Applied Clay Science 47 (2010) 351–355

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Novel synthesis of ordered mesoporous materials Al-MCM-41 from bentonite

Huaming Yang ⁎, Yuehua Deng, Chunfang Du, Shengming Jin
Department of Inorganic Materials, School of Resources Processing and Bioengineering, Central South University, Changsha 410083, China

a r t i c l e i n f o a b s t r a c t

Article history: This paper reports the synthesis of ordered mesoporous materials Al-MCM-41 with a specific surface area of
Received 23 September 2009 1018 m2/g from bentonite. Pretreated bentonite was simultaneously used as silica and aluminum sources
Received in revised form 21 November 2009 without addition of silica or aluminum reagents. Orthogonal experiments were adopted to optimize the
Accepted 23 November 2009
processing parameters. The samples were characterized by X-ray diffraction (XRD), high-resolution
Available online 29 November 2009
transmission electron microscopy (HRTEM), N2 adsorption–desorption measurements and Fourier transform
infrared spectra (FTIR) techniques. The obtained materials were hexagonal Al-MCM-41. Calcination removed
Keywords:
Mesoporous materials
the surfactant while new bonds increased the crosslinking of the frameworks. Proper Si/Al molar ratio was
Al-MCM-41 critical for the formation of highly ordered mesoporous materials.
Bentonite © 2009 Elsevier B.V. All rights reserved.
Orthogonal experiments

1. Introduction
Ordered mesoporous materials (OMM) have attracted consider-
able interests since the discovery of mesoporous molecular sieves
(M41S) by scientists from Mobil Oil Corp. (Beck et al., 1992) because
of their high surface areas and regular pore channels. Such materials
have interesting applications in catalysis (Zhao et al., 2005; Hu et al.,
2006; Li et al., 2006), catalytic supports (Perathoner et al., 2006),
sensors (Shimizu et al., 2004; Dai et al., 2007), adsorbents (He et al.,
2009; Akasaka et al., 2009), host–guest chemistry (Parala et al., 2000;
Lee et al., 2005), energy (Gao et al., 2002; Sun et al., 2007), drug
delivery (Salonen and Lehto, 2008; Angelos et al., 2008) et al. The
number of research papers dealing with mesoporous silica has very
much grown during the last decade (Berggren et al., 2005). The usual
procedure is to employ a simple organosilicate as silica source, such as
tetramethylorthosilicate (TMOS) or teraethylorthosilicate (TEOS).
However, the process suffers from the drawback of the expensive
and toxic silica source. The economic and environmental considera-
tions have recently triggered an interest in the use of inexpensive
inorganic silicate as a starting material. Water glass is a commodity
chemical with a price much lower than that of organosilicate. Natural
minerals with high content of SiO2 and Al2O3 can be considered as
alternative sources for the synthesis of OMM with lower cost and
green process.
Researchers have synthesized mesoporous materials by using
various kinds of natural layered silicates as silica source. In the 1990s,
Yanagisawa et al. (1990) presented the first method to make
mesoporous silica from kanemite (NaHSi2O5·3H2O). Fukushima and
Inagaki then used this method to synthesize OMM from kanemite
(Inagaki et al., 1993; Fukushima and Inagaki, 1996). Kang et al. (2005)
developed a synthesis route to produce mesoporous materials Al-
MCM-41 from water glass and metakaoline as silica and aluminum
sources, cetyltrimethylammonium bromide (CTAB) as a directing
agent. The obtained mesoporous materials Al-MCM-41 had a high pore
volume of 0.78 cm3/g and a high specific surface area of 877 m2/g. In
addition, coal fly ash was converted into two types of porous materials:
MCM-41 and SBA-15 by Kumar et al. (2001). Misran obtained
mesoporous materials from fly ash by a similar method (Misran
et al., 2007). Based on these studies, layered silicate minerals have
been used only as single silica or aluminum source for the synthesis of
mesoporous materials.
Montmorillonite was recently used as silica and aluminum source
to synthesize mesoporous materials. Liu et al. (2003) synthesized Al-
MCM-41 in-situ on Na-montmorillonite from montmorillonite and
silica sol as Al and Si sources, the amount of surfactant was relatively
high; pure silica sol was needed and the method was energy and time
consuming. Tang et al. (2008) obtained highly stable mesoporous
molecular sieves by microwave radiation. In their experiments, the
amount of clay minerals was very low, sodium silicate and aluminum
chloride still played the major role as Si and Al sources, the specific
surface area of the synthesized sample was low (only 576 m2/g) and
the pore sizes were widely distributed.
In this paper, we report a novel method to synthesize OMM Al-
MCM-41 from pretreated bentonite as silica and aluminum sources
without addition of silica or aluminum reagents.
2. Experimental design

⁎ Corresponding author. Tel.: +86 731 8830 549; fax: +86 731 8710 804. Bentonite was obtained from Henan, China, and had the following
E-mail address: hmyang9392@hotmail.com (H. Yang). chemical compositions (mass %): 66.50 SiO2; 8.79 Al2O3;1.64 Fe2O3;

0169-1317/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2009.11.050
352 H. Yang et al. / Applied Clay Science 47 (2010) 351–355

1.64 CaO; 3.03 MgO; 2.06 TiO2; 0.19 K2O; 0.14 Na2O; and 12.32 loss on Table 2
ignition. The bentonite mainly consisted of montmorillonite. Cetyl- The orthogonal design for preparing Al-MCM-41.

trimethylammonium bromide (CTAB, analytical pure) and solid NaOH Sample name Level combination Factors and their levels
(analytical pure) were also used.
A B C
Bentonite was firstly mixed with solid NaOH at different mass
CM1 A1B1C1 1 1 1
ratios. The mixture was heated at 600 °C for 2 h, then dispersed in
CM2 A1B2C2 1 2 2
deionized water with stirring and aged at room temperature. The total CM3 A1B3C3 1 3 3
time of stirring and aging was defined as leaching time. The CM4 A2B1C2 2 1 2
supernatant was used as Si and Al source. An amount of 80 mL CM5 A2B2C3 2 2 3
supernatant was dropped into the solution of 1 g CTAB in 50 mL CM6 A2B3C1 2 3 1
CM7 A3B1C3 3 1 3
water, pH was adjusted with diluted HCl, the solution was transferred CM8 A3B2C1 3 2 1
to a Teflon-lined steel autoclave and heated at 110 °C for 24 h. The CM9 A3B3C2 3 3 2
resultant white powder was filtered, washed and dried at 80 °C
overnight. This as-synthesized material was calcined at 540 °C for 6 h
in air at a heating rate of 5 °C/min to form Al-MCM-41 (marked as of the samples can reach a very high value, and the maximum value
CM). was 59.58 for CM6. The results of the orthogonal analysis (Table 4)
To optimize the process parameters, orthogonal experiments were showed that the mass ratio of bentonite to solid NaOH was the dominant
adopted. Three synthesis parameters involving mass ratio of bentonite factor in synthesizing Al-MCM-41 according to the calculated R values
to solid NaOH (A), leaching time (B) and pH value (C) were considered. (Xu et al., 2006). The specific surface area decreased with increasing
These parameters were varied at three levels (Table 1). The applied bentonite/NaOH mass ratio. The optimum condition derived from
ranges of the variables were chosen based on our preliminary orthogonal experiments should be that of A1B2C1. An additional
experiments (Table 2). The estimated indices selected in our experi- experiment for synthesizing sample under this condition was per-
ments were the compositions and specific BET surface areas of the formed (CM10). The specific surface area was 1007 m2/g, which is in
products. agreement with the orthogonal results. The compositions of the samples
were strongly affected by the pH value of the reaction solution. The SiO2
3. Characterization techniques content decreased with increasing pH. However, the highest SiO2
content did not yield the maximum specific surface area.
X-ray diffraction (XRD) patterns were carried out using a Rigaku
D/max 2550 with Cu Kα radiation (λ = 0.15406 nm) over the
scanning range 2θ = 1–10° for small angle XRD (SAXRD) at a voltage 4.2. Structural aspects: WAXRD and SAXRD analysis
of 40 kV and 300 mA and 2θ=10–90° for wide angle XRD (WAXRD) at
a voltage of 40 kV and 200 mA both with a step width of 0.02°. The WAXRD pattern of Al-MCM-41 (CM10) is presented in Fig. 1,
Nitrogen gas adsorption–desorption isotherms were measured at indicating that the synthesized samples were amorphous, none of
77 K using an ASAP 2020 unit. Prior to the adsorption experiment, the the reflections of bentonite remained. The SAXRD pattern (Fig. 2) of
materials were vaccum-dried at 250 °C for 6 h. The specific surface the as-synthesized sample displayed the characteristic (100), (110)
area and the pore size distribution were calculated by the Barrett– and (200) reflections of typical MCM-41 (Beck et al., 1992). After
Joyner–Halenda (BJH) method using the adsorption and desorption calcination, the reflections were shifted to somewhat higher diffrac-
isotherms. The total pore volume was obtained from the maximum tion angles, thus, calcination caused condensation of the framework.
amount of nitrogen gas adsorbed at partial pressure P/P0 = 0.999. A All the samples showed the (001) reflection at around 2.2° (Fig. 3), and
JEOL JEM-3010 electron microscope operating at accelerating voltage the peak intensity of d100 firstly increased with increasing the Si/Al
up to 200 kV was used for high-resolution TEM (HRTEM) studies. molar ratio, but decreased when Si/Al molar ratio reached 44.14,
Samples were prepared by suspending Al-MCM-41 material in suggesting that a proper range of Si/Al molar ratio existed for the
ethanol followed by sonication for 10 min in an ultrasonic bath. The formation of Al-MCM-41. The hexagonal unit cell parameter (a0),
suspension was dripped onto a carbon-coated copper grid and equal to the internal porepdiameter
ffiffiffi plus one pore wall thickness, was
allowed to dry. Fourier transform infrared spectra (FTIR) of the calculated by a0 = 2d100/ 3 (Table 3). Combined with composition
samples were obtained by using Nexus-670 spectrometer with a analysis, the larger Si/Al molar ratio did not show a higher intensity of
nominal resolution of 2 cm− 1. The effective range was from 400 to the reflections, the sample of the smallest Si/Al ratio showed the
4000 cm− 1. lowest intensity, similar to the result of Okada et al. (2007).

4. Results and discussion

4.1. Results of the orthogonal experiment Table 3

The composition and textural characteristics of the products.
The compositions obtained from chemical analysis and the specific
Samples Si/Al molar ratio SBET Pore volume a0 Dd t
surface areas calculated from BET method of Al-MCM-41 were listed in (m2/g) (cm3/g) (nm) (nm) (nm)
Table 3. All products had high specific surface areas up to 1019 m2/g. The
CM1 36.15 1018.5 0.72 4.6 3.0 1.6
main compositions of the samples were SiO2 and Al2O3, Si/Al molar ratio CM2 44.14 923.9 1.04 4.4 2.9 1.5
CM3 40.59 913.8 0.96 4.6 2.6 2.0
CM4 53.32 708.9 1.01 4.4 2.7 1.7
Table 1 CM5 13.72 840.9 0.87 4.6 2.7 1.9
Experimental factors and their levels. CM6 59.58 864.7 0.68 4.7 2.7 2.0
CM7 8.31 547.8 0.88 5.1 2.7 2.4
Control factors Mass ratio of bentonite Leaching time (B) pH value (C)
CM8 22.69 721.7 0.89 4.5 2.7 1.8
to solid NaOH (A)
CM9 14.56 675.1 0.74 4.4 2.8 1.6
Level 1 A1(1∶1) B1(12 h) C1(9) CM10 32.66 1007.3 0.91 4.4 2.7 1.7
Level 2 A2(1∶1.25) B2(16 h) C2(10)
Note: Dd—Estimated using the desorption branch of the isotherm; t—Pore wall
Level 3 A3(1∶1.5) B3(20 h) C3(11)
thickness (t = a0 − Dd).
 H. Yang et al. / Applied Clay Science 47 (2010) 351–355 353

Table 4
The analysis for orthogonal experiment.

Indices SBET (m2/g) SiO2 (wt.%) Al2O3 (wt.%)

Factors A B C A B C A B C

k1 958.07 758.4 868.29 88.76 86.76 89.26 1.88 3.95 2.23

k2 804.81 828.81 769.28 88.07 87.20 88.25 2.61 3.39 2.68
k3 648.19 823.85 773.50 84.28 87.14 83.60 5.49 2.66 5.08
R 309.88 70.41 99.01 4.48 0.44 5.66 3.61 1.29 2.85

Note: 1, 2, 3 stand for the three levels respectively in accordance with Table 1; k1, k2,
k3 and R are the calculated parameters based on orthogonal experiment.

4.3. Morphological evolution

The HRTEM images of the typical sample viewed along the [001]
and [110] directions showed regularly ordered hexagonal arrays of
mesopores with uniform pore size of about 3.0 nm (Fig. 4). Thus, the
final products were MCM-41 with long range order and regular two
dimensional hexagonal pore structures. Fig. 2. SAXRD patterns of the as-synthesized sample and Al-MCM-41.

4.5. FTIR spectra

4.4. Porosity measurements
Fig. 5 shows N2 adsorption–desorption isotherm and pore size
distribution of a typical product Al-MCM-41. The isotherm had the
typical type IV shape with a sharp capillary condensation step at
relative pressure of 0.3–0.45 and a large hysteresis loop at high
relative pressures, which confirmed the presence of uniform pores.
The P/P0 inflection point was related to the pore diameters in
mesopores range, and the sharpness of the steps also indicated the
uniformity of the mesopores. A sharp peak centered at 2.7 nm was
observed in the pore size distribution. A shoulder probably indicated
interparticle pores. A similar phenomenon was found by Jiang et al.
(2007).
Textural characteristics obtained from N2 adsorption–desorption
measurements and SAXRD of all samples were listed in Table 3. Al-
MCM-41 samples with high specific surface area up to 1019 m2/g and
pore volume up to 1.01 cm3/g was obtained. All the samples had thick
pore walls, the slightly thicker than that of mesoporous materials
derived from pure silica, the pore thickness did not regularly change
with increasing Si/Al molar ratio. Due to the thicker walls, the
products may have higher stability (Mokaya, 2009).
The FTIR spectra of original bentonite, the as-synthesized sample
and Al-MCM-41 are shown in Fig. 6. A band at 3739 cm− 1 due to Si–OH
appeared. Al–O vibration at 3618 cm− 1, clearly observed in original
bentonite, disappeared in the as-synthesized sample and Al-MCM-41,
indicating the destruction of the inner Al–O units of the octahedral
sheets. The broad band around 3450 cm− 1 was attributed to the
adsorbed water molecules. The bands at 2922 cm− 1, 2853 cm− 1,
1485 cm− 1 and 1384 cm− 1 were the characteristic bands of the
surfactant alkyl chain. Some bands observed at 1620–1657 cm− 1 were
caused by deformational vibrations of adsorbed water molecules. The
absorption bands at 1232 cm− 1 and 1226 cm− 1, characteristic of
mesoporous materials, belonged to the asymmetric stretching vibra-
tion of surface Si−O−Si groups (Wang et al., 2009), while there is no
typical band around this region for original bentonite. The bands at
1040 cm− 1 and 1089 cm− 1 in original bentonite resulting from the
vibration of Si−O−Si network (Jiang et al., 2007) were merged into

Fig. 1. WAXRD pattern of Al-MCM-41 (CM10). Fig. 3. SAXRD patterns of the products with different Si/Al molar ratios.
354 H. Yang et al. / Applied Clay Science 47 (2010) 351–355

Fig. 6. FTIR spectra of (A) original bentonite, (B) the as-synthesized sample and
(C) Al-MCM-41.

Fig. 4. HRTEM images of Al-MCM-41 (A) in the direction of the pore axis and (B) in the
direction perpendicular to the pore axis.
only one band around 1070 cm− 1 in as-synthesized sample and Al-
MCM-41. The internal and external asymmetric Si–O stretching
vibrations at 1068 cm− 1 for the as-synthesized sample were shifted
to 1082 cm− 1 after calcination, which suggested the formation of the
framework for Al-MCM-41.
Bands at 801 cm− 1 and 793 cm− 1 were attributed to the
symmetric Si–O stretching vibrations (Alam and Mokaya, 2008). The
bands at 964 cm− 1 and 962 cm− 1 were due to the stretching
vibration of surface Si–O− groups. The bands at 460 cm− 1 and
455 cm− 1 were caused by the bending vibration of Si–O− groups (Hui
and Chao, 2006). All these bands were typical of mesophase silica.
After calcination, the bands associated with the surfactant almost
disappeared, while the bands due to the asymmetric stretching
vibration, bending vibration and symmetric stretching of Si–O shifted
to higher wavenumbers, which indicated condensation of the
framework. These shifts were also consistent with the formation of
new Si–O–Al bonds during calcination. Also calcination removed the
surfactant from the products and new Si–O–Si and Si–O–Al bonds
were formed to increase the crosslinking of the framework during
calcination.
The FTIR band shift was usually caused by the substitution of
silicon by metal ions. Al was the main metal ions to be incorporated
into the framework in this work. Table 5 listed the band positions of
natural bentonite and Al-MCM-41 samples with different Si/Al molar
ratios. The band attributed to the asymmetric stretching vibration of
Si–O–Si shifted to higher wavenumber with increasing the Si/Al molar
ratios and the shift became very small when Si/Al molar ratio was
higher than 22.69, which further indicated that proper selection of the
Si/Al molar ratio was critical to the formation of highly ordered
mesoporous materials.
5. Conclusions
Highly ordered mesoporous Al-MCM-41 with specific surface
areas up to 1019 m2/g and pore volume up to 1.01 cm3/g were
synthesized from pretreated bentonite. The Al-MCM-41 samples
revealed long range order and regular hexagonal pore structure. The
mass ratio of bentonite to solid NaOH was the dominant factor in
synthesizing Al-MCM-41. Calcination removed the surfactants within
the pores, new Si–O–Si and Si–O–Al bonds increased the crosslinking
of the framework during calcination. Proper selection of the Si/Al

Table 5
FTIR band positions for natural bentonite and Al-MCM-41 with different Si/Al molar
ratio.

Sample Si/Al Si–O–Si symmetric Si–O–Si asymmetric Si–O− groups

molar stretching vibration stretching vibration bending vibration
ratio (cm− 1) (cm− 1) (cm− 1)

Bentonite 6.43 794 1040, 1090 520, 469

CM10 8.31 796 1076 459
CM11 22.69 802 1082 459
CM9 44.14 801 1082 460
CM12 59.58 800 1083 460
Fig. 5. N2 adsorption–desorption isotherm and pore size distribution of Al-MCM-41.
 H. Yang et al. / Applied Clay Science 47 (2010) 351–355
molar ratio was necessary for the formation of highly ordered
mesoporous materials.
Acknowledgements
This work was supported by the National Natural Foundation of
China (50774095), the Excellent Youth Foundation of Central South
University and Hunan Provincial Natural Science Foundation of China
(08JJ3109).
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