Microporous and Mesoporous Materials 86 (2005) 314322

www.elsevier.com/locate/micromeso

Novel synthesis of high hydrothermal stability and long-range

order MCM-48 with a convenient method
Yaofeng Shao a, Lingzhi Wang a, Jinlong Zhang a,*
, Masakazu Anpo b

a
Lab for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, PR China
b
Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, Japan

Received 16 June 2005; received in revised form 25 July 2005; accepted 30 July 2005
Available online 9 September 2005

Abstract

The high quality MCM-48 has been easily synthesized at 120 C for 24 h, and the results of which showed that not only long-
range ordering of MCM-48, but also hydrothermal stability could be signicantly improved by direct addition of NaF with F /Si
ratio of 0.1 and 0.2 to initial reacting gel without post-treatment and pH adjustment. The results of XRD, N2-adsorption and TEM
analyses indicated that MCM-48, which was synthesized via appropriate procedure, maintained their structural integrity after boi-
ling in water at 100 C for at least 3 days. Additionally, the optimum condition was F /Si ratio of 0.1 at a Na2O/SiO2 ratio of 0.25.
The adding time of NaF was critical in the formation of this high quality MCM-48. When the addition of uoride ions was 60 min
earlier than that of surfactant, the mesoporous structure of the synthesized MCM-48 could be maintained after reuxing in boiling
water for 3 days. When the additions of uoride ions and surfactant were simultaneous, however, the structure of MCM-48 was
collapsed after 12 h reuxing in boiling water. The result clearly showed that the long-range structural ordering and hydrothermal
stability could be improved only when adding NaF at the early stage of hydrolysis and polymerization of silicate. The dierent
eects of uoride anions at the dierent reacting periods of synthesizing MCM-48 are also discussed.
2005 Elsevier Inc. All rights reserved.

Keywords: Fluoride addition; Hydrothermal stability; MCM-48; Adding time; Long-range ordering

1. Introduction ous synthesis conditions, since the MCM-48 phase is

A mesoporous molecular sieve, MCM-48, invented
by Mobil [1,2] in 1992, has attracted considerable atten-
tion because of its high surface area, ordered pore struc-
ture array, and narrow pore size distribution. As an
adsorbent, catalyst, catalyst support, and template for
the synthesis of advanced nanostructures, MCM-48
may be a more potent candidate than MCM-41 and
MCM-50. However, the preparation of MCM-48 re-
quires relatively extended reaction time and more rigor-
*
Corresponding author. Tel./fax: +86 2164252062.
E-mail address: jlzhang@ecust.edu.cn (J. Zhang).
often an intermediate during the transformation from
a hexagonal phase or disordered surfactant/silica meso-
phase to a lamellar phase [39]. Especially, it is dicult
to synthesize MCM-48 with good long-range ordering
structure. Recently, Ryoo and Kim [10] reported that
the long-range structural order and textural uniformity
of MCM-41 were markedly improved by adjusting the
reacting solution using acetic acid, three separate times,
during the reaction. This procedure, however, is not
convenient because the reacting solution has to be
cooled to adjust its pH, and the synthesis reaction re-
started. The same procedure must be repeated several
times during the reaction. More recently, Kim et al.
[11] reported that initial adjustment of pH and direct

1387-1811/$ - see front matter 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.07.043
 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322
addition of NaF led to increase the long-range structural
order of MCM-41. However, until now, the above re-
ports are all focused on the MCM-41 and the method
for improvement of long-range ordering of mesoporous
materials is inconvenient. There is no detailed study on
the enhancement of structural ordering of MCM-48 by a
convenient method.
The hydrothermal stability of MCM-48 has been
known to be very low, and Xia and Mokaya reported
that the mesoporous structure of MCM-48 was com-
pletely lost after 6 h reuxing in boiling water [12].
The loss of hydrothermal stability could be a serious
barrier for the application of this material to water
and aqueous solution systems. Since the applications
such as exchanging cations, supporting metal clusters,
and catalytic reactions in aqueous solutions will be limi-
ted by the structural disintegration, it is thus important
to improve the hydrothermal stability of mesoporous
framework. Many eective improvements such as pore
wall thickening [1316], silylation [1720], stabilization
by salt eect [21,22] and hydrothermal restructuring
process [23] have been reported. Kim et al. [24] re-
ported that the addition of salts during hydrothermal
synthesis of MCM-48 resulted in a remarkable
improvement of the hydrothermal stability. However,
the use of salts during the hydrothermal synthesis is
not convenient for MCM-48 because the formation of
the MCM-48 mesophase requires narrow, specic syn-
thesis conditions. Jun et al. [25] reported that the
hydrothermal stability of MCM-48 could be improved
by post-synthesis restructuring in salt solution. How-
ever, the post-synthesis requires additional synthesis
time. Recently, many researches have been focussing
on the uorination of MCM-48 [26,27]. Fluoride ions
do inuence the nature, activity and polymerizing
capacity of silica precursors, and a uorinated silica
surface is much more hydrophobic and more resistant
to the attack of water molecules than a silanol silica
surface [28]. More recently, Kim et al. [27] also re-
ported that the hydrothermal stability of MCM-48
could be improved by post-treatment in NaF solution.
A combined eect of NaF addition and hydrothermal
post-treatment could maximize the hydrothermal stabil-
ity of MCM-48. Therefore, it is a challenging issue to
investigate eecting of adding time of NaF on the qua-
lity of synthesizing MCM-48.
However, up to now, no systematic study has been re-
ported on the possibility of synthesizing MCM-48 with
high hydrothermal stability and well-dened long-range
order of the structure by directly adding NaF with F /Si
ratio of 0.1 and 0.2 to the initial reacting gel without
post-treatment and pH adjustment for 24 h. The aim
of this research was also to investigate the dierent ef-
fects of uoride anions at the dierent reacting periods
of synthesizing MCM-48.
315
2. Experimental
2.1. Materials
The reactants used in this study were tetraethylorth-
osilicate (TEOS) as a silica source, cetyltrimethylammo-
nium bromide (CTAB) as a surfactant, sodium hydroxyl
(NaOH) as the alkali source, sodium uoride (NaF) and
deionized water.
2.2. Experimental procedures
To investigate the eect of adding time of uoride,
two sets of samples via dierent procedures (procedure
I and procedure II) were prepared. The dierentiation
of two procedures was the adding time of uoride ions:
the addition of uoride ions was 60 min earlier than that
of surfactant in procedure I, however, the additions of
uoride ions and surfactant were simultaneous in proce-
dure II.
2.2.1. Procedure I
The rst set of samples were synthesized via proce-
dure I, the materials of which were prepared as follows:
10 g of TEOS was mixed with 50 g of deionized water
and the mixture was vigorously stirred at 35 C for
40 min, then required amount of NaOH was added into
the mixture, at the same time, the required amount of
NaF was also added into the mixture. After another
60 min of vigorously stirring at 35 C, 10.61 g of CTAB
was added to the mixture and continued stirring at
35 C for 60 min. The molar composition of the nal
mixture was 1.0SiO2:0.65CTAB:(0.220.27)Na2O:
62H2O:(00.4)NaF. Finally, the mixture was heated
for 24 h at 393 K in an autoclave under static condition,
the resulting MCM-48 product was ltered, washed with
distilled water and dried at 373 K. The as-synthesized
samples were then calcined for 4 h at 550 C, after
increasing the temperature to 550 C at 1 C/min of
heating rate.
2.2.2. Procedure II
The second set of samples were also prepared as fol-
lows: the molar composition was same as the rst set of
samples, however, the adding time of uoride ions was
dierent from that in procedure I. Fluoride ions and
surfactant were simultaneously added into mixture in
procedure II. In the second set, 10 g of TEOS was mixed
with 50 g of deionized water and the mixture was vigor-
ously stirred at 35 C for 40 min, then the required
amount of NaOH was added into mixture. After stirring
at 35 C for about 60 min, the required amount of NaF
and 10.61 g of CTAB were simultaneously added into
the mixture, then continued stirring at 35 C for
60 min. The residue procedure was same as described
in procedure I.
316 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322
2.3. Hydrothermal stability test
0.1 g of calcined MCM-48 was boiled for dierent
period of time in 100 ml of distilled water, using a ask
equipped with reux condenser. XRD pattern was ob-
tained after this boiled sample was subsequently ltered
and dried in an oven at 413 K. According to the XRD
analysis, loss in the XRD intensity, as compared with
that of the same sample before the boiling treatment,
was used to judge the hydrothermal stability.
2.4. Characterization
X-ray powder diraction (XRD) patterns of all
samples were recorded on Rigaku D/MAX-2550
diractometer using CuKa radiation of wavelength
1.541 A, typically run at a voltage of 40 kV and cur-
rent of 100 mA. N2 adsorption and desorption iso-
therms were carried out by using Micromeritics
ASAP 2010. For BET (BrunauerEmmettTeller
method), the as-synthesized samples were calcined
following the procedures described in Section 2 and
the samples were then outgassed to remove moisture
and impurities at 623 K for 5 h before measurement.
TEM analyses of the samples were done using a
JEM 2000-EX (Jol) instrument and the electron beam
accelerating voltage was 200 kV.
3. Results and discussion
3.1. XRD analysis
3.1.1. Structural ordering of MCM-48 prepared via
dierent procedures
The quality and structural ordering of MCM-48
materials were assessed by powder XRD.
Fig. 1. XRD patterns of as-synthesized and calcined MCM-48 synthesized at a Na2O/SiO2 ratio of 0.25 (a) at F /Si = 0.1, (b) at F /Si = 0.2, (c)
without uoride addition.
Fig. 1 shows the XRD patterns of as-synthesized and
calcined samples prepared with directly adding dierent
contents of NaF via procedure I and without uoride
addition at a Na2O/SiO2 ratio of 0.25. According to
Fig. 1(a), the patterns of the as-synthesized and calcined
samples synthesized with directly adding 0.1 g of NaF,
eight diraction peaks (2 1 1), (2 2 0), (3 2 1), (4 0 0),
(4 2 0), (3 3 2), (4 2 2) and (4 3 1), which can be indexed
to Ia3d cubic structure, are clearly observed. As F /Si
ratio increases from 0.1 to 0.2, seven diraction peaks
are still well resolved on the pattern of calcined samples.
However, the patterns of the samples synthesized with-
out uoride addition only show two basal peaks (2 1 1)
and (2 2 0) and a weak peak (3 2 1), the other secondary
peaks are not observed (see Fig. 1(c)). Additionally, on
the basis of Fig. 1, the uorination-treated samples via
procedure I show the Miller indices (2 1 1) and (2 2 0)
are more intense than that prepared without uoride
addition. This indicates a higher organization of the
pores when uoride ions are present. More importantly,
secondary peaks are also well resolved on the patterns of
the uorination-treated samples via procedure I. The
secondary peaks indicate long-range ordering of
MCM-48 structure [11]. Both of these observations are
indicative of improved structural ordering within the
mesoporous silicas. However, the samples prepared
without uoride addition have poor structural ordering
and lower degree of organization (weak intensity I211 of
the (2 1 1) peak), which is compared with the samples
synthesized by adding uoride anions with F /Si ratio
of 0.1 and 0.2.
The similar results, which on directly adding uoride
ions with F /Si ratio of 0.1 and 0.2 to the initial reacting
gel via procedure I has signicantly enhanced the long-
range structural ordering, can also be obtained when
varying the Na2O/SiO2 ratios to 0.22 and 0.27 (seen in
Fig. 2(a) and (b)). As can be seen in Figs. 1 and 2,
 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322 317

Fig. 2. XRD patterns of calcined MCM-48 prepared with adding dierent contents of NaF at a Na2O/SiO2 ratio of (a) 0.22, (b) 0.27.

directly adding uoride ions with F /Si ratio of 0.1, 0.2 to the reacting gel via procedure I can greatly improve
and 0.3 to the initial reacting gel via procedure I has the quality of MCM-48 compared with MCM-48 pre-
greatly improved the long-range structural ordering pared via procedure II.
under dierent Na2O/SiO2 ratios. Further experiments were carried out to investigate
In order to investigate the eects of uoride anions the structural ordering of mesoporous materials synthe-
on the formation of MCM-48 at the dierent periods sized at dierent Na2O/SiO2 ratios and F /Si ratios via
of synthesis, the dierent adding time of NaF to the dierent procedures. As Table 1 shows for procedure I,
initial reacting gel was studied. Fig. 3 shows the XRD for gels with F /Si ratios more than 0.3, no precipitates
patterns of the calcined samples synthesized by adding
dierent amounts of NaF via dierent procedures. For
Table 1
samples prepared via procedure I, eight diraction peaks
Summary of molar composition and results for the system
are clearly observed. However, the samples prepared via
Numbers F /Si Na2O/SiO2 Remarks
procedure II exhibit only two basal peaks (2 1 1) and
(2 2 0), the other secondary peaks are not well resolved. Procedure I Procedure II
On the basis of Fig. 3, MCM-48 prepared via procedure 1 0.1 0.27 MCM-48 MCM-48
I has a well-dened pore ordering. However, the samples 2 0.2 0.27 No solid product Solid product
3 0.1 0.25 MCM-48 MCM-48
synthesized via procedure II have poor structural orde-
4 0.2 0.25 MCM-48 MCM-48
ring. At the same time, according to Fig. 3, the intensity 5 0.3 0.25 No solid product Solid product
of basal peak (2 1 1) of samples synthesized via proce- 6 0.1 0.22 MCM-48 MCM-48
dure I is about three times higher than that of samples 7 0.2 0.22 MCM-48 MCM-48
prepared via procedure II. The result indicates that the 8 0.3 0.22 MCM-48 MCM-48
9 0.4 0.22 No solid product Solid product
direct addition of NaF with F /Si ratio of 0.1 and 0.2

Fig. 3. XRD patterns of calcined MCM-48 synthesized at a Na2O/SiO2 ratio of 0.25 by adding dierent amounts of NaF to initial reacting gel via (a)
procedure I, (b) procedure II.
318 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322
were obtained at a Na2O/SiO2 ratio of 0.22; for F /Si
ratios greater than 0.2, also no solid product was formed
at a Na2O/SiO2 ratio of 0.25; When Na2O/SiO2 ratio
was 0.27, only the solid product of F /Si ratios more
than 0.1 disappeared. However, for procedure II, under
the same conditions, all the solid products could be ob-
tained when Na2O/SiO2 ratio was 0.22, 0.25, 0.27, and
F /Si ratios were corresponding to 0.4, 0.3, 0.2,
respectively.
These results can be explained as follows: according
to Voegtlin et al. [29], the degree of polymerization of
silicates can be enhanced in the presence of uoride ions.
Enhancement of the degree of polymerization of silicates
causes a high charge density of silicate network to im-
prove the interactions between the cationic micelles
and the anionic framework. The pore ordering can be
enhanced in the presence of NaF. In addition, for proce-
dure I, F was added at the early stage of hydrolysis and
condensation of silicate, so F anions were mainly direct
eect on silicate, F anions probably play a catalytic
role favoring the polymerization of the silicate species
[29]. Under these conditions, the enhancement of the
degree of polymerization of silicates leads to a high
charge density, which improve the interactions between
the cationic micelles and the anionic framework. The
high degree of organization (strong intensity of the
(2 1 1) peak) observed for the samples prepared via pro-
cedure I can be related to stronger interactions between
the cationic micelles and the anionic framework. How-
ever, for procedure II, which by adding uoride anions
after 60 min of polymerization of silicate and meanwhile
addition of CTAB, the F anions mainly aect on the
CTA+ but not the silicate species. There is a competition
between Br and F for CTA+ [30]. Therefore, balanc-
ing the charges of CTA+ is the main eect of uoride an-
ions for procedure II. Compared with the intrinsic
charge density of the framework of the samples pre-
pared via procedure I to that of the samples prepared
via procedure II is much lower which is supposed to
be responsible for the lower degree of organization of
the samples synthesized via procedure II than that
of the samples prepared via procedure I (less intense
of (2 1 1) peak for the samples prepared via procedure
II). On the other hand, according to Larry Kevan and
coworkers [6], the eect of dierent initial pH on the
synthesis can be explained since lower pH speeds up
the kinetics of silica polymerization. However, when
Na2O/SiO2 ratio is greater than 0.27 at 373 K, silica dis-
solves faster than silica precipitates at 373 K, so no solid
product is formed. In this investigation, the precipitates
disappeared when Na2O/SiO2 ratio was only 0.25 and
F /Si ratios were greater than 0.2, which can be ex-
plained as the above reason, because of the similarity
of nature between OH and F , F anion has similar ef-
fect on the formation of MCM-48, uoride ions addi-
tion can speed up the kinetics of silica polymerization
at a certain Na2O/SiO2 ratio, however, at high Na2O/
SiO2 ratios with low content of uoride anions or at
high content of uoride anions with low Na2O/SiO2 ra-
tios, for instance, at Na2O/SiO2 = 0.27 and F /
Si P 0.2, Na2O/SiO2 = 0.25 and F /Si P 0.3, Na2O/
SiO2 = 0.22 and F /Si P 0.4, the combined eect of
OH and F can speed up the dissolution of silicate.
Therefore, for procedure I, when Na2O/SiO2 ratio was
0.25, for F /Si ratios greater than 0.2, the silicates dis-
solve faster than precipitate, so no solid product is
formed. The other results can also be explained as the
same reason. However, for procedure II, the solid prod-
uct was still obtained at a Na2O/SiO2 ratio of 0.25 and
F /Si ratio greater than 0.3. This result also can ex-
plained by the previous reason, however, for procedure
II, only part of F anions added can be eciently eect
on the silicate to cause the polymerization and hydroly-
sis of silicate. These results further indicate that the
eect of uoride is signicantly dierent at dierent peri-
ods of synthesis of MCM-48.
3.1.2. Hydrothermal stability of MCM-48 synthesized
via dierent procedures
Fig. 4 displays the XRD patterns of materials pre-
pared via procedure I and procedure II, respectively,
which was treated in boiling water at dierent time. As
can be seen in Fig. 4(b), the structure of the calcined
samples synthesized via procedure II at F /Si = 0.07 is
completely collapsed after reuxing in boiling water
for 12 h. For procedure II, as F /Si ratio increases to
0.1 and 0.2 (see Fig. 4(d) and (f)), the MCM-48 also
loses its mesoporous structure completely upon boiling
in water for 12 h. However, two sharp and distinct
characteristic XRD peaks of (2 1 1) and (2 2 0) are still
observed for materials synthesized at F /Si = 0.07 via
procedure I (see Fig. 4(a)), even after treatment in boi-
ling water for 2 days, showing that the materials treated
are still typical for cubic MCM-48, but the intensity of
XRD peaks decreases with the extending treatment
time. For procedure I, as F /Si ratio increases to 0.1
(see Fig. 4(c)), its cubic structure still can be maintained
after reuxing in boiling water for 3 days, but as F /Si
ratio added to the reacting gel via procedure I increases
to 0.2 (see Fig. 4(e)), the cubic structure is almost lost
after reuxing in boiling water for 3 days. According
to Fig. 4, the hydrothermal stability of MCM-48, which
was synthesized via procedure I, increases with F /Si
ratio increasing from 0.07 to 0.1 and decreases with
increasing F /Si ratio from 0.1 to 0.2. The optimum
condition was F /Si ratio of 0.1.
The hydrothermal stability is signicantly dierent
between samples prepared via procedure I and proce-
dure II under the same content of addition of NaF
(0.07, 0.1, 0.2) and reuxing conditions. The hydrother-
mal stability of MCM-48 synthesized via procedure I
is signicantly higher than that prepared via procedure
 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322 319

Fig. 4. XRD patterns of calcined MCM-48 materials synthesized at a Na2O/SiO2 ratio of 0.25 and at F /Si = 0.07 via (a) procedure I, (b) procedure
II; at F /Si = 0.1 via (c) procedure I, (d) procedure II; at F /Si = 0.2 via (e) procedure I, (f) procedure II and treated in boiling water for dierent
time.

II, the mesoporous structure of the former can be According to the experimental procedure, which is the
maintained after reuxing in boiling water for 3 days, dierence between procedure I and procedure II, is only
however, the mesoporous structure of the latter is the adding time of NaF. Procedure I is addition of uo-
collapsed after reuxing in boiling water for 12 h. ride at the early stage of hydrolysis and condensation of
320 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322
silicate. However, procedure II is addition of uoride
after 60 min hydrolysis and polymerization of silicates,
where CTAB should be added immediately to the reac-
tion mixture. The dierent hydrothermal stability might
be attributed to the dierent eects of F in the reacting
gel. For procedure I, F anions mainly directly aect on
the silicate to improve the degree of polymerization of
silicate framework and also replace the silanol group
to form very stable SiF; for procedure II, however,
F anions mainly aect on the CTA+ as the counterion
to balance the charge of CTA+. Having achieved a cer-
tain degree of polymerization, only part of F anions is
eciently eective on the silicate. Therefore it is not
eective to catalyze the condensation of silicate and re-
place the silanol group. Therefore, the hydrothermal sta-
bility of samples prepared via procedure I is signicantly
higher than that of the samples synthesized via proce-
dure II, the mesoporous structure of the former can be
maintained after reuxing in boiling water for 3 days,
however, the mesoporous structure of the latter is col-
lapsed after reuxing in boiling water for 12 h.
In order to further prove the previous explanation,
further investigation was carried out. According to Table
2, one signicant dierence between the uncalcined
MCM-48 obtained via procedure I and procedure II is
that the extent of the unit cell shrinkage during calcina-
tion. Table 2 shows that the samples synthesized via pro-
cedure I show much less shrinkage upon calcination. For
example, the shrinkage of a0 is 11% for the sample syn-
thesized at 120 C for 24 h and a F /Si ratio of 0.1 via
procedure II and 11.3% for the sample prepared without
uoride addition, while the shrinkage of a0 is only 1.2%
for the sample synthesized via procedure I. The less
shrinkage of the unit cell for the samples synthesized
via procedure I with adding NaF with F /Si ratio of
0.1 and 0.2 is as a result of better wall polymerization.
This result indicates that uoride addition via procedure
I really remarkably improves the polymerization of sili-
cate. However, the degree of polymerization of silicate
has not been distinctly enhanced via procedure II. There-
fore, uoride anions directly aect on the silicate via
procedure I, however, uoride ions hardly eciently
aect on silicate to improve the polymerization of silicate
Table 2
Summary of the extent of the unit cell shrinkage (a0)
No. F /Si Na2O/SiO2 As-syn
d211 (A) a0a (A)
1 0.1 0.25 38.5810 87.1553
2 0.1 0.25 38.5139 94.3394
3 0.2 0.25 37.8857 92.8006
4 0.2 0.25 38.2136 93.6038
5 0 0.25 38.1807 93.5232
a
a0 = d21161/2.
b
There is no need to dierentiate between procedure I and procedure II, without uoride ions addition.
via procedure II. The shrinkage of a0 is 6.6% at a F /Si
ratio of 0.2 is higher than 1.2% at a F /Si ratio of 0.1.
The former degree of polymerization of silicate is lower
than that of the latter, which can be used to explain the
reason that the hydrothermal stability of MCM-48,
which was synthesized via procedure I, decreases with
increasing the F /Si ratio from 0.1 to 0.2.
3.2. N2-adsorption analysis
Low-temperature nitrogen adsorption isotherms en-
able the calculation of the specic surface area, pore vol-
ume, and mesopore size distribution. N2 adsorption
isotherms for the calcined MCM-48 materials synthe-
sized with adding dierent contents of NaF via proce-
dure I are shown in Fig. 5, which are typical type IV
adsorption isotherms. Both of the gures show a sharp
inection between relative pressure P/P0 = 0.2 and 0.3
corresponding to capillary condensation within uniform
mesopores. The sharpness of this step reects the
uniform pore size. Also, the initial region can be extra-
polated back to the origin, conrming the absence of
any detectable micropore lling at low P/P0 (P/
P0 < 0.3). Therefore, the very uniform mesopore systems
without micropore structure are observed in the calcined
materials.
The BJH plots of the derivative of the pore volume
per unit weight with respect to the pore diameter versus
the pore volume are shown in the inserted graphs in
Fig. 5. Two very narrow pore size distributions with
the average pore diameter of 2.6 nm and 2.58 nm are ob-
served, respectively. The BET surface areas were
1323.0738 m2/g and 1169.8458 m2/g, respectively. The
BET surface area and pore diameter of MCM-48 pre-
pared at F /Si ratio of 0.1 is larger than that synthesized
at F /Si ratio of 0.2.
3.3. TEM analysis
In order to investigate the pore structure of MCM-48
synthesized with adding NaF via procedure I, TEM of
the calcined-sample was obtained and shown in Fig. 6.
Fig. 6(a) is a TEM images of MCM-48 particle which
Calcined Shrinkage of a0 (%) Procedure
d211 (A) a0a (A)
35.1411 86.0778 1.2 I
34.2683 83.9398 11 II
35.3947 86.6990 6.6 I
34.0044 83.2934 11 II
33.8478 82.9098 11.3 b
 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322 321

Fig. 5. Adsorptiondesorption isotherms of nitrogen at 77 K on calcined MCM-48 synthesized at a Na2O/SiO2 ratio of 0.25 with adding dierent
contents of NaF via procedure I: (a) at F /Si = 0.1, (b) at F /Si = 0.2. The inset shows the BJH pore size distribution calculated from the desorption
branch of the isotherm.

Fig. 6. TEM image of calcined MCM-48 synthesized at a Na2O/SiO2 ratio of 0.25 and a F /Si ratio of 0.1 via procedure I (a) showing the
appearance of particle, and recorded (b) along the [1 0 0] direction, (c) along the [1 1 1] direction, (d) along the [1 1 0] direction.

show a well-dened edge and a spherical shape. High-
resolution TEM images for the selected particle along
the [1 0 0], [1 1 1], and [1 1 0] directions (Fig. 6(b)(d))
match well with the reported MCM-48 images [3134].
Along the [1 0 0] direction the TEM (Fig. 6(b)) shows
uniform pore structures, while along the [1 1 1] direction
(Fig. 6(c)) the image shows a well-dened hexagonal
arrangement. Along the [1 1 0] direction (Fig. 6(d)) a
very regular pattern without irregularities is observed.
Along the [1 0 0] and [1 1 1] directions channels are
322 Y. Shao et al. / Microporous and Mesoporous Materials 86 (2005) 314322
observed. The [1 0 0] and [1 1 1] projections reect the ac-
tual shape and structure of the channels, while the regu-
larity of the TEM image in the [1 1 0] direction in
Fig. 6(d) indicates a uniform channel system. The cubic
unit parameter a can be directly measured as about 87 A
from the hexagonal patterns [31,32] along the [1 1 1]
direction in Fig. 6(c). This is consistent with the XRD
results.
4. Conclusions
It is concluded that the high hydrothermal stable
MCM-48, the mesoporous structure of which can be
maintained after reuxing in boiling water for at least
3 days, with well-dened long-range order of the struc-
ture was easily synthesized at 120 C for 24 h by direct
addition of NaF with F /Si ratio of 0.1 and 0.2 to the
initial reacting gel via appropriate procedure without
post-treatment and pH adjustment. The results of
XRD, N2-adsorption and TEM analyses clearly support
it. The directly adding of NaF with F /Si ratio of 0.07,
0.1 and 0.2 to the reacting gel via appropriate procedure
could lead to high hydrothermally stable MCM-48,
which could maintain their structural integrity after
boiling in water at 100 C for at least 3 days. Addition-
ally, the optimum condition was F /Si ratio of 0.1 at a
Na2O/SiO2 ratio of 0.25. The adding time of NaF is crit-
ical in the formation of this high quality MCM-48. The
dierent results would be obtained via dierent synthesis
procedures. The hydrothermal stability and the meso-
scopic structure of the samples prepared via procedure
I were signicantly higher than that of the samples syn-
thesized via procedure II, the mesoporous structure of
the former could be maintained after reuxing in boiling
water for 3 days, while for the latter, the structure was
collapsed after 12 h reuxing in boiling water, addition-
ally, the structural ordering of the former was higher
than that of the latter. Further study indicated that
the dierent eects of uoride anions were caused at
the dierent reacting periods of synthesizing MCM-48.
The long-range structural ordering and hydrothermal
stability can be improved only when adding NaF at
the early stage of hydrolysis and polymerization of
silicate.
Acknowledgments
This work has been supported by Program for New
Century Excellent Talents in University (NCET-04-
0414); National Basic Research Program of China
(2004CB719500); Shanghai Nanotechnology Promotion
Center (0452nm010).
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