Microporous and Mesoporous Materials 201 (2015) 2434

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Effects of adding alcohols on ZSM-12 synthesis

Sinthuran Jegatheeswaran a, Chin-Min Cheng b, Chil-Hung Cheng a,
a
Laboratory of Porous Materials and Catalysts, Department of Chemical Engineering, Ryerson University, Toronto, Ontario M5B 2K3, Canada
b
Department of Civil, Environmental and Geodetic Engineering, The Ohio State University, Columbus, OH 43210, USA

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

Article history: This work systematically studies on adding alcohols to alter the crystal growth behavior of ZSM-12, using
Received 31 January 2014 1-propanol (1P), 2-propanol (2P), ethylene glycol (EG), 1,3-propanediol (PD), 1,6-hexanediol (HD), dieth-
Received in revised form 29 August 2014 ylene glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol (TTEG) as co-solvents. The effects of
Accepted 2 September 2014
co-solvent content, temperature, and excess mineralizer content were studied as well. Except 2P, all other
Available online 16 September 2014
co-solvents are observed to tune the crystal morphology into a discrete round-shape. Except DEG and
TTEG, all other co-solvents promote the crystallization rate of MTW phase, veried by larger zeolite crys-
Keywords:
tal size in SEM images. The observation is corroborated with the formation of cristobalite, possibly via
MTW
Triethylene glycol
Ostwald ripening mechanism. The nding enlightens us using a lower synthesis temperature to attain
Hexanediol high purity MTW phase, with an adequate amount of co-solvents. It is noteworthy that using HD as
Anisotropic growth co-solvent facilitate the anisotropic growth of MTW crystals along the b-axis (2h of 8.5), possibly due
Crystallization to the effect of co-solvents hydrophobicity as well as the backbone length. The blue shift of symmetric
and asymmetric Si-O vibration modes in FTIR spectra implies that TEG and HD are incorporated within
the ZSM-12 pore structure. This work provides potential synthetic route to form anisotropic ZSM-12
membranes with preferred orientation.
2014 Elsevier Inc. All rights reserved.

1. Introduction cheapest process to produce 2,6-DMN, in which ZSM-12 is effec-

ZSM-12(MTW) is a high-silica zeolite which was rst invented
by Rosinski and Rubin in 1974 [1]. Its framework shows
one-dimensional non-interpenetrated pore structure with 12-
membered ring channels (5.7  6.1 ). The monoclinic unit cell
parameters of MTW are a = 24.88 , b = 5.02 , c = 12.15 and
b = 107.7 [2]. Hydrothermal syntheses of MTW are mostly
facilitated in the presence of structure-directing agents (SDA) and
are highly selective to the type of SDAs. The most common applied
SDAs are hydroxides and halides of quaternary ammonium cations,
and piperazinium cations, i.e., tetraethylammonium (TEA+), meth-
yltriethylammonium (MTEA+), 1,4-Diazabicyclo[2.2.2]octane
(DABCO)-diquat, and benzyl-trimethylammonium (BTMA+) among
others [313].
The excellent thermal, mechanical and gas barrier properties of
polyethylene naphthalate (PEN) have found its extensive and
growing applications in electrical insulation, bottling, and tire rein-
forcement materials [1416]. However, the scarcity of 2,6-dimeth-
ylnaphthalene (2,6-DMN) restricts the production of PEN. The
alkylation of naphthalene with methanol is considered as the
Corresponding author. Tel.: +1 416 979 5000x2131.
E-mail address: chilhung.cheng@ryerson.ca (C.-H. Cheng).
tively employed to enhance its 2,6-DMN selectivity. This is due
to the moderate acidity, zeolite crystals with small dimensions,
and shape selective properties of ZSM-12, as well as the presence
of mesoporosity of MTW framework. Compared with ZSM-22,
Songs group discovered that ZSM-12 performs a greater catalytic
activity in the Methanol-To-Olens (MTO) process, due to its larger
micropore diameter that can accommodate bulky intermediate
species [17]. The lifetime and the selectivity to light olens were
further enhanced using smaller crystals of SAPO-34; however,
the crystal size was modulated using different structure-directing
agents, synthesis temperature, the synthesis time [18]. Smirniotis
group studied the hydroisomerization and hydrocracking reaction
paths for several n-octane isomers using ZSM-12, USY, BEA, MOR,
and LTL. They observed that ZSM-12 exhibited less coke formation
and superior catalytic stability in accelerated coking experiments
among other four zeolite catalysts. Furthermore, the distributions
of bulkier isomers were hindered and the backward debranching
reaction of mono- and di-branched isomers was prevail, due to
the shape selective character of ZSM-12 [19,20]. The shape selec-
tivity effect of ZSM-12 exerts on the alkylation of isobutane with
2-butene, producing high-octane compounds that can serve as gas-
oline additives in compliance with 1990 Clean Air Act Amend-
ments [21]. Grigoreva et al. studied the structural effect on

http://dx.doi.org/10.1016/j.micromeso.2014.09.008
1387-1811/ 2014 Elsevier Inc. All rights reserved.
 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434
styrene oligomerization using various types of zeolites, among
which ZSM-12 showed the highest activity and selectivity towards
linear dimer products [22].
Albeit the striking catalytic activity of ZSM-12, scarce publica-
tions can be found at alternating the morphology and size of
ZSM-12 crystals towards better catalytic performances. Recently,
Newalkars group investigated the morphological effect of ZSM-
12 crystals on hydroisomerization of n-hexadecane using various
types of ammonium cations as SDAs [23]. The study showed that
the ZSM-12 crystals with small dimensions exhibited higher iso-
mer yield and selectivity towards mono-branched products. Wus
group studied the catalytic conversion of methanol to propylene
(MTP) on different crystal sizes of HZSM-5 zeolites. They reported
that smaller crystal size had a higher resistance to coke and longer
catalytic lifetime due to its large surface area and pore volume [24],
attributing to the faster mass transfer of reactants within small
zeolite crystals. The success of wide industrial applications of zeo-
lites as catalysts is highly dependent on the crystal size which is
proportional to the average diffusion length [25]. Reddy et al.
investigated that catalytic performances for ethylene conversion
and n-heptane cracking were dependent on both morphology
and crystal size of ZSM-5 [26]. Bans group attempted to control
the morphology of zeolite L with an intention to enhance the num-
ber of channel entrances per unit volume. Accordingly, the reactant
molecules are more accessible within zeolites channels for chem-
ical reactions [27]. These imply that the strategies to manipulate
the morphology and size of zeolite crystals are pivotal in their
applications and performances.
Recently, researchers have focused on manipulating the size
and morphology of zeolite crystals using solvothermal synthesis
routes. Feng et al. incorporated water, ethylene glycol, and ethanol
amine as co-solvents into Na2OSiO2Al2O3-ethylenediamine pre-
cursor solutions for syntheses of ZSM-35, ZSM-5 and sodalite,
respectively [28]. The authors noted that the applied co-solvents
affected the morphology of corresponding zeolite crystals. Wangs
group added glycerol as a co-solvent into zeolite A and discovered
that the particle size was tuned [29]. Sanos group studied the crys-
tallization mechanisms and adsorption properties of mordenite by
incorporating the aliphatic alcohol in the synthesis gel [30]. Other
researchers are currently implementing micro-emulsion tech-
niques to control zeolite morphology and crystal size [3133].
Our research group, in parallel with others, developed alterna-
tive approaches to tune the morphology of Zeolite L (LTL) crystals
into shapes of disk or cylindrical stub using several co-solvents,
such as ethanol, triethylene glycol, and crown ethers among others
[3437]. We observed that the crystallization rate was greatly
enhanced while suppressing the other impurity phases. This work
investigates thoroughly a co-solvent synthesis route to manipulate
the crystal growth habits of ZSM-12, in the presence of tetraethy-
lammonium cations as the SDA. In total, 8 co-solvents were
adopted systematically based on co-solvents hydrophobicity, car-
bon backbone length, and hydroxyl and ether groups. The results
illustrate an alternative route to prepare oriented ZSM-12 thin
lms for a wide range of industrial applications [38,39].
2. Experimental
LUDOX HS-40 colloidal silica (40 wt.% in water), sodium
aluminate anhydrous (Technical grade), 1,6-hexandiol (HD) and
1,3-propanediol (PD) were purchased from SigmaAldrich. TEAOH
(35 wt.% in water), ethylene glycol (EG), diethylene glycol (DEG),
triethylene glycol (TEG) and tetraethylene glycol (TTEG) were
purchased from Alfa Aesar. 1-Propanol (1P) and 2-propanol (2P)
were purchased J.T. Baker and V.W.R. respectively. All chemicals
were used as received without further dilution or purication.
25
The selection of these co-solvents is based on their C/O ratio, car-
bon backbone length, the number of hydroxyl groups and ether
groups, shown in Scheme 1.
2.1. Synthesis
A few minor modications were made to the published proce-
dure of Gopal et al. to synthesize ZSM-12 in the presence of co-sol-
vent [6]. The resulting gel composition was Al2O3: 1.35Na2O:
80SiO2: 12.7TEAOH: xH2O: y(EG, DEG, TEG, TTEG, HD, PD, 1P or
2P), where x + y = 1040 and x = 1013.34, 986.67, 960, and 880.
The products were labeled as MTWSCTD whereas S = EG,
DEG, TEG, TTEG, HD, PD, 1P or 2P; C = 26.67, 53.34, 80 or
160 mol; T = 140 or 160 C; D = 3, 6 or 14 days. For example, the
synthesis of ZSM-12 with a gel composition of 1Al2O3: 1.35Na2O:
80SiO2: 12.7TEAOH: 960H2O: 80EG at 160 C for 6 days was
labeled as MTW-EG-80-160-6. Its synthesis is described as follows.
The alumina solution was prepared by adding 3.26 g of TEAOH and
0.1 g of sodium aluminate to 2.30 g deionised water. The silica
solution was prepared by mixing 7.33 g LUDOX HS-40 with
1.73 g of deionised water and 3.03 g of EG. When HD, 1P, and 2P
were used as co-solvents, the alumina solution was added to silica
solution. For all other co-solvents, the silica solution was charged
to the alumina solution. The following mixture was then stirred
for 1 h to attain gel homogeneity, followed by transferring into a
Teon-lined stainless steel autoclave which was already cleaned
with hydrouoric acid (HF) to eliminate any seeding effect. The
hydrothermal synthesis was then conducted at 160 C or 140 C
for 3 and 6 days statically. After the designated synthesis duration,
the solid sample was thoroughly rinsed with deionised water and
left to dry on a watch glass.
2.2. Characterizations
The powder X-ray diffraction (PXRD) patterns were acquired
using a Philip PW1830 instrument operated at 40 kV and 40 mA.
The PXRD patterns were recorded in the range of 2h between
4.5 and 45 with a step size of 0.02 and 2 s per step. The PXRD
patterns were analyzed and unit cell parameters were rened
using PowderX [40]. Scanning electron microscope (SEM, Model
JSM-6380 LV) was used to characterize the morphology and
dimensions of MTW crystals. Fourier transform infrared spectra
were recorded on Perkin Elmer Spectrum one spectrometer which
was equipped with Lithium tantalate detector for measurements in
the range from 450 to 4000 cm 1 wavenumber using the conven-
tional KBr pellet technique (0.1 mg zeolite sample per 0.1 g KBr).
Thermo gravimetric analyses on the samples were performed using
a TA SDT Q600 TGA-DSC instrument with software TA advantage
version 5.0.1. Around 1224 mg of sample was heated at a rate
of 10 C/min from 25 to 800 C. The combustion chamber was
purged with ultra-pure nitrogen gas at a rate of 100 mL/min during
the heating process. The mass of the sample as a function of tem-
perature was recorded. A reference alumina pan was also heated in
the same furnace at the same rate. TGA weight calibration was per-
formed before sample analysis.
3. Results and discussion
The synthesis of MTW crystals followed the published precursor
gel composition and synthesis conditions (160 C, and 6 days), and
was labeled as Benchmark [6]. The powder XRD (PXRD) patterns
and SEM images of Benchmark and calcined Benchmark are shown
in Figs. S1 and S2 in Supporting Information, respectively. The
PXRD patterns are identied as a pure MTW phase with unit cell
parameters of a = 25.8904, b = 5.0640, c = 24.5487 and
26 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434
Scheme 1. Selection of co-solvents based on the C/O ratio and the length of co-solvent molecule.
b = 108.26. The unit cell volume is 3056.52 3. The rened unit
cell dimensions of Benchmark are comparable with published
results [41]. Upon the removal of TEA cations using calcination,
the unit cell dimensions become a = 25.8119, b = 5.0598,
c = 24.5242 and b = 108.62. The unit cell volume drops to
3035.23 3. The larger unit cell dimensions, compared to those of
calcined Benchmark, indicates that TEA cations are occluded inside
MTW framework. The SEM images clearly display that discrete
cuboidal crystals with sharp edges are formed, in which an average
size of 0.64 0.04 lm is recorded.
3.1. Effect of co-solvent identity
Using the molar gel composition of 1Al2O3: 1.35Na2O: 80SiO2:
12.7TEAOH: 960H2O: 80(EG, DEG, TEG, TTEG, HD, PD, 1P or 2P), a
series of syntheses were conducted to study the effect of co-sol-
vents. The selection of co-solvents is based on the C/O ratio, as well
as the backbone length of co-solvent molecule, sketched in
Scheme 1. PXRD patterns of samples using EG, DEG, TEG, and TTEG
(-202)
(310)
(006)
(002)
(d)
(c)
(006)
(-202)
(002)
(b)
(a)
Fig. 1. Powder XRD patterns for MTW crystals attained at 160 C for 6 days using
1Al2O3: 1.35Na2O: 80SiO2: 12.7TEAOH: 960H2O: 80(EG or DEG or TEG or TTEG). (a)
MTW-EG-80-160-6; (b) MTW-DEG-80-160-6; (c) MTW-TEG-80-160-6; (d) MTW-
TTEG-80-160-6. The solid triangle indicates the presence of cristobalite phase.
as co-solvents are demonstrated in Fig. 1. The crystallization of
MTW phase is successfully achieved both in MTW-EG-80-160-6
(Fig. 1(a)) and MTW-TEG-80-160-6 (Fig. 1(c)), in which the latter
one exhibits the coexistence of cristobalite phase drastically. Both
samples show much stronger diffraction intensity than Bench-
mark, indicating that adding co-solvents facilitate the crystalliza-
tion of MTW phase. In Fig. 1(b) and (d), both MTW-DEG-80-160-
6 and MTW-TTEG-80-160-6 show weak crystallinity. However, in
Fig. 1(b), the peak intensities of (0 0 2), ( 2 0 2) and (0 0 6) are more
prominent, indicating the crystallization of MTW framework is ori-
ented along the b axis [42]. For MTW-TTEG-80-160-6, the diffrac-
tion features of (0 0 2), ( 2 0 2), (3 1 0), and (0 0 6) are observed
and shift towards a lower angle, indicating the unit cell dimensions
might be expanded due to the occlusion of TTEG molecules. How-
ever, the long backbone of TTEG molecule might defer the crystal-
lization of ZSM-12, leading to the poor crystallinity of resulted
sample. A sample with high MTW crystallinity, coexisting with
cristobalite, was attained when we extended the synthesis dura-
tion to 14 days (MTW-TTEG-80-160-14).
Incorporating co-solvents in zeolite precursor gels usually
yields tuned morphology of zeolite crystals [43,44]. The SEM image
shows that the morphology of MTW-EG-80-160-6 crystals turns
into a round-shape with an average size of 0.98 0.09 lm in
Fig. 2(a). The morphology of MTW-TEG-80-160-6 crystals also
exhibit round shape discrete particles with relatively larger parti-
cle size distribution in Fig. 2(c). The SEM image of MTW-DEG-80-
160-6 depicted in Fig. 2(b) shows some particles covered by a thin
lm. The SEM image of MTW-TTEG-80-160-6 shows discrete parti-
cles coated with an amorphous layer structure in Fig. 2(d). The
study systematically showed that the backbone length of co-sol-
vent is critical to the crystallization mechanism of MTW, consistent
with our previous observations on LTL [34].
Yus group reported that several diols exert a signicant effect
on the morphology of silicalite-1 due to their polarity [43]. They
speculated that the O groups of the diols alter the growth kinet-
ics of silicon species along the c-direction. The effect of O groups of
co-solvents skeleton was investigated using PD and HD as co-sol-
vents in our study. PXRD patterns of both samples show that MTW
phase was successfully formed in Fig. 3(a) and (b). However the
formation of cristobalite phase was dramatically enhanced in
MTW-HD-80-160-6 (Fig. 3(b)). Fig. 3(c) and (d) demonstrate PXRD
patterns of MTW-1P-80-160-6 and MTW-2P-80-160-6, in which
both samples show that the MTW phase coexists with cristobalite
 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434
Fig. 2. SEM images of MTW: (a) MTW-EG-80-160-6; (b) MTW-DEG-80-160-6; (c) MTW-TEG-80-160-6; (d) MTW-TTEG-80-160-6. The scale bar (b) is 50 lm; others are 1 lm.
SEM images in inset are taken at higher magnication. The shape of crystals is outlined in red line. (For interpretation of the references to color in this gure legend, the reader
is referred to the web version of this article.)
Fig. 3. Powder XRD patterns for MTW crystals attained at 160 C for 6 days using
1Al2O3: 1.35Na2O: 80SiO2: 12.7TEAOH: 960H2O: 80(PD, HD, 1P, or 2P). (a) MTW-
PD-80-160-6; (b) MTW-HD-80-160-6; (c) MTW-1P-80-160-6; (d) MTW-2P-80-
160-6. The solid triangles indicate the presence of cristobalite phase.
phase. The impurity phase formation rate follows the trend:
HD > 1P, 2P > PD.
In Fig. 4(a), the morphology of MTW-PD-80-160-6 shows dis-
crete round-shape crystals with an average size of
0.74 0.10 lm. The morphology of MTW-HD-80-160-6 crystals
becomes irregular with porous and coarse surface, shown in
Fig. 4(b). The average crystal size was estimated as
0.84 0.11 lm. The formation of hollow crystals is noticeable in
this sample. A comparable result was reported by Huangs
group that adopted EtOH as co-solvent to create hollow SOD
and LTA crystals [45]. Fig. 4(c) and (d) show SEM images of
27
MTW-1P-80-160-6 and MTW-2P-80-160-6. All samples formed
discrete particles. It is noteworthy that the crystal of MTW-1P-
80-160-6 exhibit rectangular cuboids with cavities at the center,
similar to MTW-HD-80-160-6. Rectangular cuboids are formed in
MTW-2P-80-160-6; however, the average particle size is smaller
than that of MTW-1P-80-160-6, shown in Table 1.
The PXRD pattern of MTW-EG-80-160-6 is identied as a pure
MTW phase with unit cell parameters of a = 26.0799, b = 5.1072,
c = 25.7398 and b = 106.92. The unit cell volume is 3280.03 3.
The rened unit cell dimensions of MTW-TEG-80-160-6 are as fol-
lows: a = 26.1810, b = 5.0954, c = 25.0793 and b = 108.44. The
unit cell volume is 3173.85 3. The elongated unit cell dimensions
and enlarged unit cell volumes, compared with those of Bench-
mark and calcined Benchmark, imply the incorporation of co-sol-
vent molecules inside microporous channels. Furthermore,
thermal gravimetric analyses on several MTW samples were dis-
played in Fig. 5. The major weight loss of calcined Benchmark
(Fig. 5(a)) is below 200 C, which is attributed to the removal of
physisorbed H2O molecules. We can observe two weight losses of
Benchmark in Fig. 5(b) that are around 305 C and 460 C, respec-
tively. The former is owing to the removal of TEAOH and the latter
is resulted from the burning-off of TEA cations [6]. Similar trend
can be observed in co-solvent mediated MTW samples, shown in
Fig. 5(ce). However, we notice that the rst weight loss tempera-
ture of MTW-TEG-80-160-6 and MTW-HD-80-160-6 is deferred to
around 330 C. This is likely due to the occlusion of co-solvent mol-
ecules that slow down the removal of organic molecules.
In investigations of the co-solvent identity effect on MTW crys-
tallization, we observed that adding an organic co-solvent in the
zeolite precursor solution promotes the crystallization rate of
MTW formation (Table 1). This synthesis strategy has three effects:
(1) forming MTW crystals with larger sizes, (2) facilitating the
cristobalite formation, and (3) forming an anisotropic growth of
MTW phase. The rst effect could be attributed to the buffering
effect of organic co-solvents on solubility of silica species released
28 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434

Fig. 4. SEM images of MTW: (a) MTW-PD-80-160-6; (b) MTW-HD-80-160-6; (c) MTW-1P-80-160-6; (d) MTW-2P-80-160-6. The scale bar is 1 lm. The arrows in (b) denote
the presence of cavity at the center of MTW crystals. SEM images in inset are taken at higher magnication. The shape of crystals is outlined in red line. (For interpretation of
the references to color in this gure legend, the reader is referred to the web version of this article.)

Table 1
Zeolite phase of synthesized samples using various organic co-solvents and synthesis conditions.

Co-solvent Co-solvent Synthesis conditions

identity quantity
T = 140 C T = 160 C
6 days 3 days 6 days 14 days
None None MTW (0.77 0.08 lm) MTW (0.64 0.04 lm)
EG 80 MTW + amorphous (0.68 0.05 lm) MTW (0.98 0.09 lm)
DEG 26.67 MTW (1.03 0.10 lm)
80 MTW (0.77 0.11 lm) MTW + amorphous (aggregated)
TEG 26.67 MTW + amorphous (0.59 0.07 lm) MTW (0.76 0.10 lm)
80 MTW (0.92 0.10 lm) MTW + cristobalite (1.00 0.12 lm) MTW + cristobalite
(1.03 0.16 lm)
TTEG 26.67 MTW (0.81 0.18 lm)
53.34 MTW (0.85 0.18 lm) MTW (0.96 0.12 lm)
80 MTW + cristobalite
PD 80 MTW (0.66 0.06 lm) MTW (0.74 0.10 lm)
1P 80 MTW + cristobalite (0.85 0.07 lm)
2P 80 MTW + cristobalite (0.75 0.10 lm)
HD 26.67 MTW (0.74 0.12 lm) MTW (0.73 0.11 lm) MTW (0.72 0.10 lm)
53.34
80 MTW (0.80 0.10 lm) MTW (0.73 0.08 lm) MTW + cristobalite (0.84 0.11 lm)

into precursor solutions during the nucleation stage [30,46,47].
However, DEG and TTEG seem to be outliers under the applied
synthesis conditions. The observation could be due to the content
and molecular structure of the co-solvents. We also investigate the
co-solvent content effect in this work and will show that MTW
crystallization is successfully achieved using lower co-solvent
content in the following section. Furthermore, a comparable obser-
vation was reported by Qius group, in which benzene-1,2-diol can
promote the growth of large silicalite-1 crystals, but not on using
benzene-1,3-diol and benzene-1,4-diol [48].
The formation of cristobalite phase can be observed in MTW or
MFI syntheses [3,6,49,50]. We believe that the cristobalite phase is
evolved from MTW or MFI phase via Ostwald ripening mechanism
under the applied synthesis conditions in this work [5154]. Per-
haps, the adopted co-solvents molecules might act as a space ller
to stabilize the zeolite framework [36,50]. Hence, we believe the
formation of cristobalite phase can be avoided using co-solvents
with shorter backbone length (Fig. 3), less co-solvent content,
shorter synthesis duration, or lower synthesis temperatures that
will be demonstrated in the following sections.
 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434
Fig. 5. Thermal gravimetric analyses of MTW samples. (a) Calcined benchmark; (b)
Benchmark; (c) MTW-EG-80-160-6; (d) MTW-TEG-80-160-6; (e) MTW-HD-80-
160-6.
With these in mind, two syntheses were conducted for 3 days
using HD and TEG as co-solvents. Shown in Fig. S3 are PXRD pat-
terns of MTW-HD-80-160-3 and MTW-80-TEG-160-3, in which
the latter shows a pure MTW phase while the former, MTW-HD-
80-160-3, exhibits an anisotropic growth of MTW phase with
intense diffraction peaks at 2h of 8.5, 17.5, 23.5, and 26.5 that
individually correspond to diffraction planes of (2 0 2), (4 0 4),
(0 0 6), and (6 0 6). Shown in Fig. S4, for the precursor solution using
HD as the co-solvent, the yielded solids demonstrate porous and
coarse surface. However, using TEG as the co-solvent leads to the
formation of discrete particles with the average diameter of
1.5 lm, Fig. S4(b).
The formation of anisotropic growth of MTW is observed using
HD as co-solvent at shorter synthesis duration (3 days). HD mole-
cule has hydrophilic hydroxyl groups at both ends and hydropho-
bic hexane skeleton at the center, that might form organic-silicate
interactions along the proximity of HD carbon backbone anisotrop-
ically [51,55,56]. In addition, the long backbone of HD molecules
might defer the polymerization rate of nuclei, that yields porous
sponge-like structure in Fig. S4(a) and (b). However, the aniso-
tropic growth of MTW is absent while TEG, TTEG, 1P, and 2P are
used as co-solvents respectively. It implies that the symmetry of
co-solvent polarity is also essential to direct crystal growth habit
due to its interactions with zeolite framework. To the best of our
knowledge, this is the rst illustration of forming anisotropic
MTW zeolite without using any substrate [42]. The observation
can provide a platform to synthesize oriented MTW membranes
for separation applications.
3.2. Effect of co-solvent content
As aforementioned, the co-solvent content relates with the cris-
tobalite formation as well as the poor crystallinity of MTW when
using DEG and TTEG as co-solvents. This section focuses on this
factor. Fig. 6 shows the effect of co-solvent content on MTW crys-
tallization. As the content of TEG is decreases, the formation of cris-
tobalite phase was highly suppressed (Fig. 6(a)). Further addition
of TEG resulted in a completely amorphous phase (Fig. 6(b)). The
results imply that the lower content of TEG exerts less morphology
modulation and the stabilization effect on MTW framework, which
is in parallel with our previous research publications [34]. Simi-
larly, the crystallinity of MTW sample are highly enhanced as the
TTEG content is decreased respectively shown in Fig. 6(c) and
(d). The TTEG content required for pure MTW crystallization is
much less than that of TEG. This is possibly due to the presence
29
Fig. 6. Powder XRD patterns for MTW crystals attained at 160 C for 6 days using
1Al2O3: 1.35Na2O: 80SiO2: 12.7TEAOH: (1040-x)H2O: x(TEG or TTEG or DEG),
x = 26.67, 53.34, 80, or 160. (a) MTW-TEG-26.67-160-6; (b) MTW-TEG-160-160-6;
(c) MTW-TTEG-26.67-160-6; (d) MTW-TTEG-53.34-160-6; (e) MTW-DEG-26.67-
160-6; (f) MTW-DEG-160-160-6.
of ether groups, as well as the longer backbone length, which inter-
act with the zeolite framework stronger [43]. DEG seems to work
effectively only at lower content, shown in Fig. 6(e) in which the
formation of pure MTW phase is noticeable. Further increasing
the DEG content hampers the crystallization of MTW phase that
only yields an amorphous material (Fig. 6(f)).
The SEM image of MTW-TEG-26.67-160-6 display discrete
cuboidal crystals with an average particle size of 0.76 lm
(Fig. 7(a)). As expected, the morphology of crystals becomes a rect-
angular-cuboidal and round-shape when the TTEG content is
increased shown in Fig. 7(b) and (c) individually. The SEM image
shown in Fig. 7(d) indicates the crystals of MTW phase are discrete
rectangular cuboidal shape with an average size of 1.03 0.10 lm.
The crystallinity of MTW are also highly enhanced as the HD
content is decreased from the molar equivalent of 8053.34 and
26.67, respectively, shown in Fig. S5(a) and (b). It is noted that
the formation of cristobalite phase has been greatly suppressed
using the lower HD content. The morphology of crystals becomes
a cuboidal-shape when the HD content is increased from 26.67
to 53.34 and 80, shown in Fig. S6(a) and (b).
3.3. Effect of mineralizer
To further elucidate the contributions of ether groups in TEG
and TTEG, compared with HD, several experiments are conducted
with an extra mineralizer concentration. Compared with its parent
sample, Benchmark with extra mineralizer demonstrates diffrac-
tion peaks of pure MTW phase with broadened peak width
(Fig. 8(a)). When extra mineralizer was added to MTW-HD-80-
160-6, we observed that the evolving features of MTW phase along
with intense diffraction peaks of (2 0 2), (0 0 6), and (6 0 6) in
Fig. 8(b), which is similar with the anisotropic growth along the
b-axis observed in Fig. S3. The presence of additional sodium ions
possibly (1) counter-balance the negatively-charged alumina tetra-
hedra; or (2) enhance electrostatic interactions between HD and
silicates in the precursor gel [57], that promote the anisotropic
growth along the backbone of HD molecules. The promotion of
anisotropic growth along certain axis is also observed in MOR sys-
tem using excess NaOH in the synthesis gel [58].
It is noted that adding extra sodium ions to MTW-TEG-80-160-
6 leads to prominent peak formation at 2h of 8.5, 17.5, 23.5, and
26.6 in its PXRD pattern (Fig. 8(c)), which is similar with that in
30 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434
Fig. 7. SEM images of MTW: (a) MTW-TEG-26.67-160-6; (b) MTW-TTEG-26.67-160-6; (c) MTW-TTEG-53.34-160-6; (d) MTW-DEG-26.67-160-6. The scale bar is 1 lm. SEM
images in inset are taken at higher magnication. The shape of crystals is outlined in red line. (For interpretation of the references to color in this gure legend, the reader is
referred to the web version of this article.)
Fig. 8. Powder XRD patterns for MTW crystals attained at 160 C for 6 days (a)
Benchmark with extra 1.35 Na2O; (b) MTW-HD-80-160-6 with extra 1.35 Na2O; (c)
MTW-TEG-80-160-6 with extra 1.35 Na2O; (d) MTW-TTEG-53.34-160-6 with extra
1.35 Na2O. The solid triangles indicate the presence of cristobalite phase.
Fig. S3. It has been proposed that ether groups of TEG facilitate the
MFI formation via strong interactions with silicate nuclei in the
precursor gel [43]. The addition of extra sodium ions might exert
synergistic effects with TEG molecules to induce the anisotropic
growth. However, adding extra sodium ions to MTW-TTEG-
53.34-160-6 only facilitates the formation of cristobalite phase,
shown in Fig. 8(d).
Fig. 9(a) shows the SEM image of Benchmark with extra miner-
alizer. The average particle size decreases to 0.44 0.10 lm, which
is smaller than that of Benchmark under the applied condition.
This could be owing to the higher nucleation rate when an extra
amount of mineralizer is applied, yielding a higher number of
nuclei in the precursor solution [59]. The result is in agreement
with outcomes published by Seyed et al. [60], in which the authors
attributed to the occurrence of faster nucleation in the reaction
solution. Fig. 9(b) shows a non-discrete morphology of resulted
materials, which is similar to Fig. S4(b). The structure is postulated
as aggregated akes in which the anisotropic growth along b-axis
occurs. Furthermore, due to the polarity of HD molecules [61],
the additional sodium ions induce strong interaction with alumina,
yielding ill-dened edge of zeolite crystals, which were reported in
the literature [62,63]. The morphologies of MTW-TEG-80-160-6
and MTW-TTEG-53.34-160-6 in the presence of excess sodium ions
result in a rectangular-cuboidal-like shape (Fig. 9(c) and (d) corre-
spondingly), while discrete round-shape crystals are obtained for
each of their parent materials.
3.4. Effect of temperature
The synthesis temperature plays a signicant role at zeolite
synthesis. Shown in Fig. 10(a) and (b) are PXRD patterns of MTW
using various contents of TEG at 140 C. It is noticeable that using
a lower synthesis temperature can yield the pure MTW phase for-
mation with broadened peak width. This indicates that the
resulted crystal size is smaller than that synthesized at 160 C.
The results also signify that the higher content of TEG leads to a
higher crystallization rate, even though the synthesis was con-
ducted at a lower temperature. The result is parallel to other
research outcomes [3,6]. A similar trend can be observed when
HD was used as the co-solvent, shown in Fig. 10(c) and (d).
MTW-HD-26.67-140-6 exhibits a highly crystalline sample than
MTW-TEG-26.67-140-6. The results corroborate with published
observations [49,50], and the zeolite phase selectivity and purity
can be improved at lower temperature [64]. The results also indi-
cate that HD molecules can act as a space ller to stabilize MTW
framework, under low content and low temperature.
 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434 31

Fig. 9. SEM images of MTW: (a) benchmark with extra 1.35 Na2O; (b) MTW-HD-80-160-6 with extra 1.35 Na2O; (c) MTW-TEG-80-160-6 with extra 1.35 Na2O; (d) MTW-
TTEG-53.34-160-6 with extra 1.35 Na2O.The scale bar is 1 lm. SEM images in inset are taken at higher magnication. The shape of crystals is outlined in red line. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

Similar observations can be made to EG, PD, TTEG and DEG in

Figs. S7 and S8 respectively; however, it is noteworthy that the
temperature can be applied to manipulate the crystal growth
behaviors using DEG and EG as the co-solvent respectively
(Fig. S7(b) and (c)). This also signies that moderate hydrophobic-
ity of co-solvent can facilitate the MTW formation at low temper-
ature effectively. In addition to that, the morphology of crystals
using MTW-TTEG-53.34-160-6 seems more rounded than MTW-
TTEG-53.34-140-6. The morphologies of MTW-EG-80-140-6 and
MTW-PD-140-6, shown in Fig. S8(c) and (d) are cuboidal again,
while those synthesized at higher synthesis temperature get more
round-shape crystals.

3.5. FT-IR analysis

The interaction between occluded molecules and zeolite frame-

Fig. 10. Powder XRD patterns for MTW crystals attained at different temperatures
for 6 days using 1Al2O3: 1.35Na2O: 80SiO2: 12.7TEAOH: (1040-x)H2O: xTEG or HD,
x = 26.67 and 80. (a) MTW-TEG-26.67-140-6; (b) MTW-TEG-80-140-6; (c) MTW-
HD-26.67-140-6; (d) MTW-HD-80-140-6.
Upon adding co-solvents, the modulated crystallization rate is
also noted in zeolite crystal sizes, shown in Fig. 11(a) and (b).
The corresponding particle sizes are 0.59 0.07 lm and
0.92 0.1 lm, which are correspondingly smaller than those of
160 C. This is consistent with the published data [65]. It is also
noteworthy that the cuboidal morphology prevails when the syn-
thesis temperature is at 140 C. Similar trend can be observed in
the HD case, shown in Fig. 11(c) and (d). Both MTW-HD-26.67-
140-6 and MTW-HD-80-140-6 possess comparable particle size,
signifying that the low HD content can exert the same stabilization
effect on MTW framework as the high HD content.
work can be qualitatively investigated using an infrared spectros-
copy [66]. Fig. S9 depicts the FT-IR spectra of Benchmark,
calcined Benchmark and Benchmark sample with excess Na ions.
The vibrational mode of occluded TEA+ is denoted by the peak at
1173 cm 1 which disappears upon calcination. A peak of
543 cm 1 in Fig. S9(c) is attributed to the internal vibrational mode
of SiO4 or AlO4 tetrahedra, which could result from the disappear-
ance of interaction between the occluded TEA+ and MTW frame-
work upon calcination.
A doublet peak at 786 and 803 cm 1 appears in Fig. S9(a) and
(b), due to the appearance of external symmetric SiO vibrations
of MTW framework perturbed by the occluded TEA cations
[67,68]. The doublet peak disappears upon the calcination, shown
in Fig. S9(c). Upon adding extra sodium ions, two peaks show a red-
shift from 1099 to 1096 cm 1 (internal asymmetric SiO stretching
vibration) and 786783 cm 1 (external symmetric SiO vibration),
supporting that the co-operative structural direction of TEA+ and
Na cations [16,67,6971].
32 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434

Fig. 11. SEM images of MTW: (a) MTW-TEG-26.67-140-6; (b) MTW-TEG-80-140-6; (c) MTW-HD-26.67-140-6; (d) MTW-HD-80-140-6; The scale bar is 1 lm. SEM images in
inset are taken at higher magnication. The shape of crystals is outlined in red line. (For interpretation of the references to color in this gure legend, the reader is referred to
the web version of this article.)

543 (c)

1218 580
480

1103 (b)
543
1221 477
1173 568
1107
(a)
543

1221 574 477

1173

1105

Fig. 12. FT-IR spectra (a) MTW-TEG-80-160-6; (b) MTW-TEG-80-160-6 with 1.35 extra Na ions; (c) calcined MTW-TEG-80-160-6.

A peak at 475 cm 1 denotes the OTO bending mode, whereas
T = Si or Al [72]. The peak shifts to 479 cm 1 in Fig. S9(c) upon
calcination, likely owing from the absence of interactions between
TEA cations and MTW frameworks. The relaxation of MTW
framework from the interactions with TEA cations can be seen
from the blueshift of 786789 cm 1 (symmetric SiO vibration)
and 571578 cm 1 (double ring), as well as the redshift of 1222
1220 cm 1 (external asymmetric SiO stretching vibration).
Fig. 12 depicts FT-IR spectra of MTW phase synthesized in the
presence of TEG at 160 C. In consistent with previous observa-
tions, the disappearance of peak at 1173 cm 1 upon calcination
veries that TEA cations are completely removed (Fig. 12(c)). All
 S. Jegatheeswaran et al. / Microporous and Mesoporous Materials 201 (2015) 2434
samples exhibit a peak at 543 cm 1, implying that the relaxation of
TEA+ molecules with MTW framework upon the TEG occlusion,
that yields prominent symmetric SiO vibrational modes. This is
also supported by the blueshift of the peak of 11031107 cm 1
(internal asymmetric SiO stretching), compared with Fig. S9(a).
The redshift of peak from 574 to 568 cm 1 might signify the stabil-
ization effect of excess sodium ions towards the framework defects
of double rings via charge compensation.
In parallel with Fig. S9, other peak shiftings (574580 cm 1,
477480 cm 1, 12211218 cm 1 and 11051103 cm 1) indicate
that those vibrational modes are relieved upon the removal of
occluded TEG molecules and TEA cations through calcination. Sur-
prisingly, the symmetric SiO stretching vibrational mode is shifted
drastically upon calcination, shown in Table S1. This conrms that
occluded TEG could behave as a space ller to provide a strong sta-
bilization effect for the organization of host species in the MTW
framework. For the sample synthesized using HD as the co-solvent,
similar shifting can be observed in Fig. S10 and the shifting extent
of each stretching mode is tabulated in Table S1.
4. Conclusions
Various organic co-solvents are employed to systematically
study the crystal growth behaviors of ZSM-12. All co-solvents, with
an adequate content, are able to promote the formation of pure
MTW phase with discrete zeolite crystals under shorter synthesis
duration and/or lower synthesis temperature. Detail characteriza-
tions indicate that part of co-solvent molecules are incorporated
within 1-D channels of MTW framework, exerting synergic effects
with the structure-directing agent on crystallization behaviors.
Thus, the co-solvent molecules may play several roles during the
course of crystallization: (1) a space ller within micropores to sta-
bilize MTW framework; (2) a modier in precursor gels to shape
the crystal morphology. The extent of co-solvents function
depends on the backbone length of molecules, the hydrophobicity
(C/O ratio), and the symmetry of hydrophobic compartment along
the molecule skeleton. By applying the co-solvent synthesis route,
this work also discovers several synthesis conditions yielding dis-
crete crystals, with the anisotropic growth along the b-axis; how-
ever, without using any substrate. The outcome may provide a
strategy to control the orientation of 1-D channels of MTW frame-
work in a supported membrane for gas permeation applications.
Acknowledgements
The authors thank nancial supports from NSERC Discovery
Grant (372036-2009), and Undergraduate Research Opportunities
(URO) scholarship, the Deans ofce of Faculty of Engineering and
Architectural Science (FEAS) and the Department of Chemical Engi-
neering at Ryerson University. The authors express their heart-felt
gratitude to Mr. George Kretschmann in the Department of Earth
Science at University of Toronto for acquiring extensive PXRD mea-
surements and to Mr. Qiang Li in the Department of Mechanical
and Industrial Engineering at Ryerson University for obtaining
SEM images. The authors greatly appreciate the assistance of
acquiring PXRD patterns from Dr. Srebri Petrov in the Department
of Chemistry at the University of Toronto.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.micromeso.2014.
09.008.
33
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