Benzylation of benzene with benzyl chloride on iron-containing mesoporous mordenite

Article abstract of DOI:10.1016/j.catcom.2012.08.016

Microporous mordenite with a low Si/Al ratio was synthesized by using silicic acid powder as silica source under hydrothermal condition. By treating the mordenite with acid and base, mesoporous mordenite (M-Mor) was obtained, which was characterized by X-

Full text of DOI:10.1016/j.catcom.2012.08.016

Catalysis Communications 28 (2012) 64–68
Contents lists available at SciVerse ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Benzylation of benzene with benzyl chloride on iron-containing
mesoporous mordenite
a
a
a
a
b
a,
Kunyue Leng , Shengnan Sun , Binteng Wang , Lin Sun , Wei Xu , Yinyong Sun ⁎
a
School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin, 150001, China
State Key Lab of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 7 June 2012
Received in revised form 12 August 2012
Accepted 13 August 2012
Available online 19 August 2012
Microporous mordenite with a low Si/Al ratio was synthesized by using silicic acid powder as silica source
under hydrothermal condition. By treating the mordenite with acid and base, mesoporous mordenite
(
M-Mor) was obtained, which was characterized by X-ray diffraction (XRD), N
scanning electron microscopy (SEM). Based on the M-Mor material, iron-containing mesoporous mordenite
Fe-M-Mor) was prepared by ion-exchanged method. The benzylation of benzene by benzyl chloride showed
2
sorption experiments, and
(
that Fe-M-Mor was a highly active catalyst in this reaction and could be reused. These results indicate that
Fe-M-Mor has potential applications in Friedel–Crafts alkylations, especially of large molecules.
© 2012 Elsevier B.V. All rights reserved.
Keywords:
Mesoporous
Mordenite
Iron-containing
Benzyl chloride
Benzylation
1
. Introduction
Friedel–Crafts alkylations are an important class of reactions in
volume [11,12]. Much work has been focused on the preparation of such
novel mesoporous materials for the benzylation reaction [13–26]. For
example, active species were directly introduced into the framework
of mesoporous silica materials during their synthesis or were supported
in their channels. And these mesoporous catalysts exhibited a better
catalytic performance than microporous zeolites in the benzylation
reactions. However, it is well known that mesoporous silica materials
possessed poor stability and weak acidity compared with zeolites.
Therefore, mesoporous materials with high stability and strong acidity
have been sought.
organic chemistry [1,2]. Among these reactions, the liquid phase
benzylation of benzene and other aromatic compounds by benzyl
chloride, or benzyl alcohol is used to produce diphenylmethane and
substituted diphenylmethanes which are key industrial compounds
as pharmaceutical intermediates or fine chemicals. In general, such
reactions were carried out in the presence of homogeneous Lewis
3 3 2 4
acid or protonic acid catalysts such as AlCl , FeCl and H SO . Howev-
er, these catalysts are associated with several problems such as corro-
sion, handling, high toxicity, and difficulty in separation and recovery
of the catalyst. Therefore, there have been lots of efforts to replace
these homogenous catalysts by heterogeneous solid catalysts which
are environmentally friendly catalysts [3–6]. Zeolites like H-ZSM-5
and HY, as a member of solid catalysts, have received much attention
because of their strong acidity and regular porous structure with ex-
cellent stability. Thus, some studies have reported their catalytic per-
formance in the benzylation reaction [7–10], but the results indicated
that highly acidic zeolite catalysts showed poor reactivity because of
diffusion limitation caused by their microporous network [7,8].
Recently, the discovery of ordered mesoporous silica materials such
as MCM-41 and SBA-15 is of considerable interest because of their reg-
ular pore array with uniform pore diameter, high surface area and pore
Mesoporous zeolites may be the ideal catalysts for the Friedel–Crafts
reaction of large molecules, because they can not only overcome the dif-
fusion limitation of zeolites on the reaction rate but also maintain stabil-
ity and strong acidity like conventional zeolites. Various preparative
methods have been reported on the synthesis of mesoporous zeolites
[27–33]. The catalytic performance in the benzylation of benzene by
benzyl alcohol over mesoporous ZSM-5 and mordenite has also been
studied. The results showed that mesoporous zeolites had a much
higher catalytic activity than microporous zeolites [34,35]. However,
compared with iron-containing catalysts, their catalytic reactivity is
relatively weak. To our best knowledge, the study of iron-containing
mesoporous zeolites in Friedel–Crafts alkylations has been not reported.
In the present work, mesoporous mordenite was chosen as the
research target due to its easy preparation and low cost. Based on the
material, iron-containing mesoporous mordenite was obtained by
ion-exchanged method. The catalytic performance of the sample was
evaluated by using the model reaction of the benzylation of benzene
by benzyl chloride for the first time.
⁎
Corresponding author. Tel.: +86 451 86413708; fax: +86 4006358835 00379.
E-mail address: yysun@hit.edu.cn (Y. Sun).
1566-7367/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.catcom.2012.08.016

K. Leng et al. / Catalysis Communications 28 (2012) 64–68
65
2
. Experimental section
2
.1. Materials
2 3 4 3 2 2
Silicic acid, NaAlO , HNO , NaOH, NH NO , FeCl ·4H O, benzene,
and benzyl chloride were purchased from Sinopharm Chemical
Reagent Co. and used without further purification. All used chemicals
are analytical reagents.
H-M-Mor
2
.2. Preparation of catalyst
2
.2.1. Synthesis of mordenite
H-Mor
35
NaOH, and NaAlO
particle size is below 200 mesh) was then added. The starting gels
were obtained with molar ratios of Al :25SiO :5Na O:294H O. After
2 2
were mixed with H O, and silicic acid powder
(
O
2 3
2
2
2
5
10
15
20
25
30
40
stirring for 1 h at room temperature, the mixture was transferred into
an autoclave at 343 K for 5 days for further crystallization. The product
was collected by filtration, washed with deionized water and dried at
2
Theta (degree)
Fig. 1. XRD patterns of H-Mor and H-M-Mor.
3
93 K for 12 h, then calcined at 823 K for 3 h. The resultant sample
was named as Na-Mor. The Na-Mor sample was then ion-exchanged
thrice with a solution of 1 M NH NO at 353 K for 1 h, followed by cal-
cination at 823 K for 3 h to obtain H-form mordenite labeled as H-Mor.
4
3
2
.0 nm. X-ray photoelectron spectroscopy (XPS) data was collected on
an ESCALAB 250 X-ray photoelectron spectroscopy, using Mg Kα
X-ray as the excitation source. All binding energies were referenced to
C1s of 284.6 eV.
2
.2.2. Synthesis of mesoporous mordenite
The Na-Mor sample was refluxed with a solution of 2 M HNO at
3
73 K for 2 h with a liquid-to-solid ratio of 20 ml/g. Then, the solid
3
sample was filtered, washed with deionized water, and dried at
3
0
93 K for 12 h. The obtained sample was treated with a solution of
.2 M NaOH with a liquid-to-solid ratio of 20 ml/g at 343 K for 2 h.
2.4. Catalytic tests
The product was filtered, washed with deionized water, dried and
then calcined at 823 K for 3 h. The sample was called Na-M-Mor.
The Na-M-Mor sample was then ion-exchanged thrice with a solution
The liquid phase benzylation of benzene with benzyl chloride (BC)
was carried out in a three necked round-bottomed flask equipped
with a reflux condenser and heated in a precisely controlled oil bath
under atmospheric pressure. In a typical run, 13 ml of benzene was
added to 50 mg catalyst (which had been activated overnight at
4 3
of 1 M NH NO at 353 K for 1 h, followed by calcination at 823 K for
3
2
0
h to obtain H-form mesoporous mordenite labeled as H-M-Mor.
3
83 K). The reaction mixture was maintained for 30 min at the required
.2.3. Synthesis of iron-containing mesoporous mordenite
The Na-M-Mor sample was ion-exchanged thrice with a solution of
.05 M FeCl with a solid-to-liquid ratio of 100 ml/g at room tempera-
2
reaction temperature, and then 1 ml of benzyl chloride was added. The
moment was regarded as initial reaction time. Liquid samples were
withdrawn at regular intervals and analyzed by gas chromatography.
The products were also identified by GC-MS (HP-5975C) analysis.
Since benzene was in excess, conversion was calculated based on the
benzylating reagent i.e. BC. The selectivity to the product diphenyl-
methane (DPM) was expressed as the amount of particular product
divided by amount of total products and multiplied by 100.
ture for 2 h. The product was filtered, washed with deionized water,
dried at 393 K for 12 h, and then calcined at 823 K for 3 h. The obtained
sample was labeled as Fe-M-Mor. For comparison, iron-containing
mordenite labeled as Fe-Mor was prepared as described above by
ion-exchange based on the Na-Mor sample.
2
.3. Catalyst characterization
Powder X-ray diffraction (XRD) patterns were recorded on a Rigaku
160
D/Max-2550 diffractometer equipped with a SolX detector — Cu Kα ra-
diation with wavelength of λ=1.5418 Å. SEM images were recorded
on SUPRA 55 operated with an acceleration voltage of 200 kV. Energy
dispersive X-ray (EDX) analysis was carried out in an electron micro-
scope coupled to an X-sight analyzer operated at 200 kV. Nitrogen sorp-
tion isotherms were obtained at 77 K on a Micromeritics ASAP2020 Gas
Sorption and Porosimetry system. Samples were normally prepared for
measurement after degassing at 423 K under vacuum until a final pres-
140
1
1
20
00
1
.0
0.8
80
0
0
.6
.4
−
3
sure of 1×10
Torr was reached. Temperature-programmed desorp-
3
-TPD) was carried out on FINESORB-3010 equipped
60
tion of NH (NH
3
4
2
0
0
0
0.2
0.0
with a thermal conductivity detector. The samples were first outgassed
under 823 K for 1 h before the measurement. After cooling to 373 K, the
samples were saturated in an NH
quently treated in Ar (30 ml/min) for 2 h for removing physisorbed
NH . Finally, the TPD profile was determined by increasing temperature
from 373 K to 873 K with a heating rate of 5 k/min while recording NH
3
stream (5% in Ar) for 1 h and conse-
3
6
9
12
15
Pore size (nm)
0.0
0.2
0.4
0.6
0.8
1.0
3
3
Relative pressure (P/P )
0
desorption with a thermal conductivity detector. UV–vis spectroscopy
was recorded with a U-4100 UV–vis-NIR spectrometer. The measure-
ment parameters were scan speed 300 nm/min, slit width (UV–vis)
Fig. 2. N
2
adsorption–desorption isotherms of H-Mor (■,□) and H-M-Mor (●,○) and
pore distribution curve of H-M-Mor (inset).

66
K. Leng et al. / Catalysis Communications 28 (2012) 64–68
Table 1
Textural properties and chemical composition of H-Mor and H-M-Mor.
increased because the porosity of the sample was improved. Notably,
H-M-Mor possessed a much higher mesopore volume than that of
3
Samples
Molar ratio
of Si/Al
BET surface
area (m /g)
Micropore
volume
Mesopore
volume
(cm /g)
Mean
mesopore
H-Mor. The value for H-M-Mor (0.06 cm /g) is six times as that of
a
2
3
H-Mor (0.01 cm /g). That means that the ability of mass transfer for
3
b
3
c
(cm /g)
diameter
H-M-Mor should be greatly enhanced in catalytic reactions. This fact
has been proved by the benzylation of benzene with benzyl alcohol
over both samples. The result showed that H-M-Mor had a much higher
catalytic activity than H-Mor.
c
(nm)
H-Mor
H-M-Mor
4.7
5.3
360
393
0.17
0.16
0.01
0.06
–
3.8
a
EDX analysis.
t-plot method.
BJH method (adsorption branch).
Based on the above-obtained materials, iron-containing micropo-
rous (Fe-Mor) and mesoporous mordenites (Fe-M-Mor) were prepared
by ion-exchanged method, respectively. SEM results show that Fe-Mor
and Fe-M-Mor had similar large crystal size of about 5×10×15 μm
with plate-shape morphology (Fig. 3a and c). The crystal surface of
Fe-Mor is smooth (Fig. 3b). Comparatively, the crystal surface of
Fe-M-Mor is rough, indicating that the post treatment had resulted in
the removal of some components in the crystal (Fig. 3d). These results
are in agreement with earlier reports on mesoporous mordenite
obtained by alkaline treatment [35], suggesting the formation of
mesopores inside the crystal of Fe-M-Mor.
b
c
3
. Results and discussion
3
.1. Characterization of catalyst
The XRD patterns of H-Mor and H-M-Mor samples exhibit well re-
solved diffraction peaks (Fig. 1), which are characteristic for the MOR
framework structure. The peak intensity of H-M-Mor had no obvious
change compared with that of H-Mor, indicating that the crystal struc-
ture of mordenite was remained well after acidic and alkali treatment
3.2. Catalytic activity of catalyst
under the given condition. N
IV N adsorption–desorption isotherm for H-M-Mor (Fig. 2), which is
typical for mesoporous materials, with a capillary condensation step
at a relative pressure of 0.4bP/P b0.6. A narrow mesopore distribution
centered at 3.8 nm by the Barrett–Joyner–Halenda (BJH) model was ob-
served for H-M-Mor (Fig. 2 inset). In comparison, H-Mor gave a type I
isotherm which is typical for microporous materials. The sorption data
2
sorption experiments exhibited a type
2
To evaluate the catalytic performance of Fe-Mor and Fe-M-Mor, the
benzylation of benzene by benzyl chloride was chosen. The reaction
was firstly carried out under a mild reaction temperature (343 K). The
used amount of the catalyst is 50 mg. Fig. 4 shows the catalytic activities
of Fe-Mor and Fe-M-Mor with reaction time. It can be seen that
Fe-M-Mor quickly gave a reactive ability after an induction period of
10 min. The BC conversion nearly reached 100% in a reaction time of
10 min. Among the products, only the diphenylmethane (DPM) can
be observed. Comparatively, Fe-Mor took a long induction period of
about 50 min and the BC conversion reached 60% after 40 min. The ap-
o
(
(
Table 1) showed that H-M-Mor had a higher BET surface area
2
2
393 m /g) than that of H-Mor (360 m /g). The microporous volume
3
of H-M-Mor (0.16 cm /g) is slightly lower than that of H-Mor
(
3
0.17 cm /g), suggesting that microporosity in mordenite was largely
−
3
−1
preserved after the post treatment. These results suggested that at
first the acid leaching resulted in the extraction of partial Al species in
the framework of mordenite and then the base treatment removed
the partial silica species possibly on the corresponding extraction posi-
tion of Al species. Therefore, after the whole post treatment, the micro-
porosity could be well maintained. However, the surface area was
parent reaction rate constant for Fe-M-Mor (155.4×10
min ) is
−
3
−1
about ten times as that for Fe-Mor (14.7×10
min ) (Table 2).
This result indicates that Fe-M-Mor is a more active catalyst than
Fe-Mor in the benzylation. The reaction induction period seemed to de-
pend on the catalytic activity. The higher the activity is, the shorter the
induction period. This phenomenon has been observed in earlier work
a
b
c
d
Fig. 3. SEM images of Fe-Mor (a, b) and Fe-M-Mor (c, d).

K. Leng et al. / Catalysis Communications 28 (2012) 64–68
67
Table 2
a 1
00
The number of acid sites and iron content in Fe-Mor and Fe-M-Mor and the catalytic
reaction data.
Samples
NH
3
chemisorbed
Fe content
(wt%)
Apparent reaction rate
Fe-M-Mor
8
6
4
2
0
0
0
0
0
a
b
(×103 min−1)c
constant, k
a
(mmol/g)
Fe-Mor
Fe-M-Mor
1.05
0.96
6.34
12.11
14.7
155.4
a
NH
3
-TPD.
Fe-Mor
b
c
XPS analysis.
Reaction conditions: amount of catalyst=50 mg; Benzene=146 mmol; benzyl
chloride=8.7 mmol; reaction temperature=343 K.
different type of acid sites. The low temperature desorption peak
(373–573 K) was attributed to weak acid sites, and high temperature
0
20
40
60
80
100
desorption peak (573–773 K) was due to NH
sites. The number of acid sites was 1.05 mmol/g for Fe-Mor and
.96 mmol/g for Fe-M-Mor, respectively. Obviously, the type and num-
ber of acidic sites for both catalysts are similar. This result suggested
that the catalytic activity had no good relationship with the acidity of
catalysts, which is agreement with previous reports [7,17].
3
bound to strong acid
Reaction time (min)
0
b
Moreover, to reveal the role of iron species in the reaction, the cata-
lytic performance of H-M-Mor was also evaluated under the same reac-
tion conditions (benzyl chloride as the reactant). As a result, the
reaction can not be carried out even after a reaction time of 2 h. This
means that Fe-M-Mor had a much stronger reactivity than H-M-Mor
in the reaction. The introduction of iron species can significantly en-
hance the catalytic performance of the catalyst. To make the point
clear, the state and content of iron species in Fe-Mor and Fe-M-Mor
were determined by UV–vis spectroscopy and X-ray photoelectron
spectroscopy. The UV-spectra of both samples showed a strong absorp-
tion band below 300 nm and absorption bands above 300 nm (Fig. 4c).
Generally, the absorption band below 300 nm is attributed to isolated
iron species and the absorption band between 300 and 400 nm is cor-
responding to iron oxide nanoclusters. Bulk iron oxide exhibits the ab-
sorption band between 400 and 600 nm [22]. Obviously, Fe-M-Mor
exhibited a relatively strong adsorption band around 350 nm corre-
sponding to the iron oxide nanoclusters besides the absorption band
below 300 nm. This means that Fe-M-Mor contained not only isolated
iron species but also many iron oxide nanoclusters. It has been
Fe-M-Mor
Fe-Mor
400
500
600
700
800
Temperature (K)
c
Fe-M-Mor
2 3
suggested that nano-sized Fe O clusters with a high degree of coordi-
Fe-Mor
native unsaturation should be much more reactive iron species for the
reaction and even that isolated iron species are inactive [18,19]. Thus,
the presence of more iron oxide nanoclusters could contribute to the
improvement of the catalytic activity. The nanoclusters may be formed
during the calcination of the ion-exchanged samples in air at high tem-
perature. It can be imagined that mesoporosity could be helpful for the
formation of iron oxide nanoclusters because they may be located in the
mesopore channels. The result from XPS showed that Fe-M-Mor pos-
sessed higher iron content than Fe-Mor, nearly two times as that in
Fe-Mor (Table 2). Considering that both samples were obtained by the
same ion-exchanged method, the relatively high iron content in
Fe-M-Mor could be attributed to the improvement of the exchangeabil-
ity due to the presence of mesopores. Additionally, the surface state of
iron species in both samples from XPS analysis is similar and the iron
valence is mainly tri-valence. Considering this fact that the apparent re-
2
00
300
400
500
600
700
800
Wavelength (nm)
Fig. 4. (a) Conversion of benzyl chloride with reaction time over Fe-Mor and Fe-M-Mor
catalysts at 343 K. Reaction conditions: amount of catalyst=50 mg; Benzene=
46 mmol; benzyl chloride=8.7 mmol; (b) NH
Fe-M-Mor catalysts; (c) UV–vis spectra of Fe-Mor and Fe-M-Mor catalysts.
1
3
-TPD profile of Fe-Mor and
−
3
−1
action rate constant for Fe-M-Mor (155.4×10
min ) is ten times as
−
3
−1
that for Fe-Mor (14.7×10
min ) and the iron content in Fe-M-Mor
[
7,17]. Choudhary et al. think that the reaction induction period was
is about two times as that in Fe-Mor (Table 2), the high catalytic activity
for Fe-M-Mor can not be solely attributed to the increase of iron con-
tent. The mesoporosity and more active iron sites in Fe-M-Mor should
be mainly responsible for the enhancement of catalytic activity. Based
on the above results, it can be concluded that such a big difference in
catalytic activity should be mainly attributed to the existence of
mesopores that greatly overcame the diffusion limitation from the
microporous network and more active iron sites in Fe-M-Mor.
caused by the presence of moisture in reaction mixture and the catalysts
are activated during the initial reaction period. However, further study
need be done to understand the reason of induction period clearly.
To clarify the reason of the big difference in catalytic activity for
Fe-Mor and Fe-M-Mor catalysts, their acidity was studied (Fig. 4b). As
it can be seen, both catalysts showed two desorption peaks of NH
the range of 373–773 K. These desorption peaks corresponded to two
3
in

68
K. Leng et al. / Catalysis Communications 28 (2012) 64–68
3
.3. Effect of reaction temperature
4. Conclusions
To further evaluate the catalytic performance of Fe-M-Mor, its
catalytic reactivity was tested at various reaction temperatures
Fig. 5). Obviously, the catalytic activity was decreased with reaction
temperature. For example, at 333 K the reaction was completed after
a reaction time of 20 min with an induction period of 20 min. When
the reaction temperature was further decreased to 323 K, Fe-M-Mor
took an induction period of 1 h and reached the complete conversion
of benzyl chloride after a reaction time of 1 h. The rate data for the
benzylation of benzene in excess of benzene over Fe-M-Mor catalyst
could be fitted well to a pseudo-first order rate law: ln(1/1−x)=
Iron-containing mesoporous mordenite was prepared by post treat-
ment and ion-exchanged method for the first time. The Fe-M-Mor cat-
alyst showed excellent catalytic performance in the benzylation of
benzene and benzyl chloride. The apparent reaction rate constant for
Fe-M-Mor is about ten times as that for Fe-Mor. The catalytic activity
had no good relationship with the acidity of catalysts. Such big differ-
ence in catalytic activity should be mainly attributed to the existence
of mesopores and more active iron sites in Fe-M-Mor. The study on
heterogeneous nature demonstrated that Fe-M-Mor is a heterogeneous
catalyst and could be reused. Additionally, the catalyst has found poten-
tial application in other Friedel–Crafts alkylations, especially towards
large molecular reactions.
(
k
a
(t−t
conversion of benzyl chloride, t is the reaction time and t
duction period corresponding to the time required for reaching equi-
librium temperature. A linear plot of log(1/1−x) versus t−t could
be obtained. The reaction rate increased with reaction temperature.
o
), where k
a
is the apparent rate constant, x is the fractional
o
is the in-
o
Acknowledgments
−
3
−1
At 323 K, the apparent rate constant k
a
was 30.9×10
min
min , which is nearly twice
as that at 323 K. Further increase of temperature to 343 K increased
,
The project was sponsored by the Scientific Research Starting
Funding from Harbin Institute of Technology, Open Funding from the
State Key Lab of Inorganic Synthesis and Preparative Chemistry, Jilin
University, and the Scientific Research Foundation for the Returned
Overseas Chinese Scholars, State Education Ministry.
−
3
−1
while at 333 K it reached 66.7×10
−
3
−1
k
a
to 155.4×10
min
nearly five times as much as that at 323 K.
The first-order rate constants gave a linear Arrhenius plot with an
estimated activation energy of 74 kJ/mol for the Fe-M-Mor catalyst.
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.4. Reusability of the catalyst
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