An in situ carbonaceous mesoporous template for the synthesis of hierarchical ZSM-5 zeolites by one-pot steam-assisted crystallization

Article abstract of DOI:10.1002/asia.201200744

Blackened catalyst: Zeolites with large external surface area and mesopore volume were synthesized by a one-pot templating strategy, in which the crystallization proceeded concurrently with in situ carbonization templating to produce a mesoporous structur

Full text of DOI:10.1002/asia.201200744

DOI: 10.1002/asia.201200744
An In Situ Carbonaceous Mesoporous Template for the Synthesis of
Hierarchical ZSM-5 Zeolites by One-Pot Steam-Assisted Crystallization
Yudian Song, Zile Hua, Yan Zhu, Xiaoxia Zhou, Wei Wu, Linlin Zhang, and Jianlin Shi*[a]
Zeolites, which possess uniform micropores, large specific
surface area, and intrinsic acidity, have been widely used in
many industrial processes related to adsorption, separation,
ion exchange, and catalysis.[1] However, due to the inherent
small pore sizes of conventional zeolites (<1.5 nm), the
mass transfer in them is restricted, and consequently their
performances need to be further improved, especially in
processes involving bulky molecules. A reduction in particle
size, for example in nanosized zeolite crystallites, could par-
tially resolve the diffusion problem in microporous zeolites
due to their larger external surfaces and the decreased diffu-
sion path length in the micropore channels. However, the
collection difficulty in the preparation or during applications
limited their ever wider applications.[2] Alternatively, hier-
archical zeolites, which combine the strong acidity and high
stability of crystalline microporous zeolites with the en-
hanced molecular diffusion resulting from additional meso-
porosity, have become a research focus in recent years and
have been developed through multistep post-synthesis de-
metallation or desilication treatments and templating syn-
thesis with careful design of the synthesis procedure or the
mesoscale templates.[3]
suffered from process complexity due to the hydrophobicity
of the carbon templates, and the intracrystal mesopores are
not always open to the external surface of the zeolite crys-
tals.[6] To overcome this drawbacks, Tang and co-workers in-
troduced mesopores in ZSM-5 by in situ hydrothermal treat-
ment of a solution containing alkali-dissolved SBA-15 con-
taining carbonized surfactant P123 in the mesopores.[11] As
an extension of the carbon template route, Christensen and
co-workers synthesized hierarchical zeolites using sucrose as
the mesoporous template precursor. However, high-temper-
ature carbonization pretreatment under inert gas protection
was required.[12] Recently, White et al. found that carbona-
ceous materials could be prepared from renewable inexpen-
sive carbohydrate feedstocks, such as d-fructose, and hydro-
thermal carbonization could be performed at relatively low
temperatures to yield materials with functionally useful sur-
face chemistry.[13] Based on the similarity of processing con-
ditions for both the hydrothermal carbonization of carbohy-
drate feedstocks and the zeolite crystallization transforma-
tion in the SAC process, we report herein a novel and facile
one-pot route to synthesize hierarchical zeolites with an in
situ carbonaceous template, in which the zeolite crystalliza-
tion transformation and carbonaceous template formation
were accomplished simultaneously.
In the soft templating route, organosilanes,[4] bifunctional
multiple-quaternary ammonium-type surfactants,[5] and cat-
ionic polymers[6] were explored to avoid the occurrence of
phase separation during the preparation of hierarchical zeo-
lites. Interestingly, by using ordinary surfactant templates
(e.g., F127 and P123), recently, hierarchical zeolites were
successfully synthesized by the steam-assisted crystallization
(SAC) process in our group.[7] However, excessive consump-
tion of the surfactant templates (about 44 wt% in the com-
positions) increases the material costs and brings about envi-
ronmental problems. Alternatively, hard templates like
Scheme 1 illustrates the representative synthetic route for
the preparation of hierarchical zeolites by the one-pot pro-
cess. In the first step, a homogeneous solution of the pri-
mary zeolitic units, microporogen (TPAOH), aluminosilicate
species and sucrose was simply prepared, and then the solu-
tion gradually converted into the dry gel during the subse-
nanosized carbon particles,[8] carbon nanotubes,[9] and or-
[10]
dered mesoporous carbon materials (CMKs)
are also at-
tractive. Unfortunately, these synthesis procedures usually
[a] Dr. Y. Song, Dr. Z. Hua, Dr. Y. Zhu, Dr. X. Zhou, W. Wu, L. Zhang,
Prof. J. Shi
State Key Laboratory of High Performance Ceramics and Superfine
Microstructures
Shanghai Institute of Ceramics, Chinese Academy of Sciences
No.1295 Ding-xi Road, Shanghai, 200050 (P.R. China)
Fax : (+86)21-5241-3122
E-mail: jlshi@mail.sic.ac.cn
Scheme 1. Representation of the procedure for preparation of hierarchi-
cal zeolites with an in situ carbonaceous template. TEOS=tetraethylor-
thosilicate, TPAOH=tetrapropylammonium hydroxide.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201200744.
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quent aging and drying, in which the consumption of sucrose
templates was considerably lower (about 14 wt% in the
compositions) and high-temperature pre-carbonization proc-
essing was unnecessary compared with references [7,11,12].
After that, the resultant dry gel was hydrothermally treated
in a water-steaming environment and changed into brown
powders (Figure S1 in the Supporting Information), in which
the crystallization of zeolite and the in situ hydrothermal
carbonization of sucrose subtly took place synchronously. Fi-
nally, the microporous and mesoporous templates were re-
moved through calcination in air, and then hierarchical zeo-
lites were successfully prepared (Figure S2 in the Supporting
Information).
The crystallization and porous structural features of syn-
thesized hierarchical ZSM-5 zeolites (designated as HZ-w,
where w is the mass of added water in SAC treatment) were
characterized by using XRD and N2 physisorption tech-
niques. The corresponding textural properties are summar-
ized in Table 1. As shown in Figure 1a, the XRD patterns of
Table 1. Textural properties of synthesized hierarchical zeolites.[a]
Sample
SBET [m2 gÀ1
]
Sext [m2 gÀ1
]
Vpore [cm3 gÀ1
]
Dpore [nm]
HZ-0.08
HZ-0.12
HZ-0.15
HZ-0.20
HZ-HT[b]
ZSM-5
421
458
419
363
436
287
238
247
182
88
275
50
0.79
0.63
0.47
0.25
0.56
0.14
15.5
13.0
17.9
15.4
11.2
–
Figure 1. a) XRD patterns and b) N2 adsorption/desorption isotherms of
hierarchical zeolites synthesized by using different amounts of water in
the one-pot SAC process.
precursors under higher steam concentrations.[15] However,
the BET surface area and external surface area of HZ-0.12
(458 m2 gÀ1, 247 m2 gÀ1) are higher than those of HZ-0.08
(421 m2 gÀ1, 238 m2 gÀ1), which may be due to the generation
of microporous structures of zeolite crystals, thus compen-
sating the loss of mesoporosity. With an increased amount
of water used, nevertheless, the BET surface area and exter-
nal surface area decreased to 419/182 m2 gÀ1 for HZ-0.15
and 363/88 m2 gÀ1 for HZ-0.2 respectively, along with the im-
proved zeolite crystallinity.
In this one-pot in situ carbonaceous template process for
preparation of hierarchically structured zeolites, although
the detailed formation mechanism is unclear at present, it is
considered that there are at least two intercrossed courses.
One is the hydrothermal carbonization of carbohydrate
feedstock, where it is believed that just sufficiently “hard”
carbonaceous substances could act as mesopore scaffolds, al-
though a complex mixture consisting of polysaccharides, ar-
omatic compounds, and carbon spheres with hydrophilic sur-
face could be formed in this course.[16] Another is the crys-
tallization transformation of amorphous gels, which, in an
ideal circumstance, should be restricted by or be cooperative
with the preformed carbonaceous templates for the produc-
tion of hierarchical micro- and mesoporous zeolites. Since
the steam concentration during the SAC treatment showed
inverse effect on these two courses, the crystallization trans-
formation of amorphous aluminosilicate precursors and the
hydrothermal carbonization of sucrose should be kinetically
balanced, which could be realized by tuning the amount of
[a] The surface area was calculated using the Brunauer–Emmett–Teller
(BET) method. Sext =SBETÀSmicro, where the micropore area was calculat-
ed from t plot analyses. Vtot is the single-point adsorption total pore
volume at P/P0 =0.97. [b] HZ-HT is the hydrothermal treated sample of
HZ-0.12 at 1008C for three days.
the synthesized hierarchical zeolites exhibit the well-re-
solved characteristic peaks for the MFI zeolite. Generally,
the intensity of the X-ray diffractions become stronger with
an increasing amount of added water, which means that the
increased steam concentration could accelerate the crystalli-
zation of zeolite and is consistent with the reported re-
sults.[14] Especially for HZ-0.08, slight crystallization of zeo-
lite can be found, as the amount of water added is far lower
than needed for the complete crystallization transformation
of dried gel precursors.
The N2 adsorption/desorption isotherms shown in Fig-
ure 1b of the hierarchical ZSM-5 zeolites demonstrate typi-
cal type-IV curves with steep H1 hysteresis loops and exhib-
it a significant uptake at the relative pressure (P/P0) of 0.7–
0.9, which indicates the existence of the textural mesoporos-
ity. As shown in Table 1, the BET surface area, external sur-
face area, and the total pore volume of hierarchical ZSM-5
zeolites are distinctly larger than those of conventional
ZSM-5 (287 m2 gÀ1, 50 m2 gÀ1, and 0.14 cm3 gÀ1). Further,
their total pore volumes gradually decreased from 0.79 to
0.63, 0.47, and 0.25 cm3 gÀ1 with an increasing amount of
added water amount during SAC treatment, which resulted
from the rapid crystallization transformation of amorphous
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Hierarchical ZSM-5 Zeolites
added water. For sample HZ-0.08, a small amount of water
addition during SAC treatment led to the slight crystalliza-
tion of dried gel precursor because of the low driving force
of crystallization,[15] while it was in favor of the carboniza-
tion of sucrose for the development of mesostructured car-
bonaceous templates. Meanwhile, when an excessive
amount of water was added, such as for sample HZ-0.2, the
products were highly crystalline, but with lower mesoporosi-
ty, resulting from the relatively higher steam concentration
and consequently lower carbonization rate of sucrose.[15]
Thus, only under the use of an appropriate amount of water,
such as for samples HZ-0.12 and HZ-0.15, was a compro-
mised state achieved between crystallization transformation
of amorphous gels and hydrothermal carbonization of su-
crose. Under these conditions, hierarchical ZSM-5 zeolite
could be obtained, which also implies that hierarchical zeo-
lites with adjustable micro- and mesoporosity could be syn-
thesized simply by changing the amount of water added
during SAC treatment. Moreover, the effect of the amount
of sucrose as the mesopore generator precursors on the mes-
oporosity of hierarchical zeolites was also investigated. As
shown in Table S1 and Figure S3 in the Supporting Informa-
tion, it is clear that the external surface area, pore diameter,
and pore volume will increase, but the framework becomes
less crystalline when larger amounts of sucrose are intro-
duced.
es co-existing with the mesoporous structures, which further
confirmed that the resultant hierarchical zeolites are single-
crystalline phases.[7] Additionally, the hydrothermal stability
of the representative sample HZ-0.12 was also investigated.
After hydrothermal treatment at 1008C for three days, the
as-synthesized hierarchical zeolites still retained the MFI
structure (see Figure S4a in the Supporting Information),
and the BET surface area decreased by only 6% (see Fig-
ure S4b in the Supporting Information and Table 1), which
demonstrated that the hierarchical zeolites possess better
hydrothermal stability than reported ordinary amorphous
mesoporous materials.[17]
Friedel–Crafts acylation of aromatic compounds is one of
the most important reactions for the synthesis of aromatic
ketones, which are valuable intermediates in pharmaceutical
industry.[18] In general, these reactions are catalyzed by ho-
mogeneous catalysts such as AlCl3, FeCl3, and ZnCl2, which
unfortunately suffer from serious problems such as high
moisture sensitivity, difficult separation, and undesirable en-
vironmental impact.[19] Towards the development of environ-
mentally benign process for the production of aromatic ke-
tones, the synthesized hierarchical ZSM-5 zeolites were ap-
plied and proved to be efficient heterogeneous catalysts for
the Friedel–Crafts acylation of anisole.
Catalytic test conditions employed in our investigation
were similar to literature reports,[18] where the only differ-
ence is that nitrobenzene was used as an internal standard
instead of solvent. The reaction is shown in Scheme S1 in
the Supporting Information. A high selectivity of larger than
97% to the valuable product p-methoxyacetophenone (p-
MAP) was achieved for both the hierarchical ZSM-5 (HZ-
0.12) and the commercial microporous ZSM-5 catalysts.
However, the catalytic activity of the catalysts differed con-
siderably. Figure 3 shows the anisole conversion as a function
of reaction time using hierarchical zeolite HZ-0.12 and
ZSM-5 as catalysts. Because of the relatively small size of
the anisole molecule, it is able to diffuse throughout the zeo-
litic micropores without significant hindrances. Thus, in the
case of conventional ZSM-5, the conversion of anisole
Furthermore, FESEM for HZ-0.12 was used to reveal the
detailed morphology of the hierarchical zeolites (Fig-
ure 2a,b). The low-magnification image shows that the par-
ticles are typically ellipsoidal with rough surfaces, while the
high-magnification image illustrates that there are plenty of
open mesopores on the hierarchical zeolite surfaces. The
representative HR-TEM characterization of sample HZ-
0.12 (Figure 2c,d) clearly shows the continuous lattice fring-
Figure 3. Time dependence of the anisole conversion in Friedel–Crafts
acylation of anisole with acetyl chloride using hierarchical ZSM-5 (HZ-
0.12) and conventional ZSM-5 as catalysts. Reaction conditions: catalyst
0.11 g, anisole 12.5 mmol, acetyl chloride 12.5 mmol, nitrobenzene 1.0 g,
T=1208C.
Figure 2. Representative electron microscopic images of HZ-0.12.
a,b) FESEM images at low and high magnification, respectively.
c,d) TEM images at low and high magnification, respectively.
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Jianlin Shi et al.
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+
three times with NH4 using a 10 wt.% NH4NO3 solution and then cal-
reached about 20.1% in 3 h of reaction. Comparatively,
thanks to the enhanced molecular diffusion in the additional
mesoporosity in hierarchical zeolites, HZ-0.12 samples
showed noticeably higher initial anisole reaction rate, and
the anisole conversion was 37.8% in the same time period
of 3 h. This result is consistent with previous reports,[18] in
which Serrano et al. considered a stronger inhibition effect
of the adsorbed p-MAP product than of the reactant anisole,
which were both involved in this acylation reaction. More-
over, the larger mesopore size of hierarchical zeolites was
believed to provide less steric restriction and the coke for-
mation than the micropores of pure zeolites and was in
favor of improving catalytic performance. Additionally, the
combination of a good accessibility and strong acidity in hi-
erarchical zeolite should also be responsible for the im-
proved catalytic properties as compared with amorphous
Al-MCM-41.[3,17,19] Finally, the reusability of hierarchical
zeolites was studied, and limited activity loss in the anisole
conversion was found after the second cycle (Table S2 in the
Supporting Information).
In conclusion, hierarchical ZSM-5 zeolites have been syn-
thesized by a novel and facile one-pot SAC process, in
which the mesoporous structures were created by the in situ
hydrothermal carbonization of a renewable and low-cost
carbohydrate feedstock (i.e. sucrose), accompanied by zeo-
lite crystallization. A balanced zeolite crystallization and
mesoporous structure formation can be achieved simply by
tuning the amount of water added during SAC synthesis.
The synthesized hierarchical zeolites possessed superior hy-
drothermal stabilities, and as low as 6% loss of specific sur-
face area was observed after three days of hydrothermal
treatment. In Friedel–Crafts acylation of anisole, compared
with the purely microporous counterparts, the synthesized
hierarchical ZSM-5 zeolites showed significantly higher cat-
alytic performances than conventional ZSM-5, with about
38% conversion of anisole and larger than 97% selectivity
to p-MAP in 3 h of reaction.
cined again in air at 5508C for 5 h to convert them into the H+ form.
Characterization
Powder X-ray diffraction (XRD) patterns were recorded by using
a Rigaku D/Max 2200PC diffractometer with CuKa radiation (40 kV and
40 mA) with a scanning rate of 4 minÀ1 over the 2q range of 5–508. The
nitrogen adsorption isotherms were measured on a Micromeritics Tristar
3000 porosimeter at 77 K for mesoporosity and microporosity. The sur-
face area and micropore and mesopore distributions were calculated ac-
cording to the BET and BJH theories. SEM micrographs of uncoated
powders were obtained using a field emission scanning electron micro-
scope Hitachi S4800. Transmission electron microscopy was performed
with a JEOL-2010F instrument.
Catalytic Tests
The Friedel–Crafts acylation of anisole with acetyl chloride as the acylat-
ing agent was carried out in a 25 mL three-necked round-bottom flask
with magnetic stirrer and a temperature-controlled heating jacket under
N2 atmosphere. A chilled water reflux condenser was used to minimize
the evaporation of acetyl chloride. To obtain accurate calculation of con-
version, nitrobenzene was used as the internal standard for anisole. In
a typical reaction, the catalyst (0.11 g), anisole (1.35 g, 12.5 mmol), and
nitrobenzene (1 g) were mixed with continuous stirring under room tem-
perature. Subsequently, acetyl chloride (0.98 g) was added dropwise into
the reactor and then the heating process was run until the reaction tem-
perature reached 1208C. Liquid samples were withdrawn periodically
using a microsyringe after a certain reaction time and then analyzed by
GC-MS (Agilent, 6890/5973N). Since acetyl chloride was volatile, conver-
sion was calculated based on anisole. In addition, the spent catalyst was
recycled by filtration, washing with acetone, drying, and calcining in air
atmosphere at 5508C for 4 h.
Acknowledgements
The authors gratefully acknowledge the support of this research by Na-
tional Natural Science Foundation of China (Grant No. 50872140,
21177137), Science Foundation of State Key Laboratory of Heavy Oil
Processing (2012-1-04) and Science Foundation for Youth Scholar of
State Key Laboratory of High Performance Ceramics and Superfine Mi-
crostructures (SKL200901).
Keywords: heterogeneous catalysis · mesoporous materials ·
steam assisted crystallization · template synthesis · zeolites
Experimental Section
Synthesis of Materials
In a typical run, a mixture of aluminum isopropoxide (0.2 g, 1 mmol) and
tetraethylorthosilicate (TEOS, 10.4 g, 50 mmol) was added to distilled
water (18 g, 1 mol) under continuous stirring at 408C. After 2 h, tetrapro-
pylammonium hydroxide (TPAOH, 25% in water, 4.10 g, 5 mmol) was
added dropwise into the solution. The mixture was stirred vigorously for
4 h. Then sucrose (0.69 g, 2 mmol) was added. The molar ratio of the re-
sultant solution was SiO2:0.01Al2O3:0.1TPAOH:0.04sucrose:20H2O. Stir-
ring was continued to form a solidified gel. Then the resultant gel was
aged for about 7 h and dried at 508C for about 12 h. Subsequently, as re-
ported for the steaming-assisted crystallization (SAC) process,[20] this as-
prepared gel (1.0 g) was crystallized at 1508C for 10 h, while a certain
amount of water was added in the bottom of a two-layer-structured auto-
clave. Finally, the powder was calcined at 6008C for 8 h in air to remove
the organic templates. Depending on the water usage (w g) during the
SAC treatment, the obtained hierarchical zeolite was labeled as HZ-w,
where w=0.08, 0.12, 0.15, and 0.2. For comparison, conventional ZSM-5
with the Si/Al ratio of 50 was purchased from Nanjing Jinling Petrochem-
ical Co., Ltd. Before catalysis tests, all catalysts were ion-exchanged
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Zeolites
Blackened catalyst: Zeolites with large
external surface area and mesopore
volume were synthesized by a one-pot
templating strategy, in which the crys-
tallization proceeded concurrently with
in situ carbonization templating to pro-
duce a mesoporous structure. The hier-
archical materials exhibited superior
catalytic performance over conven-
tional zeolites in Friedel–Crafts acyla-
tion of anisole.
Yudian Song, Zile Hua, Yan Zhu,
Xiaoxia Zhou, Wei Wu, Linlin Zhang,
Jianlin Shi*
&&&& — &&&&
An In Situ Carbonaceous Mesoporous
Template for the Synthesis of Hier-
archical ZSM-5 Zeolites by One-Pot
Steam-Assisted Crystallization
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Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!