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Microporous and Mesoporous Materials 112 (2008) 327–337

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Critical evaluation of the state of iron oxide nanoparticles on different

mesoporous silicas prepared by an impregnation method
Tanya Tsoncheva a,*, Jessica Rosenholm b, Mika Linden b, Freddy Kleitz c,
Michael Tiemann d, Ljubomira Ivanova a, Momtchil Dimitrov a,
Daniela Paneva e, Ivan Mitov e, Christo Minchev a
a
Institute of Organic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
b
Department of Physical Chemistry, Abo Akademi University, 20500 Turku, Finland
c
Department of Chemistry, Université Laval, Québec, Canada G1K 7P4
d
Institute of Inorganic and Analytical Chemistry, Justus Liebig University, Giessen, Germany
e
Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria

Received 17 July 2007; received in revised form 24 September 2007; accepted 9 October 2007
Available online 17 October 2007

Abstract

Mesoporous SBA-15 (space group p6mm), KIT-6 (Ia3d) and KIT-5 (Fm3m) silicas, exhibiting different 2-D and 3-D channel- or cage-
like pore structure and pore dimensions have been used as supports for iron oxide nanoparticles. The iron modification of the silica was
performed according to a frequently used impregnation technique from aqueous iron nitrate solution. The materials were characterized
by nitrogen physisorption, X-ray diffraction, TEM–EDX, Moessbauer spectroscopy, and temperature-programmed reduction (TPR)
and tested in the catalytic decomposition of methanol. It is established that the location and dispersion of iron oxide nanoparticles
are affected by the pore topology of the support. The most homogeneously dispersed iron oxide nanoparticles are observed using silica
host matrix exhibiting a 3-D channel-like structure and pore diameters about 7 nm, and the thus-obtained composites exhibit high cat-
alytic activity and selectivity in methanol decomposition to CO and hydrogen. For all the samples, characterized with a low mesopore
volume and small pore diameters/pore entrances, the formation of larger iron oxide particles, mainly located on the outer surface, is
observed. Inhomogeneously dispersed iron oxide particles with a large fraction of isolated, strongly interacting with the support, iron
species, and possessing low catalytic activity and usually high selectivity to methane, are found for the silicas with relatively larger
pores/pore entrances.
Ó 2007 Elsevier Inc. All rights reserved.

Keywords: Iron oxide nanoparticles; Mesoporous silica; SBA-15; KIT-6; Cage-like pores; Methanol decomposition

1. Introduction
Nanosized materials have received significant attention
in application fields as diverse as electronics, nonlinear
optics, medicine, chemistry and engineering, e.g. for prepa-
ration of high density magnetic recordings, magnetic fluids,
solar cells, catalysts, sensors, membranes, etc. [1–4]. The
unique properties of nanoparticles originate from their high
surface to volume ratio, i.e. by the dominant behaviour of
*
Corresponding author. Fax: +359 2 8700225.
E-mail address: tsoncheva@orgchm.bas.bg (T. Tsoncheva).
the surface atoms, which gives the materials special proper-
ties, such as superparamagnetism, a blue shift of the optical
absorption edge, and remarkable catalytic and reductive
properties [5–12]. Very often, the nanoparticles are depos-
ited onto porous carriers. However, the level of nanoparti-
cle dispersion on the carrier is influenced by a number of
parameters, such as the method of nanoparticles deposition,
the loading degree, the pore structure, pore diameter, and
pore volume of the support, and the interaction between
the support and the nanoparticles [13–19]. Due to the com-
plex interdependency of these parameters, achieving a high
level of dispersion is often a matter of trial and error. In our

1387-1811/$ - see front matter Ó 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.10.005
328 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337
previous investigations we have reported some data on the
state, catalytic properties and reductive transformations of
various metal oxide nanoparticles supported on different
mesoporous materials (silicas, carbons, oxides) [20–31].
We now extend the study to the use of a variety of mesopor-
ous silicas as supports for iron oxide nanoparticles, with
focus on investigating if there is interdependency between
the state of the iron oxide particles and the pore character-
istics of mesoporous support. The method of metal oxide
deposition, the loading, and the chemical composition of
the supports were kept constant, while the pore size, pore
geometry, and pore interconnectivity were varied. As a cat-
alytic test reaction – methanol decomposition to hydrogen,
methane and CO, was chosen, because the process is of
recent importance as a potential source of effective and eco-
logical fuel for gas turbines, vehicles and fuel cells [32–37].
The nanocomposite materials were prepared by dispersing
the calcined silica powders in an aqueous solution of iron
nitrate, followed by solvent evaporation [20,21]. As sup-
ports, we studied mesoporous silicas synthesized using tri-
block copolymers as structure-directing agents. This class
of materials has specific features, such as large and tunable
mesopore diameters, high surface areas, large pore volumes,
and the possibility of controlled particle morphology
[16,17,38,39 and refs. there in]. Furthermore, the pore
topology, pore size and pore connectivity can be tuned by
varying the copolymer concentration, the volume fraction
of the different copolymer blocks, the synthesis and aging
temperatures, and by the use of additives such as co-surfac-
tants or inorganic salts [40–51 and references therein]. In
addition to the mesopores, the materials typically also con-
tain a fair fraction of micropores in the pore walls [52–60].
This complementary porosity is strongly affected by the syn-
thesis conditions and the method chosen for the template
removal [61–63]. In the last years, SBA-15 silica, which
exhibits a 2-dimensional (2-D) hexagonal arrangement of
parallel uniform cylindrical mesopores, has been the most
studied member of the family of the block copolymer-tem-
plated materials [39,44,48]. Furthermore, the interest in
mesoporous silicas increased recently with the preparation
of the large pore 3-D Ia3d cubic mesostructure, denoted
KIT-6, which consists in an unique interpenetrating net-
work of cylindrical channels [45,64,65], being promising
for applications requiring facile molecular accessibility
and fast mass transport. Here, the pore diameters could also
easily be tailored by using simple hydrothermal treatment
of the mesophase [45,66]. The 3-D interconnected cubic
Fm3m silica material with cage-like mesopores, denoted
KIT-5 [43,47,67], is considered as a suitable host for the
inclusion and immobilization of biomolecules, as an ideal
hard template for the preparation of 3-D inverse nanoarray
replicas, and as a nanoreactor system [68,69]. Usually, the
pore entrance sizes of these materials can be efficiently
tuned by changing the aging temperature [42,43,51], or
applying acid treatments [70], accompanied in some cases
by loss of the cage-like character of the pores thus realizing
a more opened pore structure [47].
2. Experimental
2.1. Materials
SBA-15 and KIT-6 (Ia3d) silicas were prepared using
Pluronic P123 (EO20PO70EO20) triblock copolymer as
the structure-directing agent according to procedures
described in [44] and [45], respectively. The syntheses were
performed at relatively low HCl concentrations (0.3-0.5 M
depending on the mesophases). In the case of SBA-15,
SiO2/P123 molar ratios (r) of 60 and 75 were used. Silicas
with Fm3m symmetry (KIT-5) were obtained according to
[46,47] using Pluronic F127 (EO106PO70EO106) as the tem-
plate. The hydrothermal treatment temperature was varied
in the temperature interval 308–423 K. The templates were
removed by ethanol–HCl extraction followed by calcina-
tion at 823 K. Iron modifications of the template-free mes-
oporous silicas were obtained from the corresponding
nitrate precursor. Usually, 1 g of the support was impreg-
nated with 40 ml 0.0286 M aqueous solution of Fe(NO3)3
for 2 h at room temperature. After the impregnation the
samples were dried in rotary evaporator for 1 h at
313 K. The precursor was decomposed in a flow of air
at 773 K for 2 h. Materials containing 6 wt% of iron were
obtained. The samples were denoted as follows: Fe/SBA-
15(T, r), Fe/KIT-6(T) and Fe/KIT-5(T), where T repre-
sents the synthesis temperature and r is the SiO2/P123
molar ratio.
2.2. Characterization
Small-angle X-ray scattering (SAXS) and powder X-ray
diffraction (XRD) measurements were performed using a
Kratky compact small-angle system (M. Braun, Austria).
The system is equipped with a position-sensitive detector
(PSD 50m) consisting of 1024 channels of 55.5 lm width
each. A Seifert ID-300 X-ray generator, operating at a
maximum intensity of 50 kV and 40 mA, provided the Cu
Ka radiation at k = 1.542 Å. A Ni filter was used to
remove Kb radiation and a W filter protected the detector
from the primary beam. The sample-to-detector distance
was 277 mm. The sample holder was kept under vacuum
during the measurements in order to minimise the back-
ground scattering from air.
Transmission electron microscopy (TEM) was per-
formed on a Philips CM30-ST microscope; for energy-dis-
persive X-ray (EDX) analysis an EDAX PV 9900 was used.
The N2-physisorption was determined at 77 K using a
Micromeritics ASAP 2010 sorptometer. The samples were
outgassed at 423 K for 12 h before measurements. The spe-
cific surface area was elucidated using the standard BET
method. Pore volumes and pore size distribution were cal-
culated using the NLDFT kernel developed for cylindrical
pores (SBA-15, KIT-6) or spherical pores (KIT-5) using the
Autosorb 1.52 software (Quantachrome Instruments). The
t-plot method was used for the estimation of the micropore
volume.
 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337
The Moessbauer spectra were obtained in air at room
temperature with a Wissel (Wissenschaftliche Elektronik
GmbH, Germany) electromechanical spectrometer work-
ing in a constant acceleration mode. A 57Co/Cr (activ-
ity ffi 10 mCi) source and a-Fe standard were used. The
experimentally obtained spectra were fitted by the least
square-method. The parameters of hyperfine interaction
such as isomer shift (IS), quadruple splitting (QS), the effec-
tive internal magnetic field (Heff), the line widths (FWHM),
and the relative weight (G) of the partial components in the
spectra were determined.
The TPR-TGA (temperature-programmed reduction
thermogravimetric analysis) investigations were performed
in a Setaram TG92 instrument. Typically, 40 mg of the
sample were placed in a microbalance crucible and heated
in a flow of 50 vol% H2 in Ar (100 cm3/min) up to 873 K at
5 K/min and a final hold-up of 1 h. Prior to the TPR exper-
iments the samples were treated in situ in a flow of air
(10 K/min) up to 773 K, followed by a hold-up of 1 h.
The catalytic experiments were performed in a fixed-
bed reactor (0.055 g catalyst) at a methanol partial pres-
sure of 1.57 kPa and WHSV of 1.5 h1, argon being used
as a carrier gas. The temperature was raised with a rate of
1 K/min in the range of 350–770 K. On-line gas chromato-
graphic analysis was performed on a Porapak Q and a
molecular sieve column using an absolute calibration
method.
3. Results and discussion
3.1. X-ray diffraction study
The XRD patterns measured for the different mesopor-
ous silicas used as supports are shown in Fig. 1. The reflec-
Intensity, a. u.
Intensity, a. u.
SBA-15(308)
SBA-15(373,60)
SBA-15(373,75)
SBA-15(403)
0 2 4 6
2 Theta, deg
Fig. 1. SAXS patterns of various parent silicas – (a) SBA-15, (b) KIT-6 and (c) KIT-5 (the curves are shifted in y-direction in order to prevent overlapping).
329
tions can be indexed to the expected mesophases, p6mm for
SBA-15 [44,55,61,71], Fm3m for KIT-5 [47], and Ia3d for
KIT-6 [45,66], respectively. The corresponding unit cell
dimensions are given in Table 1. The repeat distances gen-
erally increase with increasing aging temperature. After the
modification of SBA-15, KIT-6 and KIT-5 series of silicas
with iron, no significant changes in the low angle X-ray dif-
fraction patterns were observed (results not shown), which
indicates that the long-range order of the silica supports are
preserved upon impregnation. The decrease in peak inten-
sities observed in the XRD patterns after modification
could be ascribed to an overall decrease in the electron den-
sity contrast between the silica wall and the mesopore due
to the location of iron oxide particles inside the mesopores
of the silicas supports. In a wide-angle region, (patterns are
not presented) no additional reflexes typical of iron con-
taining species are found, which could be attributed to their
fine dispersion.
3.2. TEM–EDX investigation
TEM images of some examples of iron modified silicas
are shown in Fig. 2, showing that the periodic order of
the mesoporous host materials is not affected by the mod-
ification. EDX measurements reveal atomic Fe/Si ratios
between 0.05 and 0.1. If we assume the samples to be
entirely composed of Fe2O3 and SiO2, this corresponds to
a weight percentage of Fe2O3 between ca. 7% and 12%; this
range was observed for most parts of the samples and fits in
with the relative quantities of iron precursor used for the
impregnation. The TEM resolution does not allow for
the distinction of iron containing particles within the silica
pores, but the EDX results indicate that iron is distributed
quite homogeneously over the samples.
KIT- 5(318)
Intensity, a. u.
KIT- 5(373)
KIT-6(308)
KIT- 5(408)
KIT- 6(373)
KIT- 6(403) KIT- 5(423)
0 2 4 6 0 2 4 6
2 Theta, deg 2 Theta, deg
330 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337

Table 1
Nitrogen physisorption parameters and unit cell dimensions for parent and iron modified SBA-15, KIT-6 and KIT-5 silicas
Sample BET (m2/g) Vtot (cm3/g) Vmic (cm3/g) Vmes (cm3/g) BET* V mes Dpores (nm) d (nm)
SBA-15(308) 431 0.39 0.04 0.35 4.5 7.6
SBA-15(373,60) 644 0.79 0.05 0.74 7.0 8.6
SBA-15(373,75) 632 0.69 0.08 0.61 6.2 8.7
SBA-15(403) 620 0.94 0.02 0.92 8.0 9.2
Fe/SBA-15(308) 379 0.36 0.04 0.32 416 0.35 4.3 7.6
Fe/SBA-15(373,60) 534 0.64 0.05 0.59 579 0.66 6.8 8.6
Fe/SBA-15(373,75) 473 0.55 0.02 0.53 527 0.59 6.0 8.7
Fe/SBA-15(403) 509 0.73 0.02 0.71 562 0.80 7.5 9.2
KIT-6(308) 359 0.26 0.10 0.16 4.4 7.7
KIT-6(373) 755 0.82 0.08 0.74 7.2 9.2
KIT-6(403) 581 0.66 0.07 0.59 8.1 9.3
Fe/KIT-6(308) 295 0.21 0.08 0.13 326 0.15 4.4 7.7
Fe/KIT-6(373) 538 0.57 0.09 0.56 580 0.64 7.2 9.2
Fe/KIT-6(403) 462 0.50 0.07 0.43 512 0.49 8.1 9.3
KIT-5(318) 341 0.21 0.09 0.12 3.8 9.5
KIT-5(373) 554 0.36 0.14 0.22 4.8 10.3
KIT-5(408) 740 0.69 0.02 0.67 7.0 11.5
KIT-5(423) 562 0.75 0.00 0.75 7.6 11.7
Fe/KIT-5(318) 118 0.11 0.02 0.09 147 0.10 4.2 9.5
Fe/KIT-5(373) 422 0.29 0.10 0.19 470 0.21 5.0 10.3
Fe/KIT-5(408) 603 0.57 0.03 0.54 667 0.61 6.2 11.5
Fe/KIT-5(423) 473 0.61 0.00 0.61 521 0.68 8.0 11.7
BET – specific surface area, Vtot – total pore volume, Vmic – microporous pore volume, Vmes – mesoporous pore volume, Dpores – pore diameters, d – unit
cell dimensions (d1 0 0 for SBA-15; d1 1 1 for KIT-5 and d2 1 1 for KIT-6), BET* and V mes calculated after mass correction.

Fig. 2. TEM images of selected silica samples after modification with iron oxide: SBA-15(373,60) (a), KIT-6(373) (b), and KIT-5(373) (c). According to
EDX measurements, the atomic Fe/Si ratios of the modified samples in these images are 0.100 for SBA-15 (a), 0.050 for KIT-6 (b), and 0.055 for KIT-5 (c).

3.3. Nitrogen physisorption
Nitrogen physisorption isotherms and pore size distribu-
tion for various parent silicas are presented in Fig. 3a, c
and e and the corresponding physicochemical parameters
are listed in Table 1. For all SBA-15 type materials the iso-
therms (Fig. 3a) are of type IV with a sharp capillary con-
densation step between 0.45 and 0.6 p/p0, typical of the
highly organized p6mm mesostructures. The pore size dis-
tribution is narrow for all synthesized materials. In accor-
dance with [44,55] a well-defined tendency of the total
pore volume and pore diameters increase with the increase
of the aging temperature and a decrease in the SiO2/P123
molar ratio is observed. The material obtained at the high-
est temperature, i.e. SBA-15(403), is characterized with the
lowest amount of micropores. All the samples of the KIT-6
series exhibit similar isotherm features as described above,
indicative of mesoporous structures with cylindrical chan-
nels (Fig. 3c). The observed steepness of the adsorption
branch obtained for KIT-6(373) is much pronounced, dem-
onstrating narrow mesopore size distribution. The position
of the adsorption curves is shifted to higher values of p/p0
with increase of aging temperature, indicating increase in
the mesopore size (Table 1), in agreement with previous
reports [45]. In contrast to the SBA-15 series, here a signif-
icant decrease in the BET surface area is found with an
aging temperature above 373 K, while under these condi-
tions the total pore volume remains almost unchanged.
At the same time all the samples exhibit higher microporos-
ity, which does not change substantially with the tempera-
ture of hydrothermal treatment. The N2-physisorption
isotherms of the samples of KIT-5 series (Fig. 3e) are of
 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337 331

3 -1
2 2

3 -1

Dv(log D), cm g
12 4 3

Dv(log D), cm g
1600 3 6 4
8 1000
1
4 4
4 3 1

1200 800

3 -1
3 -1

Vads, cm g
0
Vads, cm g

0 2 4 6 8 10 0
Pore diameter, nm 3 0 2 4 6 8 10 3
Pore diameter, nm
600
800 2
2
400
400 1
1 200

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0
3 -1

3 -1
2 2
Dv(log D), cm g

Dv(log D), cm g
6
4
3
3 3
4
3
600 2
600 2
1 1
3 -1

3 -1
2 0
Vads, cm g

Vads, cm g
0 2 4
Pore diameter, nm
6 8 10 0 2 4
Pore diameter, nm
6 8 10
2
400 400

1
200 200 1

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.60 .8 1.0
P/P0 P/P0
3 -1

3
3 -1

4
Dv(log D), cm g

4
Dv(log D), cm g

3
800 3
4 800 2
3

2
2
1
2 4
1
600
3 -1

600
3 -1

1
Vads, cm g

0 1
Vads, cm g

0
0 2 4 6 8 10
0 2 4 6 8 10
Pore diameter, nm
3 Pore diameter, nm 3
400 400

2 2
200 200
1 1
0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0

Fig. 3. Nitrogen adsorption isotherms (the curves are shifted in y-direction in order to prevent overlapping, offset value for all samples at p/p0 = 0.3 is
about 100 cm3g1 with the exception of Fe/KIT-5(318) sample, where it is 25 cm3g1) and pore size distribution (inset) for various parent (a, c and e), and
iron modified (b, d and f) SBA-15: 1-SBA-15(308), 2-SBA-15(373,60), 3-SBA-15(373,75), 4-SBA-15(403); KIT-6: 1- KIT-6(308), 2- KIT-6(373), 3- KIT-
6(403) and KIT-5: 1- KIT-5(318), 2- KIT-5(373), 3- KIT-5(408), 4- KIT-5(423) materials, respectively.

type IV with a marked capillary condensation step at high presence of larger pore entrances, and thus a more opened
relative pressures and a broad H2 hysteresis loop that is pore structure [42]. A significant amount of micropores is
indicative of large uniform cage-type pores. In agreement registered for the samples synthesized with aging tempera-
with [47], the BET surface area, pore diameter and pore tures up to 373 K, while it gradually decreases, and is even
volume tend to increase substantially with higher aging completely absent, with the further increase in temperature.
temperatures (Table 1). For the sample, synthesized at Nitrogen physisorption isotherms of all iron oxide
423 K, KIT-5(423), the shape of the hysteresis loop loaded mesoporous materials (Fig. 3b, d and f) confirm
changes and gradually closes above the lower limit of the XRD results (see Section 3.1) for the absence of signif-
hysteresis (p/p0 = 0.42), which could be ascribed to the icant structure collapse or pore blocking of the silica host
332 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337

matrix during the modification. If the increase in samples
mass upon iron oxide incorporation is corrected for (Table
1) a decrease in the total pore volume and BET surface area
is registered for all modified materials compared to the cor-
responding parent silicas. This is an evidence for the loca-
tion of iron oxide particles into the pores of the silica
supports. This effect is especially well pronounced for the
KIT-6 samples, aged at 373 K and 403 K. We would like
to also stress on the very small changes in the BET surface
area and pore volume in the case of both channel-like
structures (SBA-15 and KIT-6), obtained at the lowest
aging temperatures. This result could be attributed to the
simultaneous deposition of the iron particles in a higher
degree on the outer surface of the silica host matrix. In
addition, the microporosity remains unchanged for most
of the SBA-15 and KIT-6 based samples. This indicates
that iron species, present in the porous volume, are located
predominantly in the mesopores, which is in accordance
with the previous data for the series of iron modified
SBA-15 materials [22]. At the same time, a significant
decrease both in the microporous volume and BET surface
area, which is observed after the modified cage-like struc-
tures (KIT-5) could be assigned to the micropores blocking
by the iron particles in this case. Similar effect of significant
decrease in the microporosity with the iron deposition was
also registered for Fe/SBA-15 (100, r = 75).
3.4. Moessbauer spectroscopy
The parameters calculated based on the Moessbauer
spectra are listed in Tables 2–4. The results can be used
to compare the dispersion of the supported iron oxide
nanoparticles, applying an idealized core–shell model to
the data, under the main assumption that the doublet with
a higher QS value could be associated to surface iron atoms
possessing a higher degree of ligand coordination distor-
tion. Thus, a higher core/shell ratio could be ascribed to
the presence of larger iron particles. In most cases, the
Moessbauer spectra represent lines of doublets (Db), which
could be ascribed to Fe3+ ions in octahedral coordination,
probably belonging to hematite nanoparticles with sizes
below 10–12 nm, exhibiting superparamagnetic behaviour
[9,72]. The core/shell ratios for the various iron oxide
doped SBA-15 are close to 1, suggesting that the iron oxide
dispersion is independent of the pore characteristics of the
support for this class of materials. Core/shell ratios close to
1 are also obtained for iron doped KIT-6(373), KIT-6(408),
KIT-5(403), and KIT-5(423). On the contrary, the Moess-
bauer spectra of Fe/KIT-6(308), Fe/KIT-5(318) and Fe/
KIT-5(373) consist of a doublet and a sextet (Sx) which
indicates the presence of iron oxide particles with different
dispersion. The lower values of Heff for the sextet compo-
nent can be explained with the presence of larger hematite
particles, with sizes exceeding 10–12 nm, which thus must
be located on the outer surface of the silica support, in
agreement with the nitrogen sorption results (see above).
3.5. TPR-TGA study
An additional distinction in the state of the iron oxide
nanoparticles in the studied nanocomposites was achieved
following their reductive behaviour in TPR-TG experi-
ments (Fig. 4). In most cases, the reduction degree of the
samples does not exceed 60%, the fact once again confirm-
ing the presence of highly dispersed, strongly interacting
with the support iron oxide species [10,73–76]. Three reduc-
tion peaks, centered at 550–580, 650–720 and above 800 K,
could be distinguished in the TPR profiles of the iron mod-
ified porous silicas. The first and the second one are often
associated with the reduction of iron ions at the surface
and in the bulk of the 3-dimensional hematite nanoparti-
cles, respectively. According to [10], the third peak, proba-

Table 2
Moessbauer parameters for iron modified SBA-15 silica materials before and after (-C) the catalytic test
Sample Compound IS (mm/s) QS (mm/s) Heff (T) FWHM (mm/s) G (%)
Fe/SBA-15(308) Db 1-Fe2O3 SPM-core 0.34 0.61 – 0.40 50
Db 2-Fe2O3 SPM-shell 0.34 0.99 – 0.53 50
Fe/SBA-15(373,60) Db 1-Fe2O3 SPM-core 0.34 0.63 – 0.42 52
Db 2-Fe2O3 SPM-shell 0.33 1.09 – 0.54 48
Fe/SBA-15(373,75) Db 1-Fe2O3 SPM-core 0.34 0.68 – 0.38 50
Db 2-Fe2O3 SPM-shell 0.34 1.14 – 0.49 50
Fe/SBA-15(403) Db 1-Fe2O3 SPM-core 0.34 0.67 – 0.37 51
Db 2-Fe2O3 SPM-shell 0.34 1.13 – 0.46 49
Fe/SBA-15(308)-C Db 1-Fe2O3 SPM-core 0.35 0.65 – 0.48 50
Db 2-Fe2O3 SPM-shell 0.33 1.09 – 0.63 50
Fe/SBA-15(373,60)-C Db 1-Fe2O3 SPM-core 0.35 0.72 – 0.46 53
Db 2-Fe2O3 SPM-shell 0.35 1.23 – 0.56 47
Fe/SBA-15(373,75)-C Db 1-Fe2O3 SPM-core 0.35 0.72 – 0.45 49
Db 2-Fe2O3 SPM-shell 0.35 1.22 – 0.56 51
Fe/SBA-15(403)-C Db 1-Fe2O3 SPM-core 0.35 0.71 – 0.43 47
Db 2-Fe2O3 SPM-shell 0.34 1.20 – 0.55 53
Isomer shift (IS), quadrupole splitting (QS), effective internal magnetic field (Heff), line widths (FWHM), relative weight of the partial components in the
spectra (G).
 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337 333

Table 3
Moessbauer parameters for iron modified KIT-6 silica materials before and after (-C) the catalytic test
Sample Compound IS (mm/s) QS (mm/s) Heff (T) FWHM (mm/s) G (%)
Fe/KIT-6(308) Sx-a-Fe2O3 0.37 0.10 51.0 0.38 16
Db 1-Fe2O3 SPM-core 0.35 0.63 – 0.38 42
Db 2-Fe2O3 SPM-shell 0.34 1.05 – 0.49 42
Fe/KIT-6(373) Db 1-Fe2O3 SPM-core 0.34 0.63 – 0.42 50
Db 2-Fe2O3 SPM-shell 0.33 1.10 – 0.51 50
Fe/KIT-6(403) Db 1-Fe2O3 SPM-core 0.35 0.66 – 0.36 49
Db 2-Fe2O3 SPM-shell 0.34 1.11 – 0.45 51
Fe/KIT-6(308)-C Sx 1-Fe3O4 0.30 0.00 47.6 0.60 7
Sx 2-Fe3O4 0.63 0.00 45.1 0.80 9
Db 1-Fe2O3 SPM-core 0.35 0.62 – 0.42 40
Db 2-Fe2O3 SPM-shell 0.35 1.09 – 0.65 45
Fe/KIT-6(373)-C Db 1-Fe2O3 SPM-core 0.34 0.68 – 0.44 48
Db 2-Fe2O3 SPM-shell 0.35 1.15 – 0.59 52
Fe/KIT-6(403)-C Db 1-Fe2O3 SPM-core 0.34 0.77 – 0.42 50
Db 2-Fe2O3 SPM-shell 0.35 1.25 – 0.58 50
Isomer shift (IS), quadrupole splitting (QS), effective internal magnetic field (Heff), line widths (FWHM), relative weight of the partial components in the
spectra (G).

Table 4
Moessbauer parameters for iron modified KIT-5 silica materials before and after (-C) the catalytic test
Sample Compound IS (mm/s) QS (mm/s) Heff (T) FWHM (mm/s) G (%)
Fe/KIT-5(318) Sx-a-Fe2O3 0.37 0.11 51.2 0.32 57
Db 1-Fe2O3 SPM-core 0.35 0.72 – 0.35 20
Db 2-Fe2O3 SPM-shell 0.35 1.20 – 0.47 23
Fe/KIT-5(373) Sx-a-Fe2O3 0.37 0.11 51.0 0.40 18
Db 1-Fe2O3 SPM-core 0.34 0.72 – 0.39 43
Db 2-Fe2O3 SPM-shell 0.33 1.21 – 0.48 39
Fe/KIT-5(408) Db 1-Fe2O3 SPM-core 0.34 0.67 – 0.39 49
Db 2-Fe2O3 SPM-shell 0.34 1.10 – 0.51 51
Fe/KIT-5(423) Db 1-Fe2O3 SPM-core 0.35 0.71 – 0.38 48
Db 2-Fe2O3 SPM-shell 0.34 1.16 – 0.50 52
Fe/KIT-5(318)-C Sx-Fe3C 0.21 0.03 20.2 0.66 56
Db 1-Fe2O3 SPM-core 0.35 0.73 – 0.34 20
Db 2-Fe2O3 SPM-shell 0.34 1.22 – 0.45 24
Fe/KIT-5(373)-C Sx 1-Fe3O4 0.31 0.00 47.6 0.60 8
Sx 2-Fe3O4 0.64 0.00 45.1 0.80 10
Db 1-Fe2O3 SPM-core 0.35 0.72 – 0.46 38
Db 2-Fe2O3 SPM-shell 0.36 1.24 – 0.57 44
Fe/KIT-5(408)-C Db 1-Fe2O3 SPM-core 0.34 0.74 – 0.44 49
Db 2-Fe2O3 SPM-shell 0.35 1.20 – 0.60 51
Fe/KIT-5(423)-C Db 1-Fe2O3 SPM-core 0.35 0.74 – 0.40 48
Db 2-Fe2O3 SPM-shell 0.34 1.24 – 0.51 52
Isomer shift (IS), quadrupole splitting (QS), effective internal magnetic field (Heff), line widths (FWHM), relative weight of the partial components in the
spectra (G).

bly arises from the reduction of 2-dimensional FeOx
patches and partially, from the reduction of isolated FeOx
species, in different degree of coordination with the surface
oxygen atoms.
Based on the position and the relative part of the
observed TPR effects, some differences in the sate of iron
oxide particles, hosted into various silica supports, could
be found. Summarizing the Moessbauer and TPR results,
it could be concluded that the most homogeneously dis-
persed, easily reducible, and thus not strongly interacting
with the silica support, iron oxide nanoparticles are formed
in the Fe/KIT-6(373) composite material. On the contrary,
inhomogeneously dispersed hematite species could be
assumed for all SBA-15 modifications. The more pro-
nounced low-temperature effect in the TPR profile of the
Fe/SBA-15(308) and Fe/SBA-15(403) samples could be
attributed to the presence of iron oxide particles with
higher accessibility, caused by their location on the outer
surface or in the larger 1-dimensional channels of the sup-
port, respectively. The similar effect obtained for SBA-
15(373,75) could be also due to the presence of relatively
larger particles, but probably located nearby the entrances
of the micropores and/or in them (see Section 3.3). A large
low-temperature TPR peak is also registered for Fe/KIT-
6(308), Fe/KIT-5(318) and Fe/KIT-5(373). All these mate-
rials were obtained with silicas exhibiting small pore
334 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337

Fe/KIT-6(403)
Fe/KIT-5(423)
Fe/SBA-15(403)

Fe/KIT-5(408)
Fe/KIT-6(373)
Fe/SBA-15(373,75)

DTG, a.u.
DTG, a.u.

DTG, a.u.
Fe/KIT-5(373)

Fe/SBA-15(373,60)

Fe/KIT-5(318)
Fe/KIT-6(308)
Fe/SBA-15(308)

1h at 870K
1h at 870K 1h at 870K
450 660 870 450 660 870
450 660 870
Temperature, K Temperature, K Temperature, K

Fig. 4. TPR-TG profiles of various iron modified silicas – (a) SBA-15, (b) KIT-6 and (c) KIT-5.

volumes, pore diameters or cage entrances. Inhomoge-
neously dispersed iron oxide nanoparticles, but with a large
fraction of isolated iron species, strongly interacting with
the support, are obtained for the silicas with relatively large
pores (for the channel-like structures) or pore entrances
(for the cage-like ones).
3.6. Catalytic test
For completeness, the overall state of iron oxide nano-
particles, including their environment in the nanometer-
sized pores of the silica host matrix, is elucidated by
methanol decomposition as a catalytic test (Figs. 5–7).
For all samples a significant methanol conversion is
achieved above 550–575 K, methane and CO being the
only registered carbon containing products (for simplicity,
their distribution is presented in the figures as methane
selectivity).
The obtained iron oxide nanocomposites on the base of
SBA-15 silicas are hardly distinguished in their catalytic
activity and selectivity (Fig. 5) as well as in their phase
transformations after the catalytic test (Table 2), where
only a very low degree of the particles agglomeration is
observed. This result is not surprising, taking into account
the similarity in the Moessbauer characteristics of the par-
ticles before the catalytic test (Table 2).

100 100
Fe/SBA-15(308) Fe/SBA-15(308)
Fe/SBA-15(373,60) Fe/SBA-15(373,60)
Fe/SBA-15(373,75) Fe/SBA-15(373,75)
80 Fe/SBA-15(403) 80 Fe/SBA-15(403)
Methane selectivity, mol %
Conversion, mol %

60 60

40 40

20 20

0 0
450 500 550 600 650 700 750 450 500 550 600 650 700 750
Temperature, K Temperature, K

Fig. 5. Methanol conversion (left) and methane selectivity (right) on iron modified SBA-15, synthesized at various temperatures and silica/template ratios.
Despite the variations in the support pore characteristics, similar catalytic behaviour is observed for all samples.
 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337 335

100 100
Fe/KIT-6(308) Fe/KIT-6(308)
Fe/KIT-6(373) Fe/KIT-6(373)
Fe/KIT-6(403) Fe/KIT-6(403)
80 80

Methane selectivity, mol %

Conversion, mol %
60 60

40 40

20 20

0 0
450 500 550 600 650 700 750 450 500 550 600 650 700 750
Temperature, K Temperature, K

Fig. 6. Methanol conversion (left) and methane selectivity (right) on iron modified KIT-6 silicas, obtained at different temperatures of hydrothermal
synthesis. Higher catalytic activity, combined with lower selectivity to methane is observed for the sample with higher BET surface area and intermediate
pore diameter.

100 100
Fe/KIT-5(318) Fe/KIT-5(318)
Fe/KIT-5(373) Fe/KIT-5(373)
Fe/KIT-5(408) Fe/KIT-5(408)
80 Fe/KIT-5(423) 80 Fe/KIT-5(423)
Methane selectivity, mol %
Conversion, mol %

60 60

40 40

20 20

0 0
450 500 550 600 650 700 750 450 500 550 600 650 700 750
Temperature, K Temperature, K

Fig. 7. Methanol conversion (left) and methane selectivity (right) vs temperature on iron modified KIT-5 silicas, synthesized at different temperatures. Best
catalytic activity and lower selectivity to methane is found for the support with not very opened cage-like structure.

The catalytic effects for the Fe/KIT-6 composites
(Fig. 6) are significantly more distinguished in comparison
to those of Fe/SBA-15, which well correlates with the
observed differences in the initial iron particles state (see
above). Here, the highest catalytic activity combined with
high selectivity to CO is registered for Fe/KIT-6(373), in
agreement with the presence of a large fraction of more eas-
ily reducible iron oxide particles in this material. Contrary
to that, the activity in methanol conversion is relatively
lower, but combined with high methane selectivity for
Fe/KIT-6(403). Taking into account the similarity in the
initial phase composition and that one after the catalytic
test for both compared samples (Table 3), here once again
could be underlined that the iron oxide nanoparticles differ
significantly in their state and environment in both silicas,
being less homogeneously dispersed but highly accessible in
the silica with larger mesopores – Fe/KIT-6(403). A signif-
icantly higher methane selectivity combined with essential
reductive phase transformations during the catalytic pro-
cess (Table 3), with the formation of magnetite phase, is
observed for Fe/KIT-6(308), which could be ascribed to
the presence of relatively larger hematite particles in the
336 T. Tsoncheva et al. / Microporous and Mesoporous Materials 112 (2008) 327–337
sample before the catalytic test, and as it has been already
mentioned, located in a high extent on the outer surface.
Iron oxide nanoparticles, hosted in the KIT-5 cage-like
structures, also differ significantly in their catalytic behav-
iour (Fig. 7). More opened pore structure of KIT-5(408)
and KIT-5(423) favors the formation of relatively large
fraction of finely dispersed hematite particles (see above),
which exhibit lower catalytic activity in methanol decom-
position. On the contrary, the silicas synthesized at lower
temperatures and characterized with small pore volume
and pore entrances and larger iron oxide particles, form
composites which are highly active in methanol decompo-
sition, where the selectivity depended on the phase trans-
formations under the reaction medium (formation of iron
carbide or magnetite for Fe/KIT-5(318) and Fe/KIT-
5(373), respectively, Table 4). This assumption is in accor-
dance with our previous results for other mesoporous silica
materials, where we have found a size determined effect of
iron species on their catalytic activity and selectivity in
methanol decomposition, combined with the correspond-
ing iron oxide reductive phase transformations under the
influence of the reaction medium [20–22]. Thus, once again
we could stress that methanol decomposition can be used
as a sensitive test reaction for determining the level of dis-
persion of iron oxide species and their location.
4. Conclusions
Summarizing the results of our investigations, it could
be concluded that the state of iron species, hosted in
mesoporous silicas, as well as their reductive and cata-
lytic properties in methanol decomposition, depend on
the pore topology of the silica support. The presence of
well-developed pore structures of the host matrix seems
to be of primary importance for the stabilization of the
iron oxide nanoparticles inside the mesopores. Their
homogeneous dispersion is favored by presence of cylin-
drical pores with high degree of interconnectivity and
optimal (about 7 nm) pore size. These materials, with
3-D interconnected network of easily accessible large
cylindrical mesopores, are more suitable as a catalyst
support compared to other 2-D pore systems or cage-like
materials.
However, the location of a fraction of the iron particles
on the outer surface of the silica host, which was observed
for some of the samples prepared by the impregnation
method, makes unambiguous conclusions about a direct
relationship between the pore structure and the state of
iron species difficult to establish. This aspect requires fur-
ther investigations including other methods of iron oxide
modification, that provide exclusive location of the metal
oxide particles within the pores of the host matrix.
Acknowledgments
We thank Prof. Michael Fröba for his support. Finan-
cial support by the Bulgarian–Finland interacademic ex-
change, Bulgarian Academy of Sciences and the Deutsche
Forschungsgemeinschaft is gratefully acknowledged.
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