Microporous and Mesoporous Materials 83 (2005) 172180

www.elsevier.com/locate/micromeso

Eect of post-synthesis treatment on the stability

and surface properties of MCM-48 silica
Anne Galarneau a, Marie-France Driole a, Carolina Petitto a, Bich Chiche a,
Barbara Bonelli b, Marco Armandi b, Barbara Onida b, Edoardo Garrone b,
Francesco di Renzo a,*, Francois Fajula a
a
Laboratoire de Materiaux Catalytiques et Catalyse en Chimie Organique, UMR 5618 CNRS-ENSCM, 8 rue Ecole Normale,
F-34296 Montpellier Cedex 05, France
b
Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi 24, I-10129 Torino, Italy

Received 18 September 2004; received in revised form 27 March 2005; accepted 29 March 2005
Available online 4 June 2005

Communication presented at the 4th International Mesostructured Materials Symposium, 14 April 2004, Cape Town, South Africa

Abstract

The eect of post-synthesis hydrothermal treatments on MCM-48 has been studied by 29Si MAS-NMR and IR spectroscopies,
X-ray diraction, thermal gravimetry, and gas volumetry. Special attention has been given to the characterisation of the precursors
before calcination and a method to evaluate the pore opening of MCM-48 from diraction and volumetric data is given. The hydro-
thermal treatment does not aect the organisation of the cetyltrimethylammonium mesophase but extracts a fraction of the surfac-
tant and increases the thickness of the silica wall. The lower area of the silica-surfactant interface after hydrothermal treatment
brings about an improved stability of MCM-48 during calcination and allows the pore size of the precursor to be preserved in
the calcined solid. After calcination, the hydrothermally treated samples are less prone to rehydrate and, as a consequence, their
stability upon storage in moist atmosphere is dramatically improved.

2005 Elsevier Inc. All rights reserved.

Keywords: MCM-48; Stability; Secondary synthesis; Hydrothermal treatment; Vapour treatment; Pore size

1. Introduction early syntheses of MCM-48 poorly reproducible. The

MCM-48 is the cubic Ia3d member of the M41S fa-
mily of mesoporous silicas, obtained by self-assembly
of silicate species and alkyltrimethyl ammonium micelles
[1,2]. It was observed that cetyltrimethyl ammonium
(CTA) is the ideal surfactant to form cylindrical micelles
and favour the synthesis of hexagonal MCM-41 [3,4].
The formation of Ia3d mesophases with CTA is only
possible in a limited eld of conditions, rendering the
*
Corresponding author. Tel.: +33 467163479; fax: +33 467163470.
E-mail address: direnzo@enscm.fr (F. di Renzo).
reliability of the synthesis of MCM-48 was improved
by using gemini dicationic surfactants [3,5] or mixtures
of cationic and non-ionic surfactants [6,7]. Nevertheless,
a careful control of the duration [8] and temperature [9]
of the preparation allows the original synthesis with
CTA to provide reproducible results. Under proper con-
ditions, the use of silica instead of silicon ethoxide as a
reagent has made the MCM-48 synthesis more aord-
able [8,1012].
The resolution of the MCM-48 structure has repre-
sented a landmark in the application of electron micro-
scopy [13] and electron diraction techniques [14,15] to
the characterisation of mesostructured materials. The

1387-1811/$ - see front matter
2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.03.020
 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180
pore network of MCM-48 has been shown to consist in
two interpenetrating 3-D systems of channels separated
by a continuous saddle surface of amorphous silica. The
accessibility of the 3-D pore network renders MCM-48 a
specially promising catalyst support, much less prone to
deactivation than catalysts with mono-dimensional pore
systems. As in the case of other mesoporous silicas, the
thermal and hydrothermal stability of MCM-48 are
important issues for any application [1621].
Huo et al. observed that a post-synthesis hydrother-
mal treatment of MCM-41 or MCM-48 containing sur-
factant improved the structural order and the thermal
stability of the material [3]. The post-synthesis hydro-
thermal treatment was proposed as a method to sepa-
rately optimise the steps of mesophase formation and
wall condensation [22]. In the case of MCM-48, it was
shown that two consecutive hydrothermal treatments
of the as-synthesized solid signicantly increased the
volume and size of the pores as measured after calcina-
tion [12,23]. Brine was also used in hydrothermal treat-
ment [24] and Al-containing MCM-48 was similarly
treated as well [25].
The stabilisation eect has been related to the pH of
the hydrothermal treatment bath, lower than the pH
of the synthesis [12,23,26]. The phenomenon is parallel
to the ordering eect observed when the pH is lowered
during the synthesis [27]. The mechanism of the hydro-
thermal stabilisation has been related to a restructuring
of the pore walls. In the case of MCM-48, this has been
studied by 29Si NMR and related to a decrease of the Q3
signal and a broadening of the NMR signal [24]. In the
case of MCM-41, an increase of the Q3 and Q2 signals
after the hydrothermal treatment has instead been ob-
served [26]. The variations of the silanol fraction mea-
sured by NMR is usually related to the hydrophilic/
hydrophobic properties of the solid, a parameter which
has been considered to inuence the hydrothermal sta-
bility of the M41S materials [21,28,29]. Existing reports
attribute to the MCM-48 a more hydrophilic surface
than to MCM-41 [30].
These data are worth to be veried by using several
techniques on samples prepared with dierent methods.
The aim of this communication is to correlate the stabil-
isation eect of hydrothermal treatment with the prop-
erties of the uncalcined material, at yet studied only by
NMR, and to observe at which point the hydrothermal
treatment aects the surface hydrophilicity of the cal-
cined materials.
2. Materials and methods
The reagents used in the synthesis of MCM-48 have
been fumed silica (Aerosil 200 Degussa), hexadecyl tri-
methyl ammonium bromide (CTAB, Aldrich), sodium
hydroxide (Carlo Erba) and deionised water. The molar
173
ratios of the synthesis batches were 0.38Na/0.175CTAB/
Si/120H2O. The silica source was added to the alkaline
surfactant solution, stirred for 2 h at room temperature,
sealed in a stainless steel autoclave and heated at 423 K
for 4 h without stirring. The solid precipitate was l-
tered, washed, and subjected to two successive post-syn-
thesis treatments in de-ionised water (7.5 g H2O per
gram of solid) at 403 K for 2 h. The as-synthesized solid
and the solids obtained after each hydrothermal treat-
ment are referred to as S, T1, and T2, respectively. All
samples have been dried at 523 K before characterisa-
tion. Samples calcined in air ow at 823 K for 8 h are
indicated by a further letter C.
The samples have been characterised by X-ray dif-
fraction, N2 adsorption at 77 K, thermal gravimetry,
and 29Si MAS-NMR and FTIR spectroscopies. Powder
X-ray diraction was carried out applying a Bruker
AXS D8 diractometer by using Cu Ka radiation and
Ni lter.
The textural properties of calcined sample have been
obtained by N2 adsorptiondesorption isotherms at
77 K measured on a Micromeritics ASAP 2010 volume-
tric apparatus. Prior to the nitrogen adsorption, samples
have been outgassed at 523 K until a static vacuum of
3 10
5 bar was reached. The surface area SBET has
been evaluated by the classical BET method. In the
BET linearisation, care was taken to avoid points at a
pressure high enough for capillary condensation to aect
the adsorption. The pore volume Vp has been measured
as the adsorbed amount after capillary condensation di-
vided by the density of liquid N2. The void fraction e has
been calculated as
Vp
e 1
V p V SiO2
assuming a density 2.2 for the amorphous silica wall
[31].
The determination of the pore diameter D from
adsorption and crystallographic data for the bicontinu-
ous pore system of MCM-48 is less straightforward than
for the independent constant-section pores of MCM-41
[31]. Ravikovitch and Neimark [32,33] have applied to
MCM-48 the Schoens relations between void fraction
and surface area [34] for the gyroid Ia3d structure. Since
the appearing of these articles, the average hydraulical
diameter Dh has often been used to characterise the pore
size of MCM-48. In the case of a system with intercon-
nected pores, the hydraulical diameter Dh is larger than
the cross-section of the individual pores. In this commu-
nication, the diameter D of the pore openings is dened
as twice the curvature radius of the saddle surface and is
related to the cell size a and the wall thickness t by the
equation
a 2D t 2
174 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180
Fig. 1. The Ia3d saddle surface of MCM-48. D pore diameter, t wall
thickness, a cell size (adapted from [35]).
as represented in Fig. 1 (adapted from Ref. [35]). This
equation, coupled to the relation between the average
wall thickness t and the void fraction e
t 0.3234a1
e
from Ref. [32], allows to calculate the pore diameter D
as
a
D 1
0.6481
e
2 ing upon calcination. The shrinking of the cell size upon
The pore diameter calculated in this way can be use-
fully compared to the pore diameter DBDB obtained by
the capillary desorption pressure through the correlation
of Broekho and De Boer for cylindrical pores [36].
Under the assumption that the silica wall present a
constant thickness t and density 2.2, the surface area S
can be calculated as
2  104
S 5
t  qSiO2
where S is expressed in m2 g
1 and t in A [37].
Thermal gravimetry data were collected on a Netzsch
TG209C balance heating the sample at 5 K min
1 up to
1123 K in air ow. The textural properties of the non-
calcined mesophases have been evaluated from the ther-
mogravimetric data under the assumption that the
porosity is completely lled by the surfactant and some
water retained by the polar heads. In the interpretation
of the thermogravimetric data, the mass loss below
373 K has been attributed to water and the mass loss
at higher temperature to the surfactant. The mass ratio
between water and silica, mW, and the mass ratio be-
tween surfactant and silica, mCTA have been calculated
from these data. By assuming a density 1 for water
and a density 0.77 for cetyltrimethylammonium, the po-
tential pore volume of the uncalcined samples can be
evaluated as
V p mW mCTA =0.77 6
and the other textural properties can be obtained by the
equations from (1)(5).
For 29Si MAS-NMR spectroscopy, an ASX 400 Bru-
ker NMR apparatus has been used with 9.4 T eld and
6 kHz MAS. For FTIR measurements, powders have
been pressed into thin self-supporting wafers and spectra
have been collected on a Bruker FTIR Equinox 55 spec-
trometer, equipped with a MCT detector. Wafers have
been outgassed at increasing temperatures, r.t., 423,
573, 773 and 1073 K, in order to study the dehydration
behavior; water has been dosed at r.t. on samples out-
gassed at 773 K, to study their rehydration behaviour.
3. Results
XRD patterns for MCM-48 samples as-synthesized
(S) and submitted to two post-synthesis hydrothermal
treatments (T2) are reported in Fig. 2, before and after
calcination. A letter C characterises the calcined sam-
3
ples, SC and T2C. All samples presented a cubic Ia3d
symmetry. The cell size a is reported in Table 1 for all
samples. It can be observed that the hydrothermal treat-
ment brings about a slight increase of the cell size before
4 calcination and a signicant decrease of the cell shrink-
calcination is 24% for the as-synthesized sample, 12%
for the sample hydrothermally treated once, and 5%
for the sample hydrothermally treated twice.
Thermogravimetric data on the samples before calci-
nation are reported in Table 1. The hydrothermal treat-
ments bring about a slight increase of the amount of
water and a decrease of the surfactant content. The vol-
ume occupied by the cationic surfactant and its hydra-
tion water can be evaluated by assuming that the
hydrocarbon core of the micelles maintains the density
of liquid cetyl. The volume Vp evaluated according to
Eq. (6) corresponds to the benchmark value of the pore
volume that could be liberated by calcination if the silica
network was not aected. This potential pore volume,
reported in Table 1, signicantly decreases with the
hydrothermal treatment, indicating that the decrease
of organic content more than osets the increase of
water content.
The good structural ordering of the MCM-48 sam-
ples allows to evaluate the size of the pore openings D
and the wall thickness t of the uncalcined materials by
using Eqs. (1), (3) and (4). The opening diameter D
slightly increases with the hydrothermal treatments. Sev-
eral early papers on the hydrothermal treatment of
M41S related a signicant increase of the micelle diam-
 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180 175

8000 18000

6000
Intensity (a.u.)

12000

4000

6000
2000

0 0
0 1 2 3 4 5 6 0 0 2 3 4 5 6
(a) deg 2 (b) deg 2

Fig. 2. XRD patterns for MCM-48 as-synthesized (left-hand, S) and submitted to two post-synthesis hydrothermal treatments (right-hand, T2),
before (thinner line) and after (thicker line) calcination.

Table 1
Textural characterisation of MCM-48 as synthesized (S) and hydrothermally treated once (T1) or twice (T2)
Sample a (A) H2O (mass%) CTA (mass%) Vp (cm3 g
1) D (A) DBDB (A) t (A)
S 93.1 3.6 52.2 1.62 40.2 6.7
T1 96.8 5.9 49.5 1.57 41.4 7.0
T2 99.7 5.2 45.8 1.32 41.6 8.3
SC 74.7 0.38 24.2 27.5 13.2
T1C 88.2 0.70 32.9 32.0 11.2
T2C 94.6 0.90 37.0 37.0 10.3
Pore volume and diameter and wall thickness have been calculated from thermogravimetric data in the case of the uncalcined samples and from the
N2 adsorption isotherms at 77 K in the case of the calcined samples, denoted by a C.

eter [3,38]. This eect was later attributed to the partial

degradation of the cationic surfactant, bringing about 600 T2C
the formation of fatty amines which were proven to be
Volume cm g STP

eective swelling agents for micelles [39,40]. The nearly

-1

constant diameter observed in our data suggests that 400 T1C

3

two consecutive hydrothermal treatments at 403 K for

2 h are mild enough to leave virtually unaected the
200
micellar system. However, they are largely sucient to SC
produce important changes in the silica walls. The wall
thickness t increases by nearly 20% after two hydrother-
0
mal treatments. The increase of wall thickness justies 0 0.2 0.4 0.6 0.8 1
the decrease of the amount of organics per unit mass
p/p
of silica and the corresponding increase of Vp.
It can be observed that the calculation of the textural Fig. 3. Eects of the hydrothermal treatment. N2 adsorptiondesorp-
parameters of the uncalcined materials by using Eq. (1) tion isotherms at 77 K on MCM-48 calcined at 823 K after synthesis
implies the hypothesis of constant density of the silica (SC) and one or two further hydrothermal treatments (T1C and T2C,
respectively).
wall. The common density value for amorphous silica,
2.2, has been used in the calculations. The density value
used is not very critical and variations of less than 1 A in mal treatments. The isotherms indicate that the
both diameter and wall thickness are calculated if densi- adsorbed amount and the pressure of capillary conden-
ties as high as the 2.55 value suggested by Tanaka [41] sation are signicantly increased by the hydrothermal
are taken into account. treatments.
In Fig. 3, the adsorptiondesorption isotherms of N2 In Table 1, the pore volume Vp measured from the
at 77 K are reported for samples calcined after the syn- isotherms of Fig. 3 is reported, together with the dia-
thesis (SC) and after one (T1C) or two (T2C) hydrother- meter of the pore openings D and the wall thickness
176 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180
t calculated from the pore volume and the diraction
data. The pore volume of the calcined solids can be com-
pared with the potential pore volume of the correspond-
ing uncalcined samples, also reported in Table 1. The
MCM-48 not submitted to hydrothermal treatments
loses on calcination 76% of the volume of the micellar
system, while the sample submitted to one hydrothermal
treatment loses 55% volume and the sample submitted
to two hydrothermal system loses only 32% of the micel-
lar volume. The loss of volume upon calcination corre-
sponds to the observed shrinking of the unit cell and
to an increase of the wall thickness. In the case of the
sample not submitted to any hydrothermal treatment,
calcination brings about a twofold increase of the wall
thickness. Hydrothermally treated samples present a
lower increase of wall thickness upon calcination: less
than 20% in the case of the twice hydrothermally treated
MCM-48.
The diameter D calculated as twice the curvature ra-
dius of the saddle silica surface can be compared to the
diameter DBDB obtained from the pressure of the capil-
lary desorption step, also reported in Table 1. In the case
of porous systems with windows and interconnections,
as the 3-D pore system of MCM-48, the capillary
desorption is assumed to provide a fair evaluation of
the size of the narrower pore openings. The good agree-
ment between the D and DBDB values reported in Table 1
suggests that the model of Broekho and De Boer pro-
vides a fair evaluation of the size of pore openings in
MCM-48 as it does in MCM-41 [31].
In a general way, the data of Table 1 indicate that cell
size, pore volume, pore diameter and wall thickness are
largely aected by calcination in the absence of any
post-synthesis hydrothermal treatment, while these
parameters are scantily aected by calcination after
two hydrothermal treatments. Both hydrothermal treat-
ment and calcination bring about an increase of wall
thickness and a decrease of pore volume, but it is clearly
Fig. 4. 29Si MAS-NMR of MCM-48 as synthesized (S) and hydrothermally treated once (T1) and twice (T2) (left hand graph). Right hand graph:
same samples after calcination at 823 K.
observed that a small increase of wall thickness and de-
crease of pore volume during the hydrothermal treat-
ment in the presence of the surfactant can prevent a
much larger increase of wall thickness and decrease of
pore volume when the surfactant is eliminated by
calcination.
The higher stability of hydrothermally treated M41S
has been attributed to a better cross-linking of their sil-
ica walls [22,25]. Does this eect correspond to a change
of connectivity of the silica tetrahedra inside the walls
or does it simply correspond to the increase of wall
thickness and the corresponding decrease of the ratio
between surface silanols and fully bonded silica tetrahe-
dra inside the walls? 29Si MAS-NMR can provide quan-
titative data about the broken links in silica, be they due
to point defects or to the interruption of the network at
the pore surface. The 29Si MAS-NMR spectra are re-
ported in Fig. 4 and the results of their deconvolution
are reported in Table 2 as the fraction of silicon atoms
featuring two silanols (Q2) or one silanol (Q3).
The 29Si NMR data indicate that both hydrothermal
treatment and calcination bring about an increase of the
degree of condensation of silica, evidenced by the lower
fraction of Q2 and Q3 silicon atoms. The molar fraction
of silanols as measured by NMR is reported in Table 2
for all samples. It is interesting to observe that the de-
crease of the silanol fraction during the hydrothermal
treatment virtually prevents any further condensation
to occur upon calcination, in the case of the twice hydro-
thermally treated sample. This trend closely parallels the
observed evolution of wall thickness and pore volume
(Table 1).
The increase of wall thickness corresponds to a de-
crease of the surface area of the sample, a parameter
which has been evaluated by the monolayer volume of
adsorbed N2 in the case of the calcined samples and
from the micelle volume and the cell parameter in the
case of the uncalcined samples. The surface area data
 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180
Table 2
29
Surface characterisation and Si MAS-NMR data for MCM-48 as synthesized (S) and hydrothermally treated once (T1) or twice (T2)
Sample S (m2 g
1) SBET (m2 g
1)
S 1365
T1 1296
T2 1101
SC 590
T1C 950
T2C 1082
Surface areas have been calculated from thermogravimetric data in the case of the uncalcined samples and from the N2 adsorption isotherms at 77 K
in the case of the calcined samples, denoted by a C.
and the silanol fractions measured by NMR, both re-
ported in Table 2, present a similar trend of evolution
with hydrothermal treatment and calcination.
In the case of the uncalcined samples, the evolution of
the silanol content and of the surface area with the
hydrothermal treatment are so similar that the number
of silanols per unit area can be considered independent
of the number of hydrothermal treatments. This proba-
bly indicates that the polarity of the environment of the
cationic heads of the surfactant is scantily modied by
the hydrothermal treatment. In the case of the calcined
samples, the increase of surface area for samples sub-
jected to previous hydrothermal treatment is signi-
cantly higher than the increase of silanol content. This
indicates that the number of silanols per unit area is
probably lower for samples calcined after an hydrother-
mal treatment, despite their higher molar fraction of sil-
anols. It is clear that a comparison with the surface area
is needed for any interpretation of NMR data on the
degree of condensation of silica.
Information on the nature of the silanols can be pro-
vided by IR spectroscopy. Two kinds of measurements
have been carried out on samples calcined directly after
synthesis (SC) or after two hydrothermal treatments
(T2C):
(a) outgassing treatments at increasing temperature
provide information on the dehydration behavior,
(b) water dosage on samples outgassed at 773 K pro-
vides information on the rehydration behavior.
In order to allow comparison among dierent sam-
ples, IR spectra have been normalized at constant opti-
cal thickness (ratio between mass of the sample and area
of the wafer).
In Fig. 5, the IR spectra in the silanol region are re-
ported for samples outgassed at 298, 423, 573, 773 and
1073 K, respectively. On the samples outgassed at room
temperature, at least four silanols species occur at the
surface, like those commonly observed on silicas: free
silanols absorbing at 3743 cm
1; silanols interacting
via hydrogen bonding, giving two absorptions at 3710
and 3550 cm
1 and silanols species absorbing at
3660 cm
1, assigned to intra-particles or defective sila-
177
CBET Q2/Si Q3/Si OH/Si
0.03 0.50 0.56
0.04 0.48 0.56
0.00 0.40 0.40
77 0.02 0.28 0.32
82 0.00 0.37 0.37
78 0.00 0.33 0.33
nols. It is interesting to note that the band of free
silanols is present even after room temperature out-
gassing. This band, however, is slightly downward
shifted for the sample SC. The post-treated sample
shows more intense bands due to surface silanols, in
good agreement with the NMR results and the higher
surface area.
The spectra of the samples outgassed at 423 K do not
dier very much from those outgassed at room temper-
ature. By increasing the temperature of the treatment, a
progressive surface dehydroxylation occurs, as expected.
The intensity of the isolated silanol passes through a
maximum, due to the faster disappearing of interacting
silanols. In all cases, the post-treated sample shows more
intense silanol bands. The dierence in intensity between
as-synthesized and post-treated sample increases when
outgassing is carried out at higher temperature. The
spectra recorded after outgassing at 1073 K are espe-
cially interesting: the spectra of the post-treated sample
still presents a band of isolated silanol nearly as intense
as after outgassing at room temperature, while the spec-
tra of the as-synthesized sample presents virtually no
more measurable silanols, indicating the complete ther-
mal collapse of the solid.
In order to study the tendency to rehydration, water
vapour has been dosed by increasing the equilibrium
pressure on samples previously outgassed at 773 K. In
Fig. 6, the normalized spectra recorded under the equi-
librium pressure of 5 mbar are reported in the water
bending mode range.
Water dosage gives rise to the formation of a band
around 1620 cm
1, which is readily assigned to water
molecules interacting with isolated silanols. The inten-
sity of this band may be considered as a semi-quantita-
tive measure of the hydrophilicity of the sample, the
more intense the band the more hydrophilic the surface.
With this respect, post-treated and treated samples seem
to adsorb similar amounts of molecular water. The post-
treated sample T2C presents nearly twice the surface
area of the untreated sample SC (Table 2). If the surface
area is taken into account, the uptake of water per unit
surface seems to be much lower on the post-treated sam-
ple. The band of interacting water in the post-treated
sample is signicantly narrower than the corresponding
178 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180

2.5 2.5

2 2

Absorbance

Absorbance
298 K 423 K
1.
1.5 1.5

1 1

0.5 0.5

0 0
3
3800 3600 3400 3200 3800 3600 3400 3200
Wavenumbers (cm-1) Wavenumbers (cm-1)

3.5 4.5

773 K
573 K 3.5
Absorbance

2.5

Absorbance
2.5
1.5
1.5

0.5 0.5

-0.5 -0.5
3700 3500 3300 3800 3700 3600

Wavenumbers (cm-1) Wavenumbers (cm-1)

3.5

1073 K
2.5
Absorbance

1.5

0.5

-0.5
3800 3750 3700
Wavenumbers (cm-1)

Fig. 5. Dehydration behavior. IR spectra of MCM-48 calcined after synthesis (SC, thinner line) and after two hydrothermal treatments (T2C, thicker
line). Outgassing temperature: 298, 423, 573, 773 and 1073 K, respectively.

band in the untreated sample. This suggests that the

0.4
post-treated sample presents a lesser variety of adsorp-
tion sites and a more homogeneous surface. Moreover,
on sample T2C another band is seen at about
Absorbance

1700 cm
1, which is assigned to the formation of water

clusters.
0.15
The IR data suggests that the number of silanols per
unit area is lower for samples calcined after two hydro-
thermal treatments. Indeed, the post-treated sample
seems less prone to rehydrate. Such a behavior can sig-
-0.1
1700 1600 1500
nicantly alter the hydrothermal stability of the sample
Wavenumbers (cm-1) and also the stability of the samples in common storage
conditions can be aected. In Fig. 7, adsorptiondesorp-
Fig. 6. Rehydration behavior. IR spectra of MCM-48 calcined after
synthesis (SC, thinner line) and after two hydrothermal treatments
tion isotherms of N2 at 77 K are reported for samples
(T2C, thicker line) equilibrated with 5 mbar water vapour after calcined directly after synthesis or calcined after two
outgassing at 773 K. hydrothermal treatments and kept in moist atmosphere
 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180
300
Volume cm 3 g-1 STP 1 day
200
6 months
100
0 0
0 0.2 0.4
p/p
Fig. 7. Eect of the hydrothermal treatment on the stability upon storage of calcined MCM-48. N2 adsorptiondesorption isotherms at 77 K
measured the indicated time after calcination at 823 K for a sample calcined after no hydrothermal treatment (SC, left hand) or two hydrothermal
treatments (T2C, right hand).
at room temperature in closed vials for periods as long
as 1 year.
The texture of the untreated sample was extremely
unstable under the storage conditions. The pore volume
after 6 month storage was half the initial value, the pore
size distribution has broadened and its centre has shifted
to much larger values. The average pore size passed
from the initial 24 A to 65 A after 6 month storage
and 110 A after 10 months. In the meantime, the surface
area passed from the initial 590 m2 g
1 to 240 m2 g
1
after 6 months and 90 m2 g
1 after 10 months. This evo-
lution probably corresponds to a mechanism of collapse
of the pore walls which decreases the surface exposed to
N2 and opens large disordered cavities by merging of the
original ordered mesopores.
In the case of the sample calcined after two hydro-
thermal treatments, no evolution of this kind is ob-
served, and virtually no textural evolution at all. After
1 year storage in moist atmosphere the pore size distri-
bution of the sample is unchanged and less than 10%
pore volume is lost.
4. Conclusions
Silica-surfactant Ia3d mesophases usually present
such a large exposed silica surface that their stability
in any kind of thermal treatment is necessarily poor
[8]. When the thermal treatment corresponds to the
elimination of the surfactant, as in the case of calcina-
tion, the decrease of the exposed silica surface corre-
sponds to a signicant shrinking of the pore structure.
On the contrary, if a thermal treatment is carried out
in the presence of the surfactant template, as in the case
of the hydrothermal treatment, the area of the silica-sur-
factant interphase can decrease without aecting the
pore system, which is preserved by the surfactant scaf-
179
600 1 day
1 year
400
200
10 months
0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
p/p
folding. The hydrothermal treatment signicantly im-
proves the stability of the materials during calcination,
as the pore size and volume of the precursors can be lar-
gely preserved and the structure shrinking is virtually
eliminated.
How this stabilisation eect can be accounted for?
Has it to be attributed to a special organisation of the
silica network inside the walls or can it be justied by
the pure geometrical decrease of the fraction of exposed
silica due to the increased wall thickness? The NMR and
IR data do not provide any compelling evidence of spe-
cial organisation of the walls and of the surface, as the
nature of surface silanols is not changed by the hydro-
thermal treatment and the fraction of silanols in the
sample is essentially proportional to the surface area.
It is likely that the improved stability mainly depends
on the increased wall thickness. In the case of MCM-
41, it has been suggested that the degradation of the
porosity is triggered by the local opening of windows be-
tween mesopores [37]. The edge of these openings pre-
sents a positive curvature, and the instability of such a
surface allows the local defect to grow and destroy the
structure. If a similar mechanism can be active also in
MCM-48, the stabilizing eect of wall thickness could
be easily justied. Any increase of wall thickness may
correspond to a more than linear decrease of the proba-
bility of window openings and of the consecutive unzip-
ping of the wall.
In this respect, the IR data on the rehydration beha-
vior of the calcined samples are especially signicant.
They suggest that the hydrothermally treated samples
present a more homogeneous surface, probably corre-
sponding to the virtual absence of the local defects
which are formed during the direct calcination of the un-
treated precursor. The higher local order of the materi-
als probably contributes to the long-lasting stability of
hydrothermally treated samples in conditions in which
180 A. Galarneau et al. / Microporous and Mesoporous Materials 83 (2005) 172180
the untreated materials undergo important hydrolysis
and pore merging.
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