Journal of Colloid and Interface Science 311 (2007) 135143

www.elsevier.com/locate/jcis

Amino benzoic acid modified silicaAn improved catalyst for the

mono-substituted product in the benzylation of toluene with benzyl chloride
Farook Adam , Jeyashelly Andas
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia
Received 13 December 2006; accepted 24 February 2007
Available online 3 March 2007

Abstract
Iron and 4-(methylamino)benzoic acid have been successfully incorporated into silica extracted from rice husk. The silica/Fe/amine complex,
RHFe(5% amine), showed a ca. 24% increase in specific surface area compared to RHFe. This increase was attributed to the templated formation
of regular pores. The XRD showed the RHFe(5% amine) to be amorphous. The FriedelCrafts benzylation reaction with toluene using RH
Fe(5% amine) showed a drastic reduction in the di-substituted products to ca. 1.0%.
2007 Elsevier Inc. All rights reserved.

Keywords: FriedelCrafts; Heterogeneous catalyst; Rice husk; Extraction of silica; Benzylation

1. Introduction as an effective heterogeneous catalyst in promoting hydrolysis

Sodium silicate, the precursor for silica production is cur-
rently manufactured by smelting quartz sand with sodium car-
bonate at 1300 C. However, the high silica content of rice husk
makes it a much cheaper alternative raw material that should be
fully exploited.
Recently we had published the iron and indium substituted
silica catalyst from rice husk ash [1,2]. In the catalytic benzy-
lation reaction with RHAFe [1], the di-substituted products
were also formed to a significant extent (ca. 8%). Therefore,
there was a need to reduce the di-substituted products and also
to design a catalyst that will target the yield of only one mono-
substituted product.
Iron is a cheap metal which can be used as a catalyst for
many organic reactions and is non-toxic to human health [3].
Many findings on iron as heterogeneous catalyst have been re-
ported [36]. For example, Fe3+ exchanged with montmorillo-
nite-K10 was used as a heterogeneous catalyst in the oxidation
of many kinds of primary and secondary alcohols [3]. Besides
this, researchers had also used iron(III) complex of Chelex resin
* Corresponding author.
E-mail addresses: farook@usm.my, farook_dr@yahoo.com (F. Adam).
0021-9797/$ see front matter 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2007.02.083
of phosphodiester and phosphonate ester [5]. Moreover, Fe-
pillared montmorillonite as a Fenton-type heterogeneous cat-
alyst was successfully used in removing cinnamic acid from
water [7].
Most heterogeneous catalyst are mesoporous or derived
from mesoporous materials. Mesoporous molecular sieves
are costly, since they are synthesized by critically controlled
processes using fine chemicals as templates [810]. Modified
amorphous silica from rice husk can offer a cheap alternative
and cost much less.
Most published reports using rice husk ash as catalytic sup-
port for metals were incorporated by physical incipient-wet
methods. The resulting catalysts were prone to metal leach-
ing during the reaction [1114]. In this study, iron and 4-
(methylamino)benzoic acid were incorporated into the sodium
silicate, which was obtained from rice husk by a simple cost ef-
fective solvent extraction method. The resulting complex was
used as a catalyst in the benzylation of toluene. It must be high-
lighted that these catalysts need not be activated by calcination
as we reported in our previous work [1,2]. Leaching of metal
was also not detected. This indeed was an added advantage for
the catalysts prepared in our laboratory.
This paper details an improved room temperature isolation
of silica from rice husk and its modification. The modification
136 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143
detailed in this study resulted in higher selectivity towards the
mono-substituted products.
2. Experimental
2.1. Raw material
The chemicals used were sodium hydroxide (Systerm, 99%),
nitric acid (Systerm, 65%), benzyl chloride (Fluka, 99%),
toluene (J.T. Baker, 99.8%), 4-(methylamino)benzoic acid
(AVOCADO Organics, 97.0%).
Rice husk (RH) was collected from a rice mill in Penang,
Malaysia. All chemicals were of AR grade and were used di-
rectly without purification.
2.2. Extraction of sodium silicate from rice husk (RH)
30.0 g of rice husk was weighed and transferred into a 1.0 L
beaker. 500 mL of 1.0 M nitric acid solution was added into the
beaker and was stirred with an overhead stirrer (Model RW20.n,
Kika Labortechnik) for 24 h. It was filtered and rinsed thor-
oughly with distilled water until the pH of the rinse became
constant. The washed rice husk was dried in an oven at 110 C.
The rice husk treated with acid was weighed and was then trans-
ferred into a 1.0 L plastic container. 500 mL of 1.0 M sodium
hydroxide solution was added. The solution was then stirred
with an overhead stirrer for 24 h at room temperature. It was
then filtered through suction filtration. The dark brown filtrate
(sodium silicate solution) was kept in a covered plastic con-
tainer. Several such portions were prepared. The whole of each
portion of the sodium silicate was separately used in the follow-
ing preparations.
2.3. Preparation of RH-silica (control)
The sodium silicate solution was titrated slowly (drop by
drop) with 3.0 M nitric acid solution until it reached pH 5.
A yellowish gel formed at about pH 10.50. No further change
was observed. The suspension was aged for two days in the
mother liquor. The gel was recovered by suction filtration. The
recovered solid was washed several times with copious amount
of distilled water. It was then dried in an oven at 110 C for
24 h. The product was allowed to cool in a desiccator. Finally,
it was ground into fine powder. This white powder was labeled
as RH-silica. The yield of RH-silica was 3.20 g.
2.4. Preparation of RHFe
The sodium silicate solution was titrated slowly (drop by
drop) with 130 mL of 3.0 M nitric acid solution containing
10.0% (w/w) Fe3+ (4.42 g of Fe(NO3 )3 9H2 O). The titration
was continued with 3.0 M nitric acid solution until pH 5 was
reached. At pH 10.68, the solution became yellowish-brown
color. However, when the pH reached 6.20, a greenish gel was
observed. No further change was observed. The gel was aged
for two days. The gel was recovered by suction filtration fol-
lowed by washing several times with copious amounts of dis-
tilled water. The solid sample was then dried at 110 C for 24 h.
Finally, it was ground to a fine powder. This brown powder was
labeled as RHFe. The yield of RHFe was 3.41 g.
2.5. Preparation of RHFe modified with 5%
4-(methylamino)benzoic acid
4-(Methylamino)benzoic acid (0.31 g) which constitutes 5%
(w/w) was added into the sodium silicate solution. It was stirred
well to make sure all the 4-(methylamino)benzoic acid was dis-
solved. The solution was then titrated as described earlier for
RHFe. The gel that appeared at ca. pH 10.6 was yellowish
brown. This changed to green at pH 6.3i.e. almost simi-
lar to the observation made during the preparation of RHFe.
There was no further change in color of the gel. The suspension
was aged for two days and isolated by vacuum filtration. The
solid was washed several times with distilled water and dried
at 110 C for 24 h. It was ground to a fine powder and was la-
beled as RHFe(5% amine). The yield of RHFe(5% amine)
was 4.48 g.
2.6. Sample characterization and analysis
The prepared catalyst was characterized by FT-IR spec-
troscopy (PerkinElmer System 2000), BET surface area analy-
sis (Micromeritics Instrument Corporation Model ASAP 2000,
Norcross), powder X-ray diffractometry (Siemens Diffractome-
ter D5000, Kristalloflex), transmission electron microscopy
(Philips CM12 instrument), scanning electron microscopy
(SEM) (Leica Cambridge S360) and energy dispersive spec-
trometry (EDX) (EDX Falcon System). Gas chromatographs
were obtained by a Shimadzu GC-17A with a VB-1 non-polar
capillary column, 30 m length and 0.32 mm inner diameter.
The chromatograph was equipped with a recorder model C-
R8A Chromatopac Shimadzu and FID detector. The carrier gas
used was nitrogen. GC conditions: initial temperature = 50 C,
final temperature = 235 C, program rate = 15 C min1 , in-
jector temperature = 250 C, detector temperature 250 C.
2.7. General procedure for the catalytic benzylation reaction
Liquid phase FriedelCrafts benzylation reactions of toluene
over the prepared catalysts were carried out in a magnetically
stirred two-necked round bottom flask with a reflux condenser.
The temperature of the reaction vessel was maintained precisely
using an oil bath. The reaction was carried out under normal
atmosphere.
2.7.1. Typical catalytic reaction procedure
0.10 g of RHFe (dried at 110 C and cooled in a desiccator)
was weighed into a round bottom flask. In order to attain a sol-
vent/reactant (toluene/benzyl chloride) ratio of 15:1, 15.0 mL
of toluene and 1.0 mL of benzyl chloride were introduced into
the round bottom flask equipped with a reflux condenser and
a magnetic stirrer. The solution was refluxed for 2 h. After
cooling, the reaction mixture was filtered and the filtrate was
analyzed by GC. Duplicate experiments were carried out to
ensure reproducibility. The above procedure was repeated by
 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143
Fig. 1. The FT-IR spectra of RHFe, RHFe(5% amine) and the differential spectrum.
using RHFe(5% amine) as the catalyst. No reaction was ob-
served with RH-silica (control). Experiments were also carried
out with different masses of RHFe or RHFe(5% amine), i.e.
0.05, 0.15 and 0.20 g.
2.7.2. Variation of reaction time and solvent/reactant ratio
Catalytic activity at different reaction times (30, 60 and
90 min) were studied by conducting the experiment as de-
scribed above. By employing a similar procedure the catalytic
activity at different solvent/reactant (toluene/benzyl chloride)
ratio, i.e. 5:1 and 10:1 was also studied. The mass of catalyst
used for the study was maintained at 0.10 g.
2.8. Product analysis by gas chromatography
Reaction mixture obtained from the catalytic reaction was
analyzed by using GC. GC analysis was used to determine
the conversion percentage of the reactant and the selectivity
percentage of the products. Typically, a 0.2 L of the sample
was introduced through a rubber septum by means of a micro-
syringe into the GC.
3. Results and discussion
3.1. Catalyst characterization
3.1.1. FT-IR analysis
Fig. 1 shows the FT-IR spectrum of RHFe, RHFe(5%
amine) and the differential spectra.
Referring to Fig. 1, the broad bands between 3100 to
3800 cm1 was due to the stretching vibration of the OH bond.
This vibration was due to both silanol groups (SiOH) and ad-
sorbed water molecules on the silica surface. The two bands
137
at 1636 and 1637 cm1 corresponds to the bending vibration
of HOH bond of trapped water molecules in the silica matrix.
The bands at 1076 and 1078 cm1 were due to the structural
siloxane bond (SiOSi). The shoulder at ca. 970 cm1 had
been reported to be due to the stretching vibration of SiOFe
bond [4]. The bands at 797 and 802 cm1 are due to the de-
formation and bending modes of SiO bond [15]. Vibrations at
463 cm1 (RHFe) and 465 cm1 (RHFe(5% amine)) are also
due to the deformation of SiO bond.
These deformations are shifted in the differential spectrum
due to the existence of SiOFe and possible existence of
SiN species after the modification.
The NH vibration of 4-(methylamino)benzoic acid were
seen as sharp peaks at 3424, 3396 and 3379 cm1 . However,
the differential IR spectrum in Fig. 1 does not show the stretch-
ing vibration of this bond. This may be due to the formation
of SiON or SiN bonds. Another characteristics peak in the
differential IR spectrum is the CH stretching vibration of the
methyl group which was observed at 2851 and 2921 cm1 .
The C=O stretching vibration can be seen at 1728 cm1 in the
differential spectrum. This had shifted from 1669 cm1 after
incorporation of the amine into the silica matrix. It can also be
inferred that the large blue shift of the carbonyl frequency can
be attributed to the possible formation of ester bonds. Appear-
ance of these bands in the differential IR spectra was indicative
of the incorporation of the amine into the silica matrix. A pro-
posed structure for the amine incorporated silicairon complex
is shown in Fig. 2.
The possible mechanism for the formation of the SiN bond
in the strongly basic medium is illustrated Fig. 3.
This bond formation is possible as the amino acid was added
into the sodium silicate solution before the neutralization step.
138 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143
Fig. 2. The probable structure of the silica matrix showing the new SiN bond
and the ester bond that has been incorporated into the silica. This results in the
increase in pore structure and surface area as shown in Table 1.
It was assumed that the esterification results via the condensa-
tion process during the aging resulting in the loss of H2 O.
3.1.2. Nitrogen adsorption BET analysis
Textural properties of the samples were obtained by BET
surface area, pore volume and average pore diameter mea-
surements. The results obtained by N2 adsorptiondesorption
isotherms of both samples are summarized in Table 1.
From the BET analysis, it was found that the specific sur-
face area of RHFe(5% amine) was significantly greater than
RHFe. The BET surface area obtained in this study was much
higher than that of silicairon complex obtained from rice husk
ash, i.e. RHAFe and RHAFe700 (87 and 56 m2 g1 , respec-
tively) [1].
Recent studies have shown that amines used as templates in-
creased the surface area of the catalyst [16]. Thus, the higher
specific surface area of RHFe(5% amine) can be assumed to
be due to the presence of the amine as a template. The in-
crease may also be due to the formation of new pore structures
formed by the aminesilica complex as shown in Fig. 2. The
average pore diameter of RHFe and RHFe(5% amine) were
Fig. 3. The possible mechanism for the formation of the SiN bond.
found to be 9.21 and 5.98 nm, respectively. Hence the incor-
poration of the amine resulted in narrower pores compared to
RHFe. However, both samples were found to be mesoporous
according to the IUPAC classification [17]. The adsorption
desorption isotherms of RHFe and RHFe(5% amine) are
shown in Figs. 4 and 5, respectively.
According to the IUPAC classification, the isotherms of RH
Fe and RHFe(5% amine) are of Type IV and exhibit a H1 hys-
teresis loop. Isotherms of RHFe and RHFe(5% amine) also
indicated that capillary condensation occurred in both samples.
The presence of the hysteresis loop of type H1 was normally
observed for aggregates and agglomerates. It is also obtained
for compacts of spheroidal particles with uniform size and ar-
ray [17]. Insets of Figs. 4 and 5 show both samples to have more
or less a uniform sized pores which indicate the characteristics
of H1 hysteresis loop.
Fig. 4 shows that RHFe to have two different pore size
ranges, i.e. 33.8 and 1550 nm. As for RHFe(5% amine), it
also showed pore size range between 1650 nm (inset in Fig. 5).
The pore distribution was almost similar to that observed in
RHFe. However, for RHFe(5% amine), the narrower range
was not observed. In conclusion, the incorporation of the amine
into the silicairon complex resulted in an increased specific
surface area.
3.1.3. EDX analysis
EDX analysis was used to determine the elemental com-
position of the sample. Two different spots on the respective
samples were analyzed by EDX. Atomic % analysis are shown
in Table 2.
Table 1
The BET analyses results of RHFe and RHFe(5% amine)
Parameter RHFe RHFe(5% amine)
BET surface area (m2 g1 ) 267 331
Pore volume (cc g1 ) 0.0305 0.0433
Average pore diameter () 92.1 59.8
 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143 139

Fig. 4. The nitrogen adsorption isotherm of RHFe. The pore size distribution is shown inset.

Fig. 5. The nitrogen adsorption isotherm of RHFe(5% amine). The pore size distribution is shown inset.

Table 2 the presence of iron. The inhomogeneity of iron is also clear in

EDX results of RHFe and RHFe(5% amine) these SEM backscattered micrographs.
Sample Si (%) Fe (%) N (%)
Spot 1 Spot 2 Spot 1 Spot 2 Spot 1 Spot 2 3.1.5. TEM analysis
RHFe 18.86 21.88 4.01 10.95 Figs. 7a and 7b show the TEM micrographs of RHFe and
RHFe(5% amine) 16.35 17.46 3.50 11.57 5.20 3.54 RHFe(5% amine), respectively.
Comparing the TEM micrographs of RHFe and RHFe(5%
amine), the later showed a major difference. As can be seen in
Silicon and oxygen which were present in both samples were
Fig. 7b, a series of cross-linked lines arranged in an orderly
from siloxane (SiOSi) and silanol (SiOH) groups.
manner was observed, which were not present in Fig. 7a. These
From the results obtained, it was found that Fe3+ ions in both
cross-linked lines may be due to the sequential arrangement of
samples were not homogeneously dispersed on the surface of
well defined pores due to the amine acting as a template during
the silica matrix. The analysis however, yielded homogeneous
the syntheses. Both samples exhibited irregular shaped parti-
distribution of nitrogen atoms in RHFe(5% amine). However,
cles.
as expected nitrogen was not detected in RHFe. This indicates
that the amine had indeed been incorporated in RHFe(5%
3.1.6. XRD analysis
amine) as suggested by the FT-IR spectrum.
Iron can be identified by X-ray diffraction due to the fact that
it exhibits an opaque characteristic to light. The X-ray diffrac-
3.1.4. SEM analysis togram of RHFe(5% amine) is shown in Fig. 8.
Fig. 6 shows the SEM-backscattered electron micrographs The powder XRD for both samples clearly showed that there
of RHFe and RHFe(5% amine), respectively. It showed that were no sharp peaks present. These catalysts showed broad
both the samples were granular and porous. spectra indicating the amorphous nature of the material. The
In the backscattered electron SEM micrographs, the heavier chemical modification on RHFe did not change the amor-
elements (in this case Fe) were indicated by lighter region or phous nature in RHFe(5% amine). Although the TEM analysis
color. Thus in both Figs. 6a and 6b the lighter shade indicates of RHFe(5% amine) showed regular arrangements of pores,
140 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143

(a) (b)

Fig. 6. SEM-backscattered electron micrographs of the catalysts (a) RHFe backscattered image (b) RHFe(5% amine) backscattered image.

(a) (b)

Fig. 7. Transmission electron micrographs of (a) RHFe, (b) RHFe(5% amine). Both at 150 K magnification.

Fig. 8. The powder X-ray diffraction spectrum of RHFe. RHFe(5% amine) showed a similar XRD diffraction spectrum.
 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143 141

Scheme 1. The expected products from the FriedelCraft reaction between toluene and benzyl chloride.

these could be still in the microcrystalline form. Generally, it is

known that microcrystalline particles are too small to diffract
X-rays to yield sharp peaks in its spectrum. This indicates that
although the amine could have acted as template to form regular
pores, it was possible the experimental conditions employed did
not favor the formation of crystalline phases. Hence, the X-ray
diffraction yielded a spectrum similar to amorphous powder.

3.2. Application of RHFe and RHFe(5% amine) as catalyst

3.2.1. FriedelCrafts benzylation of toluene

In this reaction, the benzyl chloride was mixed directly with
toluene (99.5%, R & M Chemicals)the toluene acting as Fig. 9. Graph showing the percentage yield of mono-substituted products vs
mass of catalyst used.
the solvent. The equation for the FriedelCrafts benzylation of
toluene is shown in Scheme 1.
When 0.10 g of RH-SiO2 (silica extracted from RH) was
used as the catalyst, no products were observed. A similar con-
trol experiment without any catalyst also yielded no products.

3.2.2. Catalytic activity with different mass of catalyst

As illustrated in Fig. 9, as the mass of the catalysts increased,
the percentage of mono-substituted products also increased. In
the presence of RHFe(5% amine), the percentages of mono-
substituted products obtained were much higher compared to
RHFe. Higher mass of catalyst was not used as the percentage
yield of the mono-substituted product was already 99%. This
result clearly indicates that RHFe(5% amine) is a more effec-
tive catalyst compared to RHFe for the synthesis of mono-
Fig. 10. Bar chart showing the percentage of di-substituted products vs mass of
substituted products. catalysts used.
Fig. 10 shows the bar chart for the formation of di-substituted
products at different catalyst mass. The di-substituted products
products. Fig. 11 shows that as the reaction time increased,
were found to decrease for both catalyst as the catalyst mass
was increased. However, when 0.20 g of RHFe(5% amine) the percentage yield (of mono-substituted products) produced
was used as the catalyst the di-substituted products decreased to either by using RHFe or RHFe(5% amine) also increased.
a minimum value of 1.0%. Therefore, in general as the catalyst Fig. 12 shows the percentage of di-substituted products de-
mass was increased, the RHFe(5% amine) yielded a higher creasing as the reaction time increased from 30 min to 2 h.
percentage of mono-substituted products. Likewise, the yield of The reduction of di-substituted products was significantly more
the di-substituted products were found to decrease much more when RHFe(5% amine) was used.
with RHFe(5% amine).
3.2.4. Benzylation with different solvent/reactant ratio
3.2.3. Benzylation at different reaction time (toluene/benzyl chloride)
Complete conversion was achieved within 30 min with a To determine the optimum solvent/reactant ratio (toluene:
product distribution of ca. 95% mono- and 5% di-substituted benzyl chloride) needed for this FriedelCrafts benzylation
142 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143
Fig. 11. Graph showing the percentage yield of mono-substituted products vs
reaction time (min).
Fig. 12. Bar chart showing the percentage of di-substituted products vs reaction
time (min).
Fig. 13. Graph showing the percentage yield of mono-substituted products vs
solvent/reactant ratio.
reactions, 3 compositions with different ratio of the solvent
(toluene) and reactant (benzyl chloride) were studied (15:1,
10:1 and 5:1). The results obtained from the reactions are shown
graphically in Figs. 13 and 14.
From the results obtained, the best solvent/reactant ratio,
was 15 mL of toluene and 1 mL of benzyl chloride (Fig. 13).
When RHFe(5% amine) was used, it showed a linear increase
in mono-substituted products. Thus, when the concentration of
toluene was increased, the carbocation had a higher probability
of attacking the toluene, which lead to the formation of higher
mono-substituted products. Fig. 14 shows that in the presence
Fig. 14. Bar chart showing the percentage of di-substituted products vs sol-
vent/reactant ratio. A = solvent/reactant ratio (5:1). B = solvent/reactant
ratio (10:1). C = solvent/reactant ratio (15:1).
of either catalyst, the percentage of di-substituted product de-
creased.
However, the lowest di-substituted product was obtained for
the 15:1 solvent/reactant ratio for RHFe(5% amine) catalyst.
Hence it can be concluded that RHFe(5% amine) had a better
selectivity for the mono-substituted products.
3.3. The suggested role of RHFe(5% amine) catalyst in
reducing the formation of di-substituted products
As suggested by the FT-IR, TEM and EDX analysis, the
chemical incorporation of the amine can be assumed to result
in the formation of regular pores which we suggest to be as
shown in Fig. 2.
The resulting carbocation could form a dative bond with the
nitrogen, which locks the carbocation at the reaction site within
the pores. An approaching toluene molecule was smaller in
size compared to a mono-substituted product. Thus, it would
be easy for the toluene molecule to approach the carbocation
to produce more mono-substituted products. On the other hand,
the mono-substituted benzyltoluene which was bigger in size
may not be able to enter the pores. Thus, the probability for
the mono-substituted benzyltoluene to undergo further substi-
tution was reduced. This explains why the percentage yield of
di-substituted products decreased when RHFe(5% amine) was
used as the catalyst.
4. Conclusion
RHFe and RHFe(5% amine) were prepared by solvent
extraction and solgel technique. These catalysts were char-
acterized by BET, SEM/EDX, TEM, FT-IR and XRD meth-
ods. RHFe(5% amine) exhibits a higher surface area (331
m2 g1 ) compared to RHFe (267 m2 g-1 ). TEM micrographs
of RHFe(5% amine) showed the pores were arranged in a reg-
ular order. EDX micrographs of RHFe(5% amine) showed the
presence of nitrogen in the sample confirming the successful
incorporation of the amine molecule into the silica/iron ma-
trix. In the benzylation of toluene, the mono-substituted (ortho-
 F. Adam, J. Andas / Journal of Colloid and Interface Science 311 (2007) 135143
and para-) products were obtained as the major component. No
products were obtained without the presence of the catalysts.
Both catalysts showed 100% conversion towards FriedelCrafts
benzylation of toluene. RHFe(5% amine) was found to be a
better catalyst. The incorporation of amine and iron resulted
in the reduction of the di-substituted products significantly and
higher selectivity to the mono-substituted products compared to
our previous published results [1].
Acknowledgments
The authors would like to express their thanks to Leong
Guan Rice Mill Sdn. Bhd. Penang for providing the rice husk.
We would also like to thank the Malaysian Government for
the IRPA grant (09-02-05-2148 EA004) which partly supported
this work.
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