Colloids and Surfaces

A: Physicochemical and Engineering Aspects 187– 188 (2001) 109– 116

www.elsevier.nl/locate/colsurfa

MCM-41, MCM-48 and related mesoporous adsorbents:

their synthesis and characterisation
D. Kumar, K. Schumacher, C. du Fresne von Hohenesche *, M. Grün,
K.K. Unger
Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Uni6ersität, Duesbergweg 10 – 14,
55128 Mainz, Germany

Abstract

MCM-41, MCM-48, MCM-41 analogue materials and disordered silica xerogels were compared with respect to
their long range and short range order, their specific surface area, pore structure and pore structural parameters, pore
wall thickness and their surface hydroxyl group concentration. Based on X-ray diffraction data it could be seen that
the degree of long range order decreased in the order MCM-41 \ MCM-48\ MCM-41 analogues \ amorphous
silica xerogels. The particle porosity and pore wall thickness increased in the same sequence such that MCM-41
analogues and amorphous silica xerogels were more stable towards water and water vapour. The concentration of the
surface hydroxyl groups increased when moving from MCM-41 to amorphous silica xerogels from 3 mmol OH per m2
(MCM-41, MCM-48) to 5–6 mmol OH per m2 (MCM-41 analogue) and 8 – 9 mmol OH per m2 (amorphous silica
xerogel). Rehydroxylation of the materials (after calcination at 823 K) resulted in the loss of periodic structure for
MCM-41. In contrast to this, the MCM-41 analogue retained both its periodic structure and the concentration of
surface hydroxyl groups, hOH. © 2001 Elsevier Science B.V. All rights reserved.

Keywords: Ordered mesoporous silicas; MCM-41; MCM-48; Silica polymorphs

1. Introduction aims being the synthesis of novel adsorbents with

Since the discovery of the M41S family of
ordered mesoporous adsorbents by scientists at
Mobil Oil [1], these materials have attracted con-
siderable attention with respect to understanding
the formation mechanism, with one of the major
* Corresponding author. Tel.: + 49-6131-3924679; fax: +
49-6131-3922710.
E-mail address: cedric@ak-unger.chemie.uni-mainz.de (C.
du Fresne von Hohenesche).
tailor-made properties. The key to form such
adsorbents is to use organic templates, which
form organic –inorganic mesophases. The two
most investigated materials, MCM-41 with a 2-D
hexagonal structure and MCM-48 with a 3-D
cubic structure, are synthesised using n-alkylam-
monium salts as templates [2,3]. A range of tem-
plates have since been employed for the synthesis
of ordered mesoporous silicas, such as non-ionic,
polar, low molecular weight compounds, e.g. n-
alkylamines [4,5], and polymers and co-polymers

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110 D. Kumar et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 187–188 (2001) 109–116
[6,7]. We have recently used functionalised
polyethylene oxide homopolymers in the synthesis
of mesoporous silica nanobeads [8].
The classical synthesis procedures have been
modified by using novel silica precursors (n-
alkoxysilanes) rather than using sodium water
glass or Aerosil, to perform the synthesis over the
whole pH range [9] and at room temperature
[9,10]. Another aim was to extend the pore size
from 4 nm to larger mesopores [11]. By combining
the template-assisted synthesis with elements of
the Stöber reaction [12], we were able to manufac-
ture spherical mesoporous silicas with an average
particle diameter between 10 nm and 2 mm [13].
Although all materials are collectively named as
ordered mesoporous silicas, there are distinct dif-
ferences in their bulk structure and surface chem-
istry, which are reflected in their chemical
behaviour, for example their stability towards wa-
ter. In this study, we attempt to classify meso-
porous silicas ranging from highly ordered
classical MCM-41 and MCM-48 to a disordered
amorphous silica xerogel. Our aim is to character-
ise mesoporous silicas by various physico-chemi-
cal methods and to assess differences in their bulk
and surface properties with respect to disordered
silicas.
2. Experimental
2.1. Synthesis
2.1.1. Classical synthesis of MCM-41
Classical MCM-41 material was synthesised by
dissolving 2.4 g of n-cetyltrimethylammonium
bromide (Aldrich, Steinheim, Germany, 6.6
mmoles), CTAB, in 120 g of deionised water and
stirring until the solution was homogeneous and
clear. After adding 8 ml of ammonium hydroxide
(Merck KGaA, Darmstadt, Germany, 32 wt.%),
the mixture was stirred for 5 min after which 10
ml of TEOS (Merck KGaA, Darmstadt, Ger-
many) were added. The molar composition of the
gel was 1 M TEOS:1.64 M NH4OH:0.15 M
CTAB:126 M H2O. The reaction was stirred
overnight after which the solution was filtered and
washed consecutively with deionised water and
ethanol. Calcination was performed at 823 K for
5 h.
2.1.2. Con6entional hydrothermal synthesis
MCM-48 was synthesised by the conventional
hydrothermal pathway similar to the procedure
described by Monnier et al. [14]. CTAB was dis-
solved in deionised water, then sodium hydroxide
and TEOS (Merck KGaA, Darmstadt, Germany)
were added. The molar composition of the gel was
1 M TEOS:0.25 M Na2O:0.65 M CTAB:0.62 M
H2O. The solution was stirred for 1 h, charged
into a polypropylene bottle and heated at 383 K
for 3 days. The product was filtered, washed with
water and calcined at 823 K for 6 h.
2.1.3. No6el synthesis of MCM-48 spheres at
room-temperature
CTAB (Aldrich, Steinheim, Germany, 2.4 g, 6.6
mmoles) was dissolved in 50 g deionised water. To
this, 50 ml technical grade ethanol (Merck KGaA,
Darmstadt, Germany, 0.87 moles) and 12 ml of
aqueous ammonia (Merck KGaA, Darmstadt,
Germany, 32 wt.%, 0.20 moles) were added. The
solution was stirred for 10 min, after which 3.4 g
of TEOS (Aldrich, Steinheim, Germany, 98%, 16
mmoles) were added. The molar composition of
the gel was 1 M TEOS:12.5 M NH4OH:54 M
EtOH:0.4 M CTAB:174 M H2O. After stirring for
2 h at room temperature the resulting solid was
recovered by filtration, washed with deionised wa-
ter and dried in air at ambient temperature. The
template was removed by calcination at 823 K for
6 h.
2.1.4. Synthesis of MCM-41 analogue silica
beads
About 5.1 g of n-hexadecylamine (tech. 90 %,
Aldrich, Steinheim, Germany) was dissolved in a
mixture of 500 ml isopropanol (p.a., Merck
KGaA, Darmstadt, Germany) and 450 ml of
deionised water at room temperature. After this, 6
ml of aqueous ammonia (32 wt.%) was added.
Then 29 ml tetraethoxysilane (TES 28 SQ, Merck
KGaA, Darmstadt, Germany) were added while
stirring and the reaction mixture was left
overnight. The product was isolated by filtration.
Removal of the template was performed either by
 D. Kumar et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 187–188 (2001) 109–116
solvent extraction in isopropanol or by calcination
at 823 K for 5 h.
2.1.5. Post-synthetic treatment
The extracted material was calcined in a shallow
bed in a furnace (N 100, Nabertherm, Lilienthal,
Germany) at 823 K for a period of 5– 6 h with a
heating rate of 1 K per min. The rehydroxylation
was performed by refluxing the calcined sample in
hydrochloric acid (18.5 % w/w) for a period of
12 h.
2.2. Characterisation
X-ray powder diffraction data of the MCM-48
material were collected on a Seiffert TT 3000
diffractometer using CuKa radiation at a wave-
length 0.154 nm. XRD patterns were obtained
between 0.5 and 10 2 U with a scan speed of 1° per
min.
Adsorption and desorption isotherms were mea-
sured at 77 K on a Quantachrome Autosorb 6B
(Quantachrome Corporation, Boynton Beach, FL,
USA) using nitrogen. The samples were outgassed
at 423 K and 1 mPa for 14 h before adsorption
measurements.
Scanning electron micrographs were obtained
using a Zeiss DSM 962 scanning electron micro-
scope (Zeiss, Jena, Germany). Samples were de-
posited on a sample holder with an adhesive carbon
foil and sputtered with gold.
The concentration of surface hydroxyl groups
(hOH) was determined by means of isotopic ex-
change with deuterated trifluoracetic acid followed
by 1H-NMR spectroscopy according to the method
of Holik and Matêjková [15]. A detailed description
of the method can be found in the literature [16].
In comparison to this method, the silanol group
concentration was also calculated via the mass loss
between 200 and 1000°C measured by thermogravi-
metric analysis [16].
3. Results and discussion
3.1. Sur6ey of the synthesis approaches employed
and materials obtained
While the first classical procedures to synthesise
111
MCM-41 and MCM-48 were based on a hydrother-
mal reaction in autoclaves, a number of successful
attempts were undertaken to carry out the reaction
at room temperature [9,10]. We reported a room
temperature synthesis of a MCM-41 analogue
using a long-chain n-alkylamine as the template
and ammonium hydroxide (pH 10) that yielded
a highly reproducible product with respect to the
specific surface area and the pore structural
parameters [17]. Furthermore, the procedure was
found to be extremely rugged [18], and therefore,
employed as a standard procedure to prepare
mesoporous silicas in the framework of an EU
project on Mesoporous Solids (MESOP, Contract
No. ERB 4061-PL95-1357) with seven research
partners.
Although most of the ordered mesoporous silicas
are obtained as loose agglomerated powders with
low mechanical stability, efforts were undertaken
to control the morphology of the materials. Several
products have been produced as fibres, thin films
and particles with spherical morphology [19].
Our studies were focused on the synthesis of
nanometer to micrometer sized silica beads using
tetraethoxysilane as the silica source, n-hexadecy-
lamine as the template and ammonium hydroxide
(pH  10) as the morphological catalyst. Within
the first few minutes of the synthesis, a suspension
of white absolutely spherical particles was formed
[13].
The formation of the micron sized beads is
assumed to take place through nucleation and
growth of nanoparticles until the solution is super-
saturated and the particles finally precipitate. Once
the reaction is complete, the template is removed
by calcination, yielding porous particles of approx-
imately 4 nm average pore diameter and a control-
lable sphere diameter of 0.5–2.0 mm. Small changes
in the composition of the reaction mixture, impu-
rities in the reactants and alteration of the reaction
temperature gave particles that deviate from being
spherical (see Fig. 1). As demonstrated in Fig.
1(a–d), the particle morphology is extremely sensi-
tive to changes in the reaction conditions. As
discussed in the next paragraphs, the material is
significantly different from classical MCM-41 and
is, therefore, termed a MCM-41 analogue.
112 D. Kumar et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 187–188 (2001) 109–116

3.2. Bulk structure and crystallinity of
mesoporous silicas
Hexagonal (MCM-41) and cubic (MCM-48)
mesoporous silicas are examples of highly peri-
odic silica phases. This is reflected by the X-ray
diffraction pattern at low 2 U angles. Fig. 2
displays a comparison of four mesoporous silicas
with different degrees of crystallinity. While the
microporous Silicalite-1 of MFI-type structure
shows a highly distinct pattern reflecting the short
and long range orders, respectively, the X-ray

Fig. 1. SEM photographs of MCM-41 analogue material deviating from spherical morphology, (a) beads with extended fibrous fines,
(b) intergrown spherical particles, (c) twins, triplets and agglomerated beads, (d) non-spherical, irregularly shaped particles.
 D. Kumar et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 187–188 (2001) 109–116 113

Fig. 2. X-ray diffraction patterns of differently ordered porous phases, (a) Silicalite-1, (b) MCM-48, (c) MCM-41, (d) MCM-41
analogue.

pattern of MCM-41 gives up to five Bragg peaks,
similar to that of MCM-48. The two species ex-
hibit long range order. The MCM-41 analogue
made according to the method of Grün et al. [13]
gives only one broad peak, which is indicative of
a less ordered material. Disordered amorphous
silica xerogel shows a broad peak in the X-ray
diffraction pattern.
3.3. Specific surface area and pore structure
Table 1 lists the specific surface areas and the
range of pore structural parameters of micropo-
rous Silicalite-1 and various mesoporous silicas.
When using low molecular weight surfactants
MCM-41 and MCM-48, respectively, possess high
specific surface areas and high specific pore vol-
umes. The former can reach values up to 1200 m2
g − 1 in the case of MCM-41. The pore structure of
MCM-41 and MCM-48 is highly uniform; MCM-
41 exhibits a unidirectional pore system composed
of a regular hexagonal array of tubes. MCM-48
has a three dimensional pore system with two
non-intersecting gyroidal pores. The MCM-41
analogue does not posses a highly regular pore
structure and resembles more a random close
packing of nanoparticles. This structure, however,
needs more in depth investigation [20]. The re-
114 D. Kumar et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 187–188 (2001) 109–116

Table 1
Comparison of bulk structure, specific surface area and pore structural parameters of ordered and disordered silicas

Material Crystallinitya as (BET)b (m2 g−1) 6p (G)c (ml g−1) pd (BJHDes)d (nm)

MFI (Silicalite-1) Short and long range order 500 0.2 –

MCM-41 Long range order \1000 \1.0 2–9
MCM-48 Long range order \1000 \1.0 2–4.5
MCM-41 analogues Some long range order 300–1000 0.2–0.7 4–10
Silica xerogels Amorphous 50–1000 0.2–4.0 1–50

a
Based on X-ray diffraction pattern.
b
Specific surface area according to Brunnauer, Emmet and Teller [21].
c
Specific pore volume according to Gurvitch [21].
d
Average pore diameter computed from the nitrogen desorption branch using the method of Barret, Joyner and Halenda [21].

striction of the average pore diameter to small
mesopores of approximately pd 4 nm has been
overcome either by hydrothermal treatment of the
native material [24] or by using polymeric tem-
plates [11]. When comparing the as (BET) and 6p
(G) values of the MCM-41 analogue material
with the data for MCM-41 and MCM-48, respec-
tively, it is seen that the values of the specific
surface area and the specific pore volume are
much lower for the analogue, thus resembling a
disordered silica xerogel.
One important parameter, which is linked to
the pore structural parameters is the pore wall
thickness. This property can be calculated from
XRD and capillary condensation data. For
MCM-41, the pore wall thickness varies between
0.8 and 1.2 nm [22]. MCM-48 exhibits values
between 0.8 and 1.0 nm [23]. For the MCM-41
analogue a value of about 2 nm was calculated
[24]. The pore wall thickness is proportional to
the stability of mesoporous silica to water or
water vapour. MCM-41 is not stable towards
water and the structure collapses. The MCM-41
analogue material does not show changes in the
nitrogen isotherm before and after exposure to
water (data not shown). In other words this
means that a less ordered bulk structure favours
the stability towards water.
3.4. Surface hydroxyl group concentration of
mesoporous silicas
Very little attention has been paid to the degree
of hydroxylation of the surface of ordered meso-
porous silicas and their dehydroxylation/rehy-
droxylation behaviour. Dehydroxylation of silica
xerogels by calcination followed by rehydroxyla-
tion (treatment with hydrochloric acid) was re-
cently studied by Grossmann et al. [25]. Starting
from a fully hydroxylated surface with 8– 9 mmol
OH per m2 [26], the hOH value decreased with an
increase in the calcination temperature. Upon an-
nealing the samples to 873 K, rehydroxylation by
treatment with 18.5% w/w hydrochloric acid was
fully reversible. At about 1073 K the value of
hOH = 8–9, however, could not be achieved by
rehydroxylation. In contrast to amorphous silica
xerogels, Silicalite-1 is more hydrophobic and
possesses only a few hydroxyl groups at the outer
surface of the crystals. Using deuterium exchange
with deuterated trifluoracetic acid and 1H-NMR
spectroscopy [15], we measured the hOH value of a
Table 2
Comparison of surface hydroxyl group concentration, hOH, of
ordered and disordered silicas in their native state
Material hOH (mmol m−2)
MFI (Silicalite-1) Hydroxyl nests in bulk
MCM-41 2–4
MCM-48 3
MCM-41 analogues 5–6
Silica xerogels 8–9
 D. Kumar et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 187–188 (2001) 109–116
Table 3
Effect of rehydroxylation on mesoporous silicas
Material hOH (mmol hOH (mmol m−2) afterb
m−2) beforea
MCM-41 2–4 5, loss in structure
MCM-41 5–6 5–6, structure and
analogues morphology of beads
unchanged
Silica xerogels 8–9 8–9
a
Samples were calcined at 823 K for 5 h (see Section 2).
b
Samples were subjected to rehydroxylation (see Section 2).
series of mesoporous silicas (see Table 2). MCM-
41 and MCM-48 showed a similar hOH-value of
approximately hOH =3 mmol OH per m2 in their
calcined state. The MCM-41 analogue material
made according to the procedure described Grün
et al. [13] had a distinctly higher value of 5–6
mmol OH per m2, which was 40% lower than that
of the hOH value of amorphous silica xerogels.
Rehydroxylation by treatment with hydrochloric
acid under reflux gave distinctly different results
for MCM-41 and MCM-41 analogues (see Table
3). The rehydroxylated MCM-41 showed an hOH
value of 5 mmol OH per m2, which is slightly
higher than that in the native form. However,
most remarkable was the observation that its
periodic structure was lost. Astonishingly, the hOH
value of the MCM-41 analogue beads remained
unaffected by the rehydroxylation treatment.
Also, its X-ray diffraction pattern and the mor-
phology of the beads were unchanged. This
clearly indicates that the highly ordered MCM-41
materials are unstable to treatment with water
and acids, whereas its less ordered analogues are
more stable.
4. Conclusion
The comparison between ordered, less ordered
and disordered mesoporous silicas indicate that
clear trends can be seen in qualitative terms.
The loss in periodic structure is accompanied
by an increase in the degree of hydroxylation of
the surface and hence an enhancement of the
hydrophilic character. Moreover, the less ordered
115
mesoporous silicas are far more stable towards
dehydroxylation/rehydroxylation procedures (up
to a calcination temperature of approximately 873
K) than MCM-41.
Exceeding the pore wall thickness of about 1
nm, which is typical for MCM-41 and MCM-48,
respectively, makes the products much more sta-
ble against water and water vapour as found for
the MCM-41 analogue materials.
Acknowledgements
The authors would like to thank the EU for
funding within the framework of the TMR project
ERB 4061-PL95-1357.
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