Journal of Molecular Structure 1126 (2016) 147e153

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Modification of ferrierite through post-synthesis treatments. Acidic

and catalytic properties
Kamila Brylewska a, b, Karolina A. Tarach a, Włodzimierz Mozgawa b,
 ra-Marek a, *
Zbigniew Olejniczak c, Urszula Filek d, Kinga Go
a
Faculty of Chemistry, Jagiellonian University in Krakow, 3 Ingarden St., 30-060 Krako
w, Poland
b
Faculty of Materials Science and Ceramics, AGH University of Science and Technology in Krako w, 30 Mickiewicz Av., 30-059 Krako
w, Poland
c
H. Niewodniczan ski Institute of Nuclear Physics of PAN, 152 Radzikowski St., 31-342 Krako
w, Poland
d
Jerzy Haber Institute of Catalysis and Surface Chemistry, PAS, 8 Niezapominajek St., 30-239 Krakow, Poland

a r t i c l e i n f o a b s t r a c t

Article history: The main emphasis of this work was placed on a detailed characterization of structural, textural and
Received 9 November 2015 acidic properties of FER zeolites with different Si/Al ratios in terms of their activity in ethanol dehy-
Received in revised form dration reaction. Subsequent dealumination and desilication procedures were found to be an efficient
15 December 2015
methods of a secondary system of mesopore generation in the ferrierite crystals with preservation of
Accepted 16 December 2015
their microporous characteristics. Through ethanol dehydration both the acidic and the textural features
Available online 19 December 2015
have a significant influence on catalytic performance of hierarchical ferrierites. It was shown that higher
catalytic activity and selectivity to ethylene is ensured by zeolites with highly preserved microporous
Keywords:
Zeolites
characteristic, i.e. well-developed micropore area and intrinsic acidity.
Ferrierite © 2015 Elsevier B.V. All rights reserved.
Desilication
Dealumination
Ethanol dehydration

1. Introduction down procedures are based on preferential extraction of the two

Unique properties of zeolites inherent for their microporous
nature are responsible for a wide range of their applications in the
refining chemistry, petrochemistry [1,2], environmental protection
[3], and adsorption processes [4]. Both architecture of uniform
micropores of molecular dimensions (typically 0.25e1 nm) and the
presence of strong Brønsted acidity are typical of zeolite structure
only [5,6]. Despite undisputable advantages, zeolite based catalysts
have one main drawback concerning internal diffusion limitations,
particularly when large molecules are involved [7]. This limitation
leads to a decrease in catalytic activity due to restricted access of
reagents to micropores and their slow molecular transport to and
from active sites. Therefore zeolite based materials that combine
the presence of strong acid sites, responsible for the catalytic ac-
tivity, with system of mesopores, providing the overcome of in-
ternal diffusion limitations, are attractive catalysts in various
reactions. Methods of synthesis of zeolites with secondary meso-
porosity have been assembled around two main approaches. Top-
* Corresponding author.
 ra-Marek).
E-mail address: kinga.goramarek@gmail.com (K. Go
main structural units of zeolites [8], i.e. [SiO4]4- tetrahedra (via
desilication) [9], or [AlO4]5- ones (via dealumination) [10]. Bottom-
up techniques employ templates (e.g. surfactants, porous carbon or
carbon nanotubes, mesoscale cationic polymers, etc.) and further
modifications including synthesis of both nanosized zeolite crystals
[11], zeolitization of mesoporous materials and recrystallization.
Top-down methods lead to the formation of an intracrystalline
mesoporosity while the bottom-up approach focuses on the gen-
eration of an interparticle mesoporosity.
Ferrierite (FER) is a well-known medium-pore zeolite with a
system of intersecting channels of 8- and 10-membered rings
(MRs) [12]. In addition, 6-MR channels run along the [001] direc-
tion. Intersection of the 8-MR and 6-MR channels leads to forma-
tion of spherical ferrierite cages accessible through 8-MR windows
[13,14]. Both in H-form and metal-exchanged ferrierites exhibit
remarkable catalytic performance in a various acidic and redox
reactions regarding high stability toward (hydro)thermal and
chemical treatments, e.g. skeletal isomerization of n-alkenes to
isoalkenes [15,16], n-paraffin cracking [17], alkane hydro-
isomerization [18], styrene epoxidation [19], NOx reduction [20],
and N2O decomposition [21]. However, a factor that limits full

http://dx.doi.org/10.1016/j.molstruc.2015.12.046
0022-2860/© 2015 Elsevier B.V. All rights reserved.
148 K. Brylewska et al. / Journal of Molecular Structure 1126 (2016) 147e153
potential of ferrierite in some of the above reactions is a reduced
dimension of the pore system, especially 8-MR pores, in relation to
size of typical substrates. From the point of view of catalytic ap-
plications, a material with an ideal acidic properties should be
found at the crossing point of zeolitic route ensuring high con-
centration and strength of acid sites and mesoporous route guar-
anteeing the highest possible accessibility of acid sites to bulky
reagent molecules. It is a common agreement that demetalation
procedures can lead to a distortion of crystal structure, an
appearance of amorphous phase, or a total destruction of zeolite
structure. However, properly selected modification conditions
allow generating of mesopores in zeolite structure and preservation
of their crystallinity. Our studies were aimed at hierarchization of
ferrierite that allowed overcoming of the diffusion restrictions in 8-
MR ferrierite channels thus improving the catalytic efficiency of
this material. The main emphasis was placed on development of
cheap and efficient method of mesopores generation in 8-MR
zeolite, for which attempts so far undertaken were ineffective.
2. Experimental
2.1. Catalyst preparation
Parent ferrierites (Si/Al ¼ 9, HSZ-720KOA, Tosoh Co.; Si/Al ¼ 23,
CP914, Zeolyst) hereafter denoted as FER/9/P and FER/23/P were
modified by demetalation post-treatment methods. Dealumination
was carried out with 0.2 M HNO3 solution (100 ml of solution per
3 g zeolite) at 65  C for 30 min. After dealumination, samples were
colled down in ice-bath, filtrated and washed with distillate water
until neutral pH. Then, dealuminated samples Fer/9/deAl and Fer/
23/deAl were alkaline treated with 0.2 M LiOH solution (100 ml of
solution per 3 g zeolite) at 65  C for 30 min and named Fer/9/deAl/
deSi and Fer/23/deAl/deSi. As before, after desilication samples
were cooled down in ice-bath, filtered and washed with distillate
water until neutral pH. Subsequently, all samples were subjected to
threefold Naþ/NHþ 4 ion-exchange with 0.5 M NH4NO3 solution
carried out at 60  C for 1 h. Finally, the obtained materials were
again filtrated, washed (pH ¼ 7) and dried at room temperature. All
procedures applied for parent ferrierites modification were sum-
marized in Table 1. Also, notation of resulting materials was also
presented therein.
2.2. Characterization methods
2.2.1. Chemical composition, structural and textural studies
Powder X-ray diffraction (XRD) measurements were carried out
using a X'Pert Pro Philips (PANalytical Cubix diffractometer), with
CuKa radiation, l ¼ 1.5406 Å and a graphite monochromator in 2q
angle range of 10e40 . X-ray powder patterns were used for
structural identification of relative crystallinity value (%cryst.) for
all zeolites. Crystallinity of studied samples was determined as a
sum of integral intensity of the most intense reflections in range of
2q of 22 e27 and of integral intensity of parent zeolite's reflection.
Results are shown in percentage scale.
Table 1
Detailed procedures and conditions of modification of studied zeolites.
Type of modification
ion-exchange Naþ/NHþ
4 0.5 M NH4NO3, T ¼ 60  C, t ¼ 1 h
dealumination/ion-exchange Naþ/NHþ
4 0.2 M HNO3, T ¼ 65  C, t ¼ 30 min
dealumination/desilication/ion-exchange Naþ/NHþ
4 0.2 M LiOH, T ¼ 65  C, t ¼ 30 min
Si and Al concentrations in studied materials were determined
by XRF method using an Energy-Dispersive XRF spectrometer
(Thermo Scientific, ARL QUANT’X with the Rh anode, the X-rays of
4e50 kV (1 kV step), 1 mm size beam).
The N2 sorption processes at 196  C were studied on an ASAP
2420 Micromeritics after activation in vacuum at 400  C for 12 h.
Surface area (SBET) and micropore volume (Vmicro) were determined
by applying BET and t-plot methods, respectively. Pore size distri-
bution and volume of mesopores (Vmeso) were obtained by applying
the BJH model to adsorption branch of the isotherm.
2.2.2. IR spectroscopic characterization e the concentration of acid
sites
For FTIR studies, the samples were pressed into the form of self-
supporting wafers (ca. 5 mg/cm2) and evacuated in IR cell at 500  C
under vacuum for 1 h. To obtain information on the concentration
of Brønsted and Lewis acid sites the vacuum treated zeolites were
saturated with an excess of pyridine (Py) at 330  C, and then
evacuated at 170  C to removed physisorbed Py molecules. The IR
spectra were recorded with a Bruker Tensor 27 spectrometer
equipped with a MCT detector. The spectral resolution was 2 cm1.
All the spectra presented in this work were normalized to 10 mg of
sample.
2.3. Catalytic tests
Activities of the modified ferrierites were studied in ethanol
dehydration in vapour phase. For each experiment, 0.05 g of fresh
catalyst was mixed with 0.5 g of quartz grains and placed in a
differential microreactor connected on line with a gas chromato-
graph. Reaction products were analysed using a Perkin Elmer Clarus
580 equipped with Elite-Plot Q capillary column (30 m of length,
0.53 mm of inner diameter) and TCD detector. Prior to the catalytic
reaction the samples were standardized under continuous helium
flow for 30 min at 300  C. Then helium as a carrier gas was passed
over liquid ethanol maintaining a concentration of ethanol in he-
lium flow 0.56 mmol/dm3. The total flow rate of the feed stream
was kept at 35 cm3/min. The reaction temperature was changed
from 100 to 300  C. The space velocity in performed catalytic test
was kept at 1.1 gethanol/(gcatalyst$h). The calculation of TOF (turnover
frequency/s1) values was based on equation (1) given in
Refs. [22,23]:
 

Reactant flow rate mmol s1  Conversion
TOF s1 ¼

Quantity of sites mmol g 1  Catalyst weight ð g Þ
(1)
3. Results and discussion
3.1. Structural and textural characteristics
Fig. 1 presents X-ray diffraction patterns of parent and acid/base
Conditions Notation
FER/9/P
FER/23/P
FER/9/deAl
FER/23/deAl
FER/9/deAl/deSi
FER/23/deAl/deSi
 K. Brylewska et al. / Journal of Molecular Structure 1126 (2016) 147e153 149

partly plaguing micropore system [25]. The most efficient method

of mesopore formation turned out to be acid and base subsequent
treatments. This modification allowed generating of mesopores
(Smeso ¼ 108 m2/g, Vmeso ¼ 0.24 cm3/g) in ferrierite structure and
maintaining its crystallinity (86%).

3.2. IR spectroscopic characterization

3.2.1. Nature of hydroxyl groups

An analysis of position and intensity of the hydroxyl bands
typical for studied materials allowed us to obtain preliminary in-
formation on their acid properties. Several kinds of species can be
distinguished in IR spectrum in OeH stretching vibrations' region
(Fig. 2): silanols located on external and mesopore surfaces
(3745 cm1), hydroxyls attributed to extraframework aluminium
species (3645 cm1) and acidic SieOHeAl groups (3595 cm1)
[26e30]. The intensities of the SieOHeAl groups band in native
zeolite FER/23/P is noticeably (5-fold) smaller than in FER/9/P,
despite 3.5-fold difference in aluminum content between both
zeolites. Indeed, the presence of 3645 cm1 band in the IR spectrum
of FER/23/P suggests that not all Al atoms are in tetrahedral
framework positions generating acidic SieOHeAl species, part of
them exist as extraframework material.
In the case of both dealuminated zeolites, a small reduction of
the intensity of the acidic groups SieOHeAl band (3595 cm1) can
be observed due to the extraction of aluminum atoms from zeolite
structure.
It is well known [30,31] that alkaline leaching of 10- and 12-MR

Fig. 1. XRD patterns of parent and modified ferrierites recorded at room temperature.

leached ferrierites (Si/Al ¼ 9 and Si/Al ¼ 23) while data concerning

chemical composition is summarized in Table 2. Dealumination of
both zeolites resulted in an increase of Si/Al ratio due to removal of
Al atoms. Subsequent alkaline treatment of dealuminated zeolites
led to reduction of Si/Al parameter due to extraction of Si atoms
from zeolite framework (Table 2). Diffraction patterns of modified
materials are typical of FER structure (Fig. 1) [24]. All modified
materials exhibit high crystallinity (Table 2). Surprisingly, for
modified ferrierite of low aluminium content a small disturbance in
its crystallinity is evident, however, no formation of amorphous
phase was observed.
Parameters describing textural properties of zeolites were
derived from low temperature nitrogen sorption (Table 2). Both
dealumination and subsequent desilication lead to an increase of
volume and surface area of mesopores. Parameter typical of
microporous environment i.e. micropore volume was only slightly
disturbed, indicating preservation of micropore structure. A
reduction of micropore volume observed for dealuminated zeolite
FER/23/deAl comes from generation of extra-framework material Fig. 2. IR spectra of studied ferrierites in the region of OH groups vibrations.

Table 2
The chemical composition obtained from XRF analysis, the textural parameters obtained from low temperature nitrogen sorption and crystallinity of studied samples (%crys.).

Sample name Si/Al % cryst. SBET [m2/g] Smeso [m2/g] Smicro [m2/g] Vmeso [cm3/g] Vmicro [cm3/g]

FER/9/P 8.5 100 280 10 270 0.09 0.13

FER/9/deAl 10.4 98 290 45 245 0.10 0.13
FER/9/deAl/deSi 8.5 94 305 86 219 0.24 0.11
FER/23/P 29 100 295 14 281 0.07 0.13
FER/23/deAl 33 87 210 42 168 0.07 0.09
FER/23/deAl/deSi 16 86 326 108 218 0.24 0.12
150 K. Brylewska et al. / Journal of Molecular Structure 1126 (2016) 147e153
zeolites results in development of mesopore surface what is
detected in IR spectrum as a significant increase of the 3745 cm1
band of the SieOH located on external surfaces. Subsequent desi-
lication of zeolites FER/9/deAl and FER/23/deAl with LiOH results
only in a slight increase in the intensity of the silanols band.
However, the formation of mesopore system inside zeolite struc-
ture was confirmed by an increase of surface area in textural studies
(Table 2). Such observation leads to a conclusion that the formation
of secondary system of mesopores is not inherent for the growth of
the SieOH band.
The desilication as the modification associated with the selec-
tive removal of silicon caused increase in the overall amount of
aluminum in the structure, in line with Al content determined in
chemical analysis [30]. Although desilication of zeolite is consid-
ered as a silicon-selective process, it is well known that alkaline
treatment leading to the formation of secondary mesopores is also
responsible for the extraction of some aluminium species. The Al
atoms previously extracted from framework during alkaline
leaching of zeolite grains are supposed to realuminate on external
surface forming new SieOHeAl species and/or Lewis acid sites
easily available for bulky reagent molecules [31]. Therefore, in
desilicated zeolites either no changes or a small increase in in-
tensity of the SieOHeAl band is observed.
3.2.2. Quantification of acid sites e IR studies of pyridine sorption
Pyridine is widely used probe molecule in IR quantitative eval-
uation of solids. Due to kinetic diameter of Py (0.6 nm) [32], there
are steric constrains for accessibility of all acid sites in FER struc-
ture. Wichterlova' et al. [33] reported that pyridine did not cover all
bridging hydroxyls groups, even at 300  C. Also Trombetta et al. [34]
claimed that pyridine molecule is too large to reach the acidic
centers hidden in internal cavities, that are accessible through the 8
or less member ring channels. In summary, only the SieOHeAl
groups located in 10-MR and on external surface were easily
accessible and protonated pyridine [24].
In our case, an excess of pyridine was contacted with zeolite at
330  C for 15 min, then the IR cell was cooled down to 170  C and
the physisorbed molecules were evacuated at the same tempera-
ture. Indeed, for parent zeolites FER/9/P and FER/23/P the bands of
SieOHeAl groups were significantly reduced after sorption of
pyridine (spectra not shown). Only 20e30% of total intensity of the
SieOHeAl group was not covered by Py at 330  C pointing to the
existence of acid centres that are not able to protonate pyridine due
to the steric hindrance. The sites not accessible for Py molecules are
located in 6-MR channels and in 8-MR pores not available through
10-MR windows.
In the region of C]C vibration pyridine sorption led to the
appearance of the bands at frequencies 1545 cm1 and 1455 cm1
assigned to interactions of the probe with Brønsted and Lewis acid
sites, respectively [35]. Basing on the intensities of the 1545 cm1
and 1455 cm1 bands in the spectra recorded after desorption at
170  C and the values of their absorption coefficients (0.07 cm2/
Table 3
The amount of the aluminium (Al) derived from chemical analysis as well as the
Brønsted (B) and Lewis (L) acid sites concentrations determined in quantitative IR
studies of pyridine sorption.
Sample name Al [mmol/g] B [mmol/g] L [mmol/g] B þ L [mmol/g]
FER/9/P 1492 1198 10 1208
FER/9/deAl 1219 1115 20 1135
FER/9/deAl/deSi 1492 1363 51 1414
FER/23/P 457 304 19 323
FER/23/deAl 404 278 10 288
FER/23/deAl/deSi 808 320 185 505
mmol and 0.10 cm2/mmol for pyridinium ion (PyHþ) and coor-
dinatively bonded pyridine (PyL), resp. [30]) the concentration of
both Brønsted and Lewis acid sites was determined. The obtained
values were compared with the Al content derived from chemical
analysis (Table 3). For parent zeolites the discrepancy (ca. 2e30%)
between Al content obtained from chemical analysis and IR studies
points to limited accessibility of acid sites in 8-MR channels and
ferrierite cages. In comparison with total number of Al both deal-
umination and desilication enhance the number of Al sites that are
reached by pyridine (B þ L) suggesting an improvement of acces-
sibility of acid sites due to generation of additional mesoporosity.
The only exception is FER/23/deAl for which pore blocking by
aluminium extraframework material is responsible for limited acid
sites accessibility.
In parent and dealuminated zeolites small amounts of Lewis
acid sites were detected by Py, while for desilicated materials the
number of electron acceptor species able to bond the probe
increased. Especially in FER/23/deAl/deSi large amount of Lewis
acid sites easily accessible to Py originates most probably from
realumination on mesopore surface. Similar effect was not
observed for aluminium rich zeolite FER/9/deAl/deSi. Indeed, the
extent of silicon extraction was found to be dependent on
aluminium distribution through zeolite crystals. The Al excess
prevented surface zones from OH attack, thus the AlO-4 enriched
surfaces were less prone for silicon extraction [36e38]. Conse-
quently, the Al-poor ferrierite FER/23/deAl/deSi turned out to be
more prone to desilication, while Al-rich FER/9/deAl/deSi structure
was more resistant to alkaline leaching, in line with the values of
generated Smeso (Table 2).
3.3. NMR studies
In the 29Si MAS NMR spectrum of FER/23/P (Fig. 3) two main
peaks with the maxima at 116.0 and 112.1 ppm were assigned to
Si(0Al) sites. Less intense peaks at e 109 and 105.6 ppm were
assigned to Si(1Al) sites, giving the Si/Al ratios equal to 30 for FER/
23/P and 10 for FER/9/P, which are in reasonable agreement with
the Si/Al ratios from the chemical analysis (Table 1). Even for highly
siliceous FER/23/P the resolution of five different Si sites [39,40]
was not achieved due to line broadening generated by disorder,
resulted from the Al substitution of the silicate framework. In line
with literature reports the T(2)þT(3) and T(4)þT(1)þT(5) frame-
work sites can be grouped in the sites of the type T(A) and T(B),
respectively [41]. Thus, the 112.1 ppm peak was assigned to site
T(A) and the 116.0 ppm peak to site T(B), respectively. In 29Si MAS
NMR spectrum of FER/9/P (Fig. 3), for which the Al concentration is
significantly higher than in FER/23/P, three main peaks
at 115.5, 111.0, and 106.5 can be distinguished. However, in this
case of the central one a superposition of Si(1Al) and Si(0Al) sites
occurs. Additionally, a resonance line at 98.8 ppm is assigned to
Si(2Al) sites and line at 101.8 ppm is assigned either to defect sites
(SiOH) or to Si(1Al) sites.
In 27Al MAS NMR spectra of both parent ferrierites (Fig. 3) a
maximum at 54 ppm typical of tetrahedral AlIV and small peak of
octahedral AlVI at higher shielding (0 ppm) can be identified. Small
intensity of the peak at 0 ppm can indicate that the amount of
extraframework octahedral Al atoms (AlVI) is negligible and the
majority of aluminium atoms is located in the tetrahedral frame-
work positions (AlIV).
Acid leaching leads to the removal of Al atoms from zeolite
framework positions which is reflected by a reduced intensity of
AlIV resonance line, due to decreasing values of Si/Al ratio for both
zeolites. Surprisingly, highly siliceous ferrierite was more prone to
dealumination than aluminium rich zeolite. According to the 27Al
MAS NMR spectra subsequent LiOH treatment enhances the Al
 K. Brylewska et al. / Journal of Molecular Structure 1126 (2016) 147e153
29
Fig. 3. Si MAS NMR and
concentration in both ferrierites. The octahedral Al species, AlVI, are
present in noticeable amount only in hierarchical FER/23/deAl/deSi.
3.4. Catalytic studies
Catalytic activity of ferrierites was evaluated in dehydration of
ethanol in the vapour-phase at temperature ranging from 100  C to
300  C and atmospheric pressure, with space velocity of 1.1 h1.
Catalytic performance of acid and acid/alkaline treated materials
was compared with bulk zeolites in regard to the type of generated
mesoporosity and retained acidity. We attempted to correlate the
performance of the catalyst with acidic characteristic of Brønsted
and Lewis sites. However, the assessment of the role of Lewis
acidity in dehydration of ethanol is still an open issue. All ferrierites
were catalytically active in the temperature range of ca.
200e300  C giving diethyl ether (DEE) and ethylene (C2¼) as
products competitively formed at atmospheric pressure. Conver-
sion of ethanol (Fig. 4)(a) increases with reaction temperature
reaching 100% at 300  C for all FER/9/P originated samples. The bulk
FER/23/P and acid/alkaline FER/23/deAl/deSi also follow this trend.
The FER/23/deAl is poorly active; the conversion of ethanol reached
151
27
Al MAS NMR spectra of studied ferrierites.
33% only. Indeed, for the FER/23/deAl a reduced micropore volume
was observed, thus the limited acid sites accessibility is the most
probable reason of its poor catalytic performance. In a whole range
of temperatures the highest conversion of ethanol was observed for
Al-rich zeolites and it was found to decrease in the following order:
FER/9/deAl > FER/9 > FER/9/deAl/deSi. The Al-poor zeolites FER/23/
P and FER/23/deAl/deSi were mainly characterized by lower activ-
ity, however at 300  C they were even more effective than Al-rich
samples. It is well seen that the most effective catalysts were
those representing the well-defined micropore structure and pre-
senting high concentration of acid sites. As mentioned earlier, the
lowest catalytic activity was recognized for FER/23/P/deAl what is
in line with limited crystallinity and poorly accessible microporous
structure. It has been reported that in ethanol dehydration the
catalytic activity of microporous zeolites ZSM-5 was distinctly
higher than zeolites containing precisely defined porosity [30,42].
Catalytic behaviour of Brønsted acid sites in materials with dual
meso-/microporosity was previously demonstrated as being
dominated by microporous environment, what was assigned to
better fit for adsorption of small alkane or alcohol reactant mole-
cules [42]. Such conclusion is justified for studied Al-rich ferrierites
152 K. Brylewska et al. / Journal of Molecular Structure 1126 (2016) 147e153

Fig. 4. (a, b) Conversion of ethanol versus temperature and concentration of Brønsted and Lewis acid sites, (c) TOF values versus concentration of Brønsted and Lewis acid sites, (d, f)
yields and (e, g) selectivities to diethyl ether DEE and C2¼ versus temperature for studied catalysts.
 K. Brylewska et al. / Journal of Molecular Structure 1126 (2016) 147e153
despite the limited accessibility of acid sites hidden in ferrierite
cages and in 6-MR channels even for small ethanol molecule. It is
well seen that the better quality of microporous character and
intrinsic acidity are, the higher catalytic activity in this type of re-
action is. Thus, while the mesopore system can offer improved
accessibility, its fabrication at the expense of intrinsic acidity re-
duces the catalyst effectiveness. The correlation of both the con-
version with amount of acid sites available for Py (B þ L) (Fig. 4)(b)
indicates higher effectiveness of FER/9/P over FER/9/deAl/deSi. The
same conclusions were drawn for Al-poor zeolites, still purely
microporous FER/23/P was more effective that its hierarchical
analogue.
At this point it should be noted that conversion values are not
entirely capable to describe catalytic performance of zeolites
significantly differing in the amount of acid sites accommodated.
Therefore the values of TOF parameter (turnover frequency/s1)
were correlated with acidity of zeolites (expressed as B þ L)
(Fig. 4)(c). When considering the TOF values, the FER/23 originated
zeolites should be considered as catalysts of significantly higher
activity than Al-poor ferrierites. This phenomenon is the most
probably related to higher acid strength of sites well dispersed in
zeolite framework in Al-poor FER/23 originated zeolites.
Hierarchical FER/23/deAl/deSi exhibited lower TOF value than
purely microporous FER/23/P in spite of nearly twofold higher Al
concentration (the same number of Brønsted acid sites). Higher
catalytic activity in ethanol dehydration is observed for zeolites
with well-developed micropore area thus high intrinsic acidity.
Again, it can be concluded the microporous character predominates
catalytic performance for reactions undergoing without space
limitations.
Catalytic performance of ferrierites expressed as another
important estimates, i.e. the selectivities and yields of different
products, can be directly considered with regard to the concen-
tration of acid sites. The highest yield of DEE equal to 41% was
observed for FER/9 and FER/9/deAl/deSi zeolites at the temperature
of 240  C. The FER/23 originated samples were less efficient in DEE
formation. The Al-rich zeolites showed the highest yield and se-
lectivities to ethylene, however in temperature range 280e300  C
the acid/alkaline treated FER/23 was found to be as effective as FER/
9 analogues. It suggest that improved both accessibility of sites and
their enhanced concentration give the positive effect on the cata-
lytic performance in ethylene production. It should be also taken
into account that at temperatures as high as 300  C the character of
microporous environment can play predominant role in both zeo-
lites, independently from their acidity.
4. Conclusions
Subsequent dealumination and desilication procedures were
found to be a very effective method of generation of intracrystalline
mesopore system with the preservation of microporous character
of ferrierite crystals. Through ethanol dehydration, both number of
acid centres and their strength as well as the presence of meso-
porosity have a significant influence on catalytic performance of
hierarchical ferrierites. It has been proven that higher catalytic
activity and selectivity to ethylene is ensured by zeolites with
better preserved microporous characteristic, i.e. well-developed
micropore area and intrinsic acidity.
Acknowledgement
This work was financed by Grant No. 2014/13/D/ST5/02761 from
153
the National Science Centre, Poland.
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