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Room-Temperature Synthesis of ZIF-8: The Coexistence of ZnO

Nanoneedles
Minqi Zhu,† Surendar R. Venna,†,‡ Jacek B. Jasinski,§ and Moises A. Carreon*,†
†
Department of Chemical Engineering and §Conn Center for Renewable Energy Research, University of Louisville, Louisville,
Kentucky 40292
bS Supporting Information
KEYWORDS: Zeolite imidazolate frameworks, ZnO nanoneedles, kinetics of transformation
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Z eolite imidazolate frameworks (ZIFs) are novel type of

microporous crystalline materials displaying unique and
highly desirable properties from both zeolites and metal organic
to low beam current density) were employed. In order to obtain the
analytical information from individual nanoparticles, the EDS anal-
ysis was performed in the nanoprobe mode and the beam diameter
frameworks, such as remarkable high surface areas, crystallinity, of 1 nm was selected. The surface area and adsorption desorption
unimodal micropores, as well as thermal and chemical stability.1 isotherm measurements were carried out on Micromeritics Tristar
Typically, ZIFs are composed of Zn and Co atoms linked through 3000 porosimeter at 77 K using liquid nitrogen as coolant and the
N atoms by ditopic imidazolate (Im) or functionalized Im links to samples were degassed at 150 °C for 3 h before the measurements.
form neutral frameworks and to provide tunable nanosized pores Figure 1 shows the XRD patterns of the ZIF-8 samples synthe-
formed by four-, six-, eight-, and twelve-membered ring ZnN4, and sized in the presence of zinc carbonate basic at different synthesis
CoN4 tetrahedras.1b Although the great potential of ZIFs as novel times. Reflections of higher order for ZIF-8 corresponding to the
functional materials has been demonstrated recently in diverse fields, planes (011), (022), (112), (022), (013), and (222) increased as
including gas separations,2 sensing,3 and catalysis,4 to the best of our time progressed. The area under the curve of all these peaks was
knowledge, only few reports,5 including our recent work,5a has been quantified using origin software, after baseline correction, to deter-
published on the mechanistic aspects of ZIFs formation. A basic mine the relative crystallinity curve of ZIF-8 phase (see Figures
understanding on the formation mechanisms of zeolitic imidazolate S1 S6 and Table S1 in the Supporting Information). This curve
frameworks is important to rationally develop materials with tailored can be directly related to the phase transformation rate. As shown in
Figure 1, the presence of defined XRD peaks at 10 min indicates that
structural, compositional, and morphological properties. Herein, we
ZIF-8 forms even at this short synthesis time. Below 10 min, there is
followed the crystallization-time dependence of a representative
an induction period required to nucleate the ZIF-8 phase.
zeolitic imidazolate framework, ZIF-8 which has large pores of 11.6
Figure 2 shows the crystallization rate curve of ZIF-8 and the
Å accessible through small apertures of 3.4 Å.6 Interestingly, when data points represent the total measured intensity of the six
zinc carbonate basic was used as the metal source, the coexistance of primary XRD reflections of ZIF-8. Individual analysis for each
ZIF-8 and ZnO nanoneedles was observed. reflection is shown elsewhere.7 The relative crystallinity of ZIF-8
ZIF-8 crystals were prepared as follows: 2.8 mmol of zinc increased linearly during the first 2 h from ∼20 to ∼40%. Then
carbonate basic ([ZnCO3]2 3 [Zn(OH)2]3, Sigma Aldrich) were the rate of crystallization increased slowly from 2 to 24 h from ∼-
dissolved in 1.4 mol of methanol (Acros Organics, extra dry, 40 to ∼60%. Finally, after 48 h the relative crystallinity of ZIF-8
water <50 ppm). A solution consisting of 64.4 mmol of 2-methy- remained ∼80%, reaching a maximum of 100% at 120 h.
limidazole (C4H6N2, Aldrich, 99%) and 1.4 mol of methanol was The specific BET surface areas of all samples correlated with
added to the Zn based solution and vigorously stirred for different the ZIF-8 relative crystallinity (Figure 2). For example, surface
times. Finally, this solution was centrifugated at 3000 rpm, and areas increased linearly at short synthesis times and remained
washed thoroughly with methanol. This procedure was repeated 3 practically constant in the 48 120 h range. It is important to
times. The resultant crystals were dried overnight at 120 °C. mention that the apparent surface area was evaluated using the
Powder X-ray diffraction patterns were collected using a Bruker BET method and taking the data in the 0.01 < P/P0< 0.3 range.
D8-Discover diffractometer at 40 kV, 40 mA with Cu KR radiation. The relatively low observed surface areas may indicate that the
Transmission electron microscopy (TEM) studies, including TEM synthesized ZIF-8 still contains some unreacted 2-methylimida-
imaging, selected area electron diffraction (SAED), and energy- zole linker that was not desorbed from the framework. Interestingly,
dispersive X-ray spectroscopy (EDS), were performed using a in the growth regime, the kinetics of transformation followed
FEI Tecnai F20 transmission electron microscope. A field emission Avrami’s model8 (inset of Figure 2). Therefore, the relative
gun (FEG) was used for the electron source and the studies were crystallinity of ZIF-8 as a function of time in this region can be
performed at the accelerating voltage of 200 keV. Samples for TEM
analysis were prepared by dispersing the powders onto lacey-carbon
coated copper TEM grids. ZIF-8 is highly sensitive to the electron Received: June 15, 2011
beam damage. Therefore, low-dose imaging and diffraction condi- Revised: July 24, 2011
tions (highly diverged beam with increased spot size corresponding Published: July 29, 2011

r 2011 American Chemical Society 3590 dx.doi.org/10.1021/cm201701f | Chem. Mater. 2011, 23, 3590–3592
Chemistry of Materials COMMUNICATION

Figure 1. XRD patterns of ZIF-8 as a function of synthesis time: (a)

10 min; (b) 30 min; (c) 2 h; (d) 6 h; (e) 24 h; (f) 48 h; and (g) 120 h.

Figure 3. Representative TEM images of ZIF-8 as a function of

synthesis time: (a,b) 30 min; (c, d) 24 h; (e, f) 120 h. In a d, arrows
indicate ZIF-8 phase. e and f are pure ZIF-8 crystals.

times indicate that this is a metastable phase that coexists with

ZIF-8 at low (10 min) to moderate (48 h) synthesis times.
SAED and EDS study were carried out to identify the
composition and crystal structure of the nanoneedles. A typical
Figure 2. Crystallization rate curve of ZIF-8 and its correlation with specific SAED ring pattern obtained from a sample with high density of
surface area. Inset shows that the growth regime follows Avrami’s kinetics. nanoneedles is shown in Figure 4a. The radial intensity distribu-
tion profile, measured from this pattern is plotted in Figure 4b
expressed as y = 1 exp[ ktn], where k is a scaling constant, and (black line). It agrees with a database XRD pattern of wurtzite
n is the Avrami’s constant. For our case, k = 0.14, and n ≈ 0.27. ZnO (JCPDS pattern 01 075 0576), and the SAED rings at
Although typical values of Avrami’s n constant are in the 1 4 d-spacing of 0.356, 0.405, 0.524, 0.617, 0.678, 0.727, 0.738, and
range, this constant can adopt different values, including frac- 0.917 nm correspond to the reflection from: (100), (101), (102),
tional numbers below 1.9a Values of the Avrami exponent below 1 (110), (103), (112), (201), and (202) crystal planes, respec-
have been typically attributed to both decreasing nucleation and tively. The TEM image shown in Figure 4c shows nanoneedles
growth rates as crystallization proceeds.9a Values of Avrami’s with ∼20 nm diameter and lengths in the ∼100 200 nm range.
constant of 0.2 and 0.3 have been observed for some alloys.9a c The SAED pattern and the radial intensity distribution profile are
Figure 3 shows TEM images of selected samples synthesized in agreement with the EDS measurements, which confirms that
at different synthesis times. Interestingly, the presence of a nanoneedles are composed of zinc and oxygen, as shown in Figure 4d,
second phase in nanoneedle form was observed for samples where an EDS spectrum obtained from a single nanoneedle is
synthesized from 10 min to 48 h. At 30 min, ∼30 nm ZIF-8 presented. Elemental quantification of this spectrum yields 49 ( 2
crystallites, some of them already faceted coexist with nanonee- and 51 ( 2 at % of Zn and O, respectively, which is in excellent
dles displaying ∼10 20 nm diameter and lengths in the agreement with ZnO. In addition to ZnO rings, the SAED pattern
∼100 150 nm range (Figure 3a,b). As time progressed, the size consists of three additional rings at the d-spacing of 0.312, 0.268,
of the ZIF-8 crystals increased to ∼50 60 nm, with no evident and 0.155 nm, respectively. The origin of these rings it is not clear.
size growth of the nanoneedle-like phase (Figure 3c,d). Finally, at It is important to mention that ZnO nanoneedles were only
120 h, only well-faceted ∼80 90 nm hexagonal and cubic-like observed when Zn carbonate basic was used as the metal source.
crystals corresponding to pure ZIF-8 phase were observed Other zinc precursors including Zn sulfate, Zn nitrate and Zn
(Figure 3e,f). It is important to mention that only for the sample chloride led only to hexagonal and cubic faceted crystals, typical
synthesized at 120 h, pure ZIF-8 crystals were present morphology of pure ZIF-8 phase.7 Different from sulfate, nitrate
(no nanoneedles), suggesting that at this time the complete crystal- and chloride counterions, the presence of carbonate basic in the
lization of the microporous framework takes place. The TEM synthesis gel leads to a rich hydroxyl species solution environ-
images revealed that increasing the crystallization time led to an ment. It is likely then that the dehydration of these hydroxyl
increase in crystal ZIF-8 crystal size due to Ostwald ripening, a species results in the formation of ZnO nuclei. At this point, the
well-known thermodynamically driven process, in which small ZnO nanoneedles can grow by condensation of these hydroxyl
crystals disappear at the expense of the formation of larger species.10 The nanorod-like or nanoneedle-like morphology has
crystals. The disappearance of the nanoneedles at long synthesis been observed when organic amino groups are present as
3591 dx.doi.org/10.1021/cm201701f |Chem. Mater. 2011, 23, 3590–3592
Chemistry of Materials COMMUNICATION

Present Addresses
‡
School of Chemical and Biological Engineering, Georgia
Institute of Technology, Atlanta, GA 30332.

’ ACKNOWLEDGMENT
This work was supported by NSF CAREER award (CBET#1054
150). We thank Gregor Filipic for the development of the software
used to obtain the diffraction pattern intensity profile.

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*E-mail: [email protected].
3592 dx.doi.org/10.1021/cm201701f |Chem. Mater. 2011, 23, 3590–3592