Fe-MCM-22 zeolite: synthesis and study about the states of iron - Ngô Thị Thuận
1. Successful synthesis of Fe-MCM-22
under hydrothermal condition using HMI
template was confirmed by XRD.
2. As-synthesized zeolite has relatively high
surface area, 286 m2/g (BET). Its white colour
and a band at 950 cm-1 partially overshadowed
by the strong absorption centered at 1100 cm-1
in IR spectra suggested a location of iron
species at framework positions.
3. ESR results showed that iron exists under
three states in as-synthesized: Fe-MCM-22
framework iron, iron in interstitial oxide or372
hydroxide phases and iron in cation-exchange
sites corresponding with g = 4.35, g = 2.35 and
g = 2.03, respectively.
4. A more detailed discussion about the
states of iron in this catalyst by means of XPS
and Mossbauer spectroscopy is under way
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368
Journal of Chemistry, Vol. 45 (3), P. 368 - 372, 2007
Fe-MCM-22 zeolite: synthesis and study about the
states of iron
Received 13 June 2006
Ngo Thi Thuan1, Tran Thi Nhu Mai1, Giang Thi Phuong Ly1, Le Xuan Tuan
1Faculty of chemistry, VNUH, 19 Le Thanh Tong Street, Hanoi Vietnam
2Service de Chimie Analytique et Chimie des Interfaces (CHANI) – CP 255 Belgium
Summary
The Fe-MCM-22 zeolite was successfully synthesized with hexametylenimine template.
Several physicochemical techniques (XRD, SEM, BET, AAS, IR and ESR) have been used to
characterize this zeolite. Iron exists under three states: isolated ions in tetrahedral lattice
positions, in octahedral coordination as isolated ions at cationic positions and as aggregated
oxide species or hydroxide phases.
Keywords: Fe-MCM-22 zeolite, synthesis, characterization, framework iron.
I - Introduction
MCM-22 zeolite is a new patent given by
Cooperation Mobil Oil [1]. In the last ten years,
its properties were thoroughly investigated. The
framework topology of MCM-22 has been
shown to consist of layers linked together along
the c-axis by oxygen bridges and contain two
independent pore systems. Within the layers are
two-dimensional sinusoidal 10-MR channels
(4.1 × 5.1 Å), and between two adjacent layers
are 12-MR supercages (~7.1 × 7.1 × 18.2 Å)
communicating each other through 10-MR
apertures (4.0 × 5.5 Å). In addition, its typical
thin platelet morphology results in high external
surface area [2]. Dealuminated acid forms of
MCM-22 have been characterized, concluding
that the acidic properties are very similar to H-
ZSM-5 zeolite [3]. Nowadays, the synthesis
parameters for the preparation of MCM-22
zeolite have been optimized [4].
Formerly, zeolite used to be known as an
acidic catalyst. It is well known that the addition
of transition metals, especially iron, in initial gel
for zeolite synthesis was enormously studied.
The presence of different iron species in zeolite
created several new activities for this kind of
material. This material, besides the known
Bronsted acidic properties, shows such a lot of
special catalytic activities in oxidation reaction.
Until now, there are some researches which
studied the synthesis of Fe-MCM-22 zeolite [5,
6]. In this work, we have successfully prepared
Fe-MCM-22 zeolite. Several physicochemical
techniques were used to characterize the
extraframework and framework irons. The
capacity of each technique for verifying the
states of iron was discussed in detail.
II - Experimental
Fe-MCM-22 was synthesized according to
the procedure given by F. Testa et al [5], it may
be summarized as presented in Fig. 1. The
general composition of the initial gel leading to
Fe-MCM-22 was 6Na2O-60SiO2-1.5Fe(NO3)3-
30HMI-2320H2O. The white crystallized was
washed until reaching neutral pH and calcited in
369
dry air at temperature of 500°C for 6 h to
remove all HIM templates.
Instrumentation
Powder X-ray diffraction (XRD) patterns
were recorded on a Siemens D5005
diffractometer with a CuK radiation. Chemical
composition of sample was analyzed by a
Perkin–Elmer AAS instrument. SEM image was
taken by JSM 54102V machine under vacuum
condition at room temperature and ESR
spectrum was recorded at room temperature on a
Brucker ER200D ESR spectrometer equipped
with a dual cavity and a 100-kHz modulation
unit.
III - Results and Discussion
MCM-22 structure of our zeolite sample was
confirmed by comparing the XRD spectra with
the reference spectrum of MCM-22 sample
taken as standard. Its X-ray diffractogram was
similar to those reported by P.Chu et al [1] (not
shown in this article). According to F. Testa et
al [5], the typical peak of MCM-22 standard (d=
3.42 and 2 of 26.0) appeared in all sample with
high intensity (figure 2). SEM photograph of as-
synthesized zeolite was shown in figure 3,
crystal MCM-22 has form of thin plate. It is
similar to that of Fe-MCM-22 reported by F.
Testa et al [5] while surface area (286 m2/g)
measured by BET method was slightly smaller
than surface area of Fe-MCM-22 reported (308
m2/g). Some main characteristics of this material
were presented in table 1.
Figure 2: X-ray diffractogram
Fe(NO3)3.9H2O + fumed SiO2 + H2O
NaOH solution
Homogenization
Iron silicate gel
drop by drop
Orange-brown gel HIM template
Hydrothermal
crystallization at
150°C for 9 days
Separation of
crystals, washing
and drying at
Figure 1: Synthesis procedure of
Fe-MCM-22
370
Figure 3: SEM image of as-synthesized zeolite
Table 1: Main characteristics of as-synthesized
zeolite
Structure MCM-22
Color White
Surface area 286 m2/g *
Si/Fe 40
Fe wt. 0.70 (%)
(* )Measured by BET.
Infrared spectroscopy is a useful means to
study material surface. It has been more and
more extended in the characterization of zeolite.
Meaningful information concerning the iron
structure in the zeolite framework has been
obtained by exploring both the hydroxyl
stretching (3800 - 3400 cm-1) and framework
(1350 - 400 cm-1) regions [7]. Figure 4 presents
the typical framework bands of Fe-MCM-22
sample. The band at 550 cm-1 is assigned to the
vibration of double-rings in MFI lattice [8]. In
particular, the absorption in the range of 1250 -
950 cm-1 can be interpreted as deriving from the
asymmetric modes with T2 symmetry in the
isolated [SiO4] units. Because of characterizing
for the asymmetric valence vibration in the
tetrahedral TO4, this band depends on the
amount of transition metal in zeolite framework.
Bordiga et al [7] found a shoulder at 1006 cm-1
partially overshadowed by the strong absorption
centered at 1150 cm-1 on the IR spectrum of
iron-substituted silicate and assumed that the
bands at 1006 cm-1 can be explained on the
basis of a fully ionic model: in this case the
local structure surrounding the framework Fe3+
species is described by 4 [O3Si-O
-] units.
Returning to Fe-MCM-22, a band at 950 cm-1
partially overshadowed by the strong absorption
centered at 1100 cm-1 was also observed (Fig.
4). Bordiga et al [7] hypothesized that these new
bands at 950 cm-1 are mainly associated with the
vibrational modes of the O3SiO
- units
surrounding the Fe3+ centre.
Figure 4: IR spectra of as-synthesized Fe-MCM-22
371
The first visual indication of location of iron
species at framework positions in as-synthesized
zeolite is the white color of crystallized product
[9]. Information about the state of iron in as-
synthesized Fe-MCM-22 was obtained by
further ESR investigations. It is easy to observe
that ESR spectra of the sample at room
temperature are very similar to those of Fe-
ZSM-5 and Fe-MFI zeolites published
elsewhere [9, 10]. Three characteristic features
can be recognized at g = 4.35, g = 2.35 and g =
2.03. We did not detect any other signals in ESR
spectra of our sample. Assignment of these
three signals appeared in zeolite containing iron
was discussed in the literature [5, 7 - 12]. The
commonly accepted assignment of these signals
is as follows: (g = 4.35) framework iron, (g =
2.35) iron in interstitial oxide or hydroxide
phases, and (g = 2.03) iron in cation-exchange
sites, respectively [9,10]. ESR is nowadays
predominantly used to check the g ~ 4.3 signals
in order to confirm the tetrahedral substitution
[13]. The intensity of this signal is lower at high
temperature [5]. This may be explained basing
on the state transformation of iron from
framework to extra-framework with increasing
of temperature of heat treatment procedure [14].
F. Testa et al [5] said that the framework iron
tetrahedral species can be included in the ESR
signal observed at low magnetic field, where
only the middle of the spectrum was computed
to be between 4.23 and 4.56, the latter species
are considered as deformed tetrahedral species.
The signal at g ~ 2.0 is known to be strongly
affected by the water vapor content and it
diminishes with water vapor for FAPO-5
whereas it grows with water vapor for Fe-ZSM-
5 [11, 12].
-25000
-20000
-15000
-10000
-5000
0
5000
10000
15000
01234567
g=4.35 g=2.35 g=2.03
H
Figure 5: ESR spectrum of as-synthesized Fe-MCM-22
IV - Conclusions
1. Successful synthesis of Fe-MCM-22
under hydrothermal condition using HMI
template was confirmed by XRD.
2. As-synthesized zeolite has relatively high
surface area, 286 m2/g (BET). Its white colour
and a band at 950 cm-1 partially overshadowed
by the strong absorption centered at 1100 cm-1
in IR spectra suggested a location of iron
species at framework positions.
3. ESR results showed that iron exists under
three states in as-synthesized: Fe-MCM-22
framework iron, iron in interstitial oxide or
372
hydroxide phases and iron in cation-exchange
sites corresponding with g = 4.35, g = 2.35 and
g = 2.03, respectively.
4. A more detailed discussion about the
states of iron in this catalyst by means of XPS
and Mossbauer spectroscopy is under way.
Acknowledgements: This research was
supported by Vietnam National University,
Hanoi-Asia Research Center. The authors wish
to thank Mr. P. Q. Nghi (Universite du Maine,
Le Mans-France) for measuring ESR and his
helpful discussions.
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