See

discussions, stats, and author profiles for this publication at:

http://www.researchgate.net/publication/248292273

Synthesis of macrostructured MCM-48

molecular sieves

ARTICLE in MICROPOROUS AND MESOPOROUS MATERIALS · APRIL 2001

Impact Factor: 3.21 · DOI: 10.1016/S1387-1811(00)00287-0

CITATIONS DOWNLOADS VIEWS

34 47 75

6 AUTHORS, INCLUDING:

Sebastien Vaudreuil Laurent Bonneviot

Université Euro-Méditerranéenne de Fès Ecole normale supérieure de Lyon
21 PUBLICATIONS 245 CITATIONS 121 PUBLICATIONS 1,442 CITATIONS

SEE PROFILE SEE PROFILE

Mosto Bousmina Serge Kaliaguine

Euro-Mediterranean Université of Fez Laval University
199 PUBLICATIONS 3,871 CITATIONS 475 PUBLICATIONS 8,876 CITATIONS

SEE PROFILE SEE PROFILE

Available from: Mosto Bousmina

Retrieved on: 09 July 2015
 Microporous and Mesoporous Materials 44±45 (2001) 241±247
www.elsevier.nl/locate/micromeso

Synthesis of macrostructured MCM-48 molecular sieves

Ch. Danumah a, S. Vaudreuil a, L. Bonneviot b, M. Bousmina a, S. Giasson a,
S. Kaliaguine a,*,1
a
Department of Chemical Engineering, Universit
e Laval, Ste-Foy, Quebec, Canada G1K 7P4
b
Department of Chemistry, Universit
e Laval, Ste-Foy, Quebec, Canada G1K 7P4
Received 16 May 2000; accepted 6 August 2000

Abstract
Dual templating using aqueous cetyltrimethylammonium chloride/hydroxide (CTMA Cl/OH) and latex spheres was
performed to prepare powders of bimodal silica molecular sieves with mesopore and macropore systems. The CTMA/Si
ratio was chosen to generate a cubic mesopore of MCM-48 structure. According to high Brunauer±Emmett±Teller
surface area, narrow pore size distribution, X-ray di€raction powder pattern and scanning electron micrographs, the
cubic mesophase is located within the macropore walls, which is the characteristic of a hierarchical porous sys-
tem. Ó 2001 Published by Elsevier Science B.V.

Keywords: Mesopores; Macropores; Latex spheres; Amphiphiles; Electron microscopy

1. Introduction catalysis [10], sorption [11] and ®ne chemicals [12]

In recent years, a variety of ordered mesopor-
ous materials with a wide range of pore diameters
[1±5] was obtained by supramolecular assembly of
surfactant micelles as organic templates. Their
formation follows a mechanism of cooperative
interactions and organization between ionic or
polar organic templates and inorganic precursors
in aqueous solution [6±9]. They are characterized
by a very large surface area and porosity as well as
a long-range ordered pore structure [1,2]. During
the last decade, they have attracted much research
interest because of their potential applications in
* macrostructured materials [19,20]. The results
Corresponding author. Tel.: +1-418-656-2708; fax: +1-418-
656-3810.
E-mail address: kaliagui@gch.ulaval.ca (S. Kaliaguine).
1
http://jacob.gch.ulaval/kaliagui.
as their pores being larger than those of zeolites,
allow a faster di€usion and the processing of
bulkier molecules. An appropriate choice of surf-
actant, swelling agents and reaction conditions can
be used to tailor the pore diameter of these meso-
porous materials from 16 to 300 A  [1±4]. Lately,
the design of structured macroporous materials
with pore diameters ranging from 5 nm to 1 lm
and based on the use of closed packed latex
spheres or block copolymers as templates was re-
ported [5,13±18].
More recently, we showed that sedimentation±
aggregation of latex spheres in the presence of
oxide precursors also leads to the formation of
clearly show that close packing of the templating
spheres is not a requirement to generate a macro-
porous network.

1387-1811/01/$ - see front matter Ó 2001 Published by Elsevier Science B.V.

PII: S 1 3 8 7 - 1 8 1 1 ( 0 0 ) 0 0 2 8 7 - 0
242 Ch. Danumah et al. / Microporous and Mesoporous Materials 44±45 (2001) 241±247
The present work is an attempt at creating a
bimodal pore size distribution with modes in the
macroscopic and mesoscopic scale, by combining a
conventional mesoporous molecular sieves syn-
thesis method with the sedimentation±aggregation
of latex spheres.
2. Experimental
Solutions of cetyltrimethylammonium chloride/
hydroxide (CTMA Cl/OH) with two di€erent Cl/
OH ratios (69.6:30.4 and 63.3:36.6 for solution 1
and 2, respectively) were prepared from CTMACl
(Aldrich) using a strong ion-exchange base mate-
rial (Dowex SBR OH anion exchange resin, Su-
pelco). Latex beads of 400 nm diameter were
synthesized by emulsi®er-free polymerization car-
ried out at 70°C for 28 h according to a procedure
described in the literature [21,22].
The dual templated materials were synthesized
under conditions similar to those of some meso-
porous materials prepared without latex beads and
to which they were compared.
Solutions (1) and (2) were used with the re-
quired amount of tetraethylorthosilicate (TEOS,
silica source) to prepare the cubic mesoporous
molecular sieves of MCM-48 type according to the
procedure reported by Vartuli et al. [23]. The
composition of the gel expressed in terms of moles
per mole of SiO2 was as follows: 1.37 CTMA±
63.70 H2 O. For the reference materials synthesis,
TEOS was added dropwise under vigorous stirring
at 298 K. After stirring for about 1 h, the ®nal
mixture was transferred into an open polypropyl-
ene bottle and placed in a steam box where the
crystallization was carried out hydrothermally at
373 K for 2 days. After cooling at room tempera-
ture, the resulting solid product was recovered by
®ltration, washed thoroughly with distilled water
and dried in air at ambient temperature or between
60°C and 70°C to accelerate the drying. The
product was then calcined at 823 K for at least 5 h
in air.
For the dual templated materials, the latex
spheres were added before or after the addition of
TEOS to the synthesis gel. In the latter case, after
stirring the solution containing both CTMA Cl/
OH and TEOS for few minutes, the latex spheres
were added and the stirring was maintained for
about 1 h (samples 232 and 308). In the former
case, the same procedure was followed inverting
the addition of TEOS and CTMA Cl/OH. Solu-
tion (1) was used for sample 232 while solution (2)
was used for samples 308 and 312.
Powder X-ray di€raction patterns (XRD) of as-
synthesized and calcined samples were recorded
using a Siemens D5000 powder di€ractometer
using CuKa radiation (k ˆ 1:54184) over a 2h
range from 1° to 10°. Nitrogen sorption measure-
ments at 77 K were performed on an Omnisorp
sorptometer 100 instrument. Prior to each adsorp-
tion experiment, the calcined samples were out-
gassed at 573 K for at least 2 h under vacuum.
The linear part of the Brunauer±Emmett±Teller
(BET) equation (P =P 0 ˆ 0:05±0:15) is used for the
speci®c surface area determination. The Barrett±
Joyner±Halenda (BJH) formula [24] is used to
evaluate the pore size distributions based on the
desorption branch of the N2 physisorption iso-
therms.
Scanning electron micrographs (SEM) were re-
corded using a JEOL JSM-840A SEM operating at
15 kV. This technique is used for measuring the
sphere diameters and for characterizing the mac-
ropore system.
3. Results and discussion
The powder XRD patterns of all as-synthesized
and calcined samples are similar (Fig. 1). They
exhibit a high intensity peak (2 1 1) followed by a
smaller one (2 2 0) in the 2h range of 2±3°, whereas
several other peaks are observed in the 4±8° range.
Such patterns correspond to the Ia3d cubic sym-
metry reported for MCM-48 type molecular sieves
[1,2,6,25]. The value of the ratio d2 2 0 =d2 1 1 of
0.86, is indeed characteristic of this cubic sym-
metry [2,6]. The (2 1 1) line is used to calculate the
unit cell parameter reported in Table 1 for both
uncalcined and calcined samples.
All calcined powder samples exhibit similar N2 -
physisorption isotherms of type IV (Fig. 2), typical
of mesoporous solids [26,27]. While the speci®c
surface areas were calculated using the adsorption
 Ch. Danumah et al. / Microporous and Mesoporous Materials 44±45 (2001) 241±247 243

Fig. 1. XRD patterns of as-synthesized (A) and calcined (B) form of samples 232, 256, 308, 311 and 312.

Table 1
Characteristics of as-synthesized and calcined samples
Samples Latex/ Noncalcined samples Calcined samples
TEOS d-spacing Unit cell d-spacing Unit cell BET Mesopore Pore In¯ection
(weight 
(A) parametera 
(A) parametera Surface volume diameter point
ratio) 
(A) 
(A) area (ml/g) 
(A) position
(m2 /g) …P =P 0 †
256b 0 38.73 94.87 32.25 78.99 1023 0.91 23.0 0.24
232b 0.71 39.77 97.41 30.78 75.39 958 0.61 21.4 0.16
311c 0 37.11 90.90 31.98 78.33 1213 0.88 21.2 0.24
308c 1.06 38.38 94.01 28.85 70.67 1125 0.37 20.0 0.16
312c 1.00 36.49 89.38 30.24 74.07 1101 0.50 20.4 0.16
Sample 256 is reference sample for 232, and
p sample 311 is that of samples 308 and 312.
a
Unit cell parameter a ˆ d-spacing  6.
b
Synthesized with solution 1.
c
Synthesized with solution 2.

data at 0:05 < P =P 0 < 0:15 (Table 1), the main
pore sizes were obtained from the range P =P 0 ˆ
0:1±0:3 associated with the capillary condensation
in the mesopores [24]. The absence of hysteresis
between 0.1 and 0.3P =P 0 is an indication of the
reversibility of type IV isotherms. By contrast, the
adsorption at higher relative pressures (0:9±1 ˆ
P =P 0 ) indicate the presence of macropores [26].
The hysteresis in this range of pressure suggests
that these macropores are connected through
windows of smaller size leading to the so-called,
bottleneck e€ect.
Comparing the powdered materials obtained
from the synthesis performed with latex spheres
(samples 232, 308 and 312) to those performed
without latex spheres (samples 256 and 311), it
244 Ch. Danumah et al. / Microporous and Mesoporous Materials 44±45 (2001) 241±247
Fig. 2. (A) Nitrogen physisorption isotherms at 77.4 K and (B) BJH pore radius distributions for calcined samples 232, 256, 308, 311
and 312.
appears that the in¯exion point is shifted to lower
relative pressures consistent with mesopore dia-
 The mesopore
meters (Fig. 2) smaller by 1 to 2 A.
volume is also smaller for the dual templated
materials and may account for 45±67% of that of
the reference samples (Table 1). However, the
surface area stays quite high and comparable to
that of conventional mesoporous systems (Table
1).
SEM evidences the monodispersion of the size
of the latex beads (Fig. 3A). After addition of the
latex beads to the synthesis medium and hydro-
thermal treatment, the diameter of the beads is
increased by 10±15%. In comparison with the
original beads, the impregnated beads exhibit a
rougher surface characterized by many cracks
(Fig. 3B). They remain however as individual and
monodispersed spheres stuck to their neighbors at
contact points. EDAX microanalysis reveals the
presence of silicon and nitrogen consistent with a
layer deposition of the silica mesophase still asso-
ciated with the surfactant. After calcination, which
burns out the latex beads and the surfactant, the
remaining material is a pure silica (free of carbon)
with large voids (Fig. 3C and D). There are three
types of voids. The largest are spherical with a
diameter range of 200±300 nm (average 270 nm).
The second type of voids is typically of intersticial
nature and is generated by random sphere pack-
ing. Between these two types of voids, the silica
wall thickness is very regular (30 nm). The third
type of voids is characterized by black dots of 40±
100 nm, which are likely due to windows between
the two previous types of voids. The resulting egg
shell type of morphology is consistent with the
random packing of latex beads covered with silica,
the organic interior of which has been removed by
calcination. In addition, the windows are more
likely due to the lack of silica at the contact point
between beads. This overall aspect evidences the
templating e€ect of the latex beads. The spherical
voids are however smaller by 30% than the
 Ch. Danumah et al. / Microporous and Mesoporous Materials 44±45 (2001) 241±247 245

Fig. 3. (A) SEM of latex beads before impregnation, (B) SEM of latex beads impregnated by silica, (C) SEM of sample 312 showing
di€erent types of macroporous voids, (D) SEM of sample 232 showing a dispersion of macropores (not representative of the whole
sample), (E) SEM of sample 312 showing a better dispersion of macropores (compared to sample 308, Fig. 3F), and (F) SEM of sample
308 showing a poor dispersion of macropores (compared to sample 312, Fig. 3E).
246 Ch. Danumah et al. / Microporous and Mesoporous Materials 44±45 (2001) 241±247
genuine latex beads. This also can be rationalized
assuming a shrinking of the macropores associated
with the condensation of remaining silanol groups
during calcination. From Fig. 3C and F, it is
clearly seen that the spherical cavities left after
calcination are connected to each other by several
apertures thus forming a network of macropores.
Moreover, there is a better macroporous disper-
sion in sample 312 (Fig. 3E) than in sample 308
(Fig. 3F) while sample 232 exhibits intermediate
characteristics (Fig. 3D is not representative of the
whole sample). This di€erence can be related to the
key role played by the viscosity of the hydrogel.
Indeed, when latex beads are mixed with the mi-
cellar CTMA Cl/OH solution, as it is the case for
sample 312, a good dispersion is obtained before
the addition of the silica source (Fig. 3E). An al-
ternate explanation may be also found in the
wetting process between the hydrophobic poly-
styrene beads and the gel. When the beads are
indeed soaked into the solution before introducing
the silica, they are likely covered with the amphi-
philic surfactant. As a consequence, the beads
become hydrophilic and are easily and homoge-
neously incorporated into the gel. By contrast,
when TEOS is introduced before the beads, the
hydrolysis of TEOS and its self-assembly with the
surfactant take place within few minutes. This last
sequence of addition of ingredients is likely to
favor both demixtion (decreasing the concentra-
tion of free surfactant and the wettability of the
polystyrene beads) and growth of the mesophase
in absence of the latex spheres. It is worth noting
that in the absence of surfactant, macroporous
silica is dicult to obtain unless the latex to TEOS
ratio is decreased down to 0.1 or 0.02 to force the
formation of a TEOS layer on the polystyrene
surface [17,20].
The high surface area of the macroporous
structured silicas indicates that the pore walls are
mesoporous in a large extent. It is worth noting
that N2 -physisorption does not allow to measure
the macropore volume, which is likely to be very
large. By contrast, a decrease is observed, leading
to a lesser mesopore volume than in the reference
samples (Table 1). There are three possible expla-
nations for this loss: (i) a smaller mesopore dia-
meter for macrostructured silica, (ii) a large
macro±meso interface with ill-de®ned porosity and
(iii) some non-structured regions (Fig. 3F). Despite
these restrictions, the very large surface area and
pore volume strongly suggest that the samples 232,
308 and 312 are hierarchically structured material
in the macroscopic and mesoscopic scale length
where the macropore walls are made of cubic
mesoporous molecular sieves.
4. Conclusion
This work demonstrates the possibility of
building hierarchical porous structure of powdered
silica in the macroscopic and mesoscopic ranges.
This has been obtained by a mere addition of
macrolatex beads into the synthesis gel of a meso-
phase generated by self-assembly of the surfactant
and silica precursor. Mixing the latex beads with
the micellar solution before adding the inorganic
source was also demonstrated to be the best way
for getting a uniform dispersion of macropores in
the material.
According to XRD, nitrogen adsorption±
desorption studies and SEM, the mesoporous
phase of cubic structure is located within the pore
walls of the macroporous network. This kind of
material is of great interest with regard to molec-
ular di€usion control in comparison to conven-
tional mesoporous molecular sieves. They may
have potential applications in catalytic reactions
or separations involving bulky molecules.
References
[1] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T.
Kresge, K.D. Schmitt, C.T.-W. Chu, D.H. Olson, E.W.
Sheppard, S.B. McCullen, J.B. Higgins, J.L. Schlenker,
J. Am. Chem. Soc. 114 (1992) 10834.
[2] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S.
Beck, Nature 359 (1992) 710.
[3] L. Bonneviot, F. Beland, C. Danumah, S. Giasson, S.
Kaliaguine (Eds.), Mesoporous Molecular Sieves 1998,
Proc. First Int. Symp., Baltimore, July 1998, Studies in
Surface Science and Catalysis, vol. 117, Elsevier, Amster-
dam, 1998.
[4] D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Frederickson,
B.F. Chmelka, G. Stucky, Science 279 (1998) 548.
 Ch. Danumah et al. / Microporous and Mesoporous Materials 44±45 (2001) 241±247
[5] B.T. Holland, C.F. Blanford, T. Do, A. Stein, Chem.
Mater. 11 (1999) 795.
[6] A. Monnier, F. Schuth, Q. Huo, D. Kumar, D. Margolese,
R.S. Maxwell, G.D. Stucky, M. Krishnamurty, P. Petro€,
A. Firouzi, M. Janicke, B.F. Chmelka, Science 261 (1993)
1299.
[7] G.D. Stucky, A. Monnier, F. Sch uth, Q. Huo, D.
Margolese, D. Kumar, M. Krishnamurty, P. Petro€, A.
Firouzi, M. Janicke, B.F. Chmelka, Mol. Cryst. Liq. Cryst.
240 (1994) 187.
[8] A. Firouzi, D. Kumar, L.M. Bull, T. Besier, P. Sieger, Q.
Huo, S.A. Walker, J.A. Zasadsinski, C. Glinker, J. Nicol,
D. Margolese, G.D. Stucky, B.F. Chmelka, Science 267
(1995) 1138.
[9] Q. Huo, D.I. Margolese, U. Ciesla, P. Feng, T.E. Gier, P.
Sieger, R. Leon, P.M. Petro€, F. Sch uth, G.D. Stucky,
Nature 368 (1994) 317.
[10] Q.N. Le, R.T. Thomson, Mobil Co. US. Patent, US-A
5191144 (1993).
[11] P.J. Branton, P.G. Hull, K.S.W. Sing, J. Chem. Soc. Chem.
Commun. (1993) 1257.
[12] A. Corma, Chem. Rev. 97(6) (1997) 2373.
[13] A. Imhof, D.J. Pine, Nature 368 (1997) 317.
[14] O.D. Velvev, T.A. Jede, R.F. Lobo, A.M. Lenho€, Nature
389 (1997) 447.
[15] M. Antonietti, B. Berton, C. Goltnet, H.-P. Hentze, Adv.
Mater. 10(2) (1998) 154.
[16] B.T. Holland, C.F. Blanford, A. Stein, Science 281 (1998)
538.
247
[17] J.E.G.J. Wijnhoven, W.L. Vos, Science 281 (1998) 802.
[18] H. Miguez, F. Meseguer, C. Lopez, A. Mifsud, J.S. Moya,
L. Vazquez, Langmuir 13 (1997) 6009.
[19] S. Vaudreuil, M. Bousmina, S. Kaliaguine, L. Bonneviot,
submitted for publication.
[20] S. Vaudreuil, M. Bousmina, S. Kaliaguine, L. Bonneviot,
Microporous Mesoporous Mater. 44±45 (2001) 249±258,
this issue.
[21] R.L. Fedie, Thesis, University of Minnesota, Minneapolis,
1996.
[22] D. Zou, V. Derlich, K. Gandhi, M. Park, I. Sun, D. Kriz,
Y.D. Lee, G. Kim, J.J. Aklonis, R. Salovey, J. Polym. Sci.
Chem. 28 (1990) 1909.
[23] J.C. Vartuli, K.D. Schmitt, C.T. Kresge, W.J. Roth, M.E.
Leonowicz, S.B. McCullen, S.D. Hellring, J.S. Beck, J.L.
Schlenker, D.H. Olson, E.W. Sheppard, Chem. Mater. 6
(1994) 2317.
[24] E.P. Barett, L.G. Joyner, P.P. Halenda, J. Am. Chem. Soc.
73 (1951) 373.
[25] Ch. Danumah, S.M.J. Zaidi, N. Voyer, S. Giasson, S.
Kaliaguine, in: L. Bonneviot, F. Beland, C. Danumah, S.
Giasson, S. Kaliaguine (Eds.), Mesoporous Molecular
Sieves 1998, Studies in Surface Science and Catalysis, vol.
117, Elsevier, Amsterdam, 1998, p. 281.
[26] S.J. Gregg, K.S.W. Sing, Adsorption, Surface Area
and Porosity, second ed., Academic Press, New York,
1982.
[27] S. Brunauer, L.S. Deming, W.S. Deming, E. Teller, J. Am.
Chem. Soc. 62 (1940) 1723.