silanol groups
on silica decreases with increasing pretreatment
temperature [6,13b,14], the calcination at 1073 K
would more severely dehydoxylate silanol groups
than that at 823 K. The IR spectrum after water
adsorption followed by evacuation at 423 K exhibited a shoulder at 3720 cm 1 and broad bands

Fig. 5. IR spectral change of FSM-16-1073 K by water adsorption and evacuation at different temperatures: (a) before water
adsorption; (b) after water adsorption at P/P0 =0.8 and subsequent evacuation at 423 K; (c) further evacuated at 823 K.

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A. Matsumoto et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 185193

Fig. 6. Water adsorption isotherms at 298 K on FSM-16-823

K and -1073 K. Closed and open symbols stand for FSM-16823 K and -1073 K, respectively. Circular and square symbols
denote the first and the second adsorption runs, respectively.

at 3650 and 3550 cm 1 (Fig. 5(b)), which shows

that hydrogen-bonded silanol groups formed on
inter/intraparticles. Upon further evacuation at
823 K, these bands disappeared, but the 3746
cm 1-band was still asymmetric toward the lower
wavenumber side in the same manner as the case
of FSM-16-823 K (Fig. 5(c)), showing the presence of isolated or geminal silanol groups.

3.3. Water adsorption

Fig. 6 shows adsorption isotherms of water at
298 K on FSM-16-823 K and -1073 K. Regardless
of the calcination temperature, the adsorption
isotherms for the first adsorption run were of
Type V in the IUPAC classification, which is
indicative of weak adsorbent adsorbate interactions [15]. However, the adsorption isotherm for
the second run were of Type IV, suggesting rather
hydrophilic nature of the surfaces. The change of
the surface property of FSM-16 with water adsorption was accord well with that reported by
Inagaki et al. [10].
In the case of FSM-16-823 K, the adsorption
amount for the first run changed from 0 to 4
mmol g 1 at 0B P/P0 B0.5 and steeply increased
from 4 to 28 mmol g 1 at 0.5 BP/P0 B0.6, as
already reported in [12]. This steep rise is due to
capillary condensation of water caused by the
polar interaction among adjacent water molecules

rather than the interaction between the surface

and water. However, in the second run, the adsorbed amount at the lower P/P0 region (P/P0 B
0.4) was 1.52 times as high as that in the first
run. Furthermore, a steep rise of adsorbed
amount took place at lower P/P0 values from 0.45
to 0.60. In the first adsorption run, the concentration of silanol groups of freshly calcined FSM-16
was rather low and showed hydrophobic nature.
Whereas, once water molecules were condensed in
pores, the siloxane bonds would be hydrolyzed to
give silanol groups. Some of these silanol groups,
mainly isolated silanols, were thermally stable and
remained even after preevacuation with heating
up to 823 K [14], so that the surface became
hydrophilic. Because the multilayer adsorption
would take place at the lower P/P0 region (P/
P0 B 0.4) in the second run so that the narrow the
effective radius (pore radius minus the thickness
of ordinary multilayer adsorption expected at that
P/P0), the capillary condensation of water was
observed at the lower P/P0. After the water condensation completed, the adsorbed amount
monotonously increased with P/P0 by condensation on external surface.
In the case of the first adsorption run on FSM16-1073 K, the adsorbed amount at lower P/P0
before water condensation was smaller than that
on FSM-16-823 K, and the water condensation
began at a higher P/P0 value of 0.62. These
results indicate that the surface of FSM-16-1073
K is more hydrophobic than that of FSM-16-823
K, which is consistent with the results of IR
measurements. Because the apparent mesopore
size determined by nitrogen adsorption was similar for FSM-16-823 K and -1073 K, as shown in
Table 1, the difference in the P/P0 value at the
capillary condensation would indicate more hydrophobic nature or lower concentration of
silanol groups on FSM-16-1073 K. Ishikawa et al.
also measured the water adsorption isotherms on
FSM-16 samples that were calcined at different
temperatures from 823 to 1273 K [11], and found
the water adsorptivity of FSM-16 decreased with
increasing the calcination temperature. They suggested that the change in water adsorptivity is due
to the decrease of silanol concentration with the
increase of the calcination temperature [11], which
coincides with the present results.

A. Matsumoto et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 185193

The adsorption isotherm of FSM-16-1073 K in

the second run was of Type IV similar to FSM16-823 K; the capillary condensation of water
began at lower P/P0 value, 0.41. Although FSM16-1073 K showed more hydrophobic behavior
than FSM-16-823 K in the first run, the surface of
FSM-16-1073 K changed to hydrophilic by water
adsorption and hydrophobicity was not recovered
by evacuation as well as in the case of FSM-16823 K. The P/P0 value at the beginning of capillary condensation for FSM-16-1073 K was
slightly lower than that for FSM-16-873 K, which
could be due to narrower pore sizes in FSM-161073 K. Difference in the adsorption capacity of
water between FSM-16-823 K and -1073 K (ca.
0.04 ml g 1) would be ascribed to that in the
mesopore volumes (ca. 0.05 ml g 1).

3.4. Heats of adsorption

The differential heats of adsorption of water on
FSM-16-823 K and -1073 K are shown in Fig. 7.
The heats of adsorption at initial stage in the first
adsorption run showed different tendency from
those in the second run for each sample.

Fig. 7. The differential heats of adsorption of water at 298 K

on FSM-16-823 K and -1073 K. Circular and square symbols
denote the first and the second adsorption runs, respectively.

191

In the case of FSM-16-1073 K, the initial heats

of adsorption in the first run was ca. 20 kJ mol 1,
which is comparable to the heat of hydroxylation
of siloxane surface to form silanol [6]. Then the
released heat gradually increased as the adsorption proceeded, attaining the constant value of
4550 kJ mol 1. Slightly adsorbed water on surface silanol groups hydroxylates siloxane near the
silanol groups to give rise to silanol groups in
succession [6]. Since the silanol groups would
strongly interact with water molecules than siloxane, the adsorption heats would gradually increase with the progress of adsorption. The
adsorption amounts where heats of adsorption
reached the constant value were found to be equal
to those where the amounts exhibited steep rise in
the isotherms in Fig. 6. Afterwards the adsorbed
water in the mesopore behaved as free water
judging from the fact that adsorption heats were
similar to the heat of liquefaction of water vapor,
44 kJ mol 1 [23].
On the other hand, the differential heats of
adsorption in the second run were ca. 70 kJ
mol 1 at the initial stage of adsorption, and then
decreased gradually to 4550 kJ mol 1 with increase in the adsorbed amount of water. As already mentioned above, the adsorption isotherm
of water suggests that the surface changes to more
hydrophilic by the first water adsorption. Furthermore, IR results showed that a considerable
amount of silanol groups formed on FSM-161073 K by exposure to water and remained even
after evacuation at 823 K. Therefore, the high
heats at initial stage in the second adsorption run
would be due to a strong interaction between
water molecules and surface silanol groups. These
calorimetric measurements also suggest that once
the water is being adsorbed, the hydrophilic property was retained even after evacuation at 823 K.
In the case of FSM-16-823 K, the change in
initial heats of adsorption at the first adsorption
run was different from that of FSM-16-1073 K.
Although the initial heats were ca. 20 kJ mol 1 as
well as in FSM-16-1073, the heats immediately
reached the constant value of 4550 kJ mol 1.
Klier and Zettlemoyer suggested the water adsorption mechanism on silica surface as follows
[24]: water adsorbs with oxygen down on the

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A. Matsumoto et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 185193

silanol groups (SiOH) at least at the beginning

stages of adsorption. Then hydrogen-bonded clusters of water molecules may be formed even before all the silanol groups have adsorbed water
molecules to form SiOHOH2 groups [6,24]. In
the present study, the results of IR measurements
and adsorption isotherm of water indicate that
the surface of FSM-16-823 K is covered with
more silanol groups than that of FSM-16-1073 K
even before water adsorption. Therefore, water
adsorption on both SiOH and SiOHOH2 would
simultaneously take place as well as hydroxylation
of siloxane by water adsorption. The adsorption
energies of water molecule on a silanol group
(SiOH) of dehydrated silica surface and on silanol
group with adsorbed water (SiOHOH2) are 25
and 44 kJ mol 1, respectively [6,23]. Therefore,
the heat evolution at the initial stage immediately
increased to 4550 kJ mol 1. The differential
heats of adsorption of the second run showed the
similar tendency as observed in FSM-16-1073 K,
because the surface became hydrophilic by the
first water adsorption.

4. Conclusion
Pore structure of mesoporous silica FSM-16 is
stable against heat treatment up to 1073 K in
vacuo but collapsed by calcination at 1273 K.
FSM-16 calcined at 1073 K has less silanol groups
than that calcined at 823 K, although both FSM16 exhibit hydrophobic surface character regardless of calcination temperatures. The difference in
calcination temperature affects adsorption behavior of water as well as rehydroxylation of FSM16. Once water is adsorbed on the freshly calcined
FSM-16 surface, the surface becomes hydrophilic
and original hydrophobic character is never restored even after evacuation at 823 K.

Acknowledgements
The financial support by a Grant-in-Aid for
Science Research from the Ministry of Education,
Science, Sports and Culture, Japanese Government is greatly appreciated.

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