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Microporous and Mesoporous Materials 112 (2008) 138146

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Crystallization and morphology of zeolite MCM-22 inuenced

by various conditions in the static hydrothermal synthesis
Yajing Wu, Xiaoqian Ren, Youdong Lu, Jun Wang *

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering,
Nanjing University of Technology, No.5 Xin Mofan Road, Nanjing 210009, China

Received 24 October 2006; received in revised form 16 July 2007; accepted 19 September 2007
Available online 26 September 2007

Abstract

MCM-22 zeolite was synthesized in various static hydrothermal systems with hexamethyleneimine (HMI) as the structure-directing
agent. Synthesis parameters, such as silica source, alkaline source (Na+, K+ or NH 4 ), alkalinity of the reaction mixture, HMI/SiO2 ratio
and seeding, were changed to investigate their eects on the crystallization and morphology of zeolite MCM-22. The produced samples
were characterized by XRD, IR, SEM, N2 physisorption and ICP. Reaction conditions were revealed to inuence the induction period
and crystallization rate remarkably, and the sodium metasilicate as the silica source, the medium OH/SiO2 molar ratio (0.15), the high
HMI/SiO2 molar ratio and the addition of seeding could accelerate the crystallization. Moreover, by altering the reaction parameters,
various morphologies of MCM-22 product with dierent particle sizes were achieved, such as spherical, rose-like, doughnut-like and
platelet-like structures. The noteworthy observation was that with K+ as the alkaline source instead of Na+, a much shorter induction
period and faster crystallization rate were obtained, resulting in a higher crystallinity and a smaller crystal size. K+ is more favorable to
the formation of MCM-22 crystal than Na+ even at very low HMI/SiO2 ratios.
 2007 Elsevier Inc. All rights reserved.

Keywords: MCM-22; Morphology; Crystallization; Hydrothermal synthesis; Seeding

1. Introduction Zeolite MCM-22 was rst synthesized in 1990 by Mobil

Zeolites are ordered, porous crystalline aluminosilicates
with a broad variety of practical applications. Because the
size of zeolite crystals signicantly aects its performance
in catalysis, diusion, adsorption, ion exchange, etc., the
control of crystal size and morphology is crucial [13].
Zeolites are usually synthesized under hydrothermal condi-
tions, where the reaction variables include time, tempera-
ture, gel composition, reactant source, and so on. Many
studies showed that the variation of the gel composition
for synthesis exerted a signicant impact on the crystal size
and morphology [48].
*
Corresponding author. Tel.: +86 025 83587207; fax: +86 025
83365813.
E-mail address: junwang@njut.edu.cn (J. Wang).
in a hydrothermal crystallization system containing the
alumina source, silica source and structure-directing agent
[9]. Its framework structure consists of two nonintersecting
pore systems, which are both accessed through 10-mem-
bered rings [10,11]. One of them is composed of two-
dimensional 10-membered ring sinusoidal channels and
the other consists of large supercages of 0.71 0.71
1.82 nm. The major properties of MCM-22 zeolite are the
high thermal stability, high acid-catalyzed activity and
molecular shape selectivity [1219]. Typically, MCM-22
crystals are in the form of sheet-like discs or aggregates
of cross-linked discs of 25 lm in diameter and 1040 nm
in thickness [20,21]. However, only a few reports have
attempted to control crystal morphology and size of
MCM-22. Aiello et al. [22] reported that spherical crystals
of MCM-22 can be prepared by adding uoride anions into
the starting hydrogel. More recently, Hu et al. [23] used

1387-1811/$ - see front matter  2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.09.022
 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146
nonionic surfactant as additives in the crystallization pro-
cess to aect the morphology of MCM-22 crystals.
Although a number of studies on the synthesis parameters
inuencing the formation of zeolite MCM-22 appeared, the
eect of these parameters on the morphology and crystalli-
zation is still not detailed and systematically explored. In
addition, sodium is the cation most widely used in the syn-
thesis of MCM-22 [9,11,20,21], and the eect of other cat-
ions is still open to study.
In this work, without any other additives, we have
successfully synthesized highly pure MCM-22 zeolite with
various morphologies such as spherical, rose-like, dough-
nut-like and platelet-like structure, and the inuence of
synthesis parameters were studied in detail. The substitu-
tion of sodium hydroxide by potassium hydroxide in the
synthesis is revealed to facilitate the crystallization of
MCM-22 zeolite.
2. Experimental
2.1. Synthesis
Hexamethyleneimine (HMI) (98%, Jiangsu Fengyuan
Biochemical Co., LR), sodium metasilicate (19.322.8%
SiO2, Na2O/SiO2 = 1.03 0.03, Shanghai Chem. Reagent
Co., AR), water glass (25.5% SiO2, 10% Na2O, Nanjing
Tengda Chem. Co., LR), colloidal silica (40% SiO2, Zhe-
jiang Yuda Chem. Co., LR), sodium aluminate (41%
Al2O3, Shanghai Chem. Reagent Co., AR), sodium
hydroxide (96%, Shanghai Chem. Reagent Co., AR),
potassium hydroxide (82%, Shanghai Chem. Reagent
Co., AR), and ammonia aqueous (2528% NH3, Shanghai
Chem. Reagent Co., AR).
The synthesis of MCM-22 was carried out according to
the procedure described in previous reports [9,11] with
some modications. The detailed procedure using colloidal
silica as silica source is described as the following: 1.66 g of
sodium aluminate and 0.41 g of sodium hydroxide were
dissolved in 110 mL deionized water. Then, 13.78 mL
HMI was added dropwise to the stirred mixture. To the
well dispersed mixture, 30 g of colloidal silica was slowly
added with vigorous stirring. The synthesis gel was aged
at room temperature for 24 h. The composition of the
above mixture in terms of oxide molar ratio was
0.075Na2O:SiO2:0.033Al2O3:0.6HMI:35H2O. Syntheses
were carried out in a Teon-lined autoclave under static
condition at 431 K for a preset crystallization period. The
products are recovered, ltered, washed with deionized
water and nally dried at 373 K overnight to obtain the
as-synthesized products. The as-calcined products were
obtained by calcining the as-synthesized materials for
20 h in air at 823 K. For samples of MCM-22 using sodium
metasilicate or water glass as silica source, the detailed syn-
thesis procedure is as the following: 40 g of sodium metasi-
licate (or 33.7 g of water glass) was mixed with 50 mL
deionized water in a beaker; 9.87 mL HMI was added
dropwise to the above solution under vigorous stirring to
139
get the solution named A. Meanwhile, 3.21 g of aluminium
sulfate and 6.14 mL concentrated sulfuric acid (1.44 mL
concentrated sulfuric acid for water glass) was dissolved
in 16.5 mL deionized water (17.5 mL deionized water for
water glass), forming the solution named B. Then solution
B was added drop by drop to solution A. The synthesis gel
was aged at room temperature for 24 h. The composition
of the above mixture in terms of oxide molar ratio was
0.2Na2O:SiO2:0.033Al2O3:0.6HMI:35H2O. Further treat-
ments were the same as those using colloidal silica as silica
source.
2.2. Characterization
X-ray diraction (XRD) patterns were collected on the
Bruker D8 ADVANCE powder diractometer using Ni-l-
tered Cu Ka radiation source at 40 kV and 20 mA, from 5
to 50 with a scan rate of 2/min. Crystallinities were calcu-
lated by comparing the sums of intensities of the peaks
appearing at 710 and 2426 2h in the calcined samples
to those found in the fully crystalline reference material.
The reference material used in this study was prepared
from a gel with molar composition 0.075Na2O:SiO2:
0.033Al2O3:0.6HMI:35H2O using colloidal silica as silica
source, with 1% seed in synthesis gel. Scanning electron
microscope (SEM) images were recorded on a QUANTA
200 (FEI). The BrunauerEmmettTeller (BET) surface
areas were measured at the temperature of liquid nitrogen
using a Micromeritics ASAP2010 analyzer. The samples
were degassed at 573 K to a vacuum of 103 Torr before
analysis. Chemical compositions of samples were obtained
using a JarrellAsh 1100 inductively coupling plasma (ICP)
spectrometer. The FT-IR spectra were obtained on a
Nexus 870FTIR spectrometer. Samples were mixed and
ground with KBr for IR measurement in the range of
1400400 cm1.
3. Results and discussion
3.1. Inuence of the silica source
Fig. 1 shows the XRD patterns of as-calcined samples
synthesized by using colloidal silica, sodium metasilicate
and water glass as silica sources, respectively. It can be seen
that the peak positions and relative intensities are consis-
tent with the XRD results for MCM-22 observed by Rubin
and Chu [9], and except MCM-22, no other crystalline
phases were detected. Fig. 2 displays IR spectra of the as-
calcined samples obtained by using the three silica sources.
The bands near 450, 505, 555, 600, 666, 790, 810, 1090 and
1240 cm1 appeared for all samples due to the formation of
only MCM-22 phase, which is in agreement with the previ-
ous report [24].
Crystallization curves for the synthesis of MCM-22
using the three dierent silica sources are compared in
Fig. 3. It can be seen that the induction period using
sodium metasilicate as the silica source was signicantly
140 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146
Fig. 1. XRD patterns of as-calcined MCM-22 zeolite samples synthesized
from dierent silica sources: (a) colloidal silica; (b) sodium metasilicate; (c)
water glass.
Fig. 2. IR spectra of as-calcined MCM-22 zeolite samples synthesized
from dierent silica sources: (a) colloidal silica; (b) sodium metasilicate; (c)
water glass.
Fig. 3. Crystallization curves for zeolite MCM-22 synthesized from
dierent silica sources: (a) sodium metasilicate; (b) colloidal silica; (c)
water glass.
shorter in comparison with those using colloidal silica and
water glass. For sodium metasilicate, the induction period
was less than 12 h and the product was almost completely
crystallized after 6 days. Whereas for colloidal silica and
water glass, the induction periods were 2 and 2.5 days,
respectively. From this observation, the best silica source
is sodium metasilicate, which produced a high crystallinity
of MCM-22 within a much shorter crystallization time.
These dierent crystallizations may be caused by dierent
solubility of silica sources in alkaline medium. It is known
that the dissolution of silica is the rate-limiting step for zeo-
lite synthesis [21]. The rates of hydrolysis of the dierent
silica sources depend on the Na2O/SiO2 ratios [25]. When
the Na2O/SiO2 ratio was relatively rich in NaOH, the
hydrolysis was great; and when the ratio rich in silica, the
hydrolysis was practically negligible. In this study, the
Na2O/SiO2 ratio of sodium metasilicate is high compared
to those of colloidal silica and water glass. Therefore,
shorter induction period observed under sodium metasili-
cate conditions is suggested to be the result of the highest
rate of dissolution, which results in a faster formation of
silicate/aluminosilicate species in solution, and thus leads
to the much shorter nucleation period and thus shorter
overall crystallization time.
Fig. 4 shows the inuence of silica source on the mor-
phology and crystal size of the MCM-22 products.
Fig. 4a demonstrates that the morphology of the sample
prepared with colloidal silica as silica source was spherical
particles with a small hole at the center, which was formed
by the tight assemble of MCM-22 zeolite crystal discs [23].
By contrast, using sodium metasilicate and water glass as
silica sources, the MCM-22 discs were only loosely aggre-
gated to form a rose-like structure without a penetrating
hole, as illustrated in Figs. 4b and 4c. The sizes of the
assembled particles are ca. 16, 10 and 7 lm for colloidal
silica, sodium metasilicate and water glass as silica sources,
respectively. Therefore, the employed three silica sources
evidently aect the morphology and size of MCM-22
crystals. Indeed, the same phenomenon that silica source
inuences the morphology and particle size for other
zeolites like silicalite-1 has been revealed by previous
reports [2629].
Table 1 presents the eect of the silica source on SiO2/
Al2O3 ratio, crystallinity and surface area of as-calcined
MCM-22. From a gel with a SiO2/Al2O3 molar ratio of
30, MCM-22 gained a SiO2/Al2O3 ratio of 37 in product
using colloidal silica as silica source. On the other hand,
the products with SiO2/Al2O3 ratio of 32 and 30 were
obtained using sodium metasilicate and water glass as silica
sources, respectively. This indicates that in the water glass
system aluminum is easier to be incorporated into the
MCM-22 framework, but the resulted MCM-22 showed
a lower crystallinity of 92.8%. The BET surface areas of
the calcined MCM-22 obtained from colloidal silica,
sodium metasilicate and water glass were 515, 550 and
556 m2/g, respectively.
3.2. Inuence of OH/SiO2 ratio
To study the eect of alkalinity of the reaction mixture
on the crystallization kinetics and morphology of MCM-
22, the OH/SiO2 ratio was varied from 0.10 to 0.25 while
 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146 141

Table 1
Properties of as-calcined MCM-22 obtained by using dierent silica
sources
Silica source SiO2/Al2O3 Crystallinity Surface Phase
(%) area
Gel Product
(m2/g)
Colloidal silica 30 37 94.8 515 MCM-22
Sodium 30 32 100 550 MCM-22
metasilicate
Water glass 30 30 92.8 556 MCM-22

Fig. 5. XRD patterns of as-synthesized MCM-22 zeolite samples obtained

at various OH/SiO2 ratios: (a) 0.25; (b) 0.20; (c) 0.18; (d) 0.15; (e) 0.12; (f)
0.10.

without the detection of any impurities when the OH/

SiO2 ratio was 0.120.20. However, when the OH/SiO2
ratio was more than 0.20, MCM-49 was formed. When
the OH/SiO2 ratio was less than 0.12, only amorphous
gel was observed. Fig. 6 shows the crystallization curves
with four dierent OH/SiO2 ratios. It can be seen that
when the OH/SiO2 ratio was 0.12, the induction period
was 3 days and after 7 days the product was 80% of
crystallinity. Increasing the alkalinity, the induction

Fig. 4. SEM images of samples synthesized from dierent silica sources:

(a) colloidal silica; (b) sodium metasilicate; (c) water glass.

keeping the formulation at SiO2:0.033Al2O3:0.6H-

MI:35H2O and using colloidal silica as the silica source.
Fig. 5 shows XRD patterns of as-synthesized samples
obtained at various OH/SiO2 ratios. It can be seen that Fig. 6. Crystallization curves for zeolite MCM-22 obtained using colloidal
the highly crystalline MCM-22 crystals could be obtained silica as silica source with dierent NaOH/SiO2 ratios.
142 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146
period decreased substantially. When the OH/SiO2 ratio
increased from 0.12 to 0.2, the induction period was less
than 1 day, and the rate of crystallization was enhanced.
These results are consistent with the observations for other
zeolites such as Y, X and MFI zeolite [3032]. It is sug-
gested that the increase of hydroxide concentration can
accelerate the solubility of silicate species and facilitate
the generation of crystal nuclei, leading to the rapid growth
of MCM-22 crystals.
The hydroxide concentration not only aects the crys-
tallization rate, but also strongly aects the size of
obtained particle. Fig. 7 shows the SEM photographs of
as-calcined samples with various OH/SiO2 ratios without
changing other synthesis parameters. As can be seen from
Fig. 7, the average sizes of crystal particles were 18, 16, 13
and 11 lm when the OH/SiO2 ratios were 0.12, 0.15,
0.18 and 0.2, respectively. A small crystallite size was
obtained from a high OH/SiO2 ratio while a low
OH/SiO2 ratio gave large one. It is well known that
the higher alkalinity accelerates the dissolution of reac-
tant, resulting in the quickly forming of more nuclei. A
large number of nuclei consume the nutrients in the mix-
ture very fast, so a large number of smaller crystals are
Fig. 7. SEM images of samples formed from SiO2:xNaOH:0.033Al2O3:35H2O. NaOH/SiO2 ratios x are: (a) 0.2; (b) 0.18; (c) 0.15; (d) 0.12.
formed, preventing from the growth of a less number of
larger crystals [30,33].
3.3. Inuence of seeding
It is known that adding seed crystals to starting synthe-
sis gels can increase the rate of crystallization and shorten
the induction time [3439]. The eect of seed content was
studied after xing the loading ratios of the other compo-
nents at: 0.075Na2O:SiO2:0.033Al2O3:0.6HMI:35H2O with
using colloidal silica as silica source. The crystallization
curves with weight percentage of the MCM-22 crystal seed
based on the total weight of the synthesis mixture being 0,
0.1% and 1%, respectively, are plotted in Fig. 8. It can be
seen that the addition of seeds to the synthesis batch
reduced the crystallization time compared to the unseeded
system, and the crystallinity obviously increased with the
increase of the seed amount. Fig. 9 shows SEM images
for the three samples prepared by using dierent amount
of seeds. It can be seen that the morphology and size of
the three products changed remarkably with the change
of seeding amount. Larger spheres of about 16 lm were
obtained in case of unseeded system. With increasing the
 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146 143

Fig. 8. Crystallization kinetics curves of MCM-22 materials with dierent

amount of seed: (a) 1% seed; (b) 0.1% seed; (c) without seed.

amount of seeds, the size of crystals decreased obviously

and mostly in the form of platelets with the size of less than
3 lm in diameter. The decreased crystal size is considered
to originate from the increased surface area available for
crystal growth due to the presence of the seed [3436].
On the other hand, in this work the MCM-22 product in
Fig. 9a was used as the reference sample with the assump-
tion of that its crystallinity was 100%, because except
MCM-22 crystals no other crystalline phases or amor-
phous materials were observed in its SEM image. Also,
the intensities of the XRD peaks of this reference material
were very comparable to those of a commercially supplied
MCM-22 from Jinling Petrochemical Limited Corporation
(XRD not shown). In order to further verify that the refer-
ence material is fully crystallized, its adsorption capability
was measured. Its water, n-hexane and cyclohexane
adsorption values were 20.9, 19.4 and 10.8 wt%, respec-
tively, which matches the high adsorption capability of a
pure MCM-22 [9].

3.4. Inuence of alkaline source

In order to understand better formation of MCM-22,

the inuence of the inorganic cation has been systemati-
cally explored in a colloidal silica system without seed.
The reaction parameters were xed at 0.075M2O:
SiO2:0.033Al2O3:0.6HMI:35H2O (M= Na+, K+ or NH 4 ).
Fig. 10 compares the crystallization curves for Na+, K+
and NH 4 systems. Zeolite MCM-22 was the only crystal-
line phase observed in XRD patterns for these experiments.
For the K+ system, both the nucleation and crystallization
rates were much higher than those for the Na+ and NH 4
Fig. 9. SEM images of obtained in the presence of dierent amount of
systems, as indicated by its much shorter induction period
seed: (a) 1% seed; (b) 0.1% seed; (c) without seed.
and higher slope in the crystallization curve. This suggests
that K+ can implicitly facilitate both nucleation and crys-
tallization. It is also obvious from Fig. 10 that the NH 4
product even after 8 days was X-ray amorphous, and under
system gave the longest induction period and a very low the optical microscope only shapeless gel was observed.
growth rate. By using the same amount (mole) of NH4OH When the amount of ammonium hydroxide in mixture
instead of NaOH, alkalinity of the reaction mixture was increased, such that the pH of reaction mixture was 12
reduced. As expected, due to the lowered alkalinity, the 12.5, the amorphous gel was transformed to crystalline alu-
144 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146

Fig. 10. Crystallizaiton curves in the K+, Na+ and NH

4 systems.

minosilicate after 4 days, and after 9 days the MCM-22

product was only 50% crystallinity, as illustrated in
Fig. 10. The further increment of crystallization time
resulted in the impure phase.
It is known that inorganic cations play an important
role in the hydrothermal synthesis of high silica zeolites.
Warzywoda and Thompson [40] reported that in the syn-
thesis of ZSM-5 zeolite the presence of a mixted Na+ and
K+ ions enhanced the crystallization rate compared to
the pure Na+ system. Camblor and Perez-Pariente [41]
revealed that the addition of K+ to the synthesis gel of zeo-
lite beta accelerated its crystallization. Usually sodium is
the cation most widely used in zeolite MCM-22 synthesis,
and only very few studies have attempted to substitute
Na+ by K+. However, the previous investigations did not
nd a positive eect of K+ in the synthesis of zeolite
MCM-22. For instance, Vuono et al. [42] showed that
the induction time is much longer in presence of K+ than
that in presence of Na+. However, the result in Fig. 10 well
demonstrates that K+ is an excellent inorganic cation to
shorten the induction period and accelerate the crystalliza-
tion in the synthesis of MCM-22, which is more ecient
than Na+. By contrast, NH 4 is not a suitable one.
Fig. 11 shows the morphology of MCM-22 samples syn-
thesized in Na+, K+ and NH 4 systems. It can be seen that
the crystals of Na-MCM-22 resembled to form spheres
with a large size of 1516 lm and with a hole at the center
(also see Fig. 4a), whereas K-MCM-22 and NH4-MCM-22
turned out to be a doughnut-like morphology with a much
smaller particle size of 79 lm and also with a penetrating
hole at the center.

Fig. 11. SEM images of the product obtained by the Na+, K+ and NH
4
3.5. Inuence of HMI/SiO2 ratio systems: (a) Na+; (b) K+; (c) NH
4.

The eect of the HMI/SiO2 ratio in the Na+ or K+ sys-

tem on the synthesis of MCM-22 was investigated with var-
ious synthesis compositions of 0.075M2O:SiO2:0.033Al2O3:
xHMI:35H2O, in which M was K or Na, and x was varied
from 1.2 to 0.2. The crystallization conditions were xed at
the 431 K reaction temperature, using colloidal silica as
silica source and without seed. The results are listed in
Table 2. When the HMI/SiO2 ratio was 1.2, for both K+
and Na+ system, the pure MCM-22 products were
achieved with high crystallinities. After 5 days, the K+ sys-
tem resulted in the 97% crystallinity; whereas it was slightly
 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146 145

Table 2 40% crystallization of MCM-22 was obtained after 7 days,

Inuence of the HMI/SiO2 ratio in the K+ and Na+ systems on the and after 10 days the crystallinity of MCM-22 was
crystallization of zeolite MCM-22
enhanced up to 72%. By comparison, in Na+ system no
Alkaline HMI/ Time Crystallization of Other crystalline phase was detected after 7 days, and only 53%
source SiO2 (days) MCM-22 (%) phases
of crystallinity was observed after 10 days. At a very low
NaOH 1.2 5 95 HMI/SiO2 ratio of 0.2, the K+ system still produced the
NaOH 0.6 8 95
NaOH 0.3 7 0
MCM-22 crystal with a crystallinity of 56% after a 11-
NaOH 0.3 10 53 day crystallization, however, the Na+ system only resulted
NaOH 0.2 10 0 in amorphous products after 10 days, and a longer synthe-
NaOH 0.2 14 0 MCM-49 sis time (14 days) resulted in the impurity phase of MCM-
KOH 1.2 5 97 49. The further decrease of the HMI/SiO2 ratio to 0.1 only
KOH 0.6 7 100
KOH 0.3 7 40
gave MCM-49 zeolite in both K+ and Na+ system. From
KOH 0.3 10 72 these results, one can draw that in both K+ and Na+ sys-
KOH 1.2 11 56 tems, the lower HMI/SiO2 ratio would cause a longer
induction period and lower crystallization rate for MCM-
22. One possible interpretation might be that the decrease
lower (95%) from the Na+ system. When HMI/SiO2 ratio of HMI/SiO2 ratio reduces the alkalinity of the synthesis
decreased from 1.2 to 0.6, the K+ system gave 100% crys- mixture and thus leads to a decrease of the crystallization
tallinity after 7 days; whereas the Na+ system led to the rate. Another noteworthy observation is that K+ is more
95% crystallinity after 8 days. These results indicate that favorable to the formation of MCM-22 crystal than Na+
the decrease of HMI/SiO2 ratio from 1.2 to 0.6 only caused even at very low HMI/SiO2 ratios.
an insignicant reduce of crystallization. Again, when the Fig. 12 shows SEM images of the as-calcined samples
HMI/SiO2 ratio dropped from 0.6 to 0.3, in K+ system obtained by using dierent HMI/SiO2 ratios in K+ system.

Fig. 12. SEM images of the products obtained at dierent HMI/SiO2: (a) 0.2; (b) 0.3; (c) 0.6; (d) 1.2.
146 Y. Wu et al. / Microporous and Mesoporous Materials 112 (2008) 138146
It is illustrated that the MCM-22 particles obtained at
HMI/SiO2 ratios of 0.2 and 0.3 gave morphology of
sphere-like structure with a small hole at the center;
whereas the samples obtained at HMI/SiO2 ratios of 0.6
and 1.2 turned out to be a doughnut-like morphology.
With the increase of HMI/SiO2 ratio, the size of MCM-
22 particle decreased notably, with the samples at HMI/
SiO2 ratios of 1.2, 0.6, 0.3, 0.2 showing the average crystal
sizes of 16.6, 11.5, 9 and 8 lm, respectively.
4. Conclusions
It is found in this work that the reaction conditions in
the static hydrothermal synthesis of zeolite MCM-22
aects largely the kinetics of the gel chemistry, and by con-
trolling the reaction parameters the predictable crystal size
with dierent morphologies can be achieved.
Sodium metasilicate as a silica source caused a small
MCM-22 crystal size (10 lm) with a rose-like morphology,
and colloidal silica produced a large spherical particles
(16 lm). The increase of OH/SiO2 ratio resulted in the
decrease of induction period and increase of product crys-
tallintiy, and also the decrease of crystal size without
changing the morphology. Increasing the HMI/SiO2 ratio
and adding the seed in the synthesis compositions acceler-
ated the crystallization and thus produced the smaller crys-
tals of MCM-22. Further, zeolite MCM-22 could be
achieved in the presence of inorganic cations such as K+
and NH + +
4 , other than Na , and we nd that the K synthe-
sis system enhanced the crystallization rate remarkably,
leading to a doughnut-like morphology with smaller parti-
cle size. Also, MCM-22 could be obtained by using K+ ions
as the alkaline source in a relatively broader range of HMI/
SiO2 ratios than that by Na+ ions.
Acknowledgments
The authors thank the Key Natural Science Foundation
for Universities of Jiangsu Province (No. 06KJA53012),
National Natural Science Foundation of China (Nos.
20306011 and 20476046) and Ph.D. Program Foundation
of Chinese University (No. 20040291002).
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