Chemical Engineering Journal 271 (2015) 276–280

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Chemical Engineering Journal

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

Short communication

ZIF-8: A comparison of synthesis methods

Yu-Ri Lee, Min-Seok Jang, Hye-Young Cho, Hee-Jin Kwon, Sangho Kim, Wha-Seung Ahn ⇑
Department of Chemistry and Chemical Engineering, Inha University, Incheon 402-751, Republic of Korea

h i g h l i g h t s

 ZIF-8 was prepared by 7 different synthesis methods.

 Physicochemical properties of the samples were compared.
 ZIF-8 with smaller particle size showed better activity in condensation reaction.
 Fe3O4 nanoparticles entrapped in ZIF-8 enabled effective separation in liquid.

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

Article history: A zeolitic imidazolate framework, ZIF-8, was prepared via a variety of synthesis routes: solvothermal,
Received 23 December 2014 microwave-assisted, sonochemical, mechanochemical, dry-gel, and microfluidic methods. Their textural
Received in revised form 16 February 2015 properties and morphology were examined by surface area measurements and scanning electron micro-
Accepted 25 February 2015
scopy, and compared with those of commercial ZIF-8. Although the BET surface areas fell within a range
Available online 9 March 2015
of 1250–1600 m2 g1, the particle size of the samples prepared by dry-gel and sonochemical routes were
significantly smaller than the others, which led to superior performance in the Knoevenagel condensation
Keywords:
reaction. The effective incorporation of magnetic Fe3O4 nanoparticles into the ZIF-8 structure for easy
ZIF-8
Dry-gel
particle separation in the liquid phase was feasible using solvothermal, dry-gel and mechanochemical
Sonochemical synthesis synthesis methods. Dry-gel and mechanochemical synthesis produced a higher ZIF-8 yield.
Knoevenagel condensation Ó 2015 Elsevier B.V. All rights reserved.
Fe3O4 nanoparticles

1. Introduction emphasis has been placed upon size-controlled ZIF-8 synthesis

Zeolitic imidazolate frameworks (ZIFs) are porous hybrid mate-
rials with structures analogous to zeolites that are built upon 4-
connected nets of tetrahedral units, wherein metal ions, such as
Zn2+ or Co2+, are linked through N atoms in ditopic imidazolate
anions [1,2]. ZIFs have emerged as a potential material for H2 stor-
age [3], CO2 adsorption [4], alkane/alkene separation [5], and het-
erogeneous catalysis [6] owing to their structural flexibility,
which allows rational design of the pore sizes and surface func-
tionality, and their relatively high chemical and thermal stability
[7]. Among the ZIFs, ZIF-8 (Zn(mIM)2, mIM = 2-methylimidazolate)
exhibits a sod topology comprised of 1.16 nm cages connected
through six-membered windows, 0.34 nm in size (Fig. 1), and is
currently the most widely investigated ZIF material for a range of
applications [8–10].
ZIF-8 can be prepared in high purity through several different
synthesis routes [1,2,11–16]. Synthesis in an environmental-
friendly manner under facile conditions is desirable, and particular
[17–19] and the easy separation of nano- to submicron-sized ZIF-
8 by incorporating a magnetic Fe3O4 guest into the ZIF-8 particle
[11,16,20].
In the present study, ZIF-8 was synthesized using 7 different syn-
thesis methods (conventional solvothermal in different organic sol-
vents of dimethylformamide (DMF) and methanol (MeOH);
microwave-assisted; sonochemical; mechanochemical; dry-gel;
microfluidic), and their physicochemical properties were compared
with those of commercial ZIF-8 prepared using an electrochemical
method. The differences in the physicochemical properties among
the ZIF-8 samples were manifested in the probe catalytic reaction
of the Knoevenagel condensation of benzaldehyde with malononi-
trile. The feasibility of incorporating Fe3O4 nanoparticles into ZIF-8
produced via the different synthesis routes was also examined.
2. Experimental
2.1. Synthesis

⇑ Corresponding author. Tel.: +82 32 860 7466; fax: +82 32 872 0959. The detailed synthesis steps of ZIF-8 via solvothermal (in DMF
E-mail address: whasahn@inha.ac.kr (W.-S. Ahn). and MeOH), microwave-assisted, sonochemical, mechanochemical,

http://dx.doi.org/10.1016/j.cej.2015.02.094
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
 Y.-R. Lee et al. / Chemical Engineering Journal 271 (2015) 276–280
Zn2+
+ porous materials under solvothermal/hydrothermal conditions
N N
mIM ZIF-8 (sod)
Fig. 1. Crystal structure of ZIF-8: Zn (polyhedral), N (sphere), and C (line) [1].
dry-gel, and microfluidic routes (Fig. S1) are reported in Supporting
information.
2.2. Characterization
The X-ray diffraction (XRD) patterns of the ZIF-8 samples were
obtained on a Rigaku diffractometer using Cu Ka (k = 1.54 Å) radia-
tion. The N2 adsorption and desorption isotherms were obtained
on an ASAP-2020 (Micromeritics, USA) sorptometer at a liquid
nitrogen temperature. Prior to the sorption measurements, the
ZIF-8 samples were activated at 573 K for 5 h in a vacuum. The
specific surface areas of the samples were calculated using the
Brunauer, Emmett and Teller (BET) method. The morphological
features were examined by scanning electron microscopy (SEM,
Hitach S-4200).
2.3. Knoevenagel condensation reaction
ZIF-8 samples were pre-treated in a vacuum at 383 K for 6 h
before the reaction. Benzaldehyde (1.9 mmol), malononitrile
(3.8 mmol), and the ZIF-8 catalyst (20 mg) were added to 5 mL of
toluene (Sigma–Aldrich) as a solvent, and the mixture was stirred
at room temperature for 4 h. After the reaction, the resulting cata-
lyst was separated by filtration, and the products were analyzed by
gas chromatography (Agilent 7890) equipped with a flame ioniza-
tion detector (FID) and a high performance HP-5 capillary column
(30 m, 0.320 mm, 0.25 lm).
3. Results and discussion
3.1. Various synthesis of ZIF-8
The XRD patterns for all the ZIF-8 samples [(a)–(g)] synthe-
sized in this work and that of commercial ZIF-8(h) (Fig. S2) were
all in good agreement with the simulated pattern of the ZIF-8
structure. All the ZIF-8 samples showed type-I N2 adsorption iso-
therms at 77 K with no hysteresis (Fig. S3). Table 1 lists the sum-
mary of synthesis conditions and textural properties (BET surface
area, total pore volume, and external surface area) and Table 2
shows the SEM images and particle size of the synthesized and
commercial ZIF-8. The standard solvothermal synthesis in DMF
produced ZIF-8(a) with a BET surface area of 1370 m2 g1 and
uniform crystal facets, 150–200 lm in size. The product yield
based on the limiting reactant of mIM was ca. 60%.
Solvothermal synthesis in MeOH was conducted using less
energy at room temperature with improved textural properties
and a smaller particle size, but the product yield was low (ca.
43%). The synthesis of ZIF-8 in methanol at room temperature
was carried out without any auxiliary stabilizing agents, since
the synthesis reaction is promoted by molecular interactions
between the reagents and the solvent with hydrogen bond
277
donation ability, which facilitates the ligand deprotonation and
its coordination with Zn2+ [2,21,22].
Microwave heating was applied to the rapid synthesis of nano-
[23]. The microwave-assisted synthesis of ZIF-8 has been reported
but the product showed a rather low BET surface area (646 m2 g1)
[12]. This study examined ZIF-8(c) synthesis via a microwave-as-
sisted method under a variety of synthesis conditions for the
improvement in textural properties. The synthesis was initially
performed under the conditions used by Park et al. (140 °C for
3 h), and the optimal textural properties (BET surface area of
1250 m2 g1, 0.53 cm3 g1 for pore volume) were obtained at
120 °C with 80 W for 3 h. As shown in Table S1, the optimal set
of synthesis conditions was located to be within a narrow region.
Sonochemical synthesis introduces high-energy ultrasound to the
reaction mixture, which leads to rapid and homogeneous nucle-
ation, resulting in a decrease in crystallization time and smaller/
uniform particles [13]. ZIF-8(d) crystals were obtained but only
with an aid of a deprotonating agent, triethylamine. Both micro-
wave-assisted and sonochemical procedures produced ZIF-8 in
62% yield.
The mechanochemical synthesis of ZIF-8 was carried out with
Zn oxide at room temperature in a short synthesis time [14,24].
ZIF-8(e) was synthesized via mechanochemical synthesis using
an ammonium salt as a deprotonating agent without the use of a
solvent. The ZIF-8(e) obtained had an excellent BET surface area
(1256 m2 g1) and pore volume (0.64 cm3 g1) with a product yield
of ca. 82% based on the limiting reactant of Zn oxide.
In dry-gel synthesis of ZIF-8 [25], a eutectic mixture forms
upon heating a mixture with the proper ratio of Zn(OAc)2 and
mIM without the aid of an organic solvent [15]. As shown in
Table 1, ZIF-8(f) with excellent textural properties (1306 m2 g1
surface area and 0.52 cm3 g1 for pore volume) was obtained
with a product yield of ca. 84% based on the limiting reactant
of Zn salt. Microfluidic systems have some notable advantages
over a conventional reactor in promoting reactant mixing and
heat/mass transfer [16,26]. Comparable textural properties to
other samples were obtained in ZIF-8(g), as shown in Table 1,
in ca. 58% yield.
All ZIF-8 samples showed well-defined hexagonal morphologies
except for ZIF-8(e) because of the friction forces applied during its
synthesis. As shown in Table 2, the particle size differed con-
siderably depending on the synthesis method; ZIF-8(a) had the lar-
gest particle size (ca. 150–200 lm) and ZIF-8(d) and (f) had the
smallest (ca. 300–500 nm). The significant differences in particle
size were also confirmed by external surface area measurements
of the samples, i.e., the external surface area per unit mass
increased with decreasing particle size.
3.2. Knoevenagel condensation reaction with ZIF-8 as a catalyst
As shown in Table 3, the particle size of ZIF-8 showed a strong
influence on conversion in the Knoevenagel condensation reac-
tion. Smaller ZIF-8 particles with a larger external surface area
exhibited enhanced catalytic activities. Owing to the smaller dif-
fusion resistance and larger external surface area offered by
smaller particles, the ZIF-8 synthesized via dry-gel, sonochemical,
solvothermal by MeOH, mechanochemical, microwave-assisted,
and micro-fluidic synthesis method showed systematically higher
catalytic activities (98%, 96%, 91%, 89%, 87%, 84% conversion for
ZIF-8(f), (d), (b), (e), (c), (g), respectively) than the ZIF-8(a) pre-
pared by the solvothermal method in DMF (57% conversion) after
a 4 h reaction. The commercial ZIF-8(h) (23% at 0.5 h and 67% at
4 h) showed lower catalytic activity, despite the high surface
area, because of the inhomogeneous distribution of particle sizes
(see Tables 1 and 2).
278 Y.-R. Lee et al. / Chemical Engineering Journal 271 (2015) 276–280

Table 1
Textural properties of the ZIF-8 samples prepared using different synthesis conditions.

Synthesis method Zn2+ (mmol) MeIMa (mmol) Synthesis condition SBET (m2/g)b Vpore (cm3/g)c Sext (m2/g)d
Solvent Conditions
Solvothermal (DMFe) 2 2 DMF 140 °C, 24 h 1370 0.51 6.7
Solvothermal (MeOHf) 2 2 MeOH 25 °C, 24 h 1549 0.59 32.9
Microwave 2 2 DMF 120 °C, 3 h, 80 W 1250 0.53 22.1
Sonochemical 2 2 DMF (add TEAh) 1 h, 300 W 1249 0.71 53.7
Mechanochemical 0.79 1.56 No solvent (add NH4NO3) 45 min, 25 Hz 1256 0.64 31.8
DGCg 0.5 5 H2O 120 °C, 24 h 1306 0.52 54.0
Microfluidic 2 2 DMF 150 °C, 0.5 mL h1 1435 0.42 18.4
Commercial product – – – – 1580 0.64 17.8
a
MeIM = 2-methylimidazole.
b
SBET = specific surface area calculated by the BET method.
c
Vpore = total pore volume.
d
Sext = external surface area calculated by the t-plot method.
e
DMF = dimethylformamide.
f
MeOH = methanol.
g
DGC = dry-gel conversion.
h
TEA = trimethylamine.

Table 2
SEM images and particle size of the ZIF-8 samples prepared using different synthesis methods.

Solvothermal Solvothermal Microwave - Sono- Mechano Microfluidic Commercial

a b DGCc (f)
(DMF ) (a) (MeOH ) (b) assisted (c) chemical (d) Chemical (e) synthesis (g) Product (h)

500 μm 20 μm 20 μm 5 μm 20 μm 20 μm 20 μm 20 μm
SEM
image

100 μm 10 μm 10 μm 500 nm 10 μm 500 nm 10 μm 10 μm

Particle
150~200 μm 3~5 μm 5~10 μm 300~500 nm 3~15 μm 300~400 nm 5~15 μm 0.5~20 μm
size

a
DMF = dimethylformamide.
b
MeOH = methanol.
c
DGC = dry-gel conversion.

Table 3
Catalytic performances of Knoevenagel condensation reaction over ZIF-8 catalysts.a
and S5) of the ZIF-8 samples prepared using solvothermal (in
Catalysts Conversion (%) MeOH), dry-gel, and mechanochemical methods all confirmed
0.5 h 1h 2h 4h the successful incorporation of Fe3O4 nanoparticles. Although the
ZIF-8 (a) 19 36 54 57 microfluidic [16] or solvothermal [11,20] incorporation of Fe3O4
ZIF-8 (b) 55 68 80 91 nanoparticles in ZIF-8 was demonstrated earlier, guest incor-
ZIF-8 (c) 51 65 75 87 poration via dry-gel and mechanochemical routes have not been
ZIF-8 (d) 60 76 88 96
reported previously.
ZIF-8 (e) 53 67 79 89
ZIF-8 (f) 64 81 92 98 Fe3O4 nanoparticles (8–10 nm) cannot occupy the cavities of
0
ZIF-8 (g) 51 63 70 84 ZIF-8 considering the small window (3.4 A
Å) and cavity
ZIF-8 (h) 23 38 53 67 0

a
Reaction conditions: 1.9 mmol of benzaldehyde, 3.8 mmol of malononitrile,
20 mg of catalyst at room temperature.
3.3. Fe3O4 incorporation into ZIF-8
For the easy separation of micro-sized particles, as in ZIF-8, the
encapsulation of even smaller magnetic nanoparticles is employed
[27]. In the present study, Fe3O4 nanoparticles, 8–10 nm in size,
were synthesized using the procedure reported by Park et al. [28]
(see Fig. S4), and were incorporated inside the sub-micron sized
ZIF-8 samples according to the procedure reported by Lu et al.
[11] (see Supporting information for details). TEM images (Figs. 2
A) size of the material. Instead, they were entrapped dur-
(11.6 Å
ing the crystal growth of ZIF-8 to full size of 300 nm to 200 lm
depending on the synthesis method employed. The PVP adsorbed
on Fe3O4 nanoparticle surfaces provides enhanced affinity to ZIF-
8 through weak coordination interactions, and perhaps also
through hydrophobic interactions between apolar groups of PVP
and organic linkers [11]. In the steam-assisted dry-gel synthesis,
once the hydrous composites are formed by the steam as
explained before, the ZIF-8 nanoparticles are grown over the
finely distributed Fe3O4 particles without stirring, since the syn-
thesis reaction is taking place in close proximity within the
homogeneously mixed substrates and Fe3O4 nanoparticles in
solid phase. Commercial Fe3O4 nanoparticles (Sigma–Aldrich,
 Y.-R. Lee et al. / Chemical Engineering Journal 271 (2015) 276–280
Fig. 2. (a) Knoevenagel condensation reaction, (b) TEM image of Fe3O4@ZIF-8 (MeOH), (c) photographs illustrating the convenient separation of Fe3O4@ZIF-8 (MeOH) by a
magnet, and (d) XRD patterns of the Fe3O4@ZIF-8 (MeOH) before and after catalyst reuses.
20 nm) were found to be unsuitable for incorporation due to the
inhomogeneous distribution of nanoparticles in Fe3O4@ZIF-8.
Microwave-assisted and sonochemical methods could not be
used for this purpose because of the sedimentation of Fe3O4
nanoparticles during ZIF-8 synthesis. ZIF-8 crystals obtained in
these two methods were significantly smaller in size than others,
which made it relatively difficult to entrap Fe3O4 nanoparticles
within the ZIF-8 crystals in liquid phase. During the sonication,
the Fe3O4 nanoparticles tend to agglomerate, and the sedi-
mentation rate of the growing Fe3O4 nanoparticles seems to be
faster than that of the ZIF-8 crystallization. The Fe3O4 particles
tend to exist in separated phase from ZIF-8 during the synthesis,
and consequently, the incorporation of the Fe3O4 nanoparticles in
ZIF-8 did not occur. The solid product obtained after synthesis
showed dark Fe3O4 nanoparticle layer at the bottom covered with
white ZIF-8 layer at the top.
Filtration experiments during the Knoevenagel reaction were
carried out by removing ZIF-8 powders from the reaction mix-
ture after a 1 h reaction, and the filtrate solution was stirred fur-
ther for an additional duration of up to 3 h at 298 K. Fig. 2
shows that no reaction took place after ZIF-8 removal, which
suggests that the reaction was catalyzed by ZIF-8 and was truly
heterogeneous in nature. Fe3O4@ZIF-8 enabled the easy sep-
aration of ZIF-8 particles by applying a magnetic field, and
retained almost the same conversion profiles as the Fe3O4-free
ZIF-8. The XRD patterns of the fresh and reused Fe3O4@ZIF-8
were practically unchanged.
4. Conclusions
ZIF-8 was prepared using several methods: solvothermal (DMF,
MeOH), microwave-assisted, sonochemical, mechanochemical,
dry-gel, and microfluidic method. Few differences in textural prop-
erties were detected, but the dry-gel and sonochemical techniques
produced significantly smaller particles, which resulted in faster
reaction rates in the Knoevenagel condensation reaction of ben-
zaldehyde with malononitrile. The encapsulation of Fe3O4 nano-
particles within ZIF-8 was feasible using solvothermal as well as
dry-gel conversion and mechanochemical methods, which enabled
the easy separation of ZIF-8 nanoparticles in the liquid phase.
Solvent free dry-gel and mechanochemical synthesis also produced
higher solid product yields than the others.
279
Acknowledgement
This study was supported by a National Research Foundation of
Korea (NRF) grant funded by the Korean Government (MEST) (No.
2013005862).
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.cej.2015.02.094.
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