Materials Letters 82 (2012) 220–223

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Hydrothermal synthesis of zeolitic imidazolate framework-67 (ZIF-67) nanocrystals

Junfeng Qian a,⁎, Fuan Sun a, Lizhen Qin b
a
School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, PR China
b
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, PR China

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

Article history: Thermally and chemically stable zeolitic imidazolate framework (ZIF) materials have attracted extensive ap-
Received 12 March 2012 plication in gas adsorption and catalysis. Nano-sized ZIF-67 crystals (228 nm) were for the first time synthe-
Accepted 21 May 2012 sized in aqueous solutions at room temperature. As-synthesized crystals were investigated by X-ray
Available online 30 May 2012
diffraction, field-emission scanning electron microscope, thermal gravimetric analysis, gas adsorption mea-
surement. It was found that ZIF-67 nanocrystals were highly stable up to 350 °C and could be stable in boiling
Keywords:
Zeolitic imidazolate frameworks (ZIFs)
methanol at least for 5 days. Furthermore, the concentration of reagents plays an important role in control-
ZIF-67 ling particle size, and diluting the synthesis solution can increase the particle size of final products.
Nanoparticles © 2012 Elsevier B.V. All rights reserved.
Hydrothermal synthesis

1. Introduction 2. Experimental section

Zeolitic imidazolate frameworks (ZIFs), a new class of metal organic
frameworks (MOFs) that have exceptional chemical and thermal stabil-
ity [1], are being evaluated for several applications, such as gas adsorp-
tion [2], molecular separation [3,4] and catalysis [5,6]. Up to now, the
most general approach for preparing ZIF crystals is the solvothermal
method at high temperature (>100 °C) in organic liquid, such as meth-
anol, N,N-dimethylformamide (DMF), or N,N-diethylformamide (DEF).
Very recently, Pan et al. [7] have proposed a novel synthesis method for
preparing ZIF-8 (Zn(Hmim)2, Hmim= 2-methylimidazole) in aqueous
solutions at room temperature. This method not only prohibits the
use of toxic organic solvent, but also decreases the cost for preparing
ZIF materials.
ZIF-67 (Co(Hmim)2) is isostructural to ZIF-8, and is formed by
bridging 2-methylimidazolate anions and cobalt cations resulting in
a sodalite (SOD) topology with a pore size of about 0.34 nm [8]. Sim-
ilarity in structure and in organic ligands makes ZIF-67 to have close
formation mechanism with ZIF-8. In the current work, we report
the preparation of ZIF-67 nanocrystals in pure aqueous solutions at
room temperature. The particle size can be controlled from 228 nm
to 5.2 μm. Thermal and chemical stabilities of the as-synthesized
nanocrystals were also examined. We believe that ZIF-67 crystals
also have potential application in gas separation, especially in ole-
fin/paraffin separation [9].
⁎ Corresponding author. Tel.: + 86 519 8633 0251.
E-mail address: qianjunfeng80@126.com (J. Qian).
2.1. Synthesis of ZIF-67 nanoparticles
All chemicals were all purchased from Sigma-Aldrich and used as re-
ceived. In a typical synthesis, 0.45 g cobalt nitrate hexahydrate was dis-
solved in 3 mL of deionized (DI) water; then 5.5 g 2-methylimidazole
(Hmim) was dissolved in 20 mL of DI water. Those two solutions were
mixed (Co2 +:Hmim:H2O = 1:58:1100) and stirred for 6 h at room tem-
perature, then the resulting purple precipitates were collected by
centrifuging, washed with water and methanol subsequently for 3
times, and finally vacuum‐dried at 80 °C for 24 h.
2.2. Characterization
Powder X-ray diffraction (XRD) patterns were recorded at room
temperature on a Bruker D8 ADVANCE diffractometer using CuKα radi-
ation (λ = 1.54059 Å) at 40 kV and 40 mA. Thermal gravimetric analy-
sis (TGA) measurements were performed on a Netzsch STA 409
thermoanalyzer. For this purpose, ca. 10 mg samples were filled into
an alumina crucible and heated in a continuous-flow of nitrogen gas
with a ramp rate of 10 °C/min from 40 up to 800 °C. Nitrogen phy-
sisorption isotherms were measured at 77 K on an automatic volumet-
ric adsorption apparatus (Micromeritics ASAP 2020). Gas adsorption
measurements were also conducted at room temperature with a Micro-
meritics ASAP 2010MC analyzer. Before testing, the samples were out-
gassed in high vacuum at 473 K for 24 h before the start of the
sorption measurements. Microstructure and morphology of particles
were characterized by field-emission scanning electron microscope
(SEM, FEI Quanta-600). The mean particle size (MS) of the product
was determined by manual measurement of about 300 crystals in five
SEM pictures [10].

0167-577X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.05.077
 J. Qian et al. / Materials Letters 82 (2012) 220–223 221

Fig. 1. (a) XRD patterns of simulated ZIF-67 sample [1] and as-synthesized ZIF-67 nanocrystals, (b) SEM picture, (c) TGA curve and (d) N2 adsorpton/desorption isotherms of as-
synthesized ZIF-67 nanocrystals.

3. Results and discussion (Fig. 1(b)). We also found that the as-synthesized ZIF-7 nanoparticles
are stable in toluene at least for 5 days. The chemical stability of ZIF-
Fig. 1 shows the XRD pattern, SEM image, TGA curve and N2 sorp- 67 materials is comparable with that of ZIF-8 [1]. The highly chemical
tion isotherms of the as-synthesized sample. Compared with the stability makes ZIF-67 as a potential catalyst in Knoevenagel reaction [5],
standard simulation XRD pattern of ZIF-67 structure data [8], we because this kind of chemical reaction is always conducted in toluene.
found that the product was pure-phase ZIF-67 materials (Fig. 1(a)). We also found that reagent concentration played an important
SEM picture (Fig. 1(b)) reveals that the particles are nanocrystals role in controlling particle size and morphology of ZIF-67 crystals;
with polyhedral shape. The mean particle size is calculated as several syntheses were conducted at room temperature for 6 h by di-
228 nm, and the particle sizes range from 78 to 385 nm. The obtained luting the original synthesis solution (Co 2 +:Hmim:H2O = 1:58:1100)
nanoparticles can be well dispersed in methanol to form a stable sus- for 0.5–4 times. Fig. 4 shows the XRD patterns and SEM images of
pension, and can be kept for several weeks without settlement. TGA these products. We could see that the products still maintained the
curve (Fig. 1(c)) of the as-synthesized sample shows that only 3% ZIF-67 structure when the original synthesis solution was diluted
weight loss up to 350 °C, relating to the removal of guest molecules even for 4 times (Fig. 4(a)). ZIF-67 crystals with MS of 689 nm and
and unreacted species [11]. Thus the ZIF-7 material was thermally polyhedral shape could be prepared when the original synthesis solu-
stable up to 350 °C. Although the thermal stability of ZIF-67 was tion was diluted for 0.5 time (Fig. 4(b)). However, near-spherical ZIF-
slightly lower than that of ZIF-8 (ca. 500 °C) [7], it still surpassed 67 crystals with smooth surface were observed as the original
most of MOF materials [12]. Nitrogen sorption study for the as-
synthesized ZIF-67 nanocrystals reveals a reversible type I isotherm,
characteristic of microporous materials (Fig. 1(d)). The sudden up-
take at high relative pressure can be related to physisorbed liquid
nitrogen on the crystal surfaces of the nanoparticles [13]. The micro-
porous volume is about 0.17 cm 3/g, and the BET surface area is
316 m 2/g, respectively. As shown in Fig. 2, the gas adsorption capacity
of ZIF-67 nanocrystals increases largely in the order of H2, N2, CH4 and
CO2 at room temperature (~25 °C). At 116 kPa, the adsorption capac-
ity is about 0.022, 0.07, 0.24 and 0.71 mmol/g for H2, N2, CH4 and CO2,
respectively. It is clear that the ZIF-67 nanocrystals can adsorb much
more CO2 than other gases and can be potentially used as preferential
CO2 adsorbent and seeds for gas separation membrane.
The chemical stability of ZIF-67 nanocrystals was examined by
suspending the as-synthesized samples in boiling methanol. As the re-
sults shown in Fig. 3, ZIF-67 nanocrystals are stable in boiling water
for at least 5 days since the XRD pattern and the crystal morphology
did not show obvious change compared to the as-synthesized sample Fig. 2. Gas adsorption isotherms of ZIF-67 nanocrystals at room temperature (~25 °C).
222 J. Qian et al. / Materials Letters 82 (2012) 220–223

Fig. 3. (a) XRD patterns and (b–d) SEM pictures of as-synthesized ZIF-67 nanocrystals immersed in boiling methanol for 1–5 days.

Fig. 4. (a) XRD patterns and (b–d) SEM pictures of ZIF-67 crystals prepared by diluting original solution for 0.5–4 times at room temperature for 6 h.
 J. Qian et al. / Materials Letters 82 (2012) 220–223
solution was diluted for 2 times, and the MS of product was ca. 2.7 μm
(Fig. 4(c)). Rhombic dodecahedral ZIF-67 crystals with a MS of 5.2 μm
were observed as the original synthesis solution was diluted for 4
times (Fig. 4(d)). As a result, the above results indicate that the
decrease of the reagent concentration can lead to the increase in the
mean particle size of final products. The possible reason is that
decreasing the reagent concentration can slow down the nucleation
reaction rate and accelerate the crystal growth rate, resulting in the
synthesis of bigger crystals with more well-defined morphology.
4. Conclusions
In summary, ZIF-67 nanocrystals (ca.228 nm) for the first time
have been successfully synthesized in aqueous solutions at room tem-
perature for 6 h. This novel hydrothermal synthesis method not only
prohibits the usage of toxic organic solvent, but also decreases the
cost of preparation of MOF materials. Decreasing the concentration
of reagents can increase the particle size. The mean particle sizes
can be adjusted from 689 nm to 5.2 μm when the original synthesis
solutions were diluted by 0.5 to 4 times. We believe that this ap-
proach may extend to other kinds of ZIF nanocrystals, even MOF
nanocrystals.
Acknowledgment
This work was supported by the Priority Academic Program Devel-
opment (PAPD) of Jiangsu Higher Education Institutions.
223
References
[1] Park KS, Ni Z, Cote AP, Choi JY, Huang RD, Uribe-Romo FJ, et al. Exceptional chem-
ical and thermal stability of zeolitic imidazolate frameworks. Proc Natl Acad Sci
USA 2006;103:10186–91.
[2] Li JR, Kuppler RJ, Zhou HC. Selective gas adsorption and separation in metal–
organic frameworks. Chem Soc Rev 2009;38:1477–504.
[3] Shekhah O, Liu J, Fischer RA, Woll C. MOF thin films: existing and future applica-
tions. Chem Soc Rev 2011;40:1081–106.
[4] Bux H, Liang FY, Li YS, Cravillon J, Wiebcke M, Caro J. Zeolitic imidazolate frame-
work membrane with molecular sieving properties by microwave-assisted
solvothermal synthesis. J Am Chem Soc 2009;131:16000–1.
[5] Tran UPN, Le KKA, Phan NTS. Expanding applications of metal–organic frame-
works: zeolite imidazolate framework ZIF-8 as an efficient heterogeneous catalyst
for the Knoevenagel reaction. Acs Catal 2011;1:120–7.
[6] Jiang HL, Liu B, Akita T, Haruta M, Sakurai H, Xu Q. Au@ZIF-8: CO oxidation over
gold nanoparticles deposited to metal–organic framework. J Am Chem Soc
2009;131:11302–3.
[7] Pan YC, Liu YY, Zeng GF, Zhao L, Lai ZP. Rapid synthesis of zeolitic imidazolate
framework-8 (ZIF-8) nanocrystals in an aqueous system. Chem Commun
2011;47:2071–3.
[8] Banerjee R, Phan A, Wang B, Knobler C, Furukawa H, O'Keeffe M, et al.
High-throughput synthesis of zeolitic imidazolate frameworks and application
to CO2 capture. Science 2008;319:939–43.
[9] Li KH, Olson DH, Seidel J, Emge TJ, Gong HW, Zeng HP, et al. Zeolitic imidazolate
frameworks for kinetic separation of propane and propene. J Am Chem Soc
2009;131:10368–9.
[10] Pan YC, Ju MH, Wang CQ, Zhang LX, Xu NP. Versatile preparation of monodisperse
poly (furfuryl alcohol) and carbon hollow spheres in a simple microfluidic device.
Chem Commun 2010;46:3732–4.
[11] Cravillon J, Munzer S, Lohmeier SJ, Feldhoff A, Huber K, Wiebcke M. Rapid
room-temperature synthesis and characterization of nanocrystals of a prototypi-
cal zeolitic imidazolate framework. Chem Mater 2009;21:1410–2.
[12] Ferey G. Hybrid porous solids: past, present, future. Chem Soc Rev 2008;37:
191–214.
[13] Diring S, Furukawa S, Takashima Y, Tsuruoka T, Kitagawa S. Controlled multiscale
synthesis of porous coordination polymer in nano/micro regimes. Chem Mater
2010;22:4531–8.