J. Phys. Chem.

B 1998, 102, 5991-5995 5991

Multilayered SiO2/TiO2 Nanosol Particles in Two-Dimensional Aluminosilicate

Catalyst-Support

Jin-Ho Choy,* Joo-Hyoung Park, and Joo-Byoung Yoon

Department of Chemistry, Center for Molecular Catalysis, College of Natural Sciences, Seoul National
UniVersity, Seoul 151-742, Korea
ReceiVed: March 23, 1998; In Final Form: May 12, 1998

A new layered nanocomposite, which is one-to-one interstratified with a montmorillonite layer and a mixed
SiO2/TiO2 sol particle one, has been prepared by ion exchange reaction of the Na+ ion in montmorillonite
with the positively charged SiO2/TiO2 sol particles. The ion exchange reaction was performed at three different
temperatures of 45, 60, and 75 °C by mixing an aqueous suspension of 1 wt % Na+ montmorillonite with
SiO2/TiO2 sol solution where the molar ratio of Si/Ti was selected as 20/2. According to the powder X-ray
diffraction analysis, the basal spacings of layered nanocomposites calcined at 400 °C were found to increase
from 35.4 Å, to 47.3 Å, and to 60.0 Å as the ion exchange reaction temperature was raised from 40 °C, to
60 °C, and to 75 °C. Their BET and Langmuir specific surface areas and porosities, estimated from nitrogen
adsorption-desorption isotherms, become larger with the increment of basal spacing, and the highest BET
specific surface area and the largest porosity are found to be 683 m2/g and 0.50 mL/g, respectively. Despite
the large increment of the basal spacing, the porous properties such as specific surface areas, porosities, and
pore sizes, those which are calculated from t-plots and chemical shift of 129Xe NMR, respectively, are
determined to be almost constant. From the UV/vis spectra, the blue shift of the absorption edge was observed,
indicating that the TiO2 sol particles in the interlayer are quantum sized. It is therefore proposed that the
products are intercalation-type nanocomposites with the multistacked structure of the SiO2/TiO2 nanoparticles
in the interlayer space of montmorillonite.

Introduction In the present study, taking advantage of the formation of

It is well-known that a number of nanosized particles such
as TiO2, Al2O3, ZrO2, SiO2, CdS, and Fe2O3 have high activity
in oxidation-reduction catalysis or acid-base catalysis. In
particular the semiconductors such as TiO2, ZrO2, and CdS are
widely studied due to their photocatalytic activities on the
decomposition of environmental contaminants such as haloge-
nated hydrocarbons, pesticides, surfactants, and organophos-
phorus compounds.1-4 Since the semiconductor particles below
ca. 10 nm in size show higher activities than the bulk in
photocatalysis, it has become important to stabilize quantum-
sized particles in various porous nanocomposites.5-8 Nano-
composites refers to composites of more than one Gibbsian solid
phase where at least one dimension is in the range of nanometer
size and typically all solid phases are in the 1-20 nm range.9
Such typical materials are pillared clays, gels and xerogels with
nanosized particles, zeolite-inorganic nanocomposites, etc.
Among them, the pillared clays with inorganic oxides such as
Al2O3, ZrO2, Fe2O3, TiO2, and SiO2 as pillaring agent are of
interest due to their high thermal stability and porosity,10-14
those which have been considered as useful catalysts, molecular
sieves, selective adsorbents, and membrane and sensor
materials.15-20 However, there is little information on the best
synthetic conditions to obtain highly porous pillared clay, on
the interlayer structure, on the nanocrystalline structure of pillars,
and on the mechanisms during intercalation and pillaring
reactions.
* To whom all correspondence should be addressed. Tel: 82-2-880-6658.
Fax: 82-2-872-9864. E-mail: jhchoy@plaza.snu.ac.kr.
S1089-5647(98)01586-7 CCC: $15.00 © 1998 American Chemical Society
Published on Web 07/11/1998
aggregate of nanometer-sized SiO2/TiO2 sols in highly acidic
solution, we attempted to synthesize new nanocomposites with
multistacked SiO2/TiO2 sol particles (double, triple, and qua-
druple) between montmorillonite layers and to understand
interlayer structure of SiO2/TiO2 particles using powder X-ray
diffraction (XRD), nitrogen adsorption-desorption isotherms,
diffuse reflectance ultraviolet-visible (UV/vis) spectroscopy,
and 129Xe nuclear magnetic resonance (129Xe NMR) spectros-
copy.
Experiments
Materials. The montmorillonite (Kunimine Co.) with the
structural formula Na0.35K0.01Ca0.02(Si3.89Al0.11)(Al1.60Mg0.32-
Fe0.08)O10 (OH)2‚nH2O was used as a starting material without
any purification, where layer charge was determined to be
0.31e-/(Si,Al)4O10 by an n-alkylammonium method.21 The
Na+-activated montmorillonite was prepared by adding the
colloidal fractions into the 1 N sodium chloride solution, and
then it was washed thoroughly with distilled water. A 1 wt %
aqueous suspension of montmorillonite was preswelled for 1
day before ion exchange reaction.
Preparation of Sol Solutions. A silica sol solution was
prepared by mixing Si(OC2H5)4, 2 N HCl, and ethanol with a
ratio of 13.6 mL/3.5 mL/3.0 mL at room temperature. Titanium
tetrachloride (TiCl4) was also hydrolyzed by adding it to 1 N
HCl solution with a molar ratio of HCl/TiCl4 ) 6, and the
resulting translucent slurry was aged to a clear sol solution by
continuous stirring for 1 h at room temperature. Finally the
silica sol solution and the titania solution were intermixed with
5992 J. Phys. Chem. B, Vol. 102, No. 31, 1998 Choy et al.

a ratio of Si/Ti ) 10/1, and the mixture was stirred further for
1 h at room temperature and used for pillaring reaction.
Pillaring Reaction. The ion exchange reaction was carried
out by titrating the mixed solution into the clay suspension in
a ratio of Si/Ti/clay ) 20 mmol/2 mmol/1 g. The mixture was
allowed to stand for 40 h at three different temperatures (45,
60, and 75 °C) to exchange the Na+ ion in the clay with the
mixed SiO2/TiO2 sol particles. Each reaction product was
separated by centrifugation, washed thoroughly with deionized
water (abbreviated hereafter as NMs-wet; NM2-wet, NM3-wet,
and NM4-wet prepared at three different temperatures of 45,
60, and 75 °C, respectively, for ion exchange reaction), and
dried in an oven at 80 °C for 24 h (abbreviated hereafter as
NMs-80; NM2-80, NM3-80, and NM4-80). Finally all NMs-
80 were calcined at 400 °C for 2 h to obtain a stable
nanocomposite (abbreviated hereafter as NMs-400; NM2-400,
NM3-400, and NM4-400).
Sample Characterization. Powder XRD patterns for the
orientated samples were taken using a Philips PW1830 diffrac-
tometer with Ni-filtered Cu KR radiation (λ ) 1.54056 Å).
To observe the thermal behavior of NMs-80, thermogravi-
metry-differential thermal analysis (TG-DTA) carried out with
a Rigaku TAS-100 under an ambient atmosphere where the Figure 1. Powder X-ray diffraction patterns for (a) NM2-80 and NM2-
heating rate was fixed at 10 °C/min. 400, (b) NM3-80 and NM3-400, and (c) NM4-80 and NM4-400.
Chemical analyses for the samples, fused with lithium
metaborate at 900 °C and then dissolved in a 3% HNO3 solution,
were carried out with the inductively coupled plasma (ICP:
Shimazu ICPS-5000) method.
Diffuse reflectance UV/vis spectra were recorded on a Perkin-
Elmer Lambda 12 spectrometer equipped with an integrating
sphere of 60 mm in diameter using BaSO4 as a standard. The
UV/vis spectra obtained in diffuse reflectance mode [R∞] were
transformed to a magnitude proportional to the extinction
coefficient (κ) through the Kubelka-Munk function [F(R∞)].22
129Xe NMR spectroscopic analyses were performed using a

Bruker AMX-400 Fourier transform NMR spectrometer at a

frequency of 110.7 MHz at 25 °C, typically under conditions
of a 6 µs pulse and a pulse delay of 2 s. The reference signal
of 129Xe was taken as that of 304 kPa of xenon gas, which was
extrapolated to zero pressure, using the Jameson equation.23 The
NMR samples were prepared by drying them at 300 °C in a
vacuum and sealed at very low pressure (20 Torr) of xenon
gas.
Nitrogen adsorption-desorption isotherms were measured
volumetrically at the liquid nitrogen temperature with a home-
made computer-controlled measurement system.24 The calcined
samples were degassed at 300 °C for 3 h under vacuum prior
to the adsorption measurement.
Results and Discussion
Powder X-ray Diffraction Analyses. Figure 1 shows a
series of typical powder XRD patterns for the NMs-80 and NMs-
400, of which the (00l) diffraction peaks gradually shift toward
lower angle in two theta (2θ), as the ion exchange reaction
temperature was raised from 45 °C, to 60 °C, and to 75 °C.
The basal spacings of NM2-400, NM3-400, and NM4-400 are
determined to be 35.4, 47.3, and 60.0 Å with their gallery heights
of 25.8, 37.7, and 50.4 Å, respectively, by subtracting the
thickness of the aluminosilicate layer (9.6 Å) from their basal
spacings. It is noticeable that the increment of the gallery height
remains almost constant with a value of ca. 12 Å, resulting from
the multistacked aggregation of homogeneous nanosol particles
in the interlayer space of montmorillonite.
Figure 2. Thermal analysis for NMs-80: (a) thermogravimetric
analysis and (b) differential thermal analysis.
Thermal Analysis. All NMs-80 show two resembling
thermal behaviors though they are different from one another
in terms of weight changes as shown in TG-DTA curves (Figure
2). The first dramatic weight loss with a strong endothermic
peak below 250 °C is mostly attributed to the desorption of
water on internal and external surfaces of montmorillonite and
pillar, and the second gradual weight loss with a feeble
endothermic peak above 600 °C corresponds to dehydroxylation
mainly due to the decomposition of the lattice hydroxyl group
in octahedral sheets of aluminosilicate. From the thermal
analysis, the pillaring temperature of 300-500 °C is desirable,
and the resulting NMs-80 become stable at least up to 500 °C.
Chemical Analysis. Na+ montmorillonite and NMs-400
have been quantitatively analyzed by ICP to estimate pillar
contents of SiO2 and TiO2. Assuming that the chemical
composition of montmorillonite based on the Al2O3 content is
unchanged during pillaring reaction, those of pillared product
and pillar itself could be determined as shown in Table 1. It is
Multilayered SiO2/TiO2 Nanosol Particles J. Phys. Chem. B, Vol. 102, No. 31, 1998 5993

TABLE 1: Chemical Analysis Data for NMs-400 in Comparison with Those of Na+ Montmorillonite and Pillar Itself
analytical results (%) mol compositiona pillar compositionb
sample SiO2 TiO2 Al2O3 Si Ti Al Si Ti
Na+-mont. 63.0 0.0 23.5 3.89 0.00 1.71 0.00 0.00
NC-2MST 65.7 19.9 10.6 9.04 2.06 1.71 5.15 2.06
NC-3MST 63.0 23.5 9.9 9.27 2.60 1.71 5.38 2.60
NC-4MST 60.8 26.9 9.1 9.73 3.23 1.71 5.84 3.23
a
The compositions given in moles for O10(OH)2 anion basis of silicate layer. b The compositions of pillars in the interlayer of montmorillonite
are given in moles for O10(OH)2 anion basis of silicate layer; these values are calculated by subtracting the nanocomposites from Na+ montmorillonite.

Figure 4. Relationship between chemical shift of Xe peak and mean

free path.

Figure 3. 129Xe NMR spectra for (a) NM2-400, (b) NM3-400, (c)
NM4-400, and (d) Xe reference.

found that the pillar content such as SiO2 and TiO2 becomes
larger linearly with an increase of gallery height of NMs-400,
although the pillar composition of TiO2 increases more signifi-
cantly than that of SiO2. This indicates that SiO2 and TiO2 sol
particles are intercalated into the interlayer space of montmo-
rillonite with an increase of gallery height in NMs-400.
129Xe Nuclear Magnetic Resonance Spectroscopy. 129Xe

NMR spectra of xenon adsorbed in NMs-400 are shown in

Figure 3 together with that of 304 kPa xenon gas as reference
for comparison.
The chemical shift δ of xenon adsorbed in a cavity corre-
sponds to the following equation:25,26

δ ) FWδW‚Xe + FXeδXe‚Xe + δE

where δW‚Xe denotes the influence of collisions between xenon
atoms and the internal wall of the cavity, and δXe‚Xe corresponds
to the effect of collision between xenon atoms. FW and FXe
depend on the density of xenon adsorbed, i.e., on the number
of xenon atoms per cavity. δE expresses the effect of mean
electric field within the cavity. In the present work, the second
and third terms (δE and FXeδXe‚Xe) are negligible since the
samples, which do not contain any polarizing cations in the
cavity of NMs-400, are dried at 300 °C in a vacuum and sealed
at very low pressure (20 Torr) of xenon gas. In this case, the
pore diameter could be calculated from the correlation curve
between chemical shift and mean free path (t) of xenon26 as
shown in Figure 4. For the case of spherical pores, the pore
diameter (D) can be estimated by the following equation;
D ) 2(t + rXe)
where rXe is van der Waals radius of xenon (2.2 Å).
Figure 5. Nitrogen adsorption-desorption isotherms for (a) NM2-
400, (b) NM3-400, and (c) NM4-400.
All 129Xe NMR spectra of NMs-400 exhibited similar
chemical shifts of ca. 0 and 98 ppm, irrespective to their basal
spacings. The former chemical shift results from xenon
adsorbed in the macropore or free xenon, and the latter
corresponds to one adsorbed in a micropore with a size of ca.
10 Å, whose value was calculated from the above relationship.
Nitrogen Adsorption-Desorption Isotherms. Figure 5
shows the nitrogen adsorption-desorption isotherms of NMs-
400. All isotherms, characterized as type IV according to the
BDDT (Brunauer, Deming, Deming, and Teller) classification,
exhibit relatively large hysteresis, whose loops are of type B in
Boer’s five types,27,28 indicating the presence of open slit-shaped
capillaries with fairly wide bodies and narrow short necks. Such
a finding allows us to conclude that all NMs-400 are analogous
in microstructure.
5994 J. Phys. Chem. B, Vol. 102, No. 31, 1998 Choy et al.

TABLE 2: Adsorption Properties of NMs-400 in

Comparison with Those of Na+ Montmorillonite
BSa BET SWb TPc MPd PS
sample (Å) (m2/g) (Å) (mL/g) (mL/g) (Å)
mont. 9.6 30
NC-2MST 35.4 469 10.2 0.35 0.25 10.4
NC-3MST 47.3 591 10.2 0.43 0.30 10.4
NC-4MST 60.0 683 11.4 0.50 0.37 10.4
a
BS ) Basal spacing calculated from powder X-ray diffraction. b SW
) slit width. c TP ) total porosity. d MP ) microporosity. e PS ) pore
size evaluated form chemical shift of 129Xe NMR.

Their BET specific surface area and porosities, estimated from

Figure 6. t-plots calculated from nitrogen adsorption isotherms for
(a) NM2-400, (b) NM3-400, and (c) NM4-400.
the nitrogen adsorption-desorption isotherms, become larger
as the basal spacing increases. The largest BET specific surface
area and the largest porosity are found to be 683 m2/g and
0.50 mL/g, respectively, for NM4-400.
To evaluate the micropore size of NMs-400, t-plots28 are
calculated from the isotherms as shown in Figure 6, in which
the amount of nitrogen adsorbed is plotted against the statistical
thickness (t) obtained from the t-curve. The t-curve28 is the
plot of the statistical thickness (t) of adsorbed species on the
surface of nonporous adsorbents with regard to relative vapor
pressure (P/P0). The thickness t is given by σ(V/Vm), where σ
is the average thickness of the molecular single layer depending
upon the way successive layers are stacked, and V/Vm is the
number of statistical molecular layers in the film; V is the total
volume of adsorbed species, and Vm is the monolayer capacity
of a nonporous reference solid. In this work, the Harkins-Jura
equation28 was used as the standard t-curve as follows:

log(P/P0) ) 0.034 -13.99/t2

The micropore volumes and the slit widths for NM2-400,

Figure 7. Relationships between basal spacing and (a) pillar composi-
tion, (b) specific surface area, (c) porosity, and (d) pore size.
NM3-400, and NM4-400 can be calculated from the t-plots,
since the microporosity is equivalent to the intercept value given
by the line extrapolated from the high-pressure branch to the
adsorption axis, and the slit width is twice the t-value of
inflection point, giving the real pore size in the interlayer of
montmorillonite. The micropore volumes for NM2-400, NM3-
400, and NM4-400 are estimated as 0.25, 0.30, and 0.37 mL/g,
respectively, which are presented in Table 2. From these values,
we found that the major part of their total pores are mostly
composed of micropores with slit widths of 10.2, 10.2, and 11.4
Å, respectively. It is worthy to note here that the microporosity

Figure 8. Proposed model of the interlayer microstructure for NMs-400.

Multilayered SiO2/TiO2 Nanosol Particles
Figure 9. Ultraviolet-visible spectra for (a) NM2-wet, NM2-80, and
NM2-400, (b) references of TiO2 (rutile and antanse) and montmoril-
lonite used in this work.
increases as the gallery height becomes larger, but the pore size
remains unchanged with a value of 11 Å, which is in agreement
with the 129Xe NMR study. According to the above results, a
linear correlation could be deduced among their gallery heights
and porous properties such as specific surface area, total
porosity, slit width, and microporosity, as shown in Figure 7.
It is now clearly concluded that NMs-400 are the intercalation-
type nanocomposites with multistacked structure of nanoparticles
in the interlayer space of montmorillonite, as shown in Figure
8.
Ultraviolet-Visible Spectroscopy. Figure 9 shows the UV/
vis spectra of NMs-wet, NMs-80, and NMs-400 together with
those of anatase, and Na+ montmorillonite as reference com-
pounds for comparison. There are two important findings to
be underlined in the spectra of NMs-wet, NMs-80, and NMs-
400; the first is a large blue shift in the absorption threshold
and the λmax compared to the bulk anatase due to the quantum
size effect5,29,30 of nanosized TiO2 particles of ca. 20 Å in the
interlayer space of montmorillonite. The absorption threshold
is the extrapolated energy position where the peak starts to
increase steeply, and λmax is the maximum position of absorp-
tion. The second is a red shift of absorption threshold in UV/
vis spectra for NMs-400 due to the coagulation of TiO2 particles
in the interlayer space and/or the formation of Si-O-Ti
covalent bonding among intercalated TiO2, SiO2 sol particles,
and silicate layers.
Conclusion
We were successful in preparing the intercalation-type
nanocomposite with multistacked structure (double, triple, and
quadruple) of intermixed SiO2/TiO2 nanoparticles in the inter-
J. Phys. Chem. B, Vol. 102, No. 31, 1998 5995
layer space of montmorillonite. According to the XRD, nitrogen
adsorption-desorption isotherms, and 129Xe NMR analyses, it
is found that all the nanocomposites are highly porous with a
supergallery height of NM2-400 ) 25.8 Å, NM3-400 ) 37.7
Å, and NM4-400 ) 50.4 Å, and their porous properties are
stable up to at least 500 °C. The highest BET specific surface
area obtained is 683 m2/g in NM4-400, whose value is highest
in the same kind of pillared clay so far reported. From UV/vis
spectra, it is concluded that the quantum-sized TiO2 of ca. 20
Å are stabilized in the interlayer space. We are going to
characterize the local symmetry and the electronic structure of
the TiO2 particles using X-ray absorption fine structure spec-
troscopy, since they are very important in photocatalysis of
halogenated hydrocarbon, phenol, etc.
Acknowledgment. This work was in part supported by the
Korea Science and Engineering Foundation through the Center
for Molecular Catalysis and the Research Institute of Molecular
Science in Seoul National University, and by the Ministry of
Education (BSRI-97-3413).
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