CHEMPLUSCHEM

COMMUNICATIONS
DOI: 10.1002/cplu.201300193

Synthesis of Zeolitic Imidazolate Framework-7 in a Water/

Ethanol Mixture and Its Ethanol-Induced Reversible Phase
Transition
Ming He,[a, b] Jianfeng Yao,*[b] Lunxi Li,[b] Kun Wang,[b] Fanyan Chen,[b] and Huanting Wang*[b]
Soft porous crystals have emerged as an intriguing class of
hybrid nanoporous crystalline materials as they exhibit reversible dynamic frameworks that are able to respond to external
stimuli such as light, electric fields, or the presence of particular species.[1] Such structural changes in soft porous crystals are
often called gate opening and breathing, which are characterized by a large hysteresis loop between the adsorption and
desorption curves.[1a, 2] This characteristic is very attractive for
designing the new generation of adsorbents and sensors.[2] In
particular, metal-organic frameworks (MOFs) have found many
potential applications such as separation and catalysis. Unlike
zeolites with relatively rigid inorganic frameworks, MOF materials display an inherent structural flexibility because of their
weaker bonds, ranging from van der Waals interactions to coordination bonds.[1b] The MIL-53 (M = Cr, Al, Fe) family is a typical example having breathing characteristic, and exhibits an
abrupt phase transition upon water and CO2 adsorption resulting in an about 38 % expansion of the unit cell.[3]
Zeolitic imidazolate frameworks (ZIFs) are a subclass of
MOFs and display exceptional thermal stability.[4] Recent studies have shown that the sodalite unit cell of ZIF-8 can shrink or
expand under pressure by the rotation of the imidazolate linkers, exhibiting a gate-opening phenomenon.[5] ZIF-7 also
demonstrated gate-opening effects in the selective adsorption
of C2 and C3 alkanes over alkenes.[6] Aguado et al. found that
ZIF-7 exhibited a breathing effect on CO2 adsorption and desorption, and the ZIF-7 framework could be reversibly transformed between narrow pore (np) and large pore (lp) phase
upon variation of CO2 partial pressure and temperature.[7] This
extraordinary property makes ZIF-7 an excellent candidate for
CO2 separation and capture applications.[8]
ZIF-7 (Zn(bim)2) has a sodalite topology with a crystallographic six-membered-ring pore opening, which was first synthesized by Chen and co-workers using 2,2-bipyridine as the
structure-directing agent.[9] Yaghi and co-workers discovered
a series of ZIFs by high throughput screening,[4c] where ZIF-7
[a] Dr. M. He
College of Science
Nanjing Forestry University
Jiangsu 210037 (P. R. China)
[b] Dr. M. He, Dr. J. Yao, L. Li, Dr. K. Wang, F. Chen, Prof. H. Wang
Department of Chemical Engineering
Monash University
Clayton, VIC 3800 (Australia)
E-mail: jianfeng.yao@monash.edu
huanting.wang@monash.edu
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cplu.201300193.

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

was prepared in N,N-dimethylformamide (DMF) using a solvothermal synthesis method at 130 8C for 48 hours.[4c] Since then,
a great deal of effort has been made to synthesize ZIF-7 for
various applications. For example, Li et al. synthesized ZIF-7
membranes by microwave heating in DMF solvent containing
excess organic linkers.[8a, 10] Seoane et al. reported a sonocrystallization of ZIF-7 in a Zn/organic linker ratio of 1:5 using N,N-diethylformamide as solvent in shorter times (69 h) at 45
60 8C.[11] However, ZIF-7 prepared from such above-mentioned
approaches contains guest molecules in their cavities. To
remove guest molecules such as DMF from the pores of ZIF-7,
samples should be exchanged with methanol for several
days,[6a] treated at a high temperature,[7] or under an on-stream
activation process.[8a] As amide-type organic solvents are toxic
and expensive, and might cause environmental problems, the
preparation of ZIF-7 in other low- or non-toxic solvents still remains a challenge.
Herein, we report a room-temperature synthesis of ZIF-7
with the stoichiometric metal and ligand molar ratio of 1:2 in
water/ethanol solution (water/ethanol molar ratio of 1:6.8) in
the presence of ammonium hydroxide. Ammonium hydroxide
was used in this synthesis because it dissociates to NH4 + and
OH in water and then can effectively deprotonate organic ligands for coordination reactions.[9, 12] By addition of ammonium
hydroxide solution, ZIF-8 was successfully prepared from aqueous solutions of stoichiometric metal and ligand precursor.[13]
The XRD pattern of the as-synthesized product shown in Figure 1 a matches well with the simulated SOD-type ZIF-7 structure (lp-phase).[10] XRD results show that the as-synthesized
ZIF-7 structure (lp-phase)[7] is not thermally stable. A significant
phase transition occurred when the as-synthesized ZIF-7
sample was treated in open air at elevated temperature for
2 hours. At 50 8C, a small part of ZIF-7 lp-phase transformed
into the np-phase structure[7] with characteristic diffraction
peaks at 8.48 and 9.38 resulting from release of the guest molecules (i.e. ethanol). As XRD peaks of ZIF-7 np-phase right shifted, the pore size should become smaller. Different from ZIF-7
lp-phase constructed by [Zn(bim)4]2 building blocks containing guest molecules, ZIF-7 np-phase should be formed as
a result of distortion of apertures resulting from the removal of
guest molecules. With the increase of temperature to 200 8C,
the characteristic peaks of ZIF-7 lp-phase disappeared, indicating the guest molecules were totally released. The sample
could maintain ZIF-7 np-phase up to 350 8C. However, the
characteristic peaks of ZIF-7 np-phase were not very strong,
suggesting the low-ordered crystal structure. When the ther-

ChemPlusChem 2013, 78, 1222 1225

1222

CHEMPLUSCHEM
COMMUNICATIONS

www.chempluschem.org

Figure 2. CO2 adsorption/desorption isotherms of as-synthesized ZIF-7 and

ZIF-7 thermally treated at 200 8C for 2 h.

Figure 1. XRD patterns (a) of the as-synthesized ZIF-7 and the sample thermally treated in open air at 50400 8C for 2 h. SEM image (b) of the as-synthesized ZIF-7.

mal treatment temperature reached 400 8C, the XRD pattern

shows that ZIF-7 was finally converted into ZnO.
The SEM image of the as-synthesized ZIF-7 (Figure 1 b)
shows uniform micrometer-sized spherical crystals that are
composed of smaller irregular particles. ZIF-7 particles do not
have well-defined crystal faces compared with those reported
in the literature,[10] and this is probably due to the rapid deprotonation rate of organic ligands in water/ethanol ammonium
hydroxide solution, resulting in crystal growth in all directions
and to yield larger crystals. The yield of ZIF-7 is about 83 %
based on of the amount of zinc, and is a much higher yield
than when prepared in DMF.[4c]
Figure 2 shows CO2 adsorption/desorption isotherm of assynthesized ZIF-7 lp-phase at 273 K. The isotherm exhibits
a typical gate-opening effect at around 20 kPa and an outstanding CO2 adsorption capacity of 2.64 mmol g 1 at 116 kPa.
The obvious hysteresis during CO2 uptake corresponds to
a common feature of flexible frameworks.[1b] It is reported that
the aperture size of ZIF-7 is estimated to be 0.30 nm,[4c] which
is smaller than the kinetic diameter of CO2 (0.34 nm). However,
the window of ZIF-7 framework is very flexible, and a larger
molecule can diffuse through the narrow aperture by the rotation of benzimidazole linkers. In comparison, CO2 adsorption/
desorption isotherm of ZIF-7 np-phase (heat treated at 200 8C)
right shifts and the gate-opening pressure becomes higher because of the smaller window in np-phase framework. Nitrogen
adsorption/desorption isotherm was also measured for the assynthesized ZIF-7. However, no gate-opening behavior was ob 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

served in ZIF-7 for nitrogen molecules (Figure S1 in the Supporting Information). The BrunauerEmmettTeller surface area
of ZIF-7 is only 2.6 m2 g 1, suggesting that nitrogen molecules
are only absorbed on the external surface of ZIFs and they are
inaccessible to the small window of ZIF-7.
The FTIR spectra of the as-synthesized ZIF-7 and the 200 8C
treated sample are shown in Figure S2, where almost all of the
FTIR bands are in good agreement with previously reported
ZIF-7.[8b, d] For example, the bands at 1610 cm 1 can be assigned as the C=N stretch mode. The bands in the region of
6001500 cm 1 are associated with the entire ring stretching
or bending, whereas the band at 421 cm 1 corresponds to
Zn N stretching.[14] For the as-synthesized ZIF-7, there is a FTIR
band at 3592 cm 1 and a broad absorption band at around
3300 cm 1. These two bands are assigned to free hydroxy
groups and hydrogen bonded hydroxy groups, respectively.
The bands at 2960 and 1046 cm 1 are attributed to the aliphatic C H and C O stretching of ethanol. FTIR results reveal the
existence of ethanol in the as-synthesized ZIF-7.
ZIF-7 displayed breathing behavior upon variation of partial
pressure of CO2 or temperature under a certain CO2 partial
pressure, thus showing a reversible phase transition between
lp-phase and np-phase.[7] Here, we report a facile and interesting strategy to achieve phase transition from ZIF-7 np-phase
to lp-phase by immersing the ZIF-7 np-phase (200 8C treated
ZIF-7) into ethanol at room temperature. Figure 3 ac shows
XRD pattern evolution from ZIF-7 np-phase to lp-phase from
24 to 48 hours in ethanol. With the increase of time, XRD diffraction peaks of ZIF-7 np-phase continuously decrease while
ZIF-7 lp-phase begins to appear and becomes stronger. This
change is attributed to the diffusion of ethanol molecules into
the cavities and thus cage expansion. The SEM image of the
ethanol-immersed ZIF-7 (Figure 4 a) shows a similar morphology as the as-synthesized ZIF-7, indicating that the release and
adsorption of guest molecule ethanol does not damage the
ZIF-7 structure. The FTIR spectrum in Figure S3 shows the similar characteristic adsorption peaks as that of the as-synthesized
ZIF-7 sample (Figure S2). These results confirm the breathing
characteristic of ZIF-7 could be induced by the guest ethanol
molecules. The reversible phase transition of ZIF-7 provides
possibility for efficient organic vapor adsorption with phase
ChemPlusChem 2013, 78, 1222 1225

1223

CHEMPLUSCHEM
COMMUNICATIONS

Figure 3. XRD patterns showing the evolution of ZIF-7 np-phase to lp-phase

in ethanol for 24 (a), 36 (b) and 48 h (c), in DMF for 48 h (d), and in water for
48 h (e) at room temperature.

Figure 4. SEM images of the samples prepared by immersing ZIF-7 np-phase

into ethanol (a), DMF (b), and water (c) for 48 h.

changing from np- to lp-phase, and desorption with phase

changing from lp- to np-phase by heat treatment.
The phase transition from np-phase to lp-phase can also
occur in DMF solvent. Like ethanol, DMF molecules can permeate into the cavities of ZIF-7 np-phase to form ZIF-7 lp-phase
after 48 hours immersion in DMF (Figure 3 d), which is mainly
ascribed to the strong interactions between DMF and benzimidazole linker. Compared to ZIF-7 containing ethanol guest,
DMF-induced ZIF-7 lp-phase structure is more stable because
DMF is relatively difficult to remove from the cavities when
being heated.[8a] The existence of DMF in ZIF-7 lp-phase is
proven by the FTIR analysis (Figure S3). The strongest band at
1670 cm 1 is ascribed to C=O vibration among DMF. The absorption band at 1090 cm 1 is assigned to methyl rocking vibrations coupled with a C N characteristic.[15] The SEM image
(Figure 4 b) shows the DMF treated ZIF-7 exhibits a similar
morphology but having a smoother surface.
In contrast, when the ZIF-7 np-phase was immersed in
water, the np-phase structure totally destroyed and transformed into a new structure as shown in Figure 3 e. The morphology of water treated ZIF-7 changed to a plate-like structure (Figure 4 c). As ZIF-7 is formed by connecting zinc clusters
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chempluschem.org
through benzimidazole linkers, three benzene rings in benzimidazole construct a three-lobe structure[6a] that affect the
uptake and release of guest molecules. As a result of the large
polarity difference between a benzene ring and water, ZIF-7 is
very hydrophobic and water molecules cannot penetrate into
ZIF-7 cavities. Meanwhile, there should exist hydrogen bonding
between hydroxy groups of water and nitrogen atoms in benzimidazole. When the ZIF-7 np-phase was dispersed in water,
the framework subsequently distorts until it forms a more
stable crystallographic structure. Thus the six-membered-ring
pores become smaller than that of ZIF-7 np-phase, resulting in
the right shift of the XRD peak. According to the FTIR spectrum in Figure S3, no trace of water was found in the resulting
sample.
The water effect is also investigated in the synthesis of ZIF-7
by altering the water/ethanol molar ratios in the precursor solution. When the water/ethanol molar ratio is increased from
1:6.8 to 1:1, more ZIF-7 np-phase appears and the XRD peak
intensity of ZIF-7 lp-phase greatly decreases (Figure S4 a). This
is mainly due to the strong affinity of water and ethanol.[16]
With the increase of water from water/ethanol molar ratio of
1:6.8 to 1:1, more ethanol molecules binding with water molecules cannot enter into the cavities to act as guest molecules,
eventually favoring the formation of ZIF-7 np-phase. CO2 adsorption/desorption isotherm of the resulting ZIF-7 with mixed
np- and lp-phase exhibits a typical CO2 uptake (Figure S4 b)
that is very similar to the pure ZIF-7 lp-phase. By further increase of water usage to water/ethanol molar ratio of 8:1 in
the precursor solution, the XRD structure (Figure S4 a) was
found to be the same as that in Figure 3 e. Such a phase is
identified as a dense structure because almost no CO2 adsorption is observed (Figure S4 b). This phase formation is also due
to the distortion of the molecular configuration caused by polarity differences between benzimidazole linker and water.
In summary, we have demonstrated a new method for ZIF-7
preparation in water/ethanol solution at room temperature.
The reversible phase transition between ZIF-7 lp-phase and
np-phase can be achieved. The water content in the precursor
solution had significant effects on the ZIF-7 phase formation.
Increasing the water amount in the precursor solution resulted
in the formation of ZIF-7 np-phase or even a dense structure.
This work provides a facile, cheap, and sustainable method for
the synthesis of phase transformable ZIF-7.

Experimental Section
General
Zinc nitrate hexahydrate (Zn(NO3)26 H2O, 98 %), benzimidazole
(Hbim, C7H6N2, 98 %), DMF, and ammonium hydroxide (NH3, 28
30 % aqueous solution, SigmaAldrich) were purchased from
SigmaAldrich, Australia and used without further purification. Ethanol (absolute) was purchased from Merck, Australia.

Synthesis of ZIF-7 in water/ethanol solution

In a typical process, zinc nitrate hexahydrate (0.90 g, 3 mmol) was
dissolved in ethanol (10 g); Hbim (0.72 g, 6 mmol) was dissolved in
ChemPlusChem 2013, 78, 1222 1225

1224

CHEMPLUSCHEM
COMMUNICATIONS
ethanol (30 g), followed by the addition of ammonia hydroxide solution (2.8 g, 48 mmol NH3). The solutions of zinc nitrate and benzimidazole were mixed together to give the final synthesis solution
of molar composition Zn/Hbim/NH3/H2O/C2H5OH (1:2:16:43:293)
with the water/ethanol molar ratio of about 1:6.8. The solution
quickly turned into milk-like suspension, and was stirred for 10 min
at RT (  25 8C) to complete the crystallization. The as-synthesized
product (ZIF-7 lp-phase) was collected by centrifugation and
washed with ethanol three times, then dried at RT under an air
flow overnight. The ZIF-7 lp-phase was thermally treated at 50
400 8C for 2 h to investigate the phase transition to ZIF-7 np-phase.
Solvent-induced phase transition was performed by immersing ZIF7 np-phase (0.1 g; 200 8C treated ZIF-7 for 2 h) into absolute ethanol (5 mL), DMF, or deionized water under stirring, followed by
keeping the mixture still at RT for 2448 h. The resulting samples
were collected by centrifugation and washed with ethanol three
times, then dried at RT under an air flow overnight.
The effect of water on the formation of ZIF-7 lp-phase and npphase was examined. The same amount of solvent was used as in
the precursor solution and the water/ethanol molar ratio was
changed to 1:1 and 8:1, meanwhile the Zn/Hbim/NH3 molar ratios
remained at 1:2:16.

Characterization
Powder X-ray diffraction (XRD) patterns were recorded on a Philips
PW1140/90 diffractometer with CuKa radiation (25 mA and 40 kV)
at a scan rate of 2 degrees per minute with a step size of 0.028.
Scanning electron microscopy (SEM) images were obtained by
using a FEI-NOVA NanoSEM 450 scanning electron microscope operated at 15 kV. Nitrogen adsorptiondesorption isotherms were
measured at liquid-nitrogen temperature (77 K) by using a volumetric adsorption analyzer (Micromertics ASAP 2020). The CO2 adsorption measurements were conducted at 273 K with a Micromeritics
ASAP 2010MC analyzer. Fourier transform infrared (FTIR) spectra
were recorded on a PerkinElmer Fourier-Transform infrared spectrometer by using the KBr wafer technique.

Acknowledgements
This study was supported by Monash University. M.H. thanks the
Department of Chemical Engineering at Monash University for
supporting his visiting research, and financial support through
Priority Academic Program Development of Jiangsu Higher Education. J.Y. thanks Monash University for a Monash Fellowship.
H.W. thanks the Australian Research Council for a Future Fellowship.

www.chempluschem.org
Keywords: CO2 adsorption gate-opening processes phase
transitions zeolites zeolitic imidazole framework
[1] a) M. Pera-Titus, D. Farrusseng, J. Phys. Chem. C 2012, 116, 1638 1649;
b) S. Horike, S. Shimomura, S. Kitagawa, Nat. Chem. 2009, 1, 695 704.
[2] G. Frey, C. Serre, Chem. Soc. Rev. 2009, 38, 1380 1399.
[3] a) S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau, G. Ferey, J.
Am. Chem. Soc. 2005, 127, 13519 13521; b) C. Serre, F. Millange, C.
Thouvenot, M. Nogues, G. Marsolier, D. Louer, G. Ferey, J. Am. Chem.
Soc. 2002, 124, 13519 13526.
[4] a) R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M. OKeeffe,
O. M. Yaghi, Science 2008, 319, 939 943; b) X. C. Huang, Y. Y. Lin, J. P.
Zhang, X. M. Chen, Angew. Chem. 2006, 118, 1587 1589; Angew. Chem.
Int. Ed. 2006, 45, 1557 1559; c) K. S. Park, Z. Ni, A. P. Cote, J. Y. Choi, R.
Huang, F. J. Uribe-Romo, H. K. Chae, M. OKeeffe, O. M. Yaghi, Proc. Natl.
Acad. Sci. USA 2006, 103, 10186 10191.
[5] a) D. Fairen-Jimenez, S. A. Moggach, M. T. Wharmby, P. A. Wright, S. Parsons, T. Duren, J. Am. Chem. Soc. 2011, 133, 8900 8902; b) S. A. Moggach, T. D. Bennett, A. K. Cheetham, Angew. Chem. 2009, 121, 7221
7223; Angew. Chem. Int. Ed. 2009, 48, 7087 7089.
[6] a) C. Gucuyener, J. van den Bergh, J. Gascon, F. Kapteijn, J. Am. Chem.
Soc. 2010, 132, 17704 17706; b) J. van den Bergh, C. Gcyener, E. A.
Pidko, E. J. M. Hensen, J. Gascon, F. Kapteijn, Chem. Eur. J. 2011, 17,
8832 8840.
[7] S. Aguado, G. Bergeret, M. P. Titus, V. Moizan, C. Nieto-Draghi, N. Bats,
D. Farrusseng, New J. Chem. 2011, 35, 546 550.
[8] a) Y. S. Li, F. Y. Liang, H. Bux, A. Feldhoff, W. S. Yang, J. Caro, Angew.
Chem. 2010, 122, 558 561; Angew. Chem. Int. Ed. 2010, 49, 548 551;
b) T. Li, Y. C. Pan, K. V. Peinemann, Z. P. Lai, J. Membr. Sci. 2013, 425,
235 242; c) J. F. Yao, D. Li, K. Wang, L. He, G. S. Xu, H. T. Wang, J. Nanosci. Nanotechnol. 2013, 13, 1431 1434; d) T. X. Yang, Y. C. Xiao, T. S.
Chung, Energy Environ. Sci. 2011, 4, 4171 4180; e) W. Morris, N. He,
K. G. Ray, P. Klonowski, H. Furukawa, I. N. Daniels, Y. A. Houndonougbo,
M. Asta, O. M. Yaghi, B. B. Laird, J. Phys. Chem. C 2012, 116, 24084
24090.
[9] X. C. Huang, J. P. Zhang, X. M. Chen, Chin. Sci. Bull. 2003, 48, 1531
1534.
[10] Y. S. Li, H. Bux, A. Feldhoff, G. L. Li, W. S. Yang, J. Caro, Adv. Mater. 2010,
22, 3322 3326.
[11] B. Seoane, J. M. Zamaro, C. Tellez, J. Coronas, CrystEngComm 2012, 14,
3103 3107.
[12] a) J. F. Yao, R. Z. Chen, K. Wang, H. T. Wang, Microporous Mesoporous
Mater. 2013, 165, 200 204; b) A. X. Zhu, R. B. Lin, X. L. Qi, Y. Liu, Y. Y. Lin,
J. P. Zhang, X. M. Chen, Microporous Mesoporous Mater. 2012, 157, 42
49.
[13] J. F. Yao, M. He, K. Wang, R. Z. Chen, Z. X. Zhong, H. T. Wang, CrystEngComm 2013, 15, 3601 3606.
[14] Y. Hu, H. Kazemian, S. Rohani, Y. N. Huang, Y. Song, Chem. Commun.
2011, 47, 12694 12696.
[15] H. Kawasaki, H. Yamamoto, H. Fujimori, R. Arakawa, Y. Iwasaki, M. Inada,
Langmuir 2010, 26, 5926 5933.
[16] O. M. Yaghi, C. E. Davis, G. M. Li, H. L. Li, J. Am. Chem. Soc. 1997, 119,
2861 2868.
Received: May 13, 2013
Published online on July 11, 2013

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemPlusChem 2013, 78, 1222 1225

1225