LETTERS

Amphiphilic organosilane-directed
synthesis of crystalline zeolite with tunable
mesoporosity
MINKEE CHOI, HAE SUNG CHO, RAJENDRA SRIVASTAVA, CHITHRAVEL VENKATESAN, DAE-HEUNG CHOI
AND RYONG RYOO*
National Creative Research Initiative Center for Functional Nanomaterials and Department of Chemistry, Korea Advanced Institute of Science and Technology,
Daejeon 305-701, Korea
* e-mail: rryoo@kaist.ac.kr

Published online: 6 August 2006; doi:10.1038/nmat1705

eolites are a family of crystalline aluminosilicate materials over the diameter range of 2–15 nm). Mesoporous materials

Z widely used as shape-selective catalysts, ion exchange

materials, and adsorbents for organic compounds1,2 . In
the present work, zeolites were synthesized by adding a
have attracted much attention as a new adsorbent, catalyst
support, and synthesis template for other nanostructured
materials2 . Particularly in catalysis, the mesoporous structure
rationally designed amphiphilic organosilane surfactant to was very promising for reactions involving large molecular
conventional alkaline zeolite synthesis mixtures. The zeolite species, due to the possibility of overcoming the diffusion
products were characterized by a complementary combination limitation with crystalline microporous zeolites (0.3–1.5 nm
of X-ray diffraction (XRD), nitrogen sorption, scanning electron in pore diameter). The MCM-41-type mesoporous materials,
microscopy (SEM) and transmission electron microscopy (TEM). however, exhibited insufficient hydrothermal stability and acidity
The analyses show that the present method is suitable as compared with crystalline zeolites7–9 . Material scientists thereafter
a direct synthesis route to highly mesoporous zeolites. The endeavoured to improve the framework crystallinity for practical
mesopore diameters could be uniformly tailored, similar to applications. Despite tremendous efforts, the hydrothermal
ordered mesoporous silica with amorphous frameworks3 . The stability and framework acidity were still far from the properties of
mesoporous zeolite exhibited a narrow, small-angle XRD peak, crystalline zeolites.
which is characteristic of the short-range correlation between Various attempts to synthesize mesoporous aluminosilicate
mesopores, similar to disordered wormhole-like mesoporous materials with improved framework crystallinity were reported.
materials4,5 . The XRD patterns and electron micrographs of In a typical approach, molecular templates for zeolites (for
the samples taken during crystallization clearly showed the example, tetrapropylammonium and alkali metal ions) were
evolution of the mesoporous structure concomitantly to the added to the synthesis composition for ordinary mesoporous
crystallization of zeolite frameworks. The synthesis of the aluminosilicates10–12 . The synthesis approach was based on the idea
crystalline aluminosilicate materials with tunable mesoporosity that the molecular templates could direct zeolite crystallization in
and strong acidity has potentially important technological the mesopore walls, while mesoporous structures are concurrently
implications for catalytic reactions of large molecules, whereas formed according to the supramolecular templating mechanism
conventional mesoporous materials lack hydrothermal stability of the surfactant micelles. However, it turned out that the two
and acidity. different templating systems worked in a competitive, rather
The design of rational synthesis pathways for porous than a cooperative, manner. The syntheses mostly resulted in
materials is significant due to their potential applications as the formation of amorphous mesoporous material, bulk zeolite
advanced catalysts, adsorbents, optical guides and sensors. In without mesoporosity, or their physical mixtures. One exceptional
modern science, extensive research efforts have been devoted case was the synthesis of a lamellar mesostructure with a
to the synthesis of porous inorganic materials with different crystalline framework13,14 , but the structure collapsed into a non-
structural coherency over a wide range of length scale. In porous material on calcination. Multi-step synthesis strategies were
particular, there have been extensive synthesis works on proposed to solve the phase-separation problem of the zeolite and
mesoporous aluminosilicate materials such as MCM-41 (ref. 3) and mesoporous phases. In these strategies, the synthesis composition
SBA-15 (ref. 6), using surfactant as a structure-directing agent. for conventional zeolite was hydrothermally aged until the primary
The mesopore diameters of the mesoporous materials were or secondary building units for zeolite structure were formed.
quite uniform, and furthermore, were finely tunable (typically, The resultant gel mixture, which was believed to contain zeolite

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a 3h b 12 h c 30 h

500 nm 500 nm 500 nm

d 12 h e 30 h f 30 h

50 nm 200 nm 50 nm

Figure 1 Electron microscopic investigation on the formation of mesoporous MFI zeolite. a–c, SEM and d–f, TEM images of the products precipitated after various
reaction times during hydrothermal synthesis of mesoporous MFI zeolite at 150 ◦C. The SEM images show a distinct change in morphology, from a sponge-like macroporous
network to globular particles with rugged surfaces. The TEM image in d shows that the initial phase was a mesoporous material with an amorphous framework. The TEM
images in e and f and the corresponding electron diffraction pattern (inset of f) indicate that the final product was a mesoporous MFI zeolite with a polycrystalline framework.
The initial phase gradually disappeared with the reaction time, leaving macrocavities (50–200 nm in diameter) within the remaining domain (arrows in d). This phenomenon
indicates that the mesoporous zeolite particles were formed via the solution-mediated crystallization mechanism1 . To observe the genuine surface structure, the SEM images
were taken at a low electron acceleration voltage (2 kV, Hitachi S-4800), without metal coating32 . TEM images were obtained using a Philips F20 Tecnai transmission electron
microscope with an operating voltage of 200 kV. The TEM images were taken after mounting the zeolite particle on a porous carbon grid.

‘seed’ crystals, was assembled to mesoporous structure by the The phase-separation phenomenon indicates that the surfactants
addition of surfactants15–18 . Alternatively, the aged gel mixture was are expelled from the aluminosilicate domain during the zeolite
coated on the pore walls of pre-synthesized mesoporous silica19,20 . crystallization process, making it difficult for the surfactants to
The seed-assembled products exhibited well-defined small-angle modulate the zeolite crystal growth into a mesoporous structure.
X-ray diffraction (XRD) patterns, which were characteristic of an As revealed by biominerallization processes28 and some successful
ordered mesoporous material. The seed-assembled products were synthesis works29 , organic molecules that are capable of a strong
claimed to be ‘pseudozeolite’ or ‘protozeolite’ in the framework interaction with the growing crystal surface can effectively
nature, but these materials did not exhibit the long-range atomic modulate the crystallization process of inorganic materials. In
order characteristic of a crystalline zeolite framework. Although these respects, we used a rationally designed surfactant molecule
the acidity and hydrothermal stability were somewhat improved, with functional groups to enhance the interaction with growing
the properties were still far from those of crystalline zeolites21 , zeolite crystals. The key for the design was to find amphiphilic
being insufficient for many industrial applications. Recently, it surfactant molecules that contained a hydrolysable methoxysilyl
was also reported that mesoporous materials with crystalline moiety, a zeolite structure-directing group such as quaternary
zeolite framework can be synthesized through a crystallization ammonium, and a hydrophobic alkyl chain moiety. It was expected
process inside a packed bed of removable ‘solid’ nanotemplates that such amphiphilic organosilanes could strongly interact with
(for example, carbon nanoparticles22,23 , nanotubes24 , mesoporous growing crystal domains through the formation of covalent
carbons25 , and polymer beads26,27 ). However, such a process using bonds with other SiO2 and Al2 O3 sources using the methoxysilyl
a solid template has limited pore tunability depending on the moiety. To meet the requirements, we have synthesized
availability of templates. [3-(trimethoxysilyl)propyl]hexadecyldimethylammonium chloride
Herein, we report a direct synthesis route to mesoporous ([(CH3 O)3 SiC3 H6 N(CH3 )2 C16 H33 ]Cl, TPHAC) and their
zeolites with tunable mesoporous structure using the amphiphilic structural analogues. These molecules contain a surfactant-like
organosilanes as a mesopore-directing agent. As mentioned long-chain alkylammonium moiety and a hydrolysable
above, crystalline zeolite containing both micro- and mesoporous methoxysilyl group, linked together by a Si–C bond, which is
structures in a single phase is difficult to obtain if the chemically stable under various zeolite synthesis conditions30 . In
aluminosilicate gel is directly crystallized in the presence of a typical synthesis, a pre-calculated amount of TPHAC (4 mol%
ordinary organic surfactants and molecular templates for zeolites. of the total silica source) was added to the initial synthesis

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LETTERS

a 1,200 b 8
(4) 7.4 nm
7
1,000
(4)
6

Adsorbed amount (ml g– 1)

800 (3)

Distribution (ml g–1 nm–1)

5 3.9 nm
8d
(3)
600 4
Intensity (arb. units)

Intensity (arb. units)

(2)

2d
3 3.1 nm
8d 400 (2)
(1)
2
2d 30 h
200
1 2.1 nm
30 h (1)
12 h 0 0
0 0.2 0.4 0.6 0.8 1.0 1 10 100
12 h
Relative pressure (P/P0) Pore diameter (nm)
3h
3h
Figure 4 Mesoporous MFI zeolites with tunable mesopore diameters. a, N2
1 2 3 4 10 20 30 40 adsorption isotherms for mesoporous MFI zeolites, and b, the corresponding pore
2θ (°) 2θ (°)
size distribution (BJH). The isotherms for samples 2, 3 and 4 were vertically offset by
200, 400, 600 ml g−1 , respectively. The distribution of mesoporous diameters for
samples 2, 3 and 4 were offset vertically by 2, 4 and 6 ml g−1 nm−1 , respectively.
Figure 2 Powder XRD patterns for the products precipitated after various
Samples 1–3 were synthesized by the hydrothermal reaction for 5 d at 130 ◦C, using
reaction times, during hydrothermal synthesis of mesoporous MFI zeolite at
organosilanes with different chain lengths ([(CH3 O)3 SiC3 H6 N(CH3 )2 Cn H2n+1 ]Cl,
150 ◦C. Small-angle XRD patterns were recorded in the reflection mode
n = 12, 16 and 18 for samples 1, 2 and 3, respectively). Sample 4 was synthesized
(l = 0.154250 nm), using a synchrotron X-ray source of BL8C2 at Pohang Light
for 2 d at 170 ◦C with n = 16.
Source. Wide-angle XRD patterns were taken with a Rigaku Multiflex diffractometer
equipped with Cu Kα radiation (40 kV, 40 mA).

a 1,200 b 8 a structure director for the zeolite. A conventional hydrothermal

reaction was used for the crystallization. To systematically
1,000
8d investigate the zeolite crystallization process, sample aliquots
8d
were periodically taken from a synthesis mixture for MFI
6 zeolite (Si/Al = 14) during the hydrothermal reaction (see the
Adsorbed amount (ml g– 1)

Distribution (ml g–1 nm–1)

800 Methods section), and were analysed by mutually complementary

2d techniques such as transmission electron microscopy (TEM),
2d scanning electron microscopy (SEM), XRD, 13 C cross-polarization
600 4
magic-angle-spinning nuclear magnetic resonance (CP MAS
30 h NMR), and N2 adsorption isotherm.
400
30 h
SEM and TEM (Fig. 1) revealed that a mesoporous
2 aluminosilicate phase formed during the initial reaction period
3h (<3 h), under the hydrothermal synthesis condition at 150 ◦ C.
200
The initial phase had a wormhole-type mesoporous structure
3h with an amorphous framework, similar to previously reported
0 0 mesoporous silicas4,5 . 13 C CP MAS NMR analysis indicated that no
0 0.2 0.4 0.6 0.8 1.0 10 100 significant amount of TPA+ was included in the mesoporous phase.
Relative pressure (P/P0) Pore diameter (nm) The formation of the mesoporous structure, exhibiting an XRD
peak at 2θ = 2.3◦ (Fig. 2), can be attributed to the supramolecular
Figure 3 Pore structure analysis of the products precipitated after various
templating action of the amphiphilic organosilanes. As the reaction
reaction times during hydrothermal synthesis of mesoporous MFI zeolite at
time proceeded (12 h), globular MFI zeolite particles began to form.
150 ◦C. a, N2 adsorption isotherms, and b, distribution of mesopore diameters.
The zeolite particle also had a highly mesoporous structure, as
N2 adsorption isotherms were measured at 77 K with a Quantachrome AS-1MP
indicated by high-resolution SEM and TEM images. Moreover, the
volumetric adsorption analyser. The isotherms for samples at 30 h, 2 d and 8 d were
formation of the mesoporous zeolite particles was well supported
vertically offset by 100, 300 and 500 ml g−1 , respectively. Distributions of mesopore
by a small-angle XRD peak appearing at 0 .7◦ and the wide-
diameters were calculated via the Barrett–Joyner–Halenda (BJH) algorithm using the
angle XRD peaks corresponding to the MFI zeolite structure. The
adsorption branch33 . The distribution of mesoporous diameters for samples at 30 h,
electron microscopic investigation revealed that the amorphous
2 d and 8 d were offset vertically by 2, 4 and 6 ml g−1 nm−1 , respectively.
domains gradually disappeared during this period. Macrocavities,
about the size of 50–200 nm, were generated within the amorphous
domain as a result of the phase loss by dissolution. Consequently,
the XRD peak at 2.3◦ of the amorphous phases decreased in
composition of ordinary MFI zeolite (commonly known as intensity. These changes support that the initial mesophase is
ZSM-5), which included tetrapropylammonium ions (TPA+ ) as dissolved into the solution, and then the mesoporous/microporous

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a b

1 μm 500 nm

c d

Distribution (ml g –1 nm–1)

0.6
300
0.4
Ca2+- form
0.2

Adsorbed amount (ml g – 1)

0
0 10 20 30 40 50
200
Pore size (nm)

Na+- form
100

400 nm
0
0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/P0)

Figure 5 Mesoporous LTA zeolite synthesized using [(CH3 O) 3 SiC3 H6 N(CH3 ) 2 C16 H33 ]Cl. a,b, SEM images, c, TEM image, and d, pore size distribution from N2
adsorption isotherm. Inset: Mesopore diameter distribution of Na+ form.

zeolite crystals grow by using the dissolved species as the crystal It is particularly noteworthy that the mesopore diameters
nutrients. Such a solution-mediated crystallization mechanism of the MFI zeolite could be systematically varied, by changing
is very common for zeolite synthesis under alkaline conditions1 . the chain length of the organosilanes and/or the hydrothermal
A highly crystalline zeolite product was obtained after 30 h of synthesis temperature (Fig. 4). The resultant mesopore diameters
reaction at 150 ◦ C. Circular streaking in the electron diffraction were very uniform as in MCM-413 and SBA-156 . As confirmed
pattern (Fig. 1) and the line broadening in the XRD peaks (Fig. 2) by XRD and electron microscopic investigations, the uniform
indicate that the mesoporous zeolite particles were built with mesoporosity was evidently coming from the zeolite phase. The
randomly oriented zeolite nanocrystals. The zeolite (calcined at mesoporous zeolite phase exhibited globular morphologies with
550 ◦ C) showed a type-IV isotherm with a narrow distribution rugged surfaces, which could be easily distinguished from the
of mesopore diameters centred at 3.1 nm (Fig. 3). On further irregular morphologies of the amorphous mesophase. Careful
heating to 8 d, however, the mesopore diameters increased to electron microscopic investigation over a large number of
8 nm. The globular morphology of the zeolite particles remained specimens was used to confirm that there was no significant
unchanged during the prolonged heating period, but a close inclusion of bulk (not mesoporous) zeolite crystals or amorphous
examination of the SEM and TEM images revealed that the mesophase (see Supplementary Information, Fig. S3). Thus, it
size of the nanocrystalline zeolites increased due to a ripening can be reasonably concluded that, within the limitations of
process (see Supplementary Information, Fig. S1). The change the characterization, the samples were uniformly mesoporous in
occurred more conspicuously at the external surface than at the nature, being composed of crystalline zeolite frameworks. The
core of the mesoporous zeolite particles, which could be because MFI zeolite with mesoporous/microporous hierarchical structure
of faster molecular transport at the external surface. Such a could be synthesized with various Si/Al ratios above 14. The 27 Al
crystal ripening process seemed to be the main reason for the MAS NMR spectrum (see Supplementary Information, Fig. S4)
mesopore enlargement, and can be significantly suppressed by showed a single peak around 57–65 p.p.m., in agreement with
lowering the crystallization temperature. For example, a highly tetrahedral Al sites in crystalline zeolite. No peaks owing to
crystalline MFI product with 3.1 nm mesopores was obtained after the extra-framework Al (octahedral coordination, 0–10 p.p.m.)
reaction for 5 d at 130 ◦ C. The mesopore diameters and the pore were detected. It is also noteworthy that the present synthesis
volume were retained up to 12 d at 130 ◦ C (see Supplementary principle could be successfully extended to the synthesis of
Information, Fig. S2). mesoporous LTA zeolite (Fig. 5). The N2 adsorption isotherms of

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Table 1 Catalytic properties of mesoporous MFI zeolite and other aluminosilicate materials.
Reactions∗ Mesoporous MFI zeolite Bulk ZSM-5 Al-MCM-41 SAM
Methanol to olefin/gasoline 86 90 1 1
(68/26/6)† (67/28/5) — —

CHO
CHO CH C C5H11
CHO
CHO 98 3.9 25 64
+ + C6H13–CH=C–C5H11
CH2–C5H11 (98)‡ (69) (79) (75)
Jasminaldehyde

CHO
H3CO OCH3 H3CO OCH3
OCH3
+ 60 3.3 10 35
CH3

O OCH3 O
Vesidryl
∗
Catalytic activities were compared on the basis of the same weight of catalysts (see the Methods section for reaction conditions). All catalysts had the same Si/Al = 20. The Brunauer–Emmett–Teller (BET) surface area was 590 for
mesoporous MFI, 350 for ZSM-5, 948 for AlMCM-41, and 923 m2 g−1 for SAM (MCM-41-type).
† The numbers in parentheses represent % selectivity (olefin/gasoline/others).

‡ Jasminaldehyde selectivity. All other numbers indicate the reactant conversion (%).

the LTA zeolite exhibited two steep increases at relative pressures industries. The superior catalytic activity of the mesoporous
(P/P0 ) < 0.02 and 0.7 < P/P0 < 0.8. These adsorptions were zeolite compared with bulk zeolite is certainly due to the highly
interpreted as micropore filling and capillary condensation in mesoporous structure. More notably, despite the significantly
mesopores, respectively, similar to the case of mesoporous lower specific BET area, the mesoporous zeolite exhibited much
MFI zeolite. higher catalytic activity than Al-MCM-41 and SAM materials. The
The temperature-programmed desorption of ammonia was crystalline zeolite with tunable mesoporosity may have important
measured to characterize the acidity of the mesoporous MFI technological implications for many other catalytic reactions
zeolite (H+ form, Si/Al = 20). For comparison, bulk ZSM-5 involving large molecules, whereas mesoporous materials with
zeolite, aluminosilicate MCM-41 (Al-MCM-41)31 , and ZSM-5 amorphous frameworks lack hydrothermal stability and acidity.
seed-assembled mesoporous (SAM) materials16,18 were also In conclusion, the mesoporous zeolite of the present study
synthesized and studied. The temperature-programmed desorption has several attractive features such as large surface area,
profiles (see Supplementary Information, Fig. S5) indicated that interconnected mesopores with zeolitic pore walls, pore size
the mesoporous MFI zeolite possessed strong acid sites, similar to control, facile synthesis on a large scale and so on. The
ZSM-5. In contrast, the Al-MCM-41 with amorphous framework mesopore diameters can be finely tuned, typically in the
showed only weak acid sites. The seed-assembled MCM-41 material range of 2–20 nm, depending on the molecular structure of
showed a slightly enhanced acidity compared with Al-MCM-4116 , the mesopore-directing silanes and the hydrothermal synthesis
but was still much weaker than the mesoporous MFI zeolite conditions. The crystalline zeolites with tunable mesoporosity and
and ZSM-5. Table 1 shows that the mesoporous MFI zeolite strong acidity may bridge the gap between conventional bulk
and ZSM-5 were similarly active (86 versus 90% conversion) in zeolite and amorphous mesoporous aluminosilicates, particularly
the transformation of methanol to olefin/gasoline. In contrast, for catalytic applications involving large molecules. Furthermore,
the Al-MCM-41, seed-assembled MCM-41, and seed-assembled the synthesis principle developed in the present work may be
SBA-1518 exhibited no measurable catalytic conversion. From these applied to other hierarchically structured materials. These materials
results, it is clear that the seed-assembled mesoporous materials with mesoporous/microporous hierarchical structures may find
possessing only a short-range atomic order (‘pseudozeolitic’ or applications as advanced materials in various fields such as catalysis,
‘protozeolite’) cannot exhibit the true zeolite-like strong acidity. adsorption, separation and sensor technologies.
The results were also consistent with the nature of the reaction
requiring strong acidity. The activity difference between the
mesoporous MFI zeolite and ZSM-5 was not significant, owing METHODS
to the small molecular size of the reactant and products.
The mesoporous structure with strong acidity can be a SYNTHESIS OF MESOPOROUS ZEOLITE
remarkable benefit for catalytic reactions involving large organic For the synthesis of mesoporous MFI zeolite, TPHAC was added to a
molecules, in which diffusion constraints and/or adsorption of conventional alkaline mixture containing TPABr, NaOH,
reactant molecules onto the strong acid sites are the main tetraethylorthosilicate, sodium aluminate (53 wt% Al2 O3 , 43 wt% Na2 O,
Riedel–deHaën) and distilled water. The molar composition of the mixture was
concern. For example, the mesoporous MFI zeolite exhibited
1 Al2 O3 /10 TPABr/10 Na2 O/38 SiO2 /1.6 TPHAC/7,200 H2 O. In a typical
much higher catalytic activity and selectivity in the jasminaldehyde synthesis of MFI zeolite, 2.0 g sodium aluminate, 28.0 g TPABr and 8.0 g NaOH
(α-n-amylcinnamaldehyde) synthesis reaction than bulk zeolite, were first dissolved in 1,350 g H2 O. To the resultant solution, a mixture of
Al-MCM-41 and MCM-41-type SAM (Table 1). The zeolite 85.7 g tetraethylorthosilicate and 11.9 g TPHAC (66% methanol solution) was
also exhibited an outstanding catalytic activity in the synthesis added under vigorous stirring. The final mixture was further stirred for 2 h at
of vesidryl (2 ,4,4 -trimethoxychalcone). These products are room temperature to obtain a homogeneous mixture. This mixture was heated
important for the pharmaceutical, fragrance, and agrochemical with stirring at a desired temperature, in a Teflon-coated stainless-steel

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Received 3 February 2006; accepted 6 June 2006; published 6 August 2006.

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