3012 Ind. Eng. Chem. Res.

2003, 42, 3012-3018

MATERIALS AND INTERFACES

Synthesis and Characterization of Iron-Rich Highly Ordered

Mesoporous Fe-MCM-41
S. Samanta,† S. Giri,‡ P. U. Sastry,§ N. K. Mal,| A. Manna,⊥ and A. Bhaumik*,†
Departments of Materials Science and Solid State Physics, Indian Association for the Cultivation of Science,
Jadavpur, Kolkata 700 032, India, Solid State Physics Division, Bhaba Atomic Research Centre,
Trombey, Mumbai 400 085, India, Dynamic Materials Research Group, National Institute of Advance Science
& Technology (AIST), Kansai Center, 1-8-31, Osaka 563-8577, Japan, and Materials Science Department,
National University of Singapore, Kent Ridge Road, Singapore 117542
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Iron-rich and highly ordered 2D-hexagonal mesoporous ferrisilicates containing predominantly

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tetrahedrally coordinated Fe3+ in the silica network have been prepared using cetyltrimethyl-
ammonium bromide (CTAB) as the structure-directing agent (SDA) under mild alkaline
hydrothermal conditions (initial pH ) 8-8.5 in the synthesis gel). The optimum limit of iron
loading for the ordered mesophase in the present study was 8.2 wt %; beyond this limit,
disordered iron oxide/silica phase was observed in the same pH range. These mesoporous
ferrisilicate samples were characterized using XRD, N2 sorption, EPR, SEM-EDX, TEM, FT-IR
and UV-visible spectroscopies, and Mössbauer measurements. The average pore diameters were
2.2-2.8 nm, and the mesopore volumes were 0.39-0.5 cm3g-1. Moderately high Brønsted acidity
was observed in the temperature-programmed desorption (TPD) pattern of ammonia over these
mesoporous ferrisilicate materials. Wet chemical analysis, EPR, and Mössbauer spectroscopic
data suggested that most of the iron species are tetrahedrally coordinated Fe3+ attached to the
silica framework.

Introduction ecules. To date, a wide range of transition as well as

The substitution of various transition elements into
open-framework microporous and mesoporous mate-
rials1-5 has received considerable attention because of
the need to develop more efficient and stable materials
for applications in catalysis, separations, coatings, and
chemical sensing. The art of metal substitution received
a big thrust since the discovery of microporous titanium
silicate molecular sieve TS-16 and its versatile catalytic
activity7 in liquid-phase partial oxidation reactions
using dilute H2O2 as the oxidant. Iron-containing zeo-
lites8 and related molecular sieves are of particular
interest because of their unique catalytic activity in
various selective gas-phase reactions, e.g., hydrocarbon
oxidation,9 N2O decomposition,10 and selective catalytic
NO and N2O reduction in the presence of hydrocarbon
or ammonia.11,12 Mesoporous materials containing these
heteroelements13-17 have still wider potential for use
as catalysts, exchangers, and adsorbent because of their
tunable nanoscale pore openings and exceptionally high
internal surface areas accessible to bulky organic mol-
* To whom correspondence should be addressed. E-mail:
msab@mahendra.iacs.res.in.
† Department of Materials Science, Indian Association for
the Cultivation of Science.
‡ Department of Solid State Physics, Indian Association for
the Cultivation of Science.
§ Bhaba Atomic Research Centre.
| National Institute of Advance Science & Technology (AIST).
⊥ National University of Singapore.
10.1021/ie020905g CCC: $25.00 © 2003 American Chemical Society
Published on Web 05/23/2003
nontransition elements have been incorporated in these
silica-based mesostructures.4,5 Unlike tetravalent ele-
ments (Ti, Ge, Sn, Zr, etc.), whose incorporation does
not introduce any charge in the neutral silica frame-
work, each of the trivalent heteroelements incorporated
into the silica matrixes (Al, B, Ga, Fe, In, etc.) introduces
a negative charge that could be balanced by a cation.
This cation can be a mono- or divalent metal ion, as well
as ammonium or a proton. Thus, the incorporation of a
trivalent heteroelement into the SiO2 framework can
generate a cation exchange or Brønsted acid site.
However, the adsorptive and catalytic properties of the
other trivalent metal analogues of these micro- and
mesoporous metallosilicates are usually different from
those of their aluminum counterparts of zeolites. In
addition to modifications of the acidity, the presence of
multivalent metal cations in the framework can also
create isolated redox centers, which can act as good
heterogeneous oxidation catalysts in the presence of a
mild oxidant.7 Moreover, their loading in the silica
matrix can affect the overall acid strength, ion-exchange
capacity,18 and catalytic performances19 extensively.
Crystalline microporous ferrisilicates such as ZSM-5,20
-11,21 -beta,22 ferrite,23 etc., as well as amorphous
mesoporous iron silicates,24,25 have been known for
decades, and these materials have some unique char-
acteristic features. Among the trivalent heteroelements,
the incorporation of tetrahedral Fe3+ into a silica
network is known for the generation of very strong acid
sites.22 Usually, severe precautions are taken during the

preparation of the synthesis gel of such materials to
avoid the precipitation of iron oxides and hydroxides,
as the synthesis is usually carried out under moderate
to strong alkaline conditions.26 The mode of addition of
the reagents and, in some cases, the addition of the iron
source in the form of iron complexes27 have been
recommended for such preparations. Successful incor-
poration of Fe3+ into the tetrahedral lattice site of silica
can be achieved through careful preparation of the
synthesis gel and its subsequent hydrothermal treat-
ment. However, the maximum loading of Fe in crystal-
line microporous silica networks having defined inter-
atomic distances and bond angles is restricted to 3.2 mol
%,27 and amorphous mesoporous HMS materials with
broad distributions of bond lengths and bond angles can
accommodate a maximum of only 5.7 wt % of iron25 in
their frameworks. To date, reports on the synthesis28
and catalytic properties29,30 of Fe-MCM-41 have been
restricted to 1.1-2 wt % loadings of Fe only using direct
hydrothermal synthesis, template ion exchange, incipi-
ent wetness impregnation, solid-state impregnation, and
other postsynthesis methods. Because the acidities of
these ferrisilicates are related to the loading of iron,
more isolated tetrahedral Fe3+ could be conducive to the
generation of more catalytically active materials. Thus,
iron-rich ferrisilicates having predominantly tetrahedral
Fe3+ and highly ordered mesoporous frameworks, but
devoid of iron oxide impurities, are most desirable. Here,
we show that as high as 8.2 wt % Fe can successfully
be incorporated preserving the highly ordered mesopo-
rous MCM-41 framework using a simple hydrothermal
method, avoiding coprecipitation of iron oxides during
the synthesis. Detailed characterizations of these iron-
rich 2D-hexagonal mesoporous Fe-MCM-41 materials
were carried out using powder XRD, TEM, SEM, N2
sorption, EPR, FT-IR, Mössbauer, and magnetic mea-
surements and surface, as well as wet chemical analysis.
Experimental Section
Tetraethyl orthosilicate (TEOS, E-Merck, Germany)
was used as the silica source in all syntheses. The
cationic surfactant cetyltrimethylammonium bromide
(CTAB, Loba Chemie, India) was used as the structure-
directing agent, and ferric chloride (Loba Chemie, India)
was used as the iron source. NaOH (Loba Chemie,
India) was used to maintain the pH of the medium. For
the syntheses of the mesoporous Fe-MCM-41materials,
TEOS was first added to an aqueous solution of CTAB,
which was then stirred for 15 min. The aqueous solution
of CTAB was prepared by dissolving CTAB in deionized
water and then stirring the mixture for 15 min. Then,
the desired amount of FeCl3 was taken in water and
added to this aged silica sol in different mole ratios
corresponding to the desired loadings of iron. TEOS was
then allowed to hydrolyze in acidic pH slowly. After 1
h, aqueous NaOH solution was added to the solution
until the pH rose to 8-8.5. The final mixture was
vigorously stirred for 1 h and then autoclaved at 353 K
for 2-3 days. The molar ratio of various constituents
of the hydrothermal gels was
SiO2/CTAB/Fe(III)/H2O ) 1/0.25/(0.1-0.0125)/90
After the hydrothermal treatment, the solid products
were filtered, washed with water, and dried in air. The
mesophases of both the as-synthesized and template-
free samples were identified by small-angle powder XRD
Ind. Eng. Chem. Res., Vol. 42, No. 13, 2003 3013
using a Rigaku 12-kW rotating-anode X-ray generator
on which small- and wide-angle gonio- meters were
mounted. The X-ray source was Cu KR radiation (R )
0.154 06 nm) with a voltage and current of 40 kV and
30 mA, respectively. For transmission electron micros-
copy measurements, a Hitachi H-600 instrument was
used. N2 adsorption measurements were carried out
using a BELSORP 28SA apparatus at 77 K. Prior to N2
adsorption, samples were degassed for 2 h at 323 K. For
the Fourier transform infrared (FT-IR) measurements,
a Nicolet MAGNA IR 750 instrument was used. EPR
spectra were recorded in the X-band mode on a Varian
E9 spectrometer at 298 K. Before the EPR measure-
ments, the samples were dried under vacuum for 4 h
at 373 K. Magnetic measurements were carried out
using an EG&G Princeton Applied Research vibrating
sample magnetometer 155 at 295 K, with an applied
magnetic field of up to 10 kG. 57Fe Mössbauer spectra
were recorded at room temperature in a transmission
geometry using a 25 mCi 57Co source in a Rh matrix
with a Wissel velocity drive unit in constant acceleration
mode. All Mössbauer parameters were estimated with
respect to metallic R-Fe. Temperature-programmed
desorption (TPD) of ammonia was carried out with a
homemade apparatus equipped with a mass spectrom-
eter. Before the TPD measurements, samples were
purged at 373 K in nitrogen atmosphere for 2 h. This
was followed by ammonia gas adsorption at 373 K.
Decomposition of ammonium ions and desorption of NH3
were monitored (at a heating rate of 10 K/min) through
the mass spectrometer. For the determination of the
chemical composition and the oxidation state of Fe in
various samples, a Dionex 500 ion chromatograph was
employed. An atomic absorption spectrophotometer
(Perkin-Elmer AAS 3310) with a flow-injection hydride
generation attachment was used for chemical weight
analysis, with a detection limit of F1-Hg-AAS each 3
ppb and 95% accuracy. Prior to chemical analysis, solid
samples were dissolved in concentrated HF and HCl
solution, followed by evaporation, three times before the
volume was made up with distilled water. The surfac-
tant was removed from the as-synthesized mesoporous
ferrisilicate materials by acid extraction using ethanolic
hydrochloride acid for 4 h at room temperature under
vigorous stirring. For a typical acid extraction, 1.0 g of
the as-synthesized sample was added to a mixture of
75 mL of dry ethanol and 1.0 mL of 1 M HCl. Then, the
resulting mixture was stirred at room temperature for
6 h. After this extraction, the solid was filtered, washed
with dry ethanol, and then air-dried at room tempera-
ture. Surfactant was also removed in some cases through
calcination under a flow of air at 773 K for 8 h.
Results and Discussion
We have prepared Fe-rich Fe-MCM-41, optimized its
iron-loading limit, and identified the nature of Fe
species present in this mesoporous material. Physico-
chemical properties of various ferrisilicate samples
synthesized in the present study are reported in Table
1. Sample 1, pure silica MCM-41, was synthesized under
otherwise identical synthesis conditions except for the
addition of the Fe3+ precursor in the gel. Chemical
analysis of these ferrisilicate samples after the acid-
solvent extraction revealed the absence of any organic
SDA. Si/Fe mole ratios for various Fe-MCM-41 samples
as determined by AAS increased with the increasing
input gel ratio (Table 1). An optimum of this ratio for
3014 Ind. Eng. Chem. Res., Vol. 42, No. 13, 2003
Table 1. Physicochemical Properties of Different Fe-MCM-41 Samples
Si/Fe mole ratio
sample nature of
no. gel product the sample
1 ∞ - ordered
2 5.0 -a amorphous
3 10.0 10.1 ordered
4 20.0 23.2 ordered
5 40.0 41.5 ordered
6 80.0 77.6 ordered
a Si/Fe mole ratio in this iron-silica mixed oxide was 6.7.
Figure 1. XRD patterns of different Fe-MCM-41 samples: (a)
sample 2 (Si/Fe ) 6.7), (b) sample 3 (Si/Fe ) 10.1), and (c) sample
4 (Si/Fe ) 23.2). The d spacings of different planes for sample 4
are shown in the inset.
the ordered ferrisilicate mesophase was observed for
sample 3 at 10.1 (8.2 wt %). The materials obtained with
Si/Fe molar ratios of 10 or more in the synthesis gel
were two-dimensional hexagonally ordered Fe-MCM-
41 materials, whereas increasing the iron loading
further in the gel resulted in disordered porous struc-
tures (sample 2, Si/Fe ) 5). One of the great advantage
of these iron-containing mesoporous Fe-MCM-41 is
that, unlike Fe-incorporated zeolites,23 which turn pale
yellow to brown coloration during calcination, the cat-
ionic surfactants used in the present study can easily
be removed by simple acid-ethanol extraction without
changing the color of the sample and, thus, preserving
the coordination of the iron in the lattice.
A typical XRD pattern of the as-synthesized mesopo-
rous ferrisilicate Fe-MCM-41 (sample 4) is shown in
Figure 1c. The other two patterns in Figure 1, a and b,
correspond to samples 2 and 3, respectively. As seen
from Figure 1, all four low-angle peaks of the 100, 110,
200, and 210 phases corresponding to the 2D-hexagonal
mesophase of MCM-4113 were observed in samples 3 and
4, and no distinctive higher-order peaks were observed.
Among the samples whose characterization data are
presented in Table 1, except for sample 2, all other
samples (samples 3-6) were highly ordered and exhib-
ited similar X-ray diffraction patterns.13-17 The d spac-
BET surface pore mesopore
area (m2 g-1) diameter (Å) volume (cm3 g-1)
1025 27.5 0.63
176 - -
464 22.0 0.39
614 22.4 0.42
636 25.7 0.46
666 28.0 0.50
Figure 2. TEM image of Fe-MCM-41 (sample 4).
ings of various planes for sample 4 and the correspond-
ing hkl values are shown in the inset of Figure 1. The
unit cell parameter, a0, calculated from these values was
4.32 nm. Figure 2 displays the TEM image of a
representative mesoporous ferrisilicate sample. The
existence of a hexagonal arrangement of uniform me-
sopores is very clear. These results suggest that this
ferrisilicate material has a highly ordered two-dimen-
sional hexagonal mesophase. The peak positions re-
mained almost unchanged after removal of the surfac-
tant, although a slight change in the intensity was
observed. Because there were no noticeable high-angle
reflections in the XRD patterns of these mesoporous
ferrisilicate materials, the pore walls were concluded
to be amorphous in nature. Sample 2, with an input Si/
Fe mole ratio of 5.0, did not exhibit any well-resolved
diffraction peaks (Figure 1a), indicating the absence of
any long-range ordering. No diffraction line correspond-
ing to iron oxide crystallites was observed in either of
the samples synthesized using this method. For sample
2, also, no high-angle reflection was observed. This
indicates that the Fe2O3 crystallites, if formed, were
very small (less than 3 nm size) or comprised disordered
aggregates.31,32
In Figure 3, N2 adsorption/desorption isotherms for
Fe3+-containing mesoporous silica (sample 4, taken as
representative) are shown. The pore size distribution
for this sample is shown in the inset. The isotherms, as
shown in Figure 3, were of type IV.13,33 The pore size
distribution was very narrow and relatively lower in
range vis-à-vis mesoporous materials synthesized using
CTAB surfactant.13-18 The average pore diameter for
this mesoporous ferrisilicate sample, determined ac-
cording to the BJH model,33 was 2.24 nm. The adsorp-
tion/desorption isotherms and corresponding pore size
distributions for samples 3, 5, and 6 followed an identi-
cal pattern. The BET surface areas of these mesoporous
ferrisilicates were medium to high, considering the
moderately high concentrations of iron. The surface area
decreased with increasing loading of Fe, as expected
from the increase in the unit cell mass of the composites.
 Ind. Eng. Chem. Res., Vol. 42, No. 13, 2003 3015

Figure 4. UV-visible diffuse reflectance spectra of (a) surfactant-

free Fe-MCM-41 (sample 4) and (b) R-Fe2O3.

Figure 3. N2 adsorption/desorption isotherms of sample 4.

Adsorption points are marked with filled circles, whereas desorp-
tion points are marked with empty circles. The BJH pore size
distribution is shown in the inset.

The pore walls were relatively thicker (1.6-2.2 nm) than

those of siliceous mesoporous materials (1-1.5 nm).13-18
The pore size also decreased from 2.8 to 2.2 nm as the
Fe3+ loading increased from samples 6 to 3. A similar
lowering in the pore diameter was also observed for Eu-
doped silica34 vis-à-vis a pure-silica MCM-41 material
synthesized under the same conditions. The pore diam-
eter and d spacings determined by TEM image analysis
agreed well with the experimental data obtained from
XRD and N2 sorption.
In Figure 4, a UV-visible diffuse reflectance spectrum
of iron-rich mesoporous Fe-MCM-41 (a, sample 4,
representative) is shown. The corresponding spectrum
for bulk Fe2O3 is given in the Figure 4b for comparison.
The UV-visible spectra of the ferrisilicate materials
showed a very strong absorption band in the 200-330
nm wavelength range with maxima at ca. 219 and 255
nm. Other surfactant-free mesoporous materials showed
identical peak patterns. A similar high-energy absorp-
tion band associated with ligand-to-metal charge trans-
fer (LMCT) that is characteristic of isolated tetrahedral Figure 5. EPR spectrum of Fe-MCM-41 (sample 4).
coordination of Fe3+ has been observed for mesoporous
FeS-124 and Fe-HMS.25 These two bands have been EPR spectroscopy is an important tool for identifying
assigned to electronic transitions of the anion (e.g., O2-) the oxidation states of the transition elements in these
to the t2g and eg orbitals of Fe3+ within [FeO4]- tetra- ferrisilicate materials.23 It has been observed that the
hedra.35 The high-energy absorption band of this me- loading of iron has very little effect on the oxidation
soporous ferrisilicate indicated that tetrahedral coordi- states of such materials. Figure 5 displays an EPR
nation of Fe is dominant in these materials. Bulk spectrum of mesoporous Fe-MCM-41 (sample 4). In this
R-Fe2O3 exhibited a broad adsorption band at 320-670 EPR spectrum, two different signals at geff values of 4.28
nm with an absorption maximum at 560 nm (Figure 4b). and 2.00 corresponding to the presence of trivalent iron
The absence of any peak above 320 nm in the UV- in two distinct environments were observed. On the
visible spectra of these ferrisilicate materials indicated basis of earlier assignments,25 the signal at 4.28 can be
the absence of clustered Fe2O3 or Fe3O4 (having octa- ascribed to the presence of Fe3+ in an isolated distorted
hedral Fe) in these Fe-MCM-41 samples. tetrahedral environment. The contribution of this signal
3016 Ind. Eng. Chem. Res., Vol. 42, No. 13, 2003
Figure 6. Mössbauer spectra of Fe-MCM-41: (a) sample 4 and
(b) sample 3.
was much lower than that with g ) 2.00. The very
strong signal at 2.00 can support the presence of both
framework and extraframework trivalent iron in the
mesoporous silica.25 The absence of a weak signal at 2.18
can be attributed to the absence of nonframework
(superparamagnetic) iron oxide/oxi-hydroxide nanopar-
ticles dispersed in the mesoprous silica channels.
Room-temperature Mössbauer spectra of samples 3
and 4 after surfactant removal are shown in Figure 6.
Unfortunately, we could not observe Mössbauer pat-
terns for samples 5 and 6 (Si/Fe ) 41.5 and 77.6,
respectively), possibly because of the low concentrations
of Fe3+ in these samples. On the other hand, a weak
doublet spectrum was observed for samples 3 and 4. The
values of the average isomer shift (IS) and quadrupolar
splitting (QS) for samples 3 and 4 were estimated as
0.12 and 0.17 mm/s and 0.82 and 0.68 mm/s, respec-
tively. It has been observed that the values of IS and
Figure 7. SEM image of sample 4.
QS are considered as important parameters in under-
standing the nature of the framework and oxidation
state of iron. At room temperature, IS < 0.3 mm/s is
indicative of a tetrahedral iron framework, whereas
IS > 0.3 mm/s characterizes octahedral Fe3+.20,21,25 The
values of IS and QS for these Fe-MCM-41 samples
indicate a tetrahedral framework around the iron
present and an iron oxidation state of Fe3+.20-25 In
agreement with other experimental results on Fe zeo-
lites23 and Fe-HMS,25 the UV-visible diffuse reflec-
tance spectra (Figure 4) and Mössbauer results for iron-
rich Fe-MCM-41 support a tetrahedral environment
and Fe3+ oxidation state in the system. It was observed
that the value of the magnetic moment did not change
as the applied magnetic field was increased to 10 kG
for the Fe-MCM-41 samples. In the present system,
Fe3+ existed randomly as islands in the silica network
because of low iron concentration. The absence of any
field dependence of the magnetization indicates that
there is no linkage of exchange path between nearest-
neighbor iron ions. The SEM image of mesoporous Fe-
MCM-41 (sample 4) shown in Figure 7 exhibits uniform
spherical crystallites ∼0.3 to 0.4 µm in size.
The UV-visible diffuse reflectance, EPR, and Möss-
bauer spectral patterns of these materials indicate that
the iron species are essentially present as tetrahedrally
coordinated Fe3+ moieties in the Fe-MCM-41 samples.
These trivalent iron atoms substitute for some of the
silicon atoms in the pore wall and thus generate
Brønsted acidity. To understand the nature of the
interactions36 and the acid sites present in the surface,
TPD of ammonia over calcined Fe-MCM-41was carried
out. Ammonia was found to diffuse very slowly in the
temperature range of 373-673 K, having maximum
desorption in the range of 523-573 K for all samples.
This indicates medium to strong interaction of ammonia
with the Brønsted acid sites and the framework iron
species are located at the surface of the mesoporous pore
wall similar to that observed for Fe-HMS25 materials.
With increasing Fe3+ loading, the concentration of
Brønsted acid sites increases (signal intensity for the
desorption maximum continues to increase from sample
6 to 3), indicating that the incorporation of Fe3+ into

Figure 8. FTIR spectra of (a) surfactant-free and (b) as-
synthesized Fe-MCM-41 (sample 4) and ammonia adsorbed on
samples (c) 3 and (d) 4. Impurity peaks due to CO2 are marked by
an asterisk.
the tetrahedral lattice site with cation exchange capac-
ity has occurred.
FT-IR spectra of the representative as-synthesized
and surfactant-free Fe-MCM-41 samples are shown in
Figure 8 (a and b; sample 4). A broad band in the
hydroxyl region between 3700 and 3000 cm-1 with a
maximum in the range of 3400-3450 cm-1 was observed
in both cases. This band can be assigned to the frame-
work Si-O-H, as well as Si(OH)Fe groups in interac-
tion with defect sites and adsorbed water molecules.
Various C-H stretching vibrations due to the presence
of the organic surfactant molecules, which appeared in
the as-synthesized sample at 2925 and 2840 cm-1,
disappeared after the removal of the surfactant. T-O-T
framework vibrations, which appeared in the region
860-1400 cm-1, became much narrower in the region
900-1360 cm-1 after surfactant removal. The-ammonia
TPD results were confirmed by the FT-IR spectroscopic
data for the ammonia-adsorbed samples. The charac-
teristic intensity of the band for ammonium ions at
1400-1500 cm-1 continues to grow with increasing Fe3+
loading (Figure 8c vis-à-vis 8d, because of the increase
in number of acid sites), whereas the frequency showed
a slight downshift38 with increasing Fe3+ loading.
A liquid-crystal templating pathway for cationic sur-
factant micelles in aqueous solution is commonly em-
ployed for the synthesis of mesoporous silica-based
materials. The pH in such synthesis processes can be
varied widely, from mild to strong alkaline (8.5-12.0)
to strong acid (0.5-2.0) conditions. In the present case,
silicon alkoxide was first hydrolyzed by acidic ferric
chloride solution. This was followed by condensation of
the silica and iron species as the pH was increased with
aqueous NaOH solution. Unlike in previous synthesis
methods,26-30 here, the final pH of the hydrothermal
gels was kept at mild alkaline condition (between
pH ) 8.0-8.5), which assists the condensation of
ferrisilcate nuclei rather than that of individual silicate
Ind. Eng. Chem. Res., Vol. 42, No. 13, 2003 3017
and Fe3+ moieties. However, there was a limit for the
uptake of Fe3+ in the silica mesophase. The sample with
the highest Fe3+ content in the gel preserving the meso-
structure was obtained with a lowest Si/Fe mole ratio
of 10 (sample 3, Si/Fe ) 10.1, 8.2 wt % Fe in the solid).
The mechanism for the formation of this mesostructure
involved the formation of rodlike micelles of surfactant
molecules39 encapsulated by ferrisilicate nuclei. This
was followed by the polymerization of the ferrisilicate
species to form the regular array of mesopores separated
by the thick (1.6-2.2 nm thickness, Table 1) ferrisilicate
pore walls. The self-assembly of the surfactant-silicate
mesostructure is largely dependent on the strong ionic
interactions between surfactant micelles and inorganic
metallo-silicate species. As observed for other transition-
metal- (viz., Ti-, V-, Cr-, etc.)40 containing mesoporous
silica, in the case of Fe3+, there was also an optimum
limit to its incorporation. This limitation seems to be
guided by the fact that, beyond an 8.2 wt % loading of
Fe3+ in the metallosilicate precursor nuclei, more local
strain in the mesostructure is created, leading to a
disordered mesophase.
Conclusions
Highly ordered mesoporous ferrisilicate Fe-MCM-41
materials have been synthesized using a cationic sur-
factant as the structure-directing agent under mild
hydrothermal condition and at weakly alkaline pH. The
loading of iron was found to have a direct relation to
the ordering of these materials. An ordered Fe-MCM-
41 phase was observed up to the highest loading of iron
(8.2 wt % with respect to the template-free solid product)
in these mesoporous ferrisilicates. Beyond this loading
limit, disordered ferrisilicate materials were obtained.
N2 adsorption measurements indicated medium to high
BET specific surface areas, uniform mesopore openings,
and high pore volume in these Fe-MCM-41 samples
synthesized using the present hydrothermal method.
UV-visible, EPR, and Mössbauer measurements sug-
gested tetrahedral coordination of Fe3+ in an isolated
silica environment. FT-IR and acidity measurements
indicated that surface Brønsted acidity is generated by
the incorporation of each Fe3+ into the silica network
of MCM-41.
Acknowledgment
A.B. thanks DST, Govt. of India, New Delhi, India,
for providing financial assistance. S.S. is grateful to DST
for providing a Junior Research Fellowship.
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Received for review November 12, 2002
Revised manuscript received March 19, 2003
Accepted April 16, 2003
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