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Quick synthesis of zeolitic imidazolate framework

microflowers with enhanced supercapacitor and
Cite this: RSC Adv., 2015, 5, 58772
electrocatalytic performances†
Published on 02 July 2015. Downloaded by VIT University on 12/13/2024 10:35:31 AM.

Daojun Zhang,a Huaizhong Shi,a Renchun Zhang,a Zirui Zhang,a Nan Wang,a
Junwei Li,a Baiqing Yuan,*a Helong Baib and Jingchao Zhang*a

Novel zeolitic imidazolate framework-67 (ZIF-67) microflowers were synthesized by a quick and simple
method without using any template or surfactant. Enhanced specific capacitance (188.7 F g
1 at 1 A g
1)
and good cycle stability (remaining at 105% after 3000 cycles) of the ZIF-67 microflowers are observed
in aqueous KOH electrolytes, which could be ascribed to the high chemical and thermal stabilities, large
BET surface area, and small ion-transport (OH
) resistance of the hierarchical microflowers structure. In
Received 4th May 2015
Accepted 2nd July 2015
addition, the as-prepared ZIF-67 microflowers exhibited good electrocatalytic activity toward the
reduction of H2O2. The obtained sensor also presented good reproducibility, high stability and a wide
DOI: 10.1039/c5ra08226a
linear range. This work suggests that ZIF materials would be promising candidates for potential
www.rsc.org/advances applications in supercapacitors and electroanalysis.

structure is uncertain. MOFs including Co-, Co–Zn-, Zn-, In-, Ni-,

1. Introduction and Cd-based materials have also been investigated,16–22
Metal–organic frameworks (MOFs) represent a new class of however, most reports showed low capacitances.
tunable materials that have shown great potential applications The most important is that to increase the stability of MOFs
in heterogeneous catalysis, gas storage, nonlinear optics, in water and alkaline solution. To overcome the disadvantages,
nanomedicine, and energy storage.1–11 Investigations into the recently, a large number of MOFs with chemical and thermal
use of MOFs as supercapacitor electrode materials have stabilities, such as ZIF-8, ZIF-67 and MIL-101 (ref. 23–37), have
expanded in recent years. The MOFs themselves have unique been reported. The redox behavior of metal Co(II) ions inside the
structures incorporating pseudo-capacitive redox centers that ZIF-67 could provide a transport pathway for electrons, we think
can be directly used as a new type of electrode materials.5 ZIF-67 is a suitable electrode material for supercapacitor and
However, studies into the direct use of MOFs as supercapacitor electrocatalyst. It is well accepted that pseudocapacitors store
electrodes are rather rare and more challenging due to the weak charge in the rst few nanometers from the surface, so the
stability and poor electrical conductivity of most MOFs. Very hierarchical ower-like would increase redox metal centers, and
recently, Yaghi et al. reported a series of graphene-doped MOFs thereby would increase the pseudocapacitance. Thus, it is quite
nanocrystals fabricated a symmetric supercapacitor, and it was necessary to synthesize MOF material with a unique hierar-
found that the Zr-MOF exhibited a high capacitance of 726 F g
1 chical ower-like structure, which can provide more active sites
at a current density of 0.88 mA cm
3 (6.95 mA g
1).12 Wang et al. and short diffusion paths for charge carriers, which may endow
demonstrated a strategy to design and fabricate a exible MOF- the materials with enhanced electrochemical properties.
based supercapacitor (PANI-ZIF-67-CC).13 The results showed Herein, we synthesized ZIF-67 with hierarchical ower-like
that the PANI-ZIF-67-CC delivers an extraordinary areal capaci- structure, the constructed amperometric sensor from the
tance of 2146 mF cm
2 at 10 mV s
1. Wei et al. reported a combination of ZIF-67 with traditional electrode showed a linear
Ni-based and a Zn-doped Ni-based MOFs with high capaci- range for the detection of H2O2 from 2.5 mM to 1.08 mM with a
tances.14,15 However, it is unclear why specically 6 M KOH correlation coefficient of 0.9926. Moreover, ZIF-67 may be a rela-
electrolyte was used, and the long-term stability of the Ni-MOF tively good candidate of electrochemical capacitors with a specic
capacitance up to 188.7 F g
1 at a current density of 1 A g
1 and a
long cycle life which can maintain 105% of initial specic
capacitance aer 3000 cycles at a current density of 2 A g
1.
a
College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang
455002, China. E-mail: [email protected]; [email protected]; Tel:
These results strongly show that the as-made ZIF-67 hierar-
+86 03722900040
b
chical ower-like structure display excellent electrochemical
College of Chemistry, Jilin University, Changchun 130012, China
† Electronic supplementary information (ESI) available. See DOI:
properties for supercapacitor and electrochemistry sensor.
10.1039/c5ra08226a

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2. Experimental section every ligand bridge two Co centers and further assembles into a
sodalite (SOD) topology framework (Fig. 1). ZIF-67 exhibits large
2.1 Materials synthesis surface area and high stability in water.33 The identity and
2-Methylimidazole was purchased from Aldrich and used purity of the samples are conrmed by similarities between the
without further purication. Deionized water was used experimental X-ray powder diffraction (PXRD) spectra, further-
throughout all the experiments. In a typical synthesis, 174.6 mg more, our experiment shows ZIF-67 has good corrosion resis-
Co(NO3)2$6H2O (0.6 mmol) and 738.9 mg 2-methylimidazole tance of KOH aqueous solutions (Fig. 2), all these merits are
(9.0 mmol) were dissolved in 9 mL of deionized water, the mixed important applied for the electrode material of supercapacitors.
solution was stirred for 5 h at room temperature, then the Fig. 3a and b show the FESEM images of ZIF-67 at different
resulting purple precipitates were collected by centrifuging, magnications, revealing that the as-synthesized ZIF-67
washed several times with distilled water and absolute meth- product is entirely composed of microspheres with a diameter
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anol, and nally vacuum-dried at 60  C for 12 h. of 1–2 mm (Fig. 3a). Further observation suggests that the
individual microower is actually 3D owerlike hierarchical
2.2 Materials characterization assemblies of interconnected nanoparticles about tens of
nanometers in length (Fig. 3b).
The resultant phase of the microower ZIF-67 particles was
determined by X-ray diffraction by X-ray diffraction (XRD) on a
Philips X'pert Pro X-ray diffractometer with Cu Ka radiation and
operated at 40 kV and 40 mA. The surface morphology was
measurements by eld-emission scanning electron microscopy
(FESEM) on a Hitachi SU8010 instrument.

2.3 Electrochemical sensor electrode preparation and

measurement
The electrochemical measurements were examined on an elec- Fig. 1 (a) The coordination environment and (b) SOD-type structure
trochemical workstation (CHI 760D, Chenhua, Shanghai, of ZIF-67.
China) using a carbon paste electrode (CPE) as working elec-
trode, a platinum coil as counter electrode, and a Ag/AgCl
electrode as reference electrode, respectively. To prepare the
ZIF-67 modied electrode, 2.0 mg of the as-prepared material
was dispersed in 1.0 mL water to give suspension by ultra-
sonicating. A 5.0 mL of the suspension was dip-coated onto CPE
and the electrode was then dried in the atmosphere.

2.4 Electrochemical supercapacitor electrode preparation

and measurement
All the electrochemical experiments were carried out in a stan-
dard three-electrode system at room temperature. A saturated
calomel electrode (SCE) and a platinum foil were used as the
reference and counter electrodes, respectively. The working
electrodes were typically fabricated by mixing 80% of active Fig. 2 PXRD patterns of the as-synthesized ZIF-67 as well as samples
material, 10% of acetylene black, and 10% of polyvinylidene treated with 1 M KOH aqueous solutions at different time at room
uoride (PVDF), using N-methyl-2-pyrrolidone (Aldrich) as temperature.
solution to yield a slurry. Then the slurry was pressed on the
nickel foam current collector (1 cm  1 cm) and dried in
vacuum at 100  C for 10 h. The electrochemical measurements
were carried out by an electrochemical analyzer system, CHI
760D (Chenhua, Shanghai, China). The electrochemical
performance of the electrode was analyzed using cyclic vol-
tammetry (CV) and galvanostatic charge–discharge measure-
ments in 1 M KOH aqueous solution in the potential window
from 0 to 0.46 V.

3. Results and discussion

In this MOF, each cobalt ion is coordinated with four nitrogen Fig. 3 The FESEM images of ZIF-67 at low (a) and high (b)
atoms from four different 2-methylimidazolate ligands and magnifications.

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The CV experiments within a 0–0.55 V range at a scan rate supercapacitors. The cycling performance test indicates that the
from 5 to 50 mV s
1 for ZIF-67 was presented in Fig. 4. As shown capacitance of this device slightly increases with the number of
in Fig. 4a, obviously, a pair of strong redox peaks is in each charge–discharge cycles. The increasing capacitance with the
voltammogram suggesting that the capacity of ZIF-67 are cyclic charge–discharge process might be due to activation of
mainly based on Faradaic redox reactions. At a low scan rate of the ZIF-67 porous structure with time. This makes the porous
5 mV s
1, the anodic peak at 0.37 V is due to the oxidation structure of ZIF-67 in full contact with the electrolyte. The nal
process, and the cathodic peak at about 0.27 V is related to its specic capacitance of theZIF-67 hierarchical ower-like struc-
reverse process. The electrochemical capacitance of ZIF-67 ture is 105% of its initial value aer 3000 cycles (Fig. 4d). These
originates from the Faradic redox reaction of Co(II) ions results suggest that ZIF-67 hierarchical ower-like nano-
(Co2+/Co3+ redox couple) in the framework, and probably structure may be a promising candidate for high-performance
mediated by the OH
ions in the alkaline electrolyte. The supercapacitors.
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positive sweeps of the CV curves of ZIF-67 are not symmetrical To evaluate the specic surface area and the porosity of the
with the corresponding negative sweeps, which might be caused hierarchical ower-like structure, the N2 sorption property was
by polarization and ohmic resistance during the Faradaic studied and shown in Fig. S1,† it reveals a typical type IV
process. adsorption isotherm with a H3-type hysteresis loop at a relative
The current-density dependence of specic capacitance is pressure of 0.5–1.0, indicating the presence of the mesoporous
calculated from above discharge curves and plotted in Fig. 4b. structure. The pore size distribution exhibits a relatively wide
Apparently, the ZIF-67 hierarchical structure active electrode peak centered at 14.5 nm, and the BET specic surface area is
delivers specic capacitance of 202.6, 188.7, 176.6, 165.0, 153.9 412.87 m2 g
1. The specic surface area of hierarchical ower-
and 147.6 F g
1 at current densities of 0.5, 1, 2, 4, 6, and 8 A g
1, like structure is higher than the previously reported ZIF-67
respectively. In addition, the hierarchical ower-like structure nanoparticles with a BET of 316 m2 g
1.30 In order to compare
sample still retains the highest capacitance of 72.9% aer the the electrochemical performance of ZIF-67 with different
current densities increasing from 0.5 to 8 A g
1 (Fig. 4c). The morphologies, the normal ZIF-67 nanocrystal was synthesized
results in this work are higher than that previously reported according to a previous reported,30 the SEM image is shown in
mesoporous 437-MOF (81 F g
1 at 1 A g
1).18 Furthermore, the Fig. S2,† and electrochemical performance characterization for
values are comparable to the typical cobalt oxide super- supercapacitor was also studied (Fig. S3†). At the same condi-
capacitor, such as CoMoO4 nanorods (62.8 F g
1 at 1 A g
1), tion, the ZIF-67 nanocrystals active electrode delivers specic
MnMoO4 nanorods (9.7 F g
1 at 1 A g
1) and hierarchical capacitance of 155.57, 149.77, 141.99, 132.38, 127.20 and
MnMoO4/CoMoO4 nanowires (187.1 F g
1 at 1 A g
1)38 and is 121.10 g
1 at the discharge current densities of 0.5, 1, 2, 4, 6, and
even higher than nanocomposite, such as CoMoO4/MWCNTs 8 A g
1, respectively. Remarkably, the electrochemical properties
(170 F g
1 at 2 A g
1),39 but less than that of the supercapacitor of our obtained ZIF-67 hierarchical ower-like structure are
based on NiO@CoMoO4 nanocomposite40 and CoMoO4–3D better than that of ZIF-67 nanocrystals with regular structure.
graphene hybrid (NSCGH)41 electrodes. The long-term cycle The enhancement in electrochemical capacitance of the as-
ability is also key factor in practical applications of obtained ZIF-67 hierarchical ower-like structure should be
ascribed to the unique hierarchical structure and large BET
surface area, which endows massive electroactive sites for elec-
trochemical reactions and more efficient penetration of elec-
trolyte ions (OH
) into the electroactive electrode materials.
Fig. 5 shows the CVs of bare CPE (a and b) and ZIF-67-CPE
(c and d) in the absence (a and c) and presence (b and d) of
10 mM H2O2 in 0.1 M NaOH. For bare CPE, only a small
reduction peak with the onset potential of about
0.3 V was
observed when H2O2 was added in 0.1 M NaOH, however, a
sensitive reduction peak with the onset potential of about

0.3 V appeared with the ZIF-67-CPE, indicating that ZIF-67
hierarchical structure exhibited high electrocatalytic activity
toward H2O2 reduction.
Based on the ZIF-67, nonenzymatic H2O2 sensor was
developed, and the sensing property was evaluated by
amperometric i–t curve. Fig. 6 depicts the typical ampero-
metric response of ZIF-67-CPE electrode upon successive
Fig. 4 Electrochemical performance characterization of ZIF-67 hier- additions of H2O2 into a continuously stirring 0.1 M NaOH
archical flower-like structure: (a) CV curves of ZIF-67 modified elec- solution at a potential xed at
0.3 V (optimal signal–noise
trode at various sweeping rates ranging from 5 to 50 mV s
1. (b)
ratio). As shown in Fig. 6, upon addition of H2O2, a rapid
Galvanostatic charge–discharge curves of ZIF-67 at different current
densities. (c) The specific capacitances at different current densities increase in the reduction current was observed, indicating a
from 0.5 to 8 A g
1. (d) Cycling performance of ZIF-67 hierarchical fast response attributed to the excellent electrocatalytic
flower-like structure at a constant current density of 2 A g
1. activity of ZIF-67-CPE. The sensor presented a wide linear

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Fig. 7 Repeatable test of ZIF-67-CPE by successive addition of 3 mM

Fig. 5CVs of bare CPE (a and b) and ZIF-67-CPE (c and d) in the H2O2.
absence (a and c) and presence (b and d) of 10 mM H2O2 in 0.1 M
NaOH.

range from 2.5 mM to 1.08 mM (R2 ¼ 0.999) with a detection

limit of 2.5 mM (S/N ¼ 3) which is lower than Si/GO sensor
(2.6 mM),42 polynucleotide-templated silver nanoclusters/
graphene sensor (3 mM),43 silver-nanoparticle-decorated gra-
phene sensor (5 mM),44 graphene/Naon/Azure I/Au nano-
particles sensor (10 mM),45 and graphene wrapped Cu2O
nanocubes sensor (20.8 mM).46
The reproducibility and stability of the sensor were per-
formed by measuring the amperometric response to H2O2. The
average relative standard deviation (RSD) was not more than
3.9% for een successive determinations using the same
sensor, and 4.7% for six different sensors which were fabricated Fig. 8 Long-term amperometric test of ZIF-67-CPE with 80 mM H2O2.
independently by the same procedure described in Experi-
mental, indicating the good reproducibility of the method continuous running for 1600 s (Fig. 8). The as-prepared sensor
(Fig. 7). The long-term stability of the sensor was examined by a was stored in air, and the amperometric response was recorded
continuous and successive operation. The amperometric every twelve hours. It was found that the current response is
response retained about 98% of its initial value to H2O2 aer approximately 96% of the originally measured value aer two
weeks. The good operation performances of the presented
sensors could be attributed to the high stability of the ZIF-67 in
alkaline solution. The selectivity of the sensor was also exam-
ined by CVs. The results indicated that the common interfering
substances including AA, UA, glucose, and ethanol did not
interfere with the determination of H2O2.

4. Conclusions
Herein, we demonstrated ZIF-67 hierarchical ower-like struc-
ture can be synthesized by a simple method without using any
template or surfactant. Enhanced specic capacitance and good
cycle stability are observed in aqueous KOH electrolyte for ZIF-
67 hierarchical structure. In addition, the as-prepared ZIF-67
hierarchical structure exhibited good electrocatalytic activity
toward the oxidation of H2O2. The sensors presented good
reproducibility, excellent electrocatalytic activities, high
stability and wide linear range. These impressive results pre-
Fig. 6 Amperometric sensing of H2O2 by successive addition of H2O2
for ZIF-67-CPE at
0.3 V in 0.1 M NaOH. Inset: (A), amperometric sented here show great potential in designing a new type of
response at low concentration of H2O2; (B), plot of amperometric MOF structure in the future for promising applications in the
response versus the concentration of H2O2 from 2.5 mM to 1.08 mM. high performance energy storage systems and electrocatalyst.

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Acknowledgements 20 R. Dı́az, M. G. Orcajo, J. A. Botas, G. Calleja and J. Palma,

Mater. Lett., 2012, 68, 126.
Financial supports from the National Science Foundation of 21 D. Y. Lee, S. J. Yoon, N. K. Shrestha, S. H. Lee, H. Ahn and
China (no. 21405005, U1404208, 21301009), the Project Spon- S. H. Han, Microporous Mesoporous Mater., 2012, 153, 163.
sored by the Scientic Research Foundation for the Returned 22 D. Y. Lee, D. V. Shinde, E. K. Kim, W. Lee, I.-W. Oh,
Overseas Chinese Scholars, State Education Ministry, the N. K. Shrestha, J. K. Lee and S. H. Han, Microporous
Project of Science and Technology Department of Henan Prov- Mesoporous Mater., 2013, 171, 53.
ince (no. 122102310521, 122102210460, 142102210586) and 23 A. Phan, C. J. Doonan, F. J. Uribe-Romo, C. B. Knobler,
Foundation of Henan Educational Committee (no. 15A150031, M. O'Keeffe and O. M. Yaghi, Acc. Chem. Res., 2010, 43, 58.
15A150002, 13B150893) are gratefully acknowledged. We 24 B. Wang, A. P. Côté, H. Furukawa, M. O'Keeffe and
gratefully acknowledge Prof. Qisheng Huo and A. P. Yong Fan O. M. Yaghi, Nature, 2008, 453, 207.
Published on 02 July 2015. Downloaded by VIT University on 12/13/2024 10:35:31 AM.

for their helpful discussion. 25 K. S. Park, Z. Ni, A. P. Côté, J. Y. Choi, R. D. Huang,

F. J. Uribe-Romo, H. K. Chae, M. O'Keeffe and O. M. Yaghi,
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