Journal of Non-Crystalline Solids 353 (2007) 194199

www.elsevier.com/locate/jnoncrysol

Structural evolutions of hydrothermally prepared mesostructured

MCM-48 silica using dierently manufactured amorphous
silica powders
U.S. Taralkar, R.K. Jha, P.N. Joshi *

Catalysis Division, National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune, Maharashtra 411 008, India

Received 21 January 2006

Available online 17 November 2006

Abstract

The hydrothermal synthesis of Si-MCM-48 mesoporous molecular sieves was carried out using a ternary SiO2:CTAOH:H2O system
wherein dierently manufactured amorphous silica powders such as fumed silica (FMDS), spray dried precipitated silica (SDPS) and
ash dried precipitated silica (FDPS) were used as silica source materials. The changes in structural/textural properties were evaluated
using powder XRD, N2 adsorptiondesorption and scanning electron microscopy techniques. Studies on the progressive development of
MCM-48 mesophases revealed that, the reactivity of the silica source follow the trend: FMDS > SDPS > FDPS. MCM-48 synthesized
using low cost FDPS has exhibited thicker pore walls but poorer orderness, while MCM-48 prepared from relatively expensive FMDS
has thinner pore walls and more ordered structure. Moreover, the extent of contraction caused by calcinations, agglomerate size and
structural stability were found to depend on the reactivity of the silica source used.
2006 Elsevier B.V. All rights reserved.

PACS: 61.43.Gt; 61.43.j; 81.20.Be; 81.20.Fw; 61.10.Nz

Keywords: Scanning electron microscopy; Micelles; Silica; Silicates; Solgels (xerogels); Long-range order; X-ray diraction

1. Introduction
The discovery of a family of mesoporous silicates,
denoted as M41S, [1,2], has brought about the beginning
of a new age in the eld of material synthesis. Although,
these materials possess regular arrangement of uniform
channels, the atomic arrangement in these materials is
not crystalline. The pore walls are amorphous in nature.
Since surfactant chemistry is the key to the formation of
these mesostructured silica, the silicate species in solution
play an important role in the organizing the surfactant
molecules and in governing the extent of the electrostatic
interactions between the inorganic and surfactant ions.
By virtue of large internal surface area, high thermal stabil-
*
Corresponding author. Tel./fax: +91 20 25890976.
E-mail address: pn.joshi@ncl.res.in (P.N. Joshi).
ity and favorable uniformity but easily tunable pore size of
these materials, great eorts has been devoted to funda-
mental studies of sorption, ion-exchange, the formation
of intrachannel metal, metal oxide, semiconductor clusters
and inclusion of various metal complexes and other guests
[3]. Moreover, these materials have proved their potential
candidature in variety of applications in the elds of catal-
ysis, sorption, separation, optics, electronics and sensors
[4]. Among the members of M41S family, MCM-48 is
known to present a unique cubic arrangement of three-
dimensional mesopores. The silicate framework of MCM-
48 shows no long-range order in the sense of a crystalline
material and contains considerable amount of silanol
groups. In view of these structural peculiarities, MCM-48
was found to be very interesting and promising catalyst/
catalyst support, adsorbent, sensor and an excellent inor-
ganic template for the synthesis of nanostructures [512].

0022-3093/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2006.10.005
 U.S. Taralkar et al. / Journal of Non-Crystalline Solids 353 (2007) 194199
The challenges associated with synthesizing new molecular
sieves or new route for controlling the pore size distribu-
tion and enhancing the thermal, structural and textural
peculiarities of the known molecular sieve/s continue to
attract the attention not only in scientic communities
but also in industries. Investigating the inuence of various
synthesis variables on physicochemical properties and in
turn their suitability for commercially important applica-
tions constitute the essence of current research in the eld
of mesoporous molecular sieves. Since, tunable mesopore
structure is one of the distinctive features associated with
this material, several procedural variables such as gel com-
position, type and concentration of surfactant, pH, calcina-
tion, post-synthesis modications, silica source etc. whose
cause and eect relationship on the properties of MCM-
48 materials have been intensively explored [1224].
Although, several synthesis routes were developed using sil-
ica precursor selected from TEOS, ethyl silicate, fumed sil-
ica, water glass, silica sol, no systematic study was reported
on the use of dierently manufactured amorphous silica
sources, particularly in, ternary SiO2:CTAOH:H2O system
and their inuence on the pathway of structural develop-
ment and structural properties pure silica MCM-48 materi-
als. Amorphous silica generally prepared either by liquid
phase or vapor phase synthesis. Fumed silica is usually pro-
duced by ame hydrolysis of silicon tetrachloride in an
oxygenhydrogen ame. However, precipitated silicas are
industrially prepared at very dierent conditions. After
precipitation the precipitated silica is ltered, washed and
dried. Drying is practiced dierently depending on the tar-
get properties of the end products. The use of amorphous
silica powder in the preparation of synthesis gel allows to
achieve high concentrations of the reagents and to obtain
high amount of product starting from relatively low vol-
ume of synthesis gel. Furthermore, since CTAOH serves
as a simultaneous source of surfactant and OH species,
only silica source, CTAOH solution and water are required
to prepare the starting synthesis gel.
Current work presents a systematic and comparative
studies on time dependant structural development of
MCM-48 materials prepared using dierently manufac-
tured amorphous silica sources such as fumed silica
(FMDS), spray dried precipitated silica (SDPS) and ash
dried precipitated silica (FDPS) particularly in, ternary
SiO2:CTAOH:H2O system. The inuence of these silica
sources on the structural/textural, morphological proper-
ties and thermal stability of hydrothermally prepared Si-
MCM-48 has been investigated. The samples were charac-
terized by powder XRD, N2 adsorptiondesorption and
SEM.
2. Experimental
2.1. Synthesis
Attempts were made to prepare pure silica MCM-48
materials using three dierent silica sources viz. fumed
195
silica, FMDS (99.8 wt% SiO2, BET surface area 338 m2/g,
Aldrich), spray dried precipitated silica, SDPS (99.2 wt%
SiO2, BET surface area 155 m2/g, V.P. Chemicals, Pune,
India) and ash dried precipitated silica, FDPS (99.2 wt%
SiO2, BET surface area 112 m2/g, V.P. Chemicals Pune,
India). Cetyltrimethylammonium hydroxide, CTAOH,
(25% solution in methanol, Dishman Pharmaceuticals and
Chem. Ltd., Mumbai, India) was used as a common source
of surfactant and OH species.
In a typical synthesis, 6 g of FMDS were added slowly
to a solution containing 33.11 g of 25% CTAOH solution
in methanol and 16.2 g of water under constant stirring.
Stirring was continued till methanol-free homogeneous
gel was obtained. The resulting gel with molar composition
SiO2:0.275 CTAOH:9.0 H2O was then transferred to Tef-
lon-lined (250 mL capacity) autoclave. After being sealed,
it was heated at 408 K for desired length of period. The
time at which autoclave attained the 408 K temperature
was taken as zeroth hour. The product was recovered by
ltration, washed repeatedly with distilled water and then
dried at 373 K for 4 h. The removal of the template was
accomplished by calcination in air at 813 K for 6 h (heating
rate of 1 K/min, dwell time of 2 h each at 373 K, 473 K and
623 K). The yield was calculated on the basis of silica
recovery.
2.2. Characterization
Powder X-ray diraction patterns were recorded using a
Rigaku Miniex diractometer with Cu-Ka radiation. The
diraction data were recorded in the 2h range of 1.510
with a scanning rate of 1 min1. Nitrogen adsorption/
desorption isotherms were measured at 77 K with Omni-
sorp, 100 CX. The sample was degassed at 573 K for
10 h before measurement. The specic surface area of the
sample was calculated using BET method and pore size dis-
tribution was determined using BJH method. The mor-
phology of the samples was examined using scanning
electron microscope (JEOL-JSM-5200) after coating with
AuPd evaporated lm. Structural stability of selected
samples was assessed by conducting thermal stability test
that was performed by heating the calcined sample at
923 K for 6 h in air.
3. Results and discussion
3.1. Structural development
Synthesis time is a critical variable in the formation of
MCM-48 materials. The degree of ordering of the pore
structures (structural regularity) of Si-MCM-48 samples
was monitored by varying the syntheses time for each sys-
tem. In order to investigate the inuence of type of silica
source on the progressive development, except silica pre-
cursor, all other synthesis parameters such as addition
sequence, initial gel molar composition, synthesis tempera-
ture, ratio of charged reaction mass to autoclave volume,
196 U.S. Taralkar et al. / Journal of Non-Crystalline Solids 353 (2007) 194199

pH and downstream process conditions were kept con-
stant. The evolution of dierent mesophases formed during
the progressive development of Si-MCM-48 employing
FMDS, SDPS and FDPS as silica source materials are
depicted in Fig. 1. It is interesting to note that in all the
cases, the intensity of characteristic peaks of MCM-48
phase was found to increase with synthesis time, reaches
to maximum and then decreases on further heating. How-
ever, (2 1 1) peak was found to shift towards lower 2h till its
intensity reaches to maximum and then shifts to higher 2h
value. Shifting of the peak to lower 2h values suggest that,
the growth of the unit cell occurs with time. In order to ver-
ify such improvement in the degree of ordering in MCM-48
mesophases, the unit pcell parameter a0 was calculated
using the relation d211 6 and are summarized in Table 1.
In all the three systems, the unit cell parameter was found
to increase with synthesis time, reaches to maximum and
then decreases on further heating. From each system, the
sample that has shown highest a0 values was selected for
the detail characterization and labeled as MCM-48AS
XXXX where XXXX is silica source used (FMDS fumed
silica, SDPS spray dried precipitated silica and FDPS
ash dried precipitated silica). On the basis of time needed
to obtain these samples, the reactivity of the source mate-
rial has shown the trend as: FMDS > SDPS > FDPS.
Probably, lower particle size and/or higher surface area
of the fumed silica might be responsible for higher hydro-
lysis rate as compared to other sources when used under
the identical set of synthesis condition.
12 hrs 18 hrs
Intensity (A.U)
Inspection of unit cell parameters shows that use more
reactive source of silica results in the formation of
MCM-48 with bigger unit cell. The XRD pattern of
MCM-48ASFMDS also reects the better quality as com-
pared to MCM-48ASSDPS and MCM-48ASFDPS mate-
rials. Thus, the quality of MCM-48 materials was found to
commensurate with the source reactivity. Probably, when
more reactive silica source is used in the gel, higher disso-
lution rate might be operative in favoring a spatial arrange-
ment of the silicate polyanions and micellar cations leading
to synthesis of a good quality MCM-48 in shorter period.
Thus, it can be inferred that, manufacturing process of
amorphous silica source can aect the formation of a spe-
cial distribution of silicate polyanions and micellar cations
during the progressive hydrothermal treatment when iden-
tical set of synthesis conditions were employed. However,
the yield of MCM-48 materials, based on silica recovery,
was found always greater than 89% and typically ca 91%
irrespective of silica source used.
Upon calcination, MCM-48ASFMDS, MCM-48AS
SDPS and MCM-48ASFDPS resulted in the formation
of surfactant-free MCM-48 materials, which were desig-
nated as MCM-48FMDS, MCM-48SDPS and MCM-
48FDPS respectively. These surfactant-free materials have
shown considerable increase in the intensity of low angle
reection and shifting of 2h to higher values. Contraction
of the lattice occurs during the surfactant removal process
on account of condensation of the silanol groups on the
wall. An extent of such lattice contraction as a function
of type of silica source used was estimated by calculating
the dierence in unit cell parameters, before and after
calcination (denoted as Da0) and tabulated in Table 2.
It is evident from Table 2 that, the population of
34 hrs
SiOH units in the channel wall follows the trend

8 hrs 12 hrs 24 hrs as: MCM-48FMDS > MCM-48SDPS > MCM-48FDPS.

6 hrs 8 hrs 18 hrs Given that the more contraction of unit cell after calcina-
4 hrs 4 hrs 12 hrs tions is caused by fewer fractions of Si(OSi)4 structural
2 hrs 3 hrs 6 hrs units in wall, it is understandable that the wall of MCM-
1 hrs 2 hrs 3 hrs 48FMDS contain higher Q3/Q4 ratio as compared to
2 4 6 8 10 2 4 6 8 10 2 4 6 8 10 MCM-48SDPS and MCM-48FDPS. It can also be
2 Theta inferred from the XRD data that, the FWHM (full width
Fig. 1. XRD patterns of as-synthesized samples showing progressive
at half maximum) of the (2 1 1) peak follows the trend as:
development of MCM-48 using (A) fumed silica (B) spray dried MCM-48FMDS < MCM-48SDPS < MCM-48FDPS.
precipitated silica and (C) ash dried precipitated silica. Thus, use of the most reactive silica source was found to

Table 1
Variations in unit cell parameters of as-synthesized materials as a function of synthesis time using FMDS, SDPS and FDPS as a silica source
FMDS SDPS FDPS
Synthesis d211 Unit cell Synthesis d211 Unit cell Synthesis d211 Unit cell
time (h) parameter a0 (nm) time (h) parameter a0 (nm) time (h) parameter a0 (nm)
0 0 0
2 3.44 8.42 3 3.50 8.57 6 3.39 8.30
4 3.47 8.49 4 3.77 9.23 12 3.55 8.69
6 3.50 8.57 8 3.80 9.30 18 3.58 8.76
8 3.87 9.48 12 3.83 9.38 24 3.67 8.99
12 3.64 8.91 18 3.70 9.06 34 3.58 8.76
 U.S. Taralkar et al. / Journal of Non-Crystalline Solids 353 (2007) 194199 197

Table 2
X-ray data and extent of contraction of unit cell of calcined MCM-48
Sample designation d211 (nm) FWHM 2h Unit cell parameter a0 (nm) Synthesis time (h) Da0 (nm) % Contraction
MCM-48FMDS 3.08 0.212 7.54 8 1.94 20.4
MCM-48SDPS 3.15 0.284 7.71 12 1.67 17.8
MCM-48FDPS 3.31 0.306 8.10 24 0.89 09.9

lead the formation of MCM-48 material with well-devel-
oped grains.
3.2. Textural/structural properties
Nitrogen adsorption and desorption isotherms for
MCM-48FMDS, MCM-48SDPS and MCM-48FDPS
samples are illustrated in Fig. 2. The pore size distribution
curves obtained from the desorption branch using BJH
method are shown as inset. All samples have exhibited a
type IV isotherm, typical of mesoporous solids. The sharp-
ness and height of the nitrogen condensation step provide
the strong evidences of the quality of the materials
which follows the trend MCM-48FMDS > MCM-48
SDPS > MCM-48FDPS. In addition, pore size distribu-
tion curve of high quality MCM-48FMDS has shown a
maximum at 2.23 nm, which is comparable with MCM-
48SDPS but higher than MCM-48FDPS. The data con-
cerning their specic pore volume, specic surface area,
average pore diameter and the wall thickness are summa-
rized in Table 3.
The mutual inverse proportion was observed between
the BET specic surface area and wall thickness. Fumed
silica has yielded well ordered MCM-48 with thinner wall.
Considering the magnitude of wall thickness and unit cell
contraction upon calcination for each sample, it can be
concluded that more contraction in unit cell results in the
formation of thinner walled MCM-48.
3.3. Structural stability
Parent MCM-48FMDS, MCM-48SDPS and MCM-
48FDPS samples were subjected for the thermal stability
test. The dierence between the intensity of the characteristic

500
Desorption
MCM-48-FMDS

Adsorption
450

400
MCM-48-SDPS

350
Volume [cc/g]

300 MCM-48-FDPS

7
250 6 MCM-48-FMDS
MCM-48-SDPS
DV (log d) [cc/g]

5
MCM-48-FDPS
4
3
200 2
1
0
20 40 60
Pore diameter ()
150
0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure
Fig. 2. Low temperature nitrogen adsorption/desorption isotherms and pore size distribution curves [inset] for MCM-48FMDS, MCM-48SDPS and
MCM-48FDPS.
198 U.S. Taralkar et al. / Journal of Non-Crystalline Solids 353 (2007) 194199
Table 3
Textural/structural characteristics of various calcined MCM-48 phases
Sample designation Total pore volume (cc/g)
MCM-48FMDS 0.74
MCM-48SDPS 0.72
MCM-48FDPS 0.56
Fig. 3. SEM micrographs of various MCM-48 materials.
d211 XRD peak before and after the thermal test was taken
as a measure for evaluating the thermal stability. After sub-
jecting to thermal test, MCM-48FMDS has exhibited
25.51% structure collapse while 19.56% and 17.81% struc-
ture collapse was observed in case of MCM-48SDPS and
MCM-48FDPS respectively. Though % collapse for
MCM-48FMDS was highest even after thermal treatment
it has shown high diraction angle peaks, which were absent
in case of both MCM-48SDPS and MCM-48FDPS. Such
lower degree of structure collapse in MCM-48SDPS and
MCM-48FDPS might be associated with the poor order-
ness and the higher wall thickness.
3.4. Morphology
SEM micrographs of the three MCM-48 samples are
illustrated in Fig. 3. As far as the morphology of MCM-
48 materials is concerned, except some variation in agglom-
orate size, no considerable shape change was observed by
varying the silica source material.
4. Conclusions
Use of dierently manufactured amorphous silica
sources such as fumed silica (FMDS), spray dried precipi-
tated silica (SDPS) and ash dried precipitated silica
(FDPS) was found to inuence the course of development,
structural and morphological properties of hydrothermally
prepared siliceous MCM-48 materials. Under the identical
set of synthesis conditions, the reactivity trend of silica
sources observed was as: FMDS > SDPS > FDPS. In all
the three systems, the unit cell parameter was found to
increase with synthesis time, reaches to maximum and then
decreases on further heating. The population of SiOH
BET surface area (m2 g1) BJH pore diameter (nm) Wall thickness (nm)
1001 2.23 1.32
965 2.22 1.38
970 1.96 1.64
units in the channel wall was found to increases in the
order: MCM-48FMDS > MCM-48SDPS > MCM-48
FDPS. The sharpness and height of the nitrogen condensa-
tion step provide the strong evidences of the quality of the
materials which follows the trend MCM-48FMDS >
MCM-48SDPS > MCM-48FDPS. MCM-48 synthesized
using least expensive FDPS having less surface area has
exhibited thicker pore walls but poor orderness, while
MCM-48 prepared from relatively expensive FMDS hav-
ing high surface area has thinner pore walls and well
ordered. Though % collapse for MCM-48FMDS was
highest even after thermal treatment it has shown high dif-
fraction angle peaks, which were absent in case of both
MCM-48SDPS and MCM-48FDPS. Such lower degree
of structure collapse in MCM-48SDPS and MCM-48
FDPS might be associated with the poor orderness and
the higher wall thickness. Except some variation in agglom-
erate size, no considerable change was observed in the
shape of MCM-48 prepared using amorphous silica pow-
ders, which are manufactured dierently.
Acknowledgement
The work was carried out under CSIR Networking Task
Force project (P23-CMM 005A).
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