Microporous and Mesoporous Materials 213 (2015) 161e168

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Microporous and Mesoporous Materials

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

Facile synthesis of an IRMOF-3 membrane on porous Al2O3 substrate

via a sonochemical route
Yu-Ri Lee a, Sung-Min Cho a, Wha-Seung Ahn a, *, Chi-Hoon Lee b, Kyu-Ho Lee b,
Won-Seung Cho b
a
Department of Chemistry and Chemical Engineering, Inha University, Incheon 402-751, Republic of Korea
b
School of Materials Science and Engineering, Inha University, Incheon 402-751, Republic of Korea

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

Article history: A densely-packed IRMOF-3 membrane (S-IRMOF-3(Mem)), ~55 mm in thickness, on an Al2O3 disc support
Received 3 March 2015 was prepared via a sonochemical synthesis route, and the optimal fabrication conditions were estab-
Received in revised form lished. Bare IRMOF-3 particles (S-IRMOF-3(p)) were synthesized independently to analyze the contri-
11 April 2015
bution of the Al2O3 support. The overall physicochemical properties of the IRMOF-3 products produced
Accepted 13 April 2015
Available online 23 April 2015
via the sonochemical route were superior to those prepared by microwave heating. The IRMOF-3 ma-
terials produced were characterized by XRD, SEM, EDS-mapping, and N2 adsorptionedesorption mea-
surements. S-IRMOF-3(p) exhibited satisfactory CO2 adsorption capacities (54 mg/g at 298 K/1 bar;
Keywords:
Metal-organic frameworks
732 mg/g at 298 K/20 bar) and CO2/N2 selectivity (18 at 298 K/1 bar). Both S-IRMOF-3(Mem) and S-
IRMOF-3 membranes IRMOF-3(p) were assessed as a catalyst for a liquid phase Knoevenagel condensation reaction between
Sonochemical synthesis benzaldehyde and ethyl cyanoacetate. S-IRMOF-3(Mem) and S-IRMOF-3(p) showed comparable con-
Knoevenagel condensation reaction versions (87e89%) with 100% selectivity after a 4 h reaction at 333 K. The heterogeneous nature of the
catalyst was confirmed by a hot filtering experiment, and S-IRMOF-3(Mem) could be recovered easily
after the reaction and be recycled several times with little change in product yield.
© 2015 Elsevier Inc. All rights reserved.

1. Introduction classified into two categories: in situ solvothermal and secondary

Metal organic frameworks (MOFs) are porous crystalline hybrid
materials consisting of inorganic metal ions or metal atom clusters
joined together by rigid organic linker groups. MOFs normally
possess extremely large surface areas and pore volumes in well-
ordered porous structures. Moreover, diverse methods are avail-
able for intricate post-synthesis functionalization, which make
them attractive for applications, such as gas storage/separation of
CO2 and CH4, magnetism and heterogeneous catalysis [1e3].
MOFs are typically synthesized by solvothermal/hydrothermal
methods [4e7], and recently, the preparation of MOFs in mem-
brane form supported on alumina [8], silica [9], titania [10], zinc
oxide [11],and metal nets [12] has been investigated for potential
industrial applications to gas or liquid separation [13e16], electrical
devices [17], chemical sensors [18], and catalysis [19e22]. In gen-
eral, the approaches to the synthesis of MOF membranes can be
* Corresponding author. Tel.: þ82 32 860 7466; fax: þ82 32 872 0959.
E-mail address: whasahn@inha.ac.kr (W.-S. Ahn).
(seed-assisted) growth methods. In the former, the membranes are
formed on a support where nucleation and the direct growth of
crystals occur during the synthesis step without surface modifica-
tion. Although simple in procedure, it is difficult to prepare a
continuous and defect-free MOF membrane because of the insuf-
ficient heterogeneous nucleation of the crystals on the support
surfaces [23]. Pre-modification [24e26] and seed coating [27] on
the support surface are highly desirable for directing the nucleation
and growth of the MOF layer. Therefore, the latter method is
preferred to prepare dense and continuous growth of MOF mem-
brane layers. Moreover, it is easier to control the thickness of the
membrane by adding reactive seeding or organic groups on the
support. Up to now, various seeding techniques have been pro-
posed to enhance the interaction between the seed layer and
support, such as rubbing [28,29], dip-coating [30], spin coating [31],
wiping [32], microwave-assisted seeding [33], reactive seeding
[34], and repeated growth [35]. It is also worth mentioning about
ongoing research to utilize MOF nanosheets for membrane appli-
cations. Peng et al. reported a top-down strategy for fabrication of
nanosheets with 1 nm thickness and large lateral area by

http://dx.doi.org/10.1016/j.micromeso.2015.04.021
1387-1811/© 2015 Elsevier Inc. All rights reserved.
162 Y.-R. Lee et al. / Microporous and Mesoporous Materials 213 (2015) 161e168
delaminating the layered MOF structure, poly[Zn2(benzimida-
zole)4], and demonstrated their use in fabricating ultra-permeable
membranes having excellent molecular sieving properties for
H2/CO2 separation [36]. Rodenas et al., on the other hand, reported
a bottom up synthesis strategy for making copper 1,4-
benzenedicarboxylate MOF nanosheets, which were dispersed
into a polymer matrix to produce a MOF membrane with
outstanding CO2 separation performance from CO2/CH4 gas mix-
tures [37]. Qiu et al. [23] and Venna et al. [38] provided an extensive
review of the synthesis of MOF membranes and their applications
to gas and liquid separation.
Isoreticular MOFs (IRMOFs), which were first prepared by Yagi
et al. [39] are a series of size-tunable hybrid structures comprised of
oxygen-centered Zn4O tetrahedra interconnected with various
carboxylate linkers. Among them, IRMOF-3 [Zn4O(NH2-BDC)3, NH2-
BDC ¼ 2-amino benzene dicarboxylic acid] with a 3D cubic porous
network has been studied widely as a catalyst for base-catalyzed
reactions [40e42] as well as for CO2 capture [43]. Several suc-
cessful attempts to fabricate the supported IRMOF membranes via
different synthesis routes have been reported. Yoo and Jeong pre-
pared IRMOF-3/IRMOF-1 hybrid films by combining IRMOF-1
crystals as a seed on porous a-alumina supports using
microwave-induced thermal deposition (MITD) technique and
subsequent growth of IRMOF-3 on the seed layer [44]. They also
developed a crack-free IRMOF-3 membrane via surfactant-assisted
drying [45]. Abdollahian et al. prepared IRMOF thin films on several
substrate-modified zinc oxide nanowires using solvothermal and
microwave synthesis methods, which produced ca. 25 mm thick
films covering the entire substrate with interconnected crystals
[46]. These MOF membranes were normally prepared in multi-
steps and a careful pretreatment of the support with a mother
solution containing both organic and inorganic precursors was
necessary for fabricating the seed layer. Still the successful fabri-
cation of a MOF membrane with high surface coverage of MOF
crystals on its oxide support remains a difficult task, particularly for
preparing a reasonably large-sized one. For MOF-membranes, most
people examined their gas separation behavior; few studies have
assessed the supported MOF membrane as a recyclable catalyst. Jin
et al. prepared a ZIF-8 membrane on polyimide substrates for
Knoevenagel condensation reaction [19]. Aguado et al. prepared
SIM-1 (zinc carboxylimidazolate) films by direct in situ synthesis on
alumina bead for ketone transfer hydrogenation [20]. The same
group reported the fabrication of SIM-1 and SIM-2 films on various
supports such as alumina tubes, fibers, and anodic alumina disks
for Knoevenagel condensation reaction [21]. More recently, HKUST-
1/Au nanoparticle composite membrane/thin film was applied for
both gas and liquid phase catalytic reactions [22]. The sonochem-
ical method was proposed earlier for the facile synthesis of uniform
nano-sized MOF crystals [47,48]. The process promotes rapid and
homogeneous nucleation via the artificially-created cavitation that
involves formation, growth and instantaneous collapse of bubbles
in a liquid medium by ultrasonic waves, which results in a
considerable decrease in both crystal size and crystallization time
compared to those of the conventional solvothermal method
[49,50]. Khanjani et al. reported the uniform growth of MOF-5
crystals coated on a silk support prepared by ultrasound irradia-
tion using a layer-by-layer technique; the crystals were evaluated
for the adsorptive removal of a hazardous anionic dye [51].
In this study, a simple, rapid, and effective sonochemical tech-
nique was developed for the preparation of a high quality IRMOF-3
membrane on a porous Al2O3 support modified with a NH2-BDC
organic linker. The effects of various synthesis parameters on the
IRMOF-3 membrane properties were investigated, and the physi-
cochemical properties of the prepared materials were compared
with those of the IRMOF-3 samples prepared by microwave
heating. To examine the membrane synthesis steps closely, the bare
IRMOF-3 crystals without an Al2O3 support were also synthesized
by conventional solvothermal, microwave, and sonochemical pro-
tocols. The IRMOF-3 particles and membranes were examined for
their adsorption properties for CO2 and as a catalyst for a model
Knoevenagel condensation reaction between benzaldehyde and
ethyl cyanoacetate.
2. Experimental
2.1. Materials
Zinc nitrate hexahydrate (98%, Aldrich), 2-aminoterephthalic
acid (>98%, TCI), N,N-dimethylformamide (99.9%, Aldrich), ethyl-
cyanoacetate (99%, Aldrich), benzaldehyde (>99.5%, Aldrich),
dodecane (99þ%, Aldrich), and ethyl alcohol (99.9%, DUKSAN) were
purchased and used as received.
2.2. Preparation of the IRMOF-3 membranes
2.2.1. Sonochemical synthesis of an IRMOF-3 membrane (S-IRMOF-
3(Mem))
The sonicator used in this study was a VCX500 (SONICS, USA)
model with an adjustable power output (maximum 500 W at
20 kHz). For the preparation of an IRMOF-3 membrane, a pretreated
Al2O3 support (see supporting information for its preparation) was
immersed into a ligand solution containing 1.65 mmol of 2-ami-
noterephthalic acid (NH2-BDC) in 40 ml N,N-dimethylformamide

(DMF), followed by a solvothermal treatment at 120 C for 2 h.
Subsequently, the disc was removed and dried at room tempera-
ture. The secondary synthesis solution was prepared with the
composition of Zn(NO3)2∙6H2O: 0.33 NH2-BDC: 120 DMF in a
custom-made horn type 70 mL Pylex reactor. The Pyrex reactor was
then fitted to a sonicator bar, and the reaction mixture including
the Al2O3 support was subjected to an ultrasonic treatment at
different power levels (250e400 W) for 1 h. After the sonication
treatment, the membrane was recovered, washed three times with
DMF, and kept in chloroform prior to use. The obtained brown
colored Al2O3 disc was designated S-IRMOF-3(Mem). Unsupported
IRMOF-3 particles were also prepared similarly in the absence of an
alumina disc, which were designated as S-IRMOF-3(p) (see
supporting information for its preparation).
2.2.2. Microwave synthesis of an IRMOF-3 membrane (M-IRMOF-
3(Mem))
An IRMOF-3 membrane was also prepared by microwave heat-
ing for comparison. An Al2O3 disc was treated using the same sol-
vothermal process mentioned above and held vertically inside a
35 mL glass tube filled with an IRMOF-3 precursor solution at a the
molar ratio of Zn(NO3)2∙6H2O: 0.33 NH2-BDC: 120 DMF. The tube
was finally sealed with a rubber septum. The alumina support
immersed in the solution was heated by microwave irradiation

(250 W) at 130 C for 4 h. After synthesis, the membrane was
cleaned using the same procedure as described above. A yellow
colored Al2O3 disc obtained was designated M-IRMOF-3(Mem).
Unsupported IRMOF-3 particles were prepared similarly in the
absence of an alumina disc, which were designated as M-IRMOF-
3(p) (see supporting information for its preparation).
2.3. Characterization of IRMOF-3 samples
X-ray powder diffraction (XRD, Rigaku) of the IRMOF-3 samples
was performed using CuKa radiation (l ¼ 1.54 Å) at a 0.5 /min scan
rate. For the membranes, both IRMOF-3 powders were scratched off
from the top layer and those by the crushed membrane in a mortar
 Y.-R. Lee et al. / Microporous and Mesoporous Materials 213 (2015) 161e168
were used for analysis. The N2 adsorption and desorption isotherms
were obtained using a BELsorp (II)-mini (BEL, Japan) at 77 K. Prior to
the sorption measurements, the samples were activated at 383 K
for 12 h in a vacuum. The morphology of the samples was examined
by scanning electron microscopy (SEM, Hitachi S-4300). Energy
dispersive spectroscopy (EDS) was conducted to verify the status of
the Zn dispersion over the Al2O3 support.
2.4. CO2 adsorptionedesorption and recycling run
The CO2 adsorption isotherms of S-IRMOF-3(p) under static
conditions were obtained using a BELsorp(II)-mini at 298 K/1 bar
with the activated powder sample. High pressure CO2 adsorption
isotherms (0e20 bar) at 298 K were obtained using a magnetic
suspension balance (Rubotherm, Germany) with in-situ density
measurements in a closed system. Before measuring the CO2
adsorption capacity, the buoyancy effect was corrected in ultra-
high-purity He (99.999%) and the sample was also activated. The
CO2 adsorption/desorption isotherms were measured by ther-
mogravimetric analysis (TGA, SCINCO thermal gravimeter S-1000)
connected to a flow panel. Initially, the sample was treated at 110  C
to remove moisture using Ar (99.999%) as a purge gas. A sample
weight of ca. 10 mg was loaded into an alumina pan and subjected
to the CO2 adsorption studies. When no weight loss was observed,
the temperature was decreased to the adsorption temperature. The
adsorption run was tested using high purity CO2 (99.999%) at a feed
flow rate of 30 mL/min. After the CO2 adsorption run, the desorp-
tion step was followed using Ar as a purge gas.
2.5. Knoevenagel condensation reaction
IRMOF-3 particles and membranes were tested as a heteroge-
neous catalyst for the Knoevenagel condensation reaction (Scheme
2). In the case of the IRMOF-3 particles, 60 mg of the samples were
placed inside a round bottom flask in a glass reactor in a chem-
istation (PPS-2510, Japan) containing 5 ml of an ethanolic solution
containing 8 mmol of benzaldehyde and 7 mmol of ethyl cyanoa-
cetate, and the mixture was stirred at 333 K for 4 h. The products
were evaluated by gas chromatography (Agilent 7890) equipped
with a flame ionization detector (FID) and a high performance HP-5
capillary column (HP-5 column; 30 m, 0.320 mm, 0.25 mm). In the
case of S-IRMOF-3 and M-IRMOF-3 membranes, the reactions were
carried out under identical conditions except that the amount of
the reaction mixture was reduced to 10% in proportion to the
amount of IRMOF-3 deposited on the Al2O3 support; the S-IRMOF-3
membrane had ca. 6.2 mg of IRMOF-3 crystals on the support,
whereas ca. 3.6 mg was observed on the M-IRMOF-3 membrane
Scheme 1. Preparation steps for the IRMOF-3 membrane on an Al2O3 support via sonochemical (left) and microwave heating (right).
163
(estimated by the weight difference between the bare Al2O3 sup-
port and the IRMOF-3 membranes after synthesis).
A hot filtration experiment was also carried out by separating
the catalyst from the reaction mixture after a 30 min reaction while
maintaining the reaction temperature at 333 K. The filtrate mixture
was then stirred for an additional period of up to 4 h.
3. Results and discussion
3.1. Synthesis of IRMOF-3
Before preparing the IRMOF-3 membranes supported on Al2O3,
the IRMOF-3 samples in particle form were prepared by conven-
tional solvothermal (C-IRMOF-3(p)), microwave heating (M-
IRMOF-3(p)), and sonochemical methods (S-IRMOF-3(p)) to verify
the feasibility of these synthesis schemes for the crystal formation.
As shown in Table 1, the optimal synthesis conditions for M-IRMOF-
3(p) and S-IRMOF-3(p) were found to be within a rather narrow set
of conditions. The optimal textural property of M-IRMOF-3(p) (BET
surface area; 2610 m2 g1, 1.14 cm3 g1 pore volume) was obtained

at 105 C with 150 W for 105 min; a further increase in power to
200 W provided no improvement in the product textural quality
under microwave synthesis conditions. On the other hand, S-
IRMOF-3(p) with an optimal textural property (BET surface area of

2350 m2 g1, 1.01 cm3 g1 pore volume) was obtained at 132 C with
300 W after 90 min under sonochemical synthesis conditions.
Fig. S1(A) shows the XRD patterns of the samples, which are
consistent with the standard IRMOF-3 crystal diffraction pattern
reported elsewhere [39]. Fig. S1(B) shows the corresponding SEM
images of the samples. All the IRMOF-3 samples showed a cubic
structure but the particle size differed considerably depending on
the synthesis method; C-IRMOF-3(p) was ca. 100 mm, which was
significantly larger than that of M-IRMOF-3(p) (ca. 12 mm) or S-
IRMOF-3(p) (ca. 6 mm). The N2 adsorptionedesorption isotherms of
all the samples exhibited type-I isotherms at 77 K with no hyster-
esis (see Fig. S2). From these results, it was clearly established that
IRMOF-3 crystallization can be achieved by both microwave and
sonochemical treatments.
Scheme 1 shows the fabrication steps for the IRMOF-3 mem-
branes supported on Al2O3 discs. The Al2O3 support of IRMOF-3
membranes underwent thermal seeding, as proposed by McCar-
thy et al. [35], followed by either a sonochemical or microwave-
assisted solvothermal synthesis reaction. First, the surface of the
porous Al2O3 support was modified with NH2-BDC acting as a seed

layer under mild solvothermal conditions (120 C for 2 h), which
was then dried at room temperature to form a covalent bond be-
tween the organic linkers and the support. The seeded support was
164 Y.-R. Lee et al. / Microporous and Mesoporous Materials 213 (2015) 161e168

Scheme 2. Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate.

Table 1
Textural properties of IRMOF-3 particles synthesized under different synthesis conditions.

Synthesis method Conditions SBET (m2/g)a Vpore (cm3/g)b Sext (m2/g)c

Temperature (oC) Power (W) Time (min)

Solvothermal 105 e 24 h 2540 1.08 10.5

Microwave 105 100 90 800 0.36 35.1
105 820 0.37 36.3
120 1090 0.47 36.8
150 90 2130 0.98 39.5
105 2610 1.14 41.3
120 2030 0.95 38.7
200 90 1640 0.68 37.8
105 1670 0.69 37.4
120 1140 0.49 35.9
Sonochemical 132 300 30 350 0.20 e
60 1160 0.50 45.3
90 2350 1.01 49.8
120 1270 0.53 46.1
134 400 30 780 0.35 43.0
60 1010 0.45 44.1
90 1340 0.54 44.9
120 910 0.43 45.5
a
SBET ¼ specific surface area calculated using the BET method.
b
Vpore ¼ total pore volume.
c
Sext ¼ external surface area calculated using the t-plot method.

then placed in the respective reactor containing a precursor solu-

tion of IRMOF-3, and secondary growth occurred by further treat-
ment with either microwave energy or ultrasonic waves.

3.1.1. Membrane characterization

As shown in Fig. 1, the XRD patterns of both S-IRMOF-3 (Mem)
and M-IRMOF-3 (Mem) (Fig. 1d and e) contained peaks for both
IRMOF-3 particles and the alumina support (Fig. 1c and a), and it
could be concluded that the IRMOF-3 layers were formed on the
Al2O3 support in both cases. Fig. 2b and c shows the top and cross-
section microstructure of S-IRMOF-3(Mem), respectively. IRMOF-3
cubic crystals fully covering the porous Al2O3 support surface can
be seen; the crystal size was approximately 2.5 mm, forming a
tightly packed and defect-free continuous membrane (See Fig. 2b
and the insert). As shown in Fig. 2c, the S-IRMOF-3 membrane layer
was well grown and tightly bonded to the support, and the thick-
ness of the membrane was approximately 55.4 mm, which is much
thicker than that of the previously reported typical MOF mem-
branes [26,52e54]. IRMOF-3 crystals fully covered the Al2O3 disc
and EDS analysis further confirmed a soft transition of Zn and Al
signals between the S-IRMOF-3 membrane and alumina support
(Fig. 2d).
For M-IRMOF-3(Mem), the synthesis attempted under the
optimal conditions for M-IRMOF-3(p) (from 100 to 200 W, for 2 h)
did not form IRMOF-3 particles on the Al2O3 support. Only
approximately 60% of the Al2O3 surface was covered by IRMOF-3
particles when the power level was increased further from 200 to
250 W. This is in agreement with Yoo and Jeong [55], who reported
the power used to prepare a uniform IRMOF-1 film (also known as
MOF-5) under microwave irradiation in their study to be ca. 500 W. Fig. 1. XRD patterns of (a) Al2O3 support, (b) simulated IRMOF-3, (c) S-IRMOF-3(p),
Compared to the S-IRMOF-3(Mem) prepared with a 1 h ultrasonic (d) S-IRMOF-3(Mem), and (e) M-IRMOF-3(Mem).
 Y.-R. Lee et al. / Microporous and Mesoporous Materials 213 (2015) 161e168
Fig. 2. SEM images of (a) porous Al2O3 support, (b) top view, and (c) cross-sectional view of S- IRMOF-3(Mem); (d) EDS mapping of the S-IRMOF-3(Mem) (red: Zn, green: Al). S-
IRMOF-3(Mem) prepared at 400 W power for 1 h. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
treatment at 250 W, M-IRMOF-3(Mem) prepared under compara-
ble power level was comprised of larger crystals (~10 mm) and
showed relatively poor compactness, even though the synthesis
time was increased to 4 h (Fig. 3 (a) and (b)). The difference in the
surface coverage of M-IRMOF-3(Mem) and S-IRMOF-3(Mem)
products could also be seen by the photographic images of the
corresponding membrane samples (Fig. 4 (b) and (c)). Therefore,
sonochemical synthesis could produce a better IRMOF-3 supported
membrane with smaller crystals than microwave heating. Haque
et al. [56] also reported that an ultrasonic irradiation results in a
faster crystallization rate (both nucleation and crystal growth) in
the preparation of MIL-53(Fe) crystals than microwaves. A further
increase in the sonication power level from 250 to 300 W induced a
higher surface population of MOF crystals but still did not achieve
complete surface coverage, and when the power level was
increased further to 400 W, a more densely-packed S-IRMOF-3
(Mem) was finally obtained (Fig. 3 (d)). A higher energy level was
found to be necessary to produce an IRMOF-3 membrane than
IRMOF-3 particles by a sonochemical method. The IRMOF-3 parti-
cles in both cases were synthesized under significantly milder
conditions than those of the membranes, which indicates that extra
energy is needed for the particles to bond with the Al2O3 support.
3.2. CO2 adsorption studies
The textural quality of the S-IRMOF-3(p) was checked by per-
forming CO2 adsorption studies under low and high pressure con-
ditions. As shown in Fig. S3 (a), the CO2 adsorption capacity of the S-
IRMOF-3(p) obtained was ca. 54 mg/g at 298 K/1 bar with a CO2/N2
selectivity of 18 based on the amount of each gas adsorbed at 1 bar.
High-pressure adsorption was carried out using ultra high purity
165
CO2 in the pressure range, 0e20 bar at 298 K, and S-IRMOF-3(p)
captured ca. 732 mg/g under 298 K/20 bar conditions. Cyclic CO2
adsorptionedesorption showed the adsorption capacity was
maintained throughout the 10 separate capture and release cycles
(see Fig. S3 (b)). From this excellent gas adsorption performance
data, S-IRMOF-3(Mem) is expected to function effectively as a gas
separating unit.
3.3. Catalytic activity for the Knoevenagel condensation reaction
The prepared IRMOF-3 membranes were evaluated as a recy-
clable base catalyst for the Knoevenagel condensation reaction of
benzaldehyde with ethyl cyanoacetate at 333 K. For the IRMOF-3
particles, S-IRMOF-3(p) and M-IRMOF-3(p) exhibited higher cata-
lytic activity (68% and 67% conversion, respectively) than C-IRMOF-
3 (55% conversion) under the same reaction conditions in 0.5 h (see
Table S1). This was attributed to the smaller particle size of S-
IRMOF-3 (6 mm) and M-IRMOF-3 (12 mm) than that of C-IRMOF-3
(100 mm) (see Fig. S1 (B)); the larger external surface areas of 10.5,
41.3 and 49.8 m2 g1 (see Table 1) of the corresponding samples
resulted in the higher conversions in the diffusion-controlled re-
action [47,57]. No further reaction proceeded after filtering-off the
IRMOF-3(p) in a hot filtering experiment, which confirmed the
heterogeneous nature of the catalytic reaction.
In the case of the membranes, as shown in Fig. 5, S-IRMOF-
3(Mem) (64% at 0.5 h and 87% after 4 h) exhibited much higher
catalytic activity than that of M-IRMOF-3 (Mem) (24% at 0.5 h and
46% after 4 h), because M-IRMOF-3(Mem) failed to form a dense
IRMOF-3 layer on the Al2O3 support and consequently a smaller
number of IRMOF-3 particles were deposited. Small IRMOF-3 par-
ticles covering densely over the surface of the support in S-IRMOF-
Fig. 3. SEM images of the Al2O3 disc support (top view): (a) M-IRMOF-3 (Mem); 250 W for 4 h, (b) S-IRMOF-3 (Mem); 250 W for 1 h, (c) S-IRMOF-3 (Mem); 300 W for 1 h, and (d) S-
IRMOF-3 (Mem); 400 W for 1 h.

Fig. 4. Photographic images of (a) Al2O3 support, (b) M-IRMOF-3(Mem); 250 W for 4 h, (c) S-IRMOF-3(Mem); 250 W for 1 h, and (d) S-IRMOF-3(Mem); 400 W for 1 h on Al2O3 disc
supports.

Fig. 5. Knoevenagel condensation reaction of the IRMOF-3 membranes prepared using
two different methods.
Fig. 6. Recycling tests of the S-IRMOF-3 particles (black) and S-IRMOF-3 membrane
(gray) in Knoevenagel condensation reaction at 333 K. Reaction conditions: 8 mmol of
benzaldehyde, 7 mmol of ethyl cyanoacetate and 60 mg of catalyst in 5 ml of ethanol as
a solvent for S-IRMOF-3 (p), and the substrates were reduced by 10% for S-IRMOF-3
(Mem).
 Y.-R. Lee et al. / Microporous and Mesoporous Materials 213 (2015) 161e168
Fig. 7. XRD patterns of S-IRMOF-3 (Mem) (a) before and (b) after the recycling tests in
Knoevenagel condensation reaction. The reflections marked by * correspond to the
Al2O3 support.
3(Mem) would be expected to be more effective for catalytic re-
actions involving large organic substrates.
S-IRMOF-3(Mem) could be recovered easily and reused in the
liquid phase reaction compared to the solid catalyst particles.
However, a slight decrease in catalytic activity (from 87 % to 77 %)
was detected over S-IRMOF-3(Mem) after the 3rd recycle run due
to the detachment of some weakly-bonded S-IRMOF-3 particles
from the support (Fig. 6). A similar decrease in conversion was also
detected over S-IRMOF-3(p) due to the minor particle loss during
the washing/activation steps before conducting the recycle runs. On
the other hand, conversion with S-IRMOF-3(Mem) was maintained
after the third recycle run. The stability of the IRMOF-3 crystal
structure was checked after the 5th recycle by XRD, which showed
no obvious changes in the characteristic peak positions (Fig. 7),
even though the intensity of the XRD peaks decreased due to guest
inclusion inside the IRMOF-3 [58,59]. This is in contrast to the case
of the ZIF-8 membrane, which suffered complete destruction after
the 4th recycle run in the Knoevenagel condensation reaction [19].
In addition, the S-IRMOF-3(Mem) was also tested for its stability by
conducting a hot filtration experiment, which again confirmed that
no further reaction proceeded in the filtrate after filtering-off the
membrane catalyst.
4. Conclusions
The IRMOF-3 particles and membranes supported on an Al2O3
disc were prepared successfully via a sonochemical method, and
the properties of the products were compared with those produced
by microwave heating. The sonochemical method was found to be
quite efficient in preparing highly-dense IRMOF-3 membranes in a
short time, and superior in terms of the physicochemical properties
to those prepared by microwave under similar power conditions.
The products obtained were examined for their CO2 adsorption
properties, and also applied as a catalyst for the Knoevenagel
condensation reaction between benzaldehyde and ethyl cyanoa-
cetate. The IRMOF-3 particle/membrane prepared by the sono-
chemical method has excellent textural properties, which resulted
in good adsorption performance as well as a stable and recyclable
catalyst that enabled easy catalyst separation.
167
Acknowledgment
This study was supported by the Global Frontier program of the
National Research Foundation of Korea (2013M3A6B1078877).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.micromeso.2015.04.021.
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