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Synthesis of High Quality MCM-48 with Binary Cationic-Nonionic

Surfactants
Wei Zhao,†,‡ Quanzhi Li,*,‡ Lina Wang,† Jinglong Chu,† Jinkui Qu,† Shaohua Li,† and Tao Qi*,†
†
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, P. R. China, and ‡Department
of Chemistry, Fudan University, Shanghai 200433, P. R. China

Received November 6, 2009. Revised Manuscript Received February 27, 2010

Highly ordered MCM-48 was synthesized in the hydrothermal system of a mixture of cationic cetyltrimethylammo-
nium bromide (CTAB) and nonionic poly(ethylene glycol) monooctylphenyl ether (Tx-100) using water glass as the
silicon source. The effect of various factors, such as the amount of surfactant, CTAB/Tx-100, Si source, crystallization
temperature, and crystallization time, on the synthesis were discussed in detail. The local effective surfactant packing
parameter theory and the charge balance theory were used to explain the reason that various factors can affect the
product structure reasonably. Especially, the role of Tx-100 was expounded. The optimum synthesis conditions for
MCM-48 were obtained.

1. Introduction
Since the ordered M41s mesoporous silica was discovered in
1992,1 many researchers have paid attention to decreasing the
preparation cost and increasing the stability for these materials to
make them actually useful in industry. MCM-48 makes itself
remarkable from other mesostructure silica by the channels
piercing its amorphous silica body complying with the symmetry
of the cubic space groups, and the channels form two enantio-
meric, bicontinuous, branched, self-intersecting volumes sepa-
rated by an infinite wall.2 In order to allow this material to be
easily synthesized as MCM-41, Stucky,3 Chen,4 Yan,5 Ryhoo,6
and Zhao7 have reported the mixed surfactant systems to decrease
the amount of CTAB and increase the hydrothermal stability of
MCM-48. Introducing secondary surfactant into the single sur-
factant/silicate assembly system may alter the original molecular
interactions, and the interfacial packing between the inorganic
species and surfactant molecules leads to different assembled
phases and morphologies.8 Nonionic surfactant Tx-100, which is
a biodegradable neutral surfactant, is more soluble in water
and has the bigger hydrophobic region (octylphenyl) and polar
headgroup (oxyethylene). These characterizations provide for it
to disturb the electrostatic interaction by addition hydrogen-
bonding and van der Waals force9 and synthesize high quality
MCM-48 with more extensive cross-linked framework and better
thermal stability.10 So it is very suitable to be a costructure
direction agent (SDA) for the mesoporous molecular sieves
synthesis. However, the step where/when the Tx-100 plays its
*Corresponding authors: e-mail tqi@home.ipe.ac.cn (T.Q.), qzli@fudan.
edu.cn (Q.L.); Tel 86-10-82627090; Fax 86-10-62631710.
(1) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S.
Nature 1992, 359, 710–712.
(2) Golosovsky, I. V.; Mirebeau, I.; Fauth, F.; Mazaj, M.; Kurdyukov, D. A.;
Kumzerov, Y. A. Phys. Rev. B 2006, 74, 155440.
(3) Huo, Q.; Margolese, D. I.; Stucky, G. D. Chem. Mater. 1996, 8, 1147–1160.
(4) Chen, F. X.; Huang, L. M.; Li, Q. Z. Chem. Mater. 1997, 9, 2685–2686.
(5) Yan, X. W.; Chen, H. Y.; Li, Q. Z. Acta Chim. Sin. 1998, 56, 1214–1217.
(6) Ryoo, R.; Joo, S. H.; Kim, J. M. J. Phys. Chem. B 1999, 103, 7435–7440.
(7) Zhao, W.; Li, Q. Z. Chem. Mater. 2003, 15, 4160–4162.
(8) Pang, J. B.; Na, H.; Lu, Y. F. Microporous Mesoporous Mater. 2005, 86, 89–
95.
(9) Zhao, W.; Hao, Z. P.; Hu, C. J. Nanosci. Nanotechnol. 2005, 5, 1752–1754.
(10) Zhao, W.; Hao, Z. P.; Hu, C. Mater. Res. Bull. 2005, 40, 1775–1780.
role and how the different synthesis factors can influence the final
product phase still need to be investigated while these only are
referred to in a few former reports. In the present paper, we
systematically studied the effects of surfactant/SiO2, CTAB/
Tx-100, Si source, crystallization temperature, and crystallization
time on the product structure, and the optimum synthesis condi-
tions for MCM-48 were obtained. Especially, the reason that
various factors can affect the product structure was discussed in
detail. We believe this work not only can help us to further
understand the assembling behavior of the multicomponent
system containing silicate, cationic surfactant, anionic surfactant,
etc., but also is useful to synthesize other high quality mesoporous
silica for convenience.
2. Experimental Section
2.1. Synthesis. A typical synthetic procedure is as follows: the
aqueous solution of water glass (Na2O: 7.4 wt %, SiO2: 25.4 wt %,
Jiangpu Chemical Co., Shanghai) was dropwise added under
constant stirring to the mixed solution of Tx-100 (First Chemical
Co., Shanghai) and CTAB (First Chemical Co., Shanghai). This
solution was then stirred at 30
C for 1 h. The molar composition
of the resultant mixture was 1.0 SiO2:x CTAB:y Tx-100:0.282
Na2O:58 H2O, where 0.09 < x < 0.25, 0 < y < 0.04. After that,
this mixture was placed in a static autoclave at 100
C for 3 days.
The product was recovered by filtration, washed with distilled
water, and dried at 80
C. At last, this material was calcined in air
at 650
C for 5 h (10
C/min).
2.2. Characterization. The powder X-ray diffraction pat-
terns were recorded on the Rigaku D/Max-II A diffractometer
(Ni-filtered Cu KR radiation with λ=1.542 Å) operated at 40 kV
and 20 mA. The TEM images were obtained on a JEM-
2010 transmission electron microscope operated at 200 kV. N2
adsorption-desorption isotherms were determined at 77 K on a
Micromeritics TriStar 3000 instrument using nitrogen as the
adsorbent. The pore size distribution curve came from the analysis
of the adsorption branch of the isotherm by the BJH (Barrett-
Joyner-Halenda) method. 29Si MAS NMR was recorded on the
Bruker DSX-300 spectrometer (the magnetic field is 7.05 T
and the resonance frequency is 59.63 MHz). Thermal analysis
was performed on the Rigaku PTC-10A system. Samples were
heated in air with a heating rate of 10
C/min, and the test was
ended at 1000
C.

6982 DOI: 10.1021/la9042155 Published on Web 03/12/2010 Langmuir 2010, 26(10), 6982–6988
Zhao et al.
Figure 1. XRD pattern of MCM-48.
3. Results and Discussion
3.1. Characterization Results of MCM-48 Sample.
Figure 1 is the XRD pattern of the MCM-48 sample synthesized
at 100
C for 3 days. Besides the [211] and [220], two obvious
diffraction lines corresponding to the Ia3d space group of MCM-
48, [420] and [332], also are well resolved. Figure 2 is the TEM
image of this sample. The order arrangement of lattice spot
along [110] direction means the sample has excellent textural
uniformity. While, on the [111] direction, there are continuous
channels running through the structure. The nitrogen adsorption-
desorption isotherm and BJH pore size distribution for this sample
are shown in Figure 3. The isotherm can be classified as a type IV
isotherm according to the IUPAC11 with a sharp increase in the
volume of adsorbed nitrogen at a relative pressure of p/p0 =
0.25-0.35. The pore volume and BET surface area of this sample
are 1.47 cm3/g and 1201.1 m2/g, respectively. The inset figure shows
the maximum pore distribution appears at 2.39 nm. The 29Si MAS
NMR results (Figure 4) show the Q4/Q2 þ Q3 ratio of MCM-48
sample obviously increased from 0.68 to 2.19 after calcination, and
the Q4 position of as-synthesized sample (-108 ppm) shifted to the
low field region compared to that of MCM-48 (-110 ppm)
prepared by other methods. The first result means the more
extensively cross-linked framework of the calcined MCM-48
sample. For the second result, Lippmaa12 had reported that
different geometry of silicon-oxygen tetrahedral can cause the
slight solid-state 29Si chemical shift. Furthermore, Ryoo13 found
the Q4 position of calcined MCM-48 with higher structure sym-
metry usually existed in the lower field region compared to that of
its as-synthesized sample with poorer structure symmetry. Thus,
the fact that solid-state 29Si chemical shift moves to the positive
value direction suggests our MCM-48 sample probably has higher
structure symmetry than other MCM-48 samples. The thermal
analysis results (Figure 5) show both the TG and DTA spectra do
not change in the range of 650-1000
C. This means the weight
loss and phase transformation (structure collapse) do not happen
during this region (That is the reason we calcined the sample at
650
C and not 550
C.) The XRD pattern of the sample after
(11) Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscon, L.; Pierotti, R. A.;
Rouquerol, J.; Siemieniewska, T. Pure Appl. Chem. 1985, 57, 603–619.
(12) Lippmaa, E.; Magi, M.; Samoson, A.; Engelhardt, G.; Grimmer, A. G.
J. Am. Chem. Soc. 1980, 102, 4889–4893.
(13) Ryoo, R.; Kim, J. M. Chem. Commun. 1995, 711–712.
(14) Xu, J.; Luan, Z.; He, H.; Zhou, W.; Kevan, L. Chem. Mater. 1998, 10, 3690–
3698.
Langmuir 2010, 26(10), 6982–6988
Article
testing still keeps the Ia3d cubic channel system although the
diffraction intensity decreases sharply, and the 2θ value (211 peak)
even shifts to 3.2
. All of these results show that the sample is high
quality MCM-48 material.
3.2. Effect of CTAB/SiO2. Keeping the ratio of Tx-100/
CTAB constant, we first studied the effect of CTAB/SiO2 on the
synthesis. Learning from Figure 6, we found a poor hexagonal
phase product is appearing (Figure 6a) when the ratio of CTAB/
SiO2 is 0.09. Increasing this ratio to 0.12, the cubic MCM-48 is
produced (Figure 6b). Further increasing the ratio to 0.15, a
highly ordered MCM-48 is obtained (Figure 6c). However, if the
ratio is 0.18, the XRD pattern of MCM-48 becomes worse
(Figure 6d), and a remarkable phase regression phenomenon
happens when the ratio is 0.21(Figure 6e). If we increased the ratio
to the maximum 0.25, a hexagonal phase product reappears again
(Figure 6f). The lamellar phase product never forms during the
above process. Compared to other synthesis system (Table 1),
MCM-48 can be synthesized at lower ratio of CTAB/SiO2 (0.12)
using our method. This fact may be explained by the local
effective surfactant packing parameter, g = V/a0l.15 Since the
polar end of Tx-100 contains many O atoms, it can combines with
the polar headgroup of CTAþ micelle through hydrogen bonding.
This will causes effective polar headgroup area (a0) of the CTAþ
micelle decreasing. Meanwhile, due to the reason that the hydro-
gen bonding between the Tx-100 and CTAþ micelle is weaker
than the electrostatic attraction between anionic and cationic
surfactant, and that Tx-100, whose hydrophobic chain contains
benzene ring with π-electron, has more powerful dispersion force
than the straight-chain paraffin, Tx-100 will not be subjected to
strong electrostatic attraction, and its hydrophobic chain can
combine with the hydrophobic chain of CTAþ micelle by van der
Waals force; thus, it can stretch into the void of the CTAþ micelle
rather than only staying at the palisade region (the border area
between the hydrophobic and hydrophilic portion of the micelle).
As a result, the hydrophobic volume of the single CTAþ micelle
(vi) will increase, corresponding to the increase of the total
hydrophobic volume of P the whole micelleP(Vtotal). This procedure
can be stated as Vtotal= m M=1VOP-10 þ
n
N=1VCTAB; vi=Vtotal/
n, where m and n are the molecular numbers of Tx-100 and CTAþ,
respectively, and described as Scheme 1.
Both the decrease of a0 and the increase of V will result in the
enhancing of g. So the g value of 1/2-2/3, which is needed for the
forming of cubic MCM-48, will be obtained even in low concen-
tration of CATB (4.4 wt %).
Learning from Table 1, we also found the pore wall thickness
(here we refer to the calculation method proposed by Schumacher
et al.16) of MCM-48 prepared by our mixed cationic-nonionic
surfactant route is the highest among the four synthesis systems.
This result can be explained by the view of thermodynamics. In
the synthetic system of mesoporous molecular sieves, the struc-
ture of final product will correspond to the Gibbs free energy as
smaller as possible. The Gibbs free energy in the mesoporous
molecular sieves system usually comes from four aspects17 which
can be stated as ΔG=ΔGinter þ ΔGorg þ ΔGinorg þ ΔGsol. ΔGorg
results from the contributions of the organization of the
organic array. ΔGinter represents the van der Waals and electro-
static effects associated with the interaction of inorganic/organic
(15) Israelachvili, J. N.; Mitchell, D. J.; Ninham, B. W. J. Chem. Soc., Faraday
Trans. 1976, 72, 1525–1568.
(16) Schumacher, K.; Ravikovitch, P. I.; Chesne, A. D.; Neimark, A. V.; Unger,
K. K. Langmuir 2000, 16, 4648–4654.
(17) Huo, Q.; Margolese, D. I.; Ciesla, U.; Demuth, D. G.; Feng, P.; Gier, T. E.;
Sieger, P.; Firouzi, A.; Chmelka, B. F.; Schuth, F.; Stuck, G. D. Chem. Mater.
1994, 6, 1176–1191.
DOI: 10.1021/la9042155 6983
Article
Figure 2. TEM image of MCM-48 on the 110 (left) and 111 (right) cubic plane.
Figure 3. N2 adsorption and desorption isotherm and pore-size
distribution (inset) of MCM-48 sample.
Figure 4. 29
Si MAS NMR spectra of as-synthesized (a) and cal-
cined (b) MCM-48.
phase. ΔGinorg reflects the contributions arising from the inor-
ganic subphase. ΔGsol accounts for the chemical potential of
various species in mother liquor solution. On the basis of the
observation of a single isotropic line that is assigned to the
presence of rapidly rotating rodlike micelles in the 14N NMR
spectra of gels during the in situ synthesis of MCM-41 and MCM-
48, Chen and Davis et al.18 proposed that the starting point for the
(18) Chen, C.; Li, H.; Davis, M. E. Microporous Mater. 1993, 2, 17–26.
6984 DOI: 10.1021/la9042155
Zhao et al.
Figure 5. Thermal analysis results of MCM-48 sample: (a) TG, (b)
DTA. The inset is the XRD pattern of the sample after testing.
formation of MCM-41/MCM-48 phases requires that C16TMA
cations are organized into rodlike micelles first. Also, Huo and
Stucky et al.17 found that the van der Waals forces and organic
array stability are greater for bitailed surfactants than for mono-
tailed surfactants. Both of these suggest that ΔGorg is a more
important free energy contribution to biphase composite forma-
tion than other three ones, especially in the initial assembly step.
Because of the exist of Tx-100 with benzene ring that has powerful
van der Waals force, the needed concentration of CTAþ that
induces the dispersed CTAþ to be arranged orderly to form the
isotropic micellar phases will be lower in our route than in other
routes. After the adding of silicon source, on one hand, the ΔGorg
in the system will decrease arising from the distribution of new Si
species and ΔG will decrease correspondingly (since the contribu-
tions of ΔGinter, ΔGinorg, and ΔGsol are relative weak at this time)
to promote the reaction shifts toward the self-assembly process.
On the other hand, the amount of inorganic anions equilbrated
with CTAþ cation will be decreased owing to the lower concen-
tration of CTAþ. Thus, the condensation among the inorganic
anions will be augmented, and the silica wall will be thickened.
Usually, an extensively cross-linked framework will bring about
the high thermal stability. This is in agreement with the results
of 29Si MAS NMR (Figure 4) and the thermal analysis (Figure 5).
Langmuir 2010, 26(10), 6982–6988
Zhao et al.
Figure 6. Influence of the amount of CTAB on synthesized pro-
duct: (a) CTAB/SiO2 = 0.09, (b) CTAB/SiO2 = 0.12, (c) CTAB/
SiO2 = 0.15, (d) CTAB/SiO2 = 0.18, (e) CTAB/SiO2 = 0.21,
(f ) CTAB/SiO2 = 0.25.
Different from the general tendency of the H f Q f L phase
transitions, where H, Q, and L refer to the hexagonal, cubic Ia3d,
and lamellar mesophases, respectively, when we increased the
ratio of CTAB/SiO2 from 0.21 to 0.25, the regression cubic phase
did not transform to lamellar phase. Instead, a hexagonal phase
product reappeared again. As the ratio of Tx-100/CTAB is 0.2 in
this mixture, at low concentration of CTAþ, the auxiliary
surfactant role of Tx-100 will be enlarged; hydrogen-bonding
and van der Waals forces can influence the electrostatic interac-
tion strongly. In other words, assembly driving force comes from
the balance among these three forces at this time. Following the
increase of CTAþ concentration, both the interaction of CTAþ
hydrophobic chains and the interaction between CTAþ polar
head groups and silicate anions will be enhanced. At that time, the
electrostatic interaction (strong force) will overcome the effect
of hydrogen bonding, and the van der Waals force (weak force)
will become the major assembly driving force. Meanwhile, the
increase amount of CTAþ will increase the hydrophobic of
organic-inorganic interface; thus, the Tx-100 will gradually
isolate from the CTAþ micelle and the solution characterization
will near to the single CTAB cationic surfactant system. For the
single cationic surfactant system, the CTAB/SiO2 ratio of 0.25 is
far from the ratio (usually >1) needing to form lamellar phase,
while just forming the hexagonal phase.
3.3. Effect of Tx-100/CTAB. The effect of Tx-100/CTAB
(keeping CTAB/SiO2=0.15) on the synthesis is shown in Figure 7.
It is found a typical hexagonal phase product is appearing without
the addition of Tx-100 (Figure 7a). If the Tx-100/CTAB ratio is
0.133-0.167, the mixture mesophase of hexagonal and cubic Ia3d
product formed (Figure 7b,c). When the ratio is 0.2, a pure phase
MCM-48 is obtained (Figure 7d). Further increasing the ratio of
Tx-100/CTAB to 0.234, another kind of mixture mesophase of
cubic Ia3d and lamellar product formed (Figure 7e). For the
maximum ratio of 0.267, pure lamellar phase product is obtained
finally (Figure 7f). Just as discussed above, under low concentra-
tion of CTAB, Tx-100 can effetely influence the V and a0 by its
hydrogen-bonding and van der Waals force. Thus, the g value is
very sensitive to the change of the amount of Tx-100. Following
the amount of Tx-100 increase from 0 to Tx-100/CTAB=0.267,
the g gradually increased from 1/2 to 1. As a result, the H f M1 f
Q f M2 f L phase transitions occur, where M1 and M2 refer to
Langmuir 2010, 26(10), 6982–6988
Article
mixture hexagonal and cubic Ia3d mesophase and mixture cubic
Ia3d and lamellar mesophase, respectively. The fact that pure
cubic phase of MCM-48 only can be formed in a narrow range of
Tx-100/CTAB = 0.167-0.2 further proves that the hydro-
gen-bonding and van der Waals force of Tx-100 will exert
an important role in the assemble system of low CTAB concen-
tration.
3.4. Effect of Synthesis Temperature. Figure 8 shows that
when the synthesis temperature was elevated from 80 to 170
C,
the phase transitions are as follows:
hexagonal phase ð80
CÞ; cubic phase ð100
CÞ
lamella phase ð120
CÞ; poor lamella phase ð140-170
CÞ
Since the low concentration CTAB exists in the aqueous solution,
although the synthesis temperature (80
C) is above its “cloud
point” (<70
C), Tx-100 still can keep its amphiphilic part. And
its hydrophilic part will exhibit a contracted conformation due to
the hydrogen-bonded water molecules19 and the hydrogen-bond
interaction with the polar head groups of CTAþ micelle
(Figure 9). These spherical-like hydrophilic groups have strong
hydrophilic characterization. This will hinder its hydrophobic
chain stretch into the void of the CTAþ micelle to separate CTAþ
micelle. Then, a high surface curvature will be formed. When the
synthesis temperature increases to 100
C, the contracted hydro-
philic part of Tx-100 gets some extension because of the weakened
hydrogen-bond interaction and its hydrophobic characterization
will increase. This will give an advantage to its hydrophobic chain
to enter into the void of the CTAþ micelle. Together with the
increase of hydrophobic chain volume (V) of CTAþ, the surface
curvature will decrease, and then a suitable g value needed for
the cubic phase is reached. Further enhancing the temperature to
120
C, the hydrogen bonds will disappear progressively, and a
more extended conformation is expected. This provides the
hydrophobic chain of Tx-100 to penetrate the void of the CTAþ
micelle deeply and further increase the g value to meet the forming
of lamella phase. If the temperature is much higher (>140
C),
Tx-100 will lost its amphiphilic part completely and isolate from
the organic-inorganic interface entering the organic phase
(hydrophobic portion of CTAþ micelle). Here, some of these
Tx-100 molecules will form a big molecular aggregate by the
associated reaction among the hydrophobic groups of poly-
oxyethylene chains whose hydrophobic characterization increases
because of losing the hydrogen-bonded water molecules. Since
this big molecular aggregate which stays at the hydrophobic
portion of CTAþ micelle does not distribute orderly in every
CTAþ micelle, the local organic-inorganic interface of lamella
phase becomes irregular although lamella phase can generally
maintenance. When the temperature is 170
C, both the decom-
position of CTAB20 and the disaggregating of silica-polymer21
will cause the lamella phase transform to amorphous phase.
In addition, according to the principle of charge balance, the
charge density on the micelle interfaces should equal that of the
silica polymers when the system energy is the most optimum,21 i.e.
Fε ¼ N=A ð1Þ
where Fε is the charge density on silica-polymer, N the net
charge on micelles interface, and A the interface area of micelle.
(19) Blin, J. L.; Becue, A.; Pauwels, B.; Tendeloo, G. Van.; Su, B. L. Micro-
porous Mesoporous Mater. 2001, 44-45, 41–51.
(20) Huang, L. M.; Chen, X. Y.; Li, Q. Z. J. Mater. Chem. 2001, 11, 610–615.
(21) Blin, J. L.; Herrier, G.; Otjacques, C.; Su, B. L. Langmnir 2000, 16, 4229–
4236.
DOI: 10.1021/la9042155 6985
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Table 1. Parameters of MCM-48 Prepared by the Different Methods
synthesized systems CTAB/SiO2
single cationic surfactantc 0.55
mixed cationic-anionic surfactantd 0.152
e
mixed cationic-neutral amine surfactant 0.153
mixed cationic-nonionic surfactant 0.12
a
a0 = d[211](22 þ 12 þ 12)1/2, and the a0 value is based on the calcined samples. b Æhæ = a0/ξ0 - Dh/2, where ξ0 is 3.092. c Data obtained from ref 14.
d
Data obtained from ref 4. e Data obtained from ref 5.
Figure 7. Influence of the ratio of Tx-100/CTAB on synthesized
product: (a) Tx-100/CTAB = 0, (b) Tx-100/CTAB = 0.133,
(c) Tx-100/CTAB = 0.167, (d) Tx-100/CTAB = 0.2, (e) Tx-100/
CTAB = 0.234, (f) Tx-100/CTAB = 0.267.
Scheme 1. Possible Self-Assembly Procedure of This Synthesis
System
To differentiate formula 1 and then transpose, we can obtain
dA=dFε ¼ -N=Fε 2 < 0
This formula shows that the different polymer degree (or charge
density) of silicate can change the interface area of micelle and
then influence the product structure. When Fε increases (usually
following the elevating of temperature), the micelle area will
decrease and the shape of the interface will change from high
curvature to low curvature. For instance, the interface shape can
change from cylinder through gyroid to flat, corresponding to
the structure change from hexagonal MCM-41 through cubic
MCM-48 to lamella MCM-50.
3.5. Effect of Synthesis Time. As seen from Figure 10, it is
found that a typical XRD pattern of cubic Ia3d structure is
observed for the sample that synthesized only 1 day (Figure 10a).
For the second day, this pattern becomes somewhat better
(Figure 10b). On the third day, the sample with well-resolved
XRD pattern is obtained (Figure 10c). Further prolonging the
6986 DOI: 10.1021/la9042155
Zhao et al.
parameters
surfactant/SiO2 a0a/Å pore diameter (Dh)/Å pore wall thickness (Æhæ)b/Å
0.55 83.8 24.0 15.1
0.168 94.0 29.4 15.7
0.161 80.0 22.0 14.9
0.144 91.1 23.9 17.5
Figure 8. Influence of the temperature on synthesized product: (a)
80, (b) 100, (c) 120, (d) 140, and (e) 170
C.
synthesis time to the fourth day, a lamella MCM-50 is appearing
(Figure 10d). Since the cubic octasilicic acid was regarded as the
basic component of water glass,22 the hydrolysis and polycon-
densation of silicon source will be achieved in the preparation of
the gel. During the hydrothermal treatment at 100
C, this initial
polycondensation silica can around the organized CTAþ micelle
forming an organic-inorganic interface, which is an advantage to
the cubic Ia3d structure quickly. Then, the fast formation of
MCM-48 is possible. Additionally, the suitable molar compo-
sition of gel also is beneficial to the accelerated synthesis of
MCM-48. Following the hydrothermal treatment prolonging,
continue aggregating of silica-polymer will cause the organic-
inorganic interface more to be optimized, and the crystallization
of MCM-48 phase is more to be enhanced. If the synthesis time is
too long, the pH of the system will elevate because Naþ ions
released by the condensation of silicate increase. While the
high pH is beneficial to form the thermodynamic more stable
lamella phase.13
3.6. Effect of Si Source. The effect of different Si sources on
the product structure is shown in Figure 11. When water glass and
TEOS (Si(OC2H5)4) were used as Si source, the cubic MCM-48
can be obtained, and the degree of order on mesoscopic scales of
the product synthesized with water glass (Figure 11a) is better
than that of the product synthesized with TEOS (Figure 11b). The
lamella structural MCM-50 is obtained only when fumed silica
(SiO2 3 nH2O) was used as Si source (Figure 11c). Since the fumed
silica is composed of aggregated SiO2, in the basic solution, the
aggregated SiO2 will disaggregate first and then react with
NaOH, forming Na2SiO3. Finally, Na2SiO3 begins to hydrolyze/
condense. Thus, for a certain synthesis time, its silicate oligomers
are low. It means the inorganic species in the organic-inorganic
(22) Lu, C.; Ji, D. S.; Zhun, C. X. J. Shanghai Jiaotong Univ. 1997, 31, 86–89.
Langmuir 2010, 26(10), 6982–6988
Zhao et al.
Figure 9. Different conformations of Tx-100 at different temperatures.
Figure 10. Influence of the time on synthesized product: (a) 24,
(b) 48, (c) 72, and (d) 96 h.
interface will carry high charge. According to the “charge density
matching” theory,23 the organic phase which is composed of polar
head of CTAþ micelle also will carry high charge. Then a lamella
phase forms. For TEOS, the hydrolysis of Si(OC2H5)4 to Si(OH)4
and the condensation of Si(OH)4 can happen quickly in basic
conditions during the hydrothermal treatment, However, due to
(23) Wiebcke, M.; Grube, M.; Koller, H.; Engelhardt, G.; Felsche, J. Micro-
porous Mater. 1993, 2, 55–63.
Langmuir 2010, 26(10), 6982–6988
Article
Figure 11. Influence of the Si source on synthesized product:
(a) water glass, (b) TEOS, (c) fume silica.
the ethanol produced from TEOS, some region of silica wall will
appear disorder/discontinuous as the silica wall thickens. Also,
ethanol can act as a cosurfactant entering into organic phase and
swell micelles. Consequently, g value might be enhanced and
other phase (lamella phase) would be formed. Both of these will
decrease the quality of MCM-48. Just as mentioned above, water
glass is the polymerization product of silicic acid. Meeting the
initial orientation CTAþ ions (by aid of Tx-100), liquid crystal
formation and initial polycondensation even can happen in the
gel step. Though the hydrothermal treatment step, the cubic
DOI: 10.1021/la9042155 6987
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Ia3d phase can be optimized continuously, and a highly order
MCM-48 will be obtained.
The above result also can be explained by the view of thermo-
dynamic formula24
ðδG=δAÞA ¼A0 ¼ 0
ΔGðA, FÞ ¼ ΔGintra ðAÞ þ ΔGwall ðFÞ þ ΔGinter ðA, FÞ þ ΔGsol
When other synthesis conditions keep constant, ΔGwall and
ΔGinter(A,F) will be the more important free energy than ΔGintra
and ΔGsol for the synthesis system if we only observe the effect of
different Si sources on the product structure. So the eq 3 can be
simplified to ΔG(A,F) = ΔGwall(F) þ ΔGinter(A,F). When (δG/
δA)A=A0=0, A0 will only be related to the charge density of silica
polymer (F). In fact, every synthetic system always has an
optimum value of the head area (A0) under the different synthetic
conditions, and the different A0 will correspond to the different
structure. When the fumed silica is used as Si source, the polymer
silicate anions with high charge density will give an advantage to
form, while high charge density interface will cause the A value to
decrease.25 Thus, the product is the lamellar structural MCM-50.
In the case of TEOS, the condensation rate of its Si species is
(24) Stucky, G. D.; Huo, Q.; Firouzi, A.; Chmelka, B. F. Stud. Surf. Sci. Catal.
1997, 105, 3–28.
(25) Marra, J. J. Phys. Chem. 1986, 90, 2145–2150.
6988 DOI: 10.1021/la9042155
Zhao et al.
relatively faster, and this rate will cause the A value of this system
near to the A0 value needed for the formation of MCM-48 with
double continue gyroid structure (Ia3d). For water glass, the
condensation rate of its Si species is fast and also is advantageous
to the formation of the cubic Ia3d structure. Owing to the higher
ð2Þ polymerization degree of the silica frame, the XRD pattern of its
product will be better than that of the product synthesized by TEOS.
4. Conclusion
ð3Þ High quality MCM-48 was synthesized by a binary CTAB and
Tx-100 surfactant system using lower CTAB amount compared
to other synthesized routes. At low concentration of CTAB, the
auxiliary surfactant role of Tx-100 will be enlarged,and hydrogen-
bonding and van der Waals force could influence the electrostatic
interaction strongly. This will result in the g value being very
sensitive to the change of Tx-100 amount. Both the conformation
of polyoxyethylene chains and the condensation rate of different
Si sources will influence the final product phase effetely. The
optimum synthetic conditions of MCM-48 under the low molar
ratio (0.144:1) of mixed surfactants to silica are as follows: molar
composition is 1.0 SiO2:0.15 CTAB:0.03 Tx-100:58 H2O; hydro-
thermal condition is that crystallize at 100
C for 3 days.
Acknowledgment. This work is supported by the projects of
National Key Technologies R&D Program (2006BAC02A05),
National Basic Research Program of China (973 Program,
2007CB613501), and the Knowledge Innovation Program of
the Chinese Academy of Sciences (Grant KGCX2-YW-214).
Langmuir 2010, 26(10), 6982–6988