Journal of Colloid and Interface Science 331 (2009) 432–438

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Synthesis of ZSM-5 with intracrystal or intercrystal mesopores by polyvinyl

butyral templating method
Haibo Zhu a , Zhicheng Liu b , Dejin Kong b , Yangdong Wang b , Xiaohong Yuan b , Zaiku Xie a,b,∗
a
School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
b
Shanghai Research Institute of Petrochemical Technology, SINOPEC, 1658 Pudong Beilu, Shanghai 201208, China

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

Article history: Three facile routes were utilized to synthesize ZSM-5 materials with intracrystal or intercrystal
Received 23 September 2008 mesopores, where the polyvinyl butyral gel served as mesopore directing template. The three routes
Accepted 28 November 2008 were divided into two synthesis strategies: the hydrothermal treatment of silica/PVB composite and re-
Available online 6 December 2008
crystallization of preformed zeolite precursor with the assistance of PVB gel. The fabrication of silica/PVB
Keywords:
composite was accomplished by two routes including sol–gel process and impregnation method. The
Zeolite resulting composite was undergone hydrothermal treatment. During the crystallization PVB was occluded
ZSM-5 in the ZSM-5 crystal, creating intracrystal mesopores in the zeolite. The last route for the synthesis of
Mesoporous zeolite mesoporous ZSM-5 was realized by re-crystallization of preformed ZSM-5 zeolite in the presence of PVB.
Polyvinyl butyral This route involved the pre-crystallization of the amorphous aluminosilicate to produce the pre-formed
Templating synthesis ZSM-5 precursor. Upon further crystallization of the mixture of PVB gel and pre-formed ZSM-5, the
Hydrothermal synthesis ZSM-5 precursor was transformed into ZSM-5 aggregate of nanocrystals, while the PVB gel was occluded
in the ZSM-5 particles. Removal of the template generated the typical microporosity associated with
ZSM-5 structure along with intercrystal mesoporosity produced from the PVB. The mesoporous ZSM-5
exhibited enhanced catalytic activity in the toluene disproportionation and transalkylation with C9 and
C10 aromatics.
© 2008 Elsevier Inc. All rights reserved.

1. Introduction
Aluminosilicate zeolites, the most well-known microporous ma-
terials, are crystalline microporous materials that are extensively
used as catalysts in oil refining process, petrochemistry industry,
and fine chemical synthesis, as adsorbent and ion exchanger in in-
dustrial separation or purification of fluid, and are also regarded
as the promising functional materials for various applications in
sensor, electronic device, and other advanced materials [1–3]. Zeo-
lites’ excellent performances are due to their well-defined channels
and cavities in the range of 3–15 Å. The uniform micropore net-
work of molecular dimension can accommodate guest molecules
selectively, which endows zeolites with the shape selectivity and
molecular sieve effect that play an important role in their catalysis
applications. However, the relative small pore size of the microp-
orous materials results in an unacceptably slow diffusion of reac-
tants and products to and from the active sites located inside the
zeolite crystals, severely preventing their further practical applica-
tions.
*
Corresponding author at: Shanghai Research Institute of Petrochemical Technol-
ogy, SINOPEC, 1658 Pudong Beilu, Shanghai 201208, China. Fax: +86 21 68462283.
E-mail address: xiezk@mail.sript.com.cn (Z. Xie).
To overcome the drawback from the zeolite pore size limitation,
researchers have proposed several different strategies. One possi-
bility is to synthesize a nanosized zeolite crystal with the size of
0.5–50 nm, and thereby the diffusion path in zeolite crystal will
be shortened [4–8]. However, the colloid property of the nano-
sized zeolite makes the synthesis process difficult to handle. Also,
the synthesis of nanosized zeolite often consumes a large amount
of organic template. These obstacles lead to the difficulty in the
synthesis and application of nanosized zeolite. The success in the
synthesis of mesoporous materials with ordered pore and chan-
nel in the range of 2–50 nm may provide another method for the
solution of such problem [9–13]. Unfortunately, the mesoporous
materials have their intrinsic weaknesses in terms of acidity and
hydrothermal stability, which has dramatically restricted their ap-
plication.
Recently, the synthesis of mesoporous zeolite with both mi-
croporosity and mesoporosity is successfully accomplished [14–
16]. Upon post-treatment of the synthesized zeolite or templating
method during the zeolite crystallization, an additional mesopores
system (sizes between 2 and 50 nm) can be introduced into each
individual zeolite crystal. Post-treatment of zeolite under acidic or
basic condition will result in dealumination or desilication from
zeolite framework, therefore the resultant vacancies in the struc-

0021-9797/$ – see front matter © 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2008.11.071
 H. Zhu et al. / Journal of Colloid and Interface Science 331 (2009) 432–438
ture will produce mesopores in zeolite [17,18]. Meanwhile meso-
pores can be introduced directly into the zeolite crystals by con-
ducting the crystallization in the presence of mesopore directing
agent, such as carbon black [19], CMK-3 [20], nanosized CaCO3
[21], cationic polymer [22], amphiphilic organosilane surfactant
[23], and silane-functionalized polymer [24]. These mesopore tem-
plates are incorporated into the zeolite crystals during its growth.
The removal of the template by different treatment manners will
produce highly mesoporous zeolite single crystals that combine the
desired properties of zeolites and mesoporous materials.
In this paper, we used polyvinyl butyral gel as the mesopore
directing agent for synthesis of mesoporous ZSM-5 by three ap-
proaches [25]. Upon different synthesis strategy, the ZSM-5 with
intracrystal or intercrystal mesopores can be prepared.
2. Materials and methods
2.1. Chemicals
All the reagents including tetrapropylammonium hydroxide
(TPAOH, 25 wt%), polyvinyl butyral (PVB), NaAlO2 , tetraethyl or-
thosilicate (TEOS), and Aerosil-200 were purchased from Sino-
pharm Chemical Reagent Company (China) and used as received.
2.2. Synthesis of conventional ZSM-5 without PVB
Conventional ZSM-5 was synthesized without PVB polymer as
the following procedure. Briefly, 0.30 g of NaAlO2 was dissolved
in a solution of 20.03 g of TPAOH. Then 10.02 g of Aerosil-200
was added slowly in the resultant solution, and kept on stirring
for a long time in order to dissolve the silica. The last gel was
introduced in Teflon-lined stainless steel autoclave and kept at
140 ◦ C for 3 days. After the hydrothermal synthesis, the product
was washed with distilled water and dried at 100 ◦ C. Lastly, the
product was calcined in air at 550 ◦ C for 4 h.
2.3. Synthesis of ZSM-5 with intracrystal mesoporosity by direct
hydrothermal treatment of PVB/silica composite from sol–gel process
In a flask, 4 g of PVB, 30 g of alcohol, and 40 g of TEOS were
added with stirring until a clear solution was obtained. After that
a solution consisting of NaAlO2 (0.27 g) and TPAOH (20 g, 25 wt%)
was then added to the mixture dropwisely. The hydrolysis of TEOS
resulted in a homogeneous PVB/silica sol. After a short while the
sol would become viscous and turned into transparent gel. This
gel was dried in the oven at 60 ◦ C over night in order to evaporate
the alcohol. The obtained synthesis powder was introduced into
a Teflon-lined steel autoclave, heated to 140 ◦ C and kept there for
72 h. The as-synthesized zeolite was isolated by filtration, washed
with water, and dried at 100 ◦ C for 2 h. The organic template and
the PVB gel were removed by controlled combustion in air in a
muffle furnace at 550 ◦ C for 8 h. For clarity, the zeolite synthesized
by the method above was denoted as Sample-A.
2.4. Synthesis of ZSM-5 with intracrystal mesoporostity by
hydrothermal crystallization of PVB impregnated Aerosil-200
10 g of Aerosil-200 was impregnated with 40 g of PVB in al-
cohol solution (10 wt%) by two times, and then the mixture was
dried at 80 ◦ C for a few h in order to remove the alcohol. The so-
lution mixed with 0.28 g of NaAlO2 , 20 g of TPAOH (25 wt%), and
5 g of H2 O was added to the PVB impregnated Aerosil-200. After
that, the mixture was undergone hydrothermal synthesis at 140 ◦ C
for 3 days. The last product (denoted as Sample-B) was obtained
by filtration, wash, dry, and calcination.
433
2.5. Synthesis of hierarchical ZSM-5 with intercrystal mesoporostity by
the re-crystallization of zeolite precursor in the presence PVB
The procedure of this synthesis is same as the description in
the previous report [26]. The aluminosilicate gel for the synthe-
sis of preformed ZSM-5 zeolite precursor solution was prepared by
a mixture of Aerosil-200, NaAlO2 , H2 O, and TPAOH with a com-
position of SiO2 :Al2 O3 :H2 O:TPAOH at 100:1.03:500:15.3. This alu-
minosilicate gel was stirred for 5 h at room temperature, and was
then charged into autoclave for pre-crystallization at 100 ◦ C for 8 h.
After the pre-crystallization, the pre-formed ZSM-5 precursor was
mixed with PVB solution (10%). Then the mixture re-crystallized at
140 ◦ C for 64 h, giving a composite of ZSM-5 and PVB. The result-
ing sample was then filtered, dried at 100 ◦ C and lastly calcined
in a muffle furnace at 550 ◦ C. This mesoporous ZSM-5 sample was
denoted as Sample-C in the following discussion.
2.6. Characterization
The phase purity of all samples was examined by X-ray diffrac-
tion (XRD), which was carried on a Bruker diffractometer equipped
with CuK α (λ = 0.15418 nm) radiation. Scanning electron mi-
croscopy (SEM) micrographs were taken with a JSM-7401F scan-
ning electron microscope operated at an accelerating voltage of
5 keV. TEM micrographs were recorded on a Tecnai 20 S-TWIN
instrument operated at 200 kV with the CeB6 filament as an elec-
tron beam. The sample was dispersed in alcohol by ultrasonic; the
resultant suspension was then dipped on a carbon-coated cop-
per grid. The obtained copper grid supported sample was used
for TEM characterization. Nitrogen adsorption and desorption mea-
surements were performed at liquid nitrogen temperature on a
Micromeritics ASAP 2010. The samples were degassed in vacuum at
250 ◦ C overnight prior to the measurement. The BET surface area
was calculated from the linear part of the BET plot according to
IUPAC recommendation. The total pore volume was evaluated at
P / P 0 = 0.97, while the micropore volume was obtained by t-plot
method.
2.7. Catalytic activity test
Catalytic activity of ZSM-5 samples was evaluated using a reac-
tion of toluene disproportionation and transalkylation with C9 and
C10 aromatics in a continuous fixed-bed microreactor. The H-form
zeolite used for catalytic reaction was obtained by calcination (4 h
at 540 ◦ C) of samples through an ion exchange in NH4 NO3 solu-
tion (10%), and then pressed, crushed, and sieved to 14–20 mesh.
1 g zeolite supported by 5 g of sea sand was packed into the re-
actor and activated in the desired reaction temperature (550 ◦ C)
under hydrogen gas with a pressure of 2.8 MPa for 2 h. A mix-
ture of toluene, C9 , and C10 aromatics with a weight ratio of 50:
40: 10 at weight hourly space velocity (WHSV) of 2.5 h−1 was
then charged into the reactor by metering pump, and the hydro-
gen gas with a molar ratio of 4:1 for hydrogen to mixture (toluene,
C9 , and C10 aromatics) was also introduced into the reactor. The
reaction products were collected and analyzed with an Agilent
4890 gas chromatograph equipped with a capillary column of PEG
20 M × 0.25 mm × 50 m. The conversions of toluene (XT ), C9 (XC9 ),
and C10 (XC10 ) either by disproportionation or transalkylation were
defined respectively as
(toluene mol%) F − (toluene mol%) P
XT = ,
(toluene mol%) F
(C9 mol%) F − (C9 mol%) P
XC 9 = ,
(C9 mol%) F
(C10 mol%) F − (C10 mol%) P
XC10 = ,
(C10 mol%) F
434 H. Zhu et al. / Journal of Colloid and Interface Science 331 (2009) 432–438
Fig. 1. XRD patterns of conventional ZSM-5 and mesoporous ZSM-5.
where the subscripts F and P represent the component in the feed
stream and in the product stream, respectively.
3. Results and discussion
As stated above three different routes are developed for the
synthesis of mesoporous ZSM-5 by using PVB gel as the template.
Usually porous carbon materials are widely used as mesopore
template for the synthesis of mesoporous zeolite. In the carbon
templating synthesis the zeolite nucleation proceeds in the pores,
subsequently the crystal grows and encapsulates the carbon mate-
rials [19]. Removal of carbon that is trapped in zeolite crystal by
combustion gives rise to mesopores in zeolite. Therefore, the pore
in carbon materials is necessary for its hard template effect. The
PVB used in our synthesis is nonporous materials which has no
pore for zeolite nucleation. But it has shown satisfactory affinity to
silica due to the hydroxyl group in its structure. Accordingly, the
PVB gel can be well dispersed in silica. When the silica is con-
verted into crystalline zeolite under the hydrothermal synthesis,
the PVB can be occluded in zeolite particle during the crystal-
lization process. Calcinations of the occluded PVB gel will create
corresponding mesopores in the zeolite.
Fig. 1 shows the XRD patterns of ZSM-5 samples synthesized
by different methods. They all exhibit the characteristic diffraction
peaks occurred at 2θ of 7.9◦ , 8.8◦ , 23.1◦ , 23.9◦ , and 24.4◦ , which
are exclusively indexed to the structure of MFI topology [27]. It is
noted that the three samples crystallized in the presence of PVB
also show good crystallinity, hence the existence of PVB gel in the
synthesis system does not exert negative effect on the formation of
ZSM-5 zeolite. However, the XRD pattern of Sample-C is different
from those of other three samples. Obviously, the diffraction lines
for Sample-C are slightly broadened, which indicates that Sample-
C matrix contains very small crystalline domains. Estimated from
the Scherrer equation the particle size of Sample-C is about 80
nm. TEM images in the following discussion are consistent with
this XRD observation, which confirms that the Sample-C is poly-
crystalline with the aggregate of nanosized unites.
Fig. 2 gives a series of SEM images on the different ZSM-5 sam-
ples. Sample-A and Sample-B are synthesized by PVB template,
while the gel composition for their crystallization is identical to
that of conventional ZSM-5. There is no clear difference among
conventional ZSM-5, Sample-A and Sample-B in their morphology.
The appearance of Sample-A and Sample-B is not significantly in-
fluenced by PVB template, and their morphology is same as that
of conventional zeolite. These three samples are all uniform sphere
without observable amorphous, and their particle size distribution
is in the same range of 300–500 nm. Outstandingly, the morphol-
ogy of Sample-C is not very regular in the low magnification SEM.
Besides some large sphere particle lots of small particles with ir-
regular shape around 100 nm is also observed. From the high
resolution of SEM it can be seen that the surface of the large par-
ticle is smooth, and this particle (400 nm) is composed of many
nanodimension particles that are less than 100 nm in diameter.
These small primary particles appear to be tightly packed together,
forming the aggregate of nanosized particles. It can be concluded
from SEM that the PVB gel in the synthesis has little effect on the
morphology of Sample-A and Sample-B, but largely changes the
appearance of Sample-C.
TEM micrographs of the mesoporous ZSM-5 samples are illus-
trated in Fig. 3. For conventional ZSM-5, no evident bright spot
relative to the mesopore is observed in the TEM. On the contrary,
the TEM of Sample-A indicates that there are lots of mesopores
in the single crystal. From the high resolution TEM concentrating
on the edge of Sample-A particle it can be seen that a large num-
ber of mesopores shown as bright parts appear on the surface of
ZSM-5 crystal. The mesopores located in the edge of Sample-A is
about 20 nm with no regular shape. In contrast with Sample-A,
there is less mesopores in Sample-B and the mesopore is smaller.
Observed from TEM the mesopore in Sample-B is about 5 nm.
Distinctly different from Sample-A and Sample-B with single crys-
talline structure, the Sample-C is polycrystalline with aggregate
of nanosized particles. High resolution TEM shows that the large
sphere (400 nm) of Sample-C is composed of nanocrystals (30 nm).
The small nanocrystals are intergrown together, forming the large
ZSM-5 particle with polycrystalline structure. The mesopores in
Sample-C are intercrystal pores that results from the interparticle
voids between the nanosized ZSM-5. Indeed, the nanosized zeo-
lite unites in the aggregate are closely packed. When the sample
is dealt with ultrasonic dispersion for a long time, TEM also shows
that the small unites in a particle are not apt to come loose and
the agglomerated particles are still intact.
Fig. 4 provides the nitrogen adsorption and desorption isotherm
of the conventional and mesoporous ZSM-5 zeolite. The conven-
tional ZSM-5 exhibits Type I isotherm with only one adsorption in
the initial pressure, which belongs to a typical adsorption isotherm
of microporous material. By contrast, the isotherms of other three
samples synthesized in the presence of PVB show another ad-
sorption step and a hysteresis loop in the range of P / P 0 > 0.6,
corresponding to the nitrogen filling in mesopores [28]. The pres-
ence of additional mesopores in these samples is a consequence
of the removal of PVB gel from as-synthesized zeolite. Table 1
summaries the BET surface areas, micropore volume, mesopore
volume, and external surface area of four samples. It should be
noted that the PVB gel added in the three samples’ synthesis is in
the same amount (PVB/SiO2 = 0.25), but the mesopore volume re-
sulting from PVB gel template is slightly different. The mesoporos-
ity in three ZSM-5 zeolite is in a sequence of V meso(Sample-A) >
V meso(Sample-C) > V meso(Sample-B) , which is relative to their synthe-
sis methods. Thus, the procedure of direct hydrothermal treatment
of the PVB/silica composite from sol–gel process is the most effi-
 H. Zhu et al. / Journal of Colloid and Interface Science 331 (2009) 432–438 435

(a) (b)

(c)

(d)

Fig. 2. (a) SEM of conventional ZSM-5 synthesized without the PVB gel. (b) SEM of mesoporous ZSM-5 (Sample-A). (c) SEM of mesoporous ZSM-5 (Sample-B). (d) SEM of
mesoporous ZSM-5 (Sample-C) with low and high magnification.

cient route for introducing mesoporosity into ZSM-5 by PVB gel. significantly with the increase of the mesopore volume, suggesting
However, the surface area of mesoporous ZSM-5 does not enhance that the mesoporosity has little contribution to the surface area.
436 H. Zhu et al. / Journal of Colloid and Interface Science 331 (2009) 432–438

(a)

(b)

(c)

(d)

Fig. 3. (a) TEM image of regular ZSM-5 synthesized by conventional method. (b) TEM image of mesoporous ZSM-5 (Sample-A) synthesized by hydrothermal treatment of
PVB/silica composite. (c) TEM image of mesoporous ZSM-5 (Sample-B) synthesized by direct hydrothermal treatment of PVB impregnated Aerosil-200. (d) TEM of mesoporous
ZSM-5 (Sample-C) synthesized by re-crystallization of preformed ZSM-5 in the presence of PVB.
 H. Zhu et al. / Journal of Colloid and Interface Science 331 (2009) 432–438 437

Fig. 4. N2 adsorption/desorption isotherm of conventional and mesoporous ZSM-5.

Table 1
Textural property of the four different samples

Sample S BET a V total b V micro b V meso

(m2 g−1 ) (cm3 g−1 ) (cm3 g−1 ) (cm3 g−1 )
Con-ZSM-5 361 0.18 0.12 0.00
Sample-A 445 0.32 0.12 0.20
Sample-B 381 0.22 0.12 0.10
Sample-C 364 0.24 0.12 0.12
a
BET method.
b
V total = V ads P / P 0 = 0.97.
c
t-Plot method.

The nitrogen adsorption analysis supports the observations from

the TEM images, further proving that the ZSM-5 synthesized in
the presence of PVB has mesoporosity.
The synthesized mesoporous ZSM-5 can be categorized into two
types according to their mesopore structure. The first category of
materials is the ordinary single crystal zeolite but has additional
mesopore in each individual zeolite crystal. Sample-A and Sample-
B belong to such category. As shown in the characterization,
Sample-A and Sample-B feature the typical crystallographic micro-
pores characteristic of the MFI zeolite structure and an additional
intracrystal mesopore system in a single crystal. The pore structure
of Sample-C is different from Sample-A and Sample-B. Sample-C
is the polycrystalline ZSM-5 which aggregates from nanosized ze-
olite particles. Clearly, the polycrystalline Sample-C also features
the well-defined micropore system of ZSM-5. Moreover, it has an
intercrystal mesopore system, which results from the packing of
the nanosized zeolite crystals.
The difference in the hierarchical pore structure among the
three samples is dependent on the synthesis methods. The syn-
thesis procedures of Sample-A and Sample-B are different, but the
silica/PVB composite is used as precursor for the hydrothermal
crystallization of mesoporous zeolite. The silica/PVB composite for
Sample-A synthesis is prepared by sol–gel technique, whereas the
silica/PVB composite for Sample-B synthesis is fabricated by im-
pregnation process. When the composite undergoes hydrothermal
treatment the silica crystallizes into single ZSM-5 zeolite, mean- Fig. 5. Comparison of conversions of the toluene, C9 , and C10 aromatics over the
while the PVB gel is encapsulated into the zeolite crystal. The conventional ZSM-5 and mesoporous ZSM-5.
removal of PVB by combustion can release corresponding intracrys-
tal mesopores in zeolite. However, the procedure for the Sample-
and they cannot continue crystallizing to form a single crystal. Dur-
C synthesis is significantly different from those of Sample-A and
ing the re-crystallization process the zeolite nanocluster assembles
Sample-B. The pre-formed zeolite nanocluster re-crystallized in the
presence of PVB for the synthesis of Sample-C. The addition of PVB around the polymer gel to form the aggregate of nanosized ZSM-5.
in the zeolite system disturbs its crystal growth process. The PVB The PVB is trapped in the aggregate; therefore the mesopores are
gel keeps the pre-formed ZSM-5 nanocluster apart from each other, created in the particles. The removal of PVB gel by combustion
438 H. Zhu et al. / Journal of Colloid and Interface Science 331 (2009) 432–438
gives the void between the nanosized zeolite particles, so the inter-
crystal mesopores in the aggregate of nanosized zeolite is opening.
The effect of mesopore on the catalytic performance of ZSM-
5 can be reflected from the catalytic reaction of toluene dispro-
portionation and transalkylation with C9 and C10 aromatics. Con-
ventional ZSM-5 as well as mesoporous ZSM-5 (Sample-A and
Sample-C) is used for comparing their catalytic difference at the
reaction temperature of 340–420 ◦ C. The toluene, C9 , and C10
aromatics catalytic conversion over the ZSM-5 zeolite are com-
plex processes, including the disproportionation of toluene, the
transalkylation of toluene with C9 and C10 , as well as some side
reactions. The catalytic activities of zeolites are evaluated from the
conversion of reactants. Fig. 5 gives the comparison of the conver-
sions of the toluene, C9 , and C10 aromatics over the conventional
ZSM-5 and mesoporous ZSM-5. When the temperature is raised,
the conversions of toluene, C9 , and C10 aromatics over these three
zeolites exhibit a same tendency, and the conversions gradually in-
crease with the temperature elevation. The conversions of toluene
over the three zeolites almost keep at a same degree. On the con-
trary, mesoporous ZSM-5 shows higher catalytic conversions to-
wards C9 and C10 aromatics. Form the comparisons it is can be
seen that the catalytic reactions of large molecules in mesoporous
ZSM-5 will be improved significantly.
The different catalytic performance between conventional ZSM-
5 and mesoporous ZSM-5 is relative to the difference in their pore
structures. It is well known that the microporous ZSM-5 has 10-
ring pore with diameter no larger than 0.56 nm. Only toluene can
diffuse into and out of the inner pore of ZSM-5 freely. However,
C9 and C10 aromatics are larger than the crystallographic pore of
MFI structure. Therefore, catalytic reactions of C9 and C10 aromat-
ics can only occur on the external surface of conventional ZSM-5
crystals. When the mesopore is introduced into microporous ZSM-
5, additional pathway is provided for C9 and C10 transportation
which leads the remarkable enhancement of their diffusion rate.
Hence, the mesoporous ZSM-5 shows a better catalytic activity in
this large molecule involved reaction.
4. Summary
Mesoporous ZSM-5 zeolites have been synthesized in the pres-
ence of PVB gel matrix through three synthesis routes. After burn-
ing off the PVB gel in as-synthesized zeolite, mesoporous ZSM-5
are obtained. ZSM-5 with intracrystal mesoporosity can be syn-
thesized by direct crystallization of silica/PVB composite. Two
routes are developed for the fabrication of silica/PVB composite,
which are the hydrolysis of TEOS in the presence of PVB and
the impregnation of Aerosil-200 with PVB solution. Upon the re-
crystallization of the pre-formed ZSM-5 precursor in the presence
of PVB the ZSM-5 aggregate with intercrystal mesoporosity is syn-
thesized. Characterization techniques have verified that the PVB
templated ZSM-5 samples do not only possess intrinsic micropore
but also have mesopore. However, the efficiency of PVB templating
effect is dependent on the synthesis method. Mesoporous ZSM-
5 synthesized by hydrothermal treatment of silica/PVB composite
obtained from sol–gel process has the largest mesopore volume.
While the ZSM-5 synthesized from PVB impregnated Aerosil-200
possesses the least mesopore volume. Meanwhile the mesoporous
ZSM-5 exhibited improved catalytic activity in the toluene dispro-
portionation and transalkylation with C9 and C10 aromatics. The
enhanced catalytic performance is due to the presence of meso-
pores for increasing the diffusion rate of the reactant.
Acknowledgment
This wok is supported by Major State Basic Research Develop-
ment Program of the People’s Republic of China (2003CB615802).
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