Microporous and Mesoporous Materials 219 (2016) 103e111

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Microporous and Mesoporous Materials

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

Synthesis and characterization of all-silica DDR zeolite by microwave

heating
Jianming Zhang a, Meng Li a, Yanjun Lin b, Cheng Liu a, c, Xiangyan Liu a, d, Lu Bai a, e,
Deng Hu a, **, Gaofeng Zeng a, Yanfeng Zhang a, c, *, Wei Wei a, Yuhan Sun a, c
a
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai
201210, China
b
Lu'an Mining Corporation, Changzhi, Shanxi 046000, China
c
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
d
University of Chinese Academy of Sciences, 19 Yuquan Rd, Shijingshan District, Beijing 100049, China
e
Shanghai University, School of Material Science, 99 Shangda Rd, Baoshan District, Shanghai 200444, China

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

Article history: All-silica zeolite DDR was prepared by microwave-aided hydrothermal synthesis and characterized by X-
Received 9 May 2015 ray diffraction, scanning electron microscopy, infra-red spectroscopy, nitrogen adsorption, elemental
Received in revised form analysis and thermal gravimetric analysis. Microwave-aided heating signicantly reduced the synthesis
21 July 2015
time from 25 d to 3 d and crystal size from 8 mm to 2 mm. With the help of seeding, the synthesis time
Accepted 24 July 2015
Available online 5 August 2015
and crystal size were further reduced to 6 h and 0.7 mm respectively. The crystal size decreased with seed
content. The fragmentation of seed crystals had positive impact on reducing crystal size and increasing
product yield. The aging of mother liquor and decrease of H2O/SiO2 had little impact on crystal size.
Keywords:
Zeolite
2015 Elsevier Inc. All rights reserved.
DDR
All-silica
Hydrothermal synthesis
Microwave synthesis

1. Introduction
Zeolites/molecular sieves are a group of crystalline materials
with uniform molecular sized pores, unique adsorption property
and acidity, which have been extensively used in various industries
as catalysts and sorbents [1]. Taking advantage of zeolites's unique
pore system, adsorption property and great stability, zeolite
membranes have the great potential to separate gas or liquid
mixtures through the difference in adsorption and diffusion [2e5].
Among various types of zeolite membranes, small pore zeolite
membranes (zeolite with 8-MR) have been extensively studied,
such as SAPO-34 [6e14], high silica CHA [15e17] and DDR mem-
branes [18e22], because their pore sizes are perfect for many
important industrial separation processes, like CO2eCH4 separa-
tion. All-silica DDR (Si-DDR) membranes, with pores
* Corresponding author. CAS Key Laboratory of Low-carbon Conversion Science
and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sci-
ences, Shanghai 201210, China. Tel.: 86 21 20350997.
** Corresponding author.
E-mail addresses: hud@sari.ac.cn (D. Hu), zhangyf@sari.ac.cn (Y. Zhang).
~0.36
0.44 nm, allows the selective diffusion of CO2 (kinetic
diameter 0.33 nm) to the inner pore structure, while excludes the
larger CH4 (0.38 nm) molecule. The all-silica hydrophobic frame-
work makes it insensitive to the H2O in the feed [6e14].
Despite the huge potential applications of DDR zeolite and
membrane, the synthesis of zeolite DDR was very challenging
mainly due to the extremely long crystallization time and complex
reactions involved. Gies et al. rst reported the synthesis of DDR
with 6e9 weeks synthesis time, which make it difcult for any real
application [23]. Den Exter et al. optimized the synthesis and ob-
tained pure DDR crystals in 25 days [24]. Tomita et al. prepared DDR
membranes in 2 d by secondary growth method, which indicated
that seeding can signicantly reduce the synthesis time [19].
Gascon et al. reduced the synthesis time from 25 d to 2 d by adding
0.02 wt% seeds to facilitate nucleation [25]. Yang et al. reported the
synthesis of DDR in uoride medium in 9 d (no seeding) or 1 d
(seeding). The use of KF as mineralizing agent increased the solu-
bility of silica, which enhanced the nucleation, thus led to shorter
synthesis time and smaller crystals (~5 mm) [26]. Gucuyener et al.
found the proper cleaning of Teon liner eliminates the memory
effect (or the interference of other phase) and thus improves the

http://dx.doi.org/10.1016/j.micromeso.2015.07.025
1387-1811/ 2015 Elsevier Inc. All rights reserved.
104 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111
reproducibility [27]. Yang et al. prepared DDR with the aid of ball-
milled Sigma-1 seeds, an aluminum-containing structural analog of
DDR. The synthesis time was shorten to 9 h and crystal size was
1~3 mm. DDR crystals with various morphology, such as hexagonal
thin plate, rhombus block, and hexagonal prism, were obtained by
changing the pH of the mother liquor [28,29]. Sen et al. prepared
DDR zeolite at room temperature in 2~5 d by a novel sonochemical
method (without seeding) [30]. Kim et al. prepared Si-DDR parti-
cles of 1.3~10 mm by varying the seed amount. These Si-DDR par-
ticles were deposited onto porous a-Al2O3 discs via sonication-
induced assembly, constituting close packed h0h-oriented layers
[31].
Despite substantial progresses made in recent years, the
requirement of long reaction time, poor phase purity and low
reproducibility are still the obstacles to the further research and
applications of DDR zeolite. It is extremely desirable to get sub-
micron DDR crystals with uniform crystal size distribution, which is
important for zeolite membrane synthesis and adsorption appli-
cation. After the rst publication on microwave synthesis of zeolite
Y and MFI in 1993 [32], microwave-aided synthesis has gained
tremendous interest due to many advantages, such as shorter
synthesis time, free of undesired phase, uniform and smaller
crystals, as compared with conventional heating. Many zeolites as
well as zeolite membranes (such as LTA, MFI, AFI, FAU, SOD, and
ETS-4 etc) were successfully prepared by microwave-aided syn-
thesis [5,33,34]. However, there is no report about the synthesis of
zeolite DDR by microwave heating. In this manuscript, we suc-
cessfully prepared sub-micron all-silica DDR zeolite by microwave-
aided hydrothermal synthesis. The obtained DDR samples were
characterized by XRD, SEM, nitrogen adsorption, IR and thermog-
ravimetric analyses.
2. Experimental
2.1. Chemicals
1-adamantane amine (1-ADA, 99 wt%) was provided by
Shanghai Nuotai Chemical Corporation. Ethylenediamine (EDA,
99 wt%) was provided by Shanghai Richjoint Chemical Reagents.
Hydrogen uoride aqueous solution (40 wt% HF) and potassium
uoride (99.5 wt% KF) were obtained from Aladdin Chemistry Corp.
Silica sol (Ludox AS40, 40 wt% SiO2) was obtained from Sigma-
eAldrich. All chemicals were used without further purication.
2.2. DDR synthesis without seeding
The mother liquor has the molar ratio of 1-adamantane amine
(1-ADA):SiO2:ethylenediamine (EDA):H2O 47:100:404:11,240. In
a typical synthesis, 1-ADA, EDA and DI water were mixed and
stirred at room temperature for 3 h. Then Ludox AS40 colloidal
silica (40 wt% SiO2 suspensions in water) was added. After 3 h
stirring, the resulting solution was kept at 433 K for 1 h~3 d with
microwave heating (Milestone Ethos A advanced microwave sys-
tem, with stirring). After synthesis, the solution was then cooled to
room temperature and centrifuged at 6000 rpm for 30 min to
separate the powder product, which was then washed with DI
water. This centrifugation procedure was repeated three times, and
the pellet was dried at 373 K overnight. After drying, the powder
product was calcined in air at 973 K for 10 h to remove the organic
template.
2.3. DDR synthesis with seeding
The DDR powder prepared by 3 d MW heating at 433 K was ball-
milled into sub-micron particles, which were used as seeds for
seeded synthesis. The default seed content was 20 mg seed/1.2 g
SiO2 in the mother liquor. The seeds were added in the last step and
the resultant mixture was stirred for 10 min before MW synthesis.
Everything else was the same as non-seeded synthesis.
2.4. DDR synthesis with aging
Compared with the procedure of DDR synthesis with seeding,
almost everything was the same. The only difference is that the
prepared mother liquor was aged at room temperature for 3 d and
7 d before microwave-aided synthesis at 433 K for 24 h. After aging,
ball-milled seed was added into the mother liquor before synthesis
(20 mg seed/1.2 g SiO2 in the mother liquor).
2.5. DDR synthesis with KF as mineralizing agent
Compared with the procedure of DDR synthesis with seeding,
almost everything was the same except the recipe of mother liquor.
The molar ratio of the mother liquor was 47Adam:100
SiO2:100 KF$2H2O:8000H2O and synthesis condition was microwave
heating at 433 K for 3~12 h with seeding (20 mg seed/1.2 g SiO2 in the
mother liquor).
2.6. Instrumentation
Scanning electron microscopy (SEM) images were acquired us-
ing a Hitachi S4800 eld effect scanning electron microscope at
10 kV. Samples for SEM analysis were coated with a gold-palladium
target. X-ray diffraction (XRD) patterns were obtained with a
Rigaku Ultima-III X-ray diffractometer using Cu Ka X-radiation.
Thermogravimetric analyses (TGA) were performed on a Per-
kineElmer Pyris 1 thermogravimetric analyzer at a heating rate of
10  C/min under owing nitrogen. Thermal analyses were per-
formed on a PerkineElmer Pyris 1 differential scanning calorimetry
(DSC), at a heating rate of 10  C/min under owing nitrogen. The
BET surface area of calcinated DD3R samples was obtained on a
nitrogen physisorption analyzer (ASAP 2020 M, Micromeritics) at
77 K. Infra-red spectra of DDR samples were acquired on a Nicolet
Nexus 470 FT-IR spectrometer using KBr pellets in the range of
600e4000 cm1. Elemental analysis was conducted on an induc-
tively coupled plasma atomic emission spectrometer (ICP-AES).
3. Results and discussion
All silica DDR was prepared with 1-adamantane amine as
organic template by microwave-aided hydrothermal synthesis
(mother liquor molar ratio of 1-adamantane amine: silica: ethyl-
enediamine: water 47:100:404:11,240, at 433 K). This recipe was
used by many research groups and high quality all-silica DDR
crystals can be obtained reproducibly by regular hydrothermal
synthesis [24,25,27e29]. The issue of zeolite DDR synthesis by
hydrothermal method is the long synthesis time (~25 d), which
suggests that the nucleation and crystal growth of DDR zeolite are
very slow. It is generally accepted that microwave-aided synthesis
can accelerate the synthesis of many zeolites, such as LTA, MFI, AFI,
FAU, SOD, and ETS-4 etc, due to the so-called microwave effect
[5,32e34]. Muhammad et al. predicted that microwave-aided
synthesis might shorten the synthesis of zeolite DDR [35]. As
shown in Fig. 1, the product was still amorphous after 24 h
microwave-aided hydrothermal synthesis. After 48 h microwave
heating, characteristic peaks of DDR zeolite were observed with
good signal/noise ratio, which indicated good crystallinity of ob-
tained product. After 72 h microwave-aided synthesis, high quality
XRD pattern was obtained and no impurity was detected. The XRD
pattern of calcined DDR perfectly matched the standard DDR
 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111
Fig. 1. The effect of MW synthesis time on the powder XRD patterns of DDR samples
prepared by MW heating at 433 K.
pattern [24,25,27e29]. The SEM images in Fig. 2 are consistent with
the XRD patterns. As shown in Fig. 2, irregular shaped particles
~10 mm were observed after 24 h synthesis. The close-up SEM im-
age shows these particles consist of tiny spherical particles
(~20 nm), which should be the primary particles from silica source
Fig. 2. The effect of MW synthesis time on the morphology of DDR samples (MW heating at 433 K).
105
Ludox AS40. This result indicated that no crystalline product was
obtained after 24 h MW synthesis, which is consistent with the
amorphous XRD pattern. After 48 h synthesis, characteristic
rhombohedral shaped crystals with size ~2 mm were obtained. The
crystal size distribution was not uniform, ranging from submicron
to 3 mm. There are still some unconverted amorphous spherical
silica particles on the crystal surface. After 3 d MW synthesis, well-
developed rhombohedral DDR crystals with ~2 mm in diameter
were obtained and further increase of synthesis time led no change
of crystallinity. The synthesis of DDR crystals by regular hydro-
thermal synthesis require >20 d (no seeding) and the obtained DDR
crystals is much bigger, ~8 mm [24]. Compared with traditional
lengthy hydrothermal synthesis, the microwave-aided hydrother-
mal synthesis signicantly reduced the synthesis time (~90%
reduction) and crystal size (~75% reduction). The reduction of
synthesis time and crystal size might be the consequence of fast
dissolution of the gel and rapid homogeneous heating of the syn-
thesis mixture, which lead to more nucleation [34]. This is signi-
cant for the synthesis of DDR zeolite, since almost all published
papers about DDR synthesis require the rst step 25 d synthesis to
obtain the DDR seeds, except Sen et al. prepared DDR zeolite in 5 d
without addition of seeds [30].
Fig. 3 shows the FT-IR spectra of the as-synthesized and calcined
DDR samples (prepared by MW heating at 433 K for 3 d). The peaks
at 1344 and 1457 cm1 were assigned to the bending vibration and
deformation vibration of CH and CH2 from the template. The peaks
at 2851 and 2911 cm1 can be ascribed to the CH and CH2 stretching
106 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111
Fig. 3. FT-IR spectra of DDR samples made by MW heating at 433 K for 6 h (as syn-
thesized) and 3 d (as synthesized and calcined).
vibrations from the template. The peak at 1640 represents the
deformation vibration of NeH on the amino groups. The adsorption
peaks of NeH (3600~3300 cm1) and CeN (1250~1020 cm1)
stretching vibrations were covered by other peaks. After calcina-
tions, the peaks from the organic template disappeared, which
indicated complete template removal. Infrared spectroscopy is also
a powerful tool to investigate the atomic ordering of zeolitic ma-
terials. As-prepared and calcined DDR samples exhibit bands at ca.
462, and 792 cm1 which can be assigned to SieOeSi bending and
SieO tetrahedral vibration, respectively. The small peaks between
500 and 650 cm1 were attributed to double ring external linkage
of the zeolite structure [30]. The IR spectrum of sample prepared by
6 h MW synthesis (with seeding) was similar to those of as-
prepared and calcined DDR samples (MW 3 d without seeding).
The IR result indicated the presence of zeolite-like structure. The
hydrophobicity of the calcined DDR was conrmed by the weak
adsorption at ~3000 cm1, which showed only a small amount of
water [24]. Thermogravimetric analyses in Fig. 4 showed ~11 wt%
weight loss associated with template removal (MW 72 h without
seeding and MW 12 h with seeding), which is similar to literature
result [24]. The elemental analysis (by ICP-AES) conrmed the all-
Fig. 4. Thermogravimetric analyses of DDR samples made by MW heating at 433 K.
silica nature of the obtained DDR product. The BET surface area
determined by nitrogen adsorption (Fig. 5) is 306 m2/g, which is
similar to literature data [28,29]. These data indicated that high
quality all-silica DDR crystals were obtained by MW-aided hydro-
thermal synthesis.
For zeolite synthesis, it is generally accepted that seeding is an
effective way of reducing synthesis time, crystal size and template
consumption [3e5]. Literature result indicated that seeding is
especially effective for the synthesis of zeolite DDR. Tomita et al.
rstly prepared DDR membranes in 2 d by secondary growth
method, which indicated that seeding can signicantly reduce the
synthesis time [19]. After that, many research groups successfully
applied the seeding technique to the synthesis of zeolite DDR
instead of DDR membrane and reduced the synthesis time from
25 d to 2~3 d [25e29,31]. However, no one can obtain sub-micron
all-silica DDR crystals. So the DDR crystals prepared by microwave
heating were ball-milled into smaller particles and used as seeds
for further study. The purpose of ball-milling is to break the large
DDR crystals into smaller particles and generate more external
surface area and defects. Regarding the seeding effect, it is generally
accepted that smaller crystals with more defects are better since
more external surface area (with defects) might lead to more sec-
ondary nuclei [1e4,39]. Balled-milled Sigma-1 seeds (DDR struc-
ture with Al) were used for the synthesis of DDR zeolite and high
silica DDR was obtained with signicantly reduced synthesis time
[28,29]. Fig. S1 and Fig. 6 show the XRD patterns and SEM images of
corresponding DDR samples. After 24 h ball-milling, the peak at
15.37 (plane [202]) was the only sharp peak left and other peaks
were signicantly weakened. After 48 h ball-milling, most of DDR
peaks almost disappeared and peaks at ~30 broadened signi-
cantly, which indicated fragmentation and amorphization of DDR
crystals [36e38]. Researchers studied the ball-milling of various
zeolites, such as zeolite A, X, ZSM-5, Y and L [36e38]. Zielinski et al.
observed the decrease and broadening of zeolite peaks without any
shift with the increase of milling time. This is attributed to
amorphization of zeolite crystals by breaking external SieOeSi and
SieOeAl bonds of zeolite structure. They concluded that the pro-
cess of amorphization and breaking of original zeolite crystals are
two parallel, but more or less independent processes [38].
SEM images in Fig. 6 showed irregular shaped particles ranging
from 50 to 400 nm, much smaller than the 2 mm crystals before
ball-milling. The typical rhombohedral shaped DDR crystals were
almost completely gone (there are still some particles with sharp
Fig. 5. Nitrogen adsorptionedesorption isotherm of DDR sample (made by MW
heating at 433 K for 3 d).
 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111 107

Fig. 6. The effect of ball-milling on the morphology of DDR zeolite.

edge, which come from the fragmentation of DDR crystals), which
indicated successful fragmentation. These ball-milled DDR crystals
were used as seeds in the microwave-aided synthesis.
Fig. S2 shows the XRD patterns of products obtained by MW
heating seeding. The default seed content was 20 mg seed/1.2 g
SiO2 in the mother liquor, which is in line with literature data
[1,24,28,29]. After 1.5 h MW synthesis, the broad peak at 30 was
still the highest, which might come from the seeds added into the
mother liquor. This indicated that the DDR seeds are pretty stable in
the mother liquor under synthetic condition. However, the weak
DDR peaks between 15 and 20 (2q) can be observed, which are
absent in the XRD pattern of DDR seeds after ball-milling. This

Fig. 7. The effect of synthesis time on the morphology of DDR samples (MW heating seeding at 433 K, 20 mg seeds/1.2 g SiO2 in the mother liquor).
108 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111
Fig. 8. The effect of seed content on the crystal morphology (MW heating at 433 K for 6 h).
result indicated that DDR crystals started to form after only
1.5 h MW heating. The crystallinity of the DDR zeolite increased fast
with synthesis time and reached maximum between 6 and 12 h.
Further increase of synthesis time led little change of crystallinity
and yield (>80% for 6e24 h synthesis). The corresponding SEM
images in Fig. 7 showed the evolvement of DDR crystals with
synthesis time. After 1.5 h MW synthesis, a mixture of submicron
DDR crystals (200 nme700 nm, rhombohedral shaped crystals) and
lots of amorphous material (irregular shape, micron-size particles
and tiny 20 nm spherical particles) was obtained. Since the DDR
seeds used in the synthesis are sub-micron irregular shaped par-
ticles, the appearance of rhombohedral shaped DDR crystals indi-
cated these crystals are newly formed, not coming from the seeds.
At 3 h, characteristic rhombohedral shaped DDR crystals, ranging
from 0.5 to 1.0 mm, with some amorphous material were obtained.
After 6 h, well-developed rhombohedral shaped DDR crystals with
1 mm in size were observed and no amorphous silica particles were
seen on the surface of DDR crystals. The crystal size distribution
seems to be much narrower as the synthesis time was extended.
Further increase of reaction time led to little change of crystal size,
crystallinity and morphology. Apparently, the addition of seeds
shortened the induction period and generated secondary nuclei.
Compared with non-seeding synthesis, the crystal size was reduced
from 2 to 1 mm with much narrower particle size distribution. It is
worthy to point out that extremely low yield (<5%) was obtained
when DDR seeds were not ball-milled. This result suggests that
small seeds with defects are important for DDR synthesis. This is a
hassle for DDR synthesis, since ball-milling is a lengthy process and
might introduce unwanted impurity into the seeds.
Fig. S3 and Fig. 8 show the effect of seed content on the XRD
patterns and crystal morphology. Good XRD patterns were ob-
tained in 6 h for all samples, which indicated good reproducibility
for the seeded MW-aided synthesis. The SEM images in Fig. 8 shows
a small reduction of crystal size from 1 mm to ~0.7 mm when the
seeds were increased from 20 mg to 200 mg. This result indicates
that the addition of seeds leads to more external surface and sec-
ondary nuclei which result into smaller crystals [39]. However, ten
folds increase of seed content only led to ~30% reduction of crystal
size, which suggests that crystal size is not sensitive to seed con-
tent. Since 200 mg seeds/1.2 g SiO2 precursor is a very high seed
content, further increase of seed content is not a good option to
reduce crystal size. Yang et al. claimed 0.1wt% seed content led to
 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111
Fig. 9. The effect of H2O/SiO2 ratio on the morphology of DDR samples (MW at 433 K for 6 h, 20 mg seed/1.2 g SiO2).
high yield and good crystallinity in the synthesis of zeolite DDR
[29]. Here we want to make small DDR crystals, so lower seed
content experiment was not carried out. When 200 mg un-milled
seeds (~2 mm) were used, the crystal size was bigger (~1.2 mm),
which indicates ball-milling has positive effect on reducing crystal
size, due to generation of more external surface area and defects.
Fig. S4 and Fig. 9 show the effect of H2O/SiO2 ratio on the
crystallinity and crystal morphology. The H2O/SiO2 ratio was
reduced to increase the super-saturation of the mother liquor,
which should lead to more nuclei, thus result into smaller crystals.
Based on the XRD patterns shown in Fig. S4, pure phase DDR
samples with good crystallinity were obtained when H2O/SiO2 ratio
was reduced to 50 and 30. Further decrease of H2O/SiO2 ratio to 15
led to the formation of Dodecasil 3C (ZSM-39, IZA structure code:
MTN). As shown in Fig. 9, the crystal size and morphology remained
unchanged as the H2O/SiO2 ratio decreased to 50. This indicated
that the increase of nutrients concentration had little impact on the
nucleation process, which might be caused by the poor solubility of
the template. At H2O/SiO2 ratio of 30, product morphology
exhibited dramatic change. A mixture of isolated rhombohedra and
irregular shaped crystals were obtained, although XRD patterns
109
indicated no presence of other phases. These irregular shaped
crystals actually composed of tiny rhombohedra (~500 nm in
length) as shown in the close-up SEM image, which should be DDR
crystals. When H2O/SiO2 ratio was reduced to 15, typical octahedral
shaped all-silica MTN crystals with uniform size ~800 nm were
obtained.
Fig. S5 and Fig. 10 show the effect of aging on the synthesis of
DDR crystals. The main purpose of aging is the separation of the
nucleation and growth stages of the zeolite synthesis. The mother
liquor is allowed to age at one temperature and is then crystallized
at a second (usually higher) temperature [39]. Usually, aging has
positive impact on reducing crystal size due to the generation of
more nuclei [2e5,39]. The mother liquor was aged at room tem-
perature for 3 d and 7 d before microwave synthesis at 433 K for
12 h. The XRD patterns in Fig. S5 show high quality DDR crystals,
but the crystal size and morphology remained unchanged even
after 7 d aging (Fig. 10). This result indicates that aging didn't
facilitate the nucleation, therefore no change in the nal crystal size
was observed.
Yang et al. reported the synthesis of DDR in uoride medium
and claimed the addition of KF as mineralizing agent reduced
110 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111

Fig. 10. The effect of aging time on the morphology of DDR samples (MW at 433 K for 1 d, 20 mg seed/1.2 g SiO2).

synthesis time and crystal size [26]. So the KF system was also
investigated by microwave heating. The molar ratio of the mother
liquor was 47Adam:100SiO2:100 KF$2H2O:8000H2O and synthesis
condition was microwave heating at 433 K for xh with seeding.
Similar result was obtained compared with non-KF system. The
characteristic peaks of DDR zeolite was observed after 3 h synthesis
and crystallinity reached maximum at ~6 h (Fig. S6). The SEM im-
ages in Fig. 11 exhibited similar trend. After 6 h, well-developed
rhombohedral shaped DDR crystals with size ~1 mm were obtained.
Table 1 lists the comparison of DDR crystals and membranes
prepared by different methods. The rst in situ synthesis of DDR
required 6e9 weeks [23] and modied in situ synthesis shortened

Fig. 11. The effect of MW synthesis time on the morphology of DDR samples prepared in uoride media (MW heating at 433 K, 20 mg seed/1.2 g SiO2).
 J. Zhang et al. / Microporous and Mesoporous Materials 219 (2016) 103e111 111

Table 1 Appendix A. Supplementary data

Comparison of DDR crystals and membranes prepared by various methods.

Synthesis method Seeding Synthesis time(d) Total time (d) Ref. Supplementary data related to this article can be found at http://
Crystals Membrane
dx.doi.org/10.1016/j.micromeso.2015.07.025.

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[32] P. Chu, F.G. Dwyer, J.C. Vartuli, US Patent 4,778,666, 1988.
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