Materials Letters 78 (2012) 199201

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis of ordered MCM-48 by introducing economical anionic

surfactant as co-template
Jingjing Wang a, Jinming Lu a, Jianhua Yang a, Wei Xiao b, Jinqu Wang a,
a
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, 116024 Dalian, PR China
b
PetroChina Northeast Rening & Petrochemical Engineering Co. Ltd Jilin Design Institute, PR China

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

Article history: Highly ordered mesoporous MCM-48 molecular sieve has been successfully synthesized using mixed surfac-
Received 13 October 2011 tant of cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium dodecyl sulfate (SDS) as tem-
Accepted 13 March 2012 plates at low surfactant-to-silica ratio (molar) of 0.177. Our work provides a commercially important
Available online 28 March 2012
approach to synthesize ordered mesoporous material by introducing cheap anionic surfactant SDS as co-
template. The molar composition of surfactant mixture was CTAB: SDS = 6.08. The characterization of the
Keywords:
Solgel preparation
material shows that the pore diameter and BET surface area of as-prepared MCM-48 is 2.72 nm and
Porous materials 861.8 m 2 g 1, respectively. The possible formation mechanism of MCM-48 using mixed surfactant template
MCM-48 has been discussed according to Gibbs free energy theory and surfactant packing parameter theory.
Mixed surfactant template 2012 Elsevier B.V. All rights reserved.
Cheap anionic co-template

1. Introduction
MCM-48 with novel symmetry of Ia3d cubic space groups has
attracted much attention since the pioneering work by the scientists
at the Mobil Corporation in 1992 [1,2]. Due to the uniform mesopores
around 2 nm, unique three-dimension interwoven gyroidal channel
structure, higher surface area and large adsorption capacity, MCM-48
material shows great potential application in large molecular catalysts,
sensors, adsorbents, electronic, optical, and medical devices [3]. Cationic
surfactant CTAB (cetyltrimethyl ammonium bromide) was most widely
adopted single template, and such synthesis consume large amount of
relative expensive CTAB. Therefore, remarkable work has been done
by introducing co-template into the single surfactant/silicate assembly
system leading to lower surfactant cost based on altering the original
molecular interactions, and the interfacial packing between the inor-
ganic species and surfactant molecules [48]. Several kinds of surfac-
tants such as nonionic and cationic surfactants have been applied as
co-template in synthesizing MCM-48, while some co-surfactants were
either expensive or hard to obtain although decreased surfactant cost
to some extent. Anionic surfactant is a noticeable co-template favoring
the formation of ordered mesoporous silica structures due to the strong
electrostatic interaction with cationic CTAB. However, there were lack
of reports in the literature by using mixtures of cationic and anionic sur-
factants as a structure directing agent for the synthesis of MCM-48
[911] except CTAB/SL (sodium laurate) system [4].
In view of the fact that SDS (sodium dodecyl sulfate) is relatively
cheap anionic surfactant and has been widely used in industrial elds
in the processing of various formulations, SDS was rstly attempted
to synthesis MCM-48 as co-template. The surfactant-to-silica ratio
(molar) successfully decreased from 0.5 in single CTAB route [2] to
0.177 which is equivalent to CTAB/SL approach [4]. Moreover, due
to partial charge neutralization or decreasing charge density of the
micelle in mixed-surfactant systems, the surfaces of these materials
are usually more hydrophobic than that of mesoporous silica synthe-
sized using single cationic surfactants as mentioned by Chandra when
synthesis 2D hexagonal mesoporous titanium silicate using mixed
surfactant system as template [9]. Research on the synthesis of meso-
porous materials templated by SDS co-template route may provide
more options for economical and large-scale productions. Further-
more, investigation on the synthesis approach may be theoretically
important because the complex self-assembled phase behavior in
CTAB/SDS solution may lead to new mesoporous structure.
Herein, highly ordered mesoporous MCM-48 molecular sieve was
synthesized using the mixture of SDS and CTAB as supermolecular
template under hydrothermal crystallization. The as-prepared meso-
porous MCM-48 was characterized by XRD, SEM, TEM and nitrogen
adsorption and desorption analysis, and the possible formation mech-
anism was also discussed.
2. Experimental section

2.1. Chemicals

Corresponding author. Tel.: + 86 411 84986415; fax: + 86 411 84986149. Sodium dodecyl sulfate (SDS, C12H25OSO3Na, Tianjin Bodi Chemi-
E-mail address: wjinqu@dlut.edu.cn (J. Wang). cal Holding Co., Ltd.), cetyltrimethylammonium bromide (CTAB,

0167-577X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.03.040
200
211
MCM-48
intensity/(a.u.)
220
420
332
2 4 6 8
2Theta/(degree)
Fig. 1. XRD pattern of synthesized sample by cationic and anionic surfactant systems.
C16H33N(CH3)3Br) were purchased from Beijing Aoboxing Biotech
Company Ltd., tetraethyl orthosilicate (TEOS) and sodium hydroxide
(NaOH) were purchased from Tianjin Kermel reagent Co., Ltd. All che-
micals were used as received without any further purication. Deio-
nized water was used in this study.
2.2. Synthesis of MCM-48 using CTAB/SDS mixed system as template
The typical synthetic procedure of mesoporous silica is as follows:
certain amount of CTAB was dissolved in deionized water. Once the
reagent was dissolved, SDS and NaOH were added. The reagents
above were well mixed at 308 K under magnetic stirring. Then TEOS
was drop wisely added into the solution under vigorous stirring at
the same temperature. After stirring for 2 h, the resulting synthetic
gel was heated under static hydrothermal conditions at 373 K in a
stainless steel autoclave for 72 h. The precipitated products were
ltered, then washed with deionized water to neutral and dried in
air at 333 K overnight. Then the as-synthesized samples were
calcined at 823 K (1 K /min) for 6 h to remove the template. The
molar composition of the initial gel mixture was SiO2:CTAB:SDS:
NaOH:H2O = 1:0.152:0.025:0.5:62.
2.3. Characterization
As-synthesized mesoporous MCM-48 molecular sieve was charac-
terized by X-ray powder diffraction (XRD) on a Rigaku-Dmax 2400
diffractometer equipped with graphite monochromatized Cu Ka radi-
ation in the 2 angle ranging from 0.6 to 10.
Nitrogen adsorption and desorption analysis was carried out with
an Autosorb-1 adsorption analyzer (Quantachrome Instruments) at
77 K. The surface area and pore size distribution were calculated by
Fig. 2. (a) SEM image (b, c) TEM images and electron diffraction pattern (left inset in b) of MCM-48 synthesized by cationic and anionic surfactants.
J. Wang et al. / Materials Letters 78 (2012) 199201
using multipoint BET analysis and the BarrettJoynerHalenda (BJH)
method, respectively.
Transmission electron microscopy (TEM) was carried out on a Phi-
lips Tecnai G2 20 instrument, operating at 200 kV. For TEM measure-
ments, all mesoporous materials were crushed in an agate mortar,
dispersed in ethanol, and deposited on a microgrid.
Scanning electron microscopy (SEM) images were taken with a
KYKY2800B microscope at an acceleration voltage of 15 kV and a
working distance of 10 mm after gold coating.
3. Results and discussion
3.1. XRD result of the as-synthesized MCM-48
10
Small-angle X-ray diffraction pattern of a representative sample is
shown in Fig. 1. It can be seen all four peaks for the 211, 220, 420, and
332 planes with strong intensity corresponding to the Ia3d space
group of cubic mesophase MCM-48 were observed clearly from the
calcined sample. The XRD pattern suggests that the material obtained
is highly ordered and consistent with the previous reports [12].
3.2. SEM and TEM results of the synthesized MCM-48
The SEM image of MCM-48, as shown in Fig. 2a, shows that the as-
synthesized MCM-48 block is constructed from small particles. The
TEM images and electron diffraction pattern (left inset) of the cal-
cined MCM-48 viewed along 110 direction are shown in Fig. 2b, c,
which are in good agreement with previous reports [1]. Three-
dimension well-ordered pore structures can be clearly observed.
These results also illustrate that the MCM-48 materials synthesized
by co-template method at low surfactant/Si ratio possess excellent
quality and well-ordered uniform channel structure.
3.3. N2 adsorptiondesorption isotherm measurement of synthesized
MCM-48
The calcined MCM-48 is further characterized by N2 adsorption
desorption isotherm as shown in Fig. 3. It can be calculated that the
BET surface area of this sample is 861.8 m 2 g 1 and pore volume is
0.862 cm 3 g 1. The pore size distribution, calculated from the
desorption curve using BJH model, shows an average pore size of
about 2.72 nm. It corresponds to the hysteresis loop in the 0.30.4
p/p0 region of the isotherm, which exhibits the presence of the typical
mesoporosity of the calcined MCM-48 [10]. The sample has a hyster-
esis loop at relative high pressure (p/p0) which means that some larg-
er sized pores (i.e. macropores) exist in this material. That is
supposed to be intercrystalline voids between MCM-48 particles in
particle aggregations as can be seen in SEM images in Fig. 2a.

600
adsorption
desorption
volume adsorbed cm3/g STP
500
400
dv / dD
300
200 1 2 3 4 5 6 7 8 9 10
0.0 0.2 0.4
Ralative Pressure (P/P0)
Fig. 3. N2 adsorption and desorption isotherms and pore-size distribution (inset) of
MCM-48 sample.
3.4. Possible synthesis mechanism of MCM-48 in CTAB/SDS system
Above studies have shown that highly ordered MCM-48 can be
synthesized at low surfactant/Si amount of 0.177 by introducing eco-
nomical anionic surfactant SDS as co-surfactant while the surfactant/
Si amount for pure CTAB systems is 0.5 [2]. The main reason is
because the structure of nal product in the synthetic system of
mesoporous molecular sieves will lead to the Gibbs free energy as
small as possible. Zhao and Li et al. [13] mentioned that the starting
point for the formation of MCM-48 phases requires that CTAB cations
are self-assembled into rodlike micelles rst. Also, the van der Waals
forces and organic array stability are greater for bitailed surfactants
than for mono-tailed surfactants. Cationic and anionic surfactant sys-
tems with extremely low critical micelle concentration will theoreti-
cally template to synthesis mesoporous MCM-48 under lower
concentration than single cationic system.
The anionic surfactant SDS has a strong electrostatic interaction
with CTA + based on previous investigations on the aggregation
behaviors between CTAB and SDS in aqueous solution [14]. According
to geometric packing model [15] the g = V/a0l value is fairly sensitive
to the change of SDS amount which can effectively inuence the V
and a0 through electrostatic interaction (Fig. 4). The anionic SDS
may counteract part of the CTA + cationic charges in the CTA + assem-
blies, and thus a0 decreased. In addition, the SDS molecules may in-
sert into the hydrophobic part of the mixed micelles which increasing
V. The g value will increase to a suitable value (1/2 to 2/3) which
favors the formation of cubic phase MCM-48 under low total surfac-
tant cost.
J. Wang et al. / Materials Letters 78 (2012) 199201 201
Pore diameter (nm)
Fig. 4. Possible synthesis mechanism of silicate MCM-48 using CTAB/SDS as template.
0.6 0.8 1.0
4. Conclusions
In conclusion, highly ordered MCM-48 mesoporous molecular
sieve has been fabricated using SDS as co-template using lower sur-
factant/Si amount of 0.177. It suggests that the extremely strong syn-
ergism effects of the mixed system of cationicanionic surfactants
help to enhance the ability to form the self-assembled structure and
favor the formation of cubic MCM-48. The possible formation mecha-
nism of MCM-48 using mixed surfactant template was explained by
the surfactant packing parameter theory and Gibbs free energy theo-
ry. This work provides an economical approach to synthesize highly
ordered MCM-48, which is crucial for the large-scale applications.
Acknowledgments
This work was supported by the National Natural Science Founda-
tion of China (NSFC Grant No: 20176004).
References
[1] Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS. Nature 1992;359:7102.
[2] Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schlenker JL, et al. J Am
Chem Soc 1992;114:1083443.
[3] Wan Y, Zhao DY. Chem Rev 2007;107:282160.
[4] Chen FX, Huang LM, Li QZ. Chem Mater 1997;8:26856.
[5] Chen FX, Yan XW, Li QZ. Stud Surf Sci Catal 1998;117:27380.
[6] Ryoo R, Joo SH, Kim JM. J Phys Chem B 1999;103:743540.
[7] Han Y, Li DF, Zhao L, Song JW, Yang XY, Xiao FS, et al. Angew Chem Int Ed 2003;42:
36337.
[8] Wei FY, Liu ZW, Lu J, Liu ZT. Microporous Mesoporous Mater 2010;131:2249.
[9] Chandra D, Bhaumik A. Ind Eng Chem Res 2006;45:487983.
[10] Chen F, Yan XW, Li QZ. Mesoporous Mol Sieves 1998;117:27380.
[11] Chen F, Song F, Li QZ. Microporous Mesoporous Mater 1999;29:30510.
[12] Zhao W, Li QZ. Chem Mater 2003;15:41602.
[13] Zhao W, Li QZ, Wang L, Chu J, Qu JK, Qi T, et al. Langmuir 2010;26:69828.
[14] Maiti K, Mitra D, Mitra RN, Panda AK, Das PK, Moulik SP, et al. J Phys Chem B
2010;114:7499508.
[15] Huo Q, Margolese DI, Stucky GD. Chem Mater 1996;8:114760.