Materials Letters 239 (2019) 94–97

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

Fast decomposition of hydrogen peroxide by Zeolitic imidazolate

framework-67 crystals
Wei Chen a, Fangming Chen a, Gao Zhang b, Shu Kong a, Wen Cai a, Jian Wang a, Liping Du a, Chunsheng Wu a,⇑
a
Institute of Medical Engineering, Department of Biophysics, School of Basic Medical Sciences, Xi’an Jiaotong University Health Science Center, Xi’an, Shaanxi 710061, China
b
School of Pharmacy, Xi’an Jiaotong University Health Science Center, Xi’an, Shaanxi 710061, China

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

Article history: The decomposition of hydrogen peroxide was determined in the neutral solution of ZIF-67 crystals. The
Received 28 September 2018 fast decomposition of H2O2 can be observed by naked eyes in seconds after mixing the reactants. A crum-
Received in revised form 13 November 2018 pled surface was observed for ZIF-67 crystals after the decomposition reaction. The decomposition reac-
Accepted 12 December 2018
tion was found to follow the first-order kinetics. Temperature-dependent studies calculated that the
Available online 20 December 2018
activation energy was 37 kJ mol
1. Based on the obtained results, a possible mechanism was proposed.
Ó 2018 Elsevier B.V. All rights reserved.
Keywords:
ZIF-67
Hydrogen peroxide
Porous materials
Functional

1. Introduction oximinopropanedione [15], N,N0 -bis(3-allylsalicylidene)o-

Zeolitic imidazolate frameworks (ZIFs), formed by bridging
metal ions center and 2-methylimidazolate (HMIM) in a sodalite
(SOD) topology are sub-family of metal organic frameworks
(MOFs) with similar structure to crystalline zeolite with excep-
tional chemical and thermal stability [1]. Due to their convenient
synthesis, unique structure and flexible component, ZIFs are
reported to be applied in various fields, from gas separation [2],
gas adsorption [3], catalyst [4], drug delivery [5], to sensing devices
[6].
Hydrogen peroxide is a widely used chemical in numerous
applications such as cleaning and bleaching. An important aspect
of hydrogen peroxide is the control of its decomposition, leading
to the loss of efficiency [7]. The hydrogen peroxide reacts with ura-
nyl ion to form the insoluble uranyl peroxide could make the reac-
tor inoperative, develop local hot spots and induce corrosion [8,9].
Moreover, the hydrogen peroxide is a harmful agent for living
being, especially for the aquaculture [10]. Various materials,
including granular activated carbon [11], transition metal oxides
[12], metal complexes [13], have been reported for the decomposi-
tion of hydrogen peroxide. Cobalt complexes and oxides have been
reported as homogeneous and heterogeneous catalysts in the
decomposition of hydrogen peroxide [14,15]. Cobalt complexes
including complexes of cobalt(II) with 1,4-piperazine-bis(carbo
thiosulfene diethylamide) [14], 1-phenyl 1-hydrazonyl 2-
⇑ Corresponding author.
E-mail address: wuchunsheng@xjtu.edu.cn (C. Wu).
phenylenediamine [16], etc. have been reported as effective
catalysts. ZIF-67 has a high porosity (surface area 1595 m2/g, pore
limiting diameter 3.3 Å) and active metal ions center, allowing the
small molecules to access in a heterogeneous way. Inspired by this,
ZIF-67 as a novel catalyst for decomposing hydrogen peroxide was
reported.
2. Experimental section
2.1. Synthesis of ZIF-67 nanoparticles and kinetic measurements
All chemicals were purchased from Sinopharm Chemical
Reagent Co., Ltd. Typically, 1.164 g Co(NO3)26H2O and 1.312 g
HMIM were dissolved in 100 mL methanol, respectively. The two
solutions were mixed and stirred at room temperature for 1 h.
The products were collected by the centrifugation method, washed
with methanol and deionized water several times and dried under
vacuum at 50 °C for 24 h.
Various amounts of ZIF-67 were added to a constant concentra-
tion of hydrogen peroxide at 25 °C. The concentration of the hydro-
gen peroxide in the solution was determined by the titanium
oxysulfate colorimetric method (kabs = 415 nm).
2.2. Characterization
UV–Vis spectrophotometer (UNIC UV2600) was applied in the
determining the concentration of hydrogen peroxide. Power
X-ray diffraction (XRD) were recorded on a using Shimadzu

https://doi.org/10.1016/j.matlet.2018.12.064
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
 W. Chen et al. / Materials Letters 239 (2019) 94–97
XRD-6100 Cu Ka radiation (k = 1.54059 Å) at 40 kV and 30 mA. The
morphology and microstructure were characterized by the scan-
ning electron microscope (SEM, TESCAN MALA3 LMH).
3. Results and discussion
ZIF-67 crystals with a polyhedral shape and smooth surface
and an average size of 1 lm could be found obviously (Fig. 1a).
Energy Dispersive Spectroscopy (EDS) result showed there are
Co, C, and O elements in the crystals. A crumpled structure was
formed after the decomposing hydrogen peroxide reaction
(Fig. 1b). Compared with ZIF-67, the increase concentration of
oxygen elements in the crystals was observed. XRD patterns
proved the crystal structure of ZIF-67 was in good accordance
with the stimulated one [17]. Besides, there is no obvious differ-
ence in the crystalline of ZIF-67 through the catalyst reaction. The
formation of cobaltous oxide and the coordination of H2O2 to the
crystals could lead to the higher concentration of oxygen ele-
Fig. 1. SEM images of ZIF-67 NPs (a) before and (b) after decomposing hydrogen peroxide reaction; EDAX analysis of ZIF-67 NPs (c) before and (d) after reaction; (e) XRD
pattern of ZIF-67 NPs; (f) DLS analysis of ZIF-67 NPs.
95
ments [18]. Besides, it was difficult to determine the Co/O ratio
of the structure since the nanoflakes are only distributed on the
surface. Hence, the possible composition and formation mecha-
nism of the crumpled materials were still unclear. The size and
dispersity of ZIF-67 did increased after the reaction, which was
in good accordance with SEM results. Dynamic light scattering
(DLS) results showed the increase of size after the reaction,
caused by the crumpled surface (Fig. 1f).
The titanium oxysulfate colorimetric method was used to deter-
mine the decomposition (Fig. S1). A slow catalytic activity was
observed in the absence of Co(NO3)2 and Fe-MIL-53, respectively.
However, in the heterogeneous phase of ZIF-67, the catalytic dis-
proportionation was enhanced considerably. Compared with Horse
Radish Peroxidase (HRP), ZIF-67 crystal has a much higher catalytic
activity. The fast decomposition of hydrogen peroxide could be
obviously observed by the naked eyes (Supporting video). After
adding the hydrogen peroxide to the crystals’ solution, the bubbles
were formed within several seconds.
96 W. Chen et al. / Materials Letters 239 (2019) 94–97
Video S1.
The decomposition of hydrogen peroxide followed the first-
order decay kinetics, similar to previous reports [15,19]. To the
fixed concentration of H2O2, the higher concentration of catalyst
lead to the higher decomposition rate. The decomposition rate
coefficient k was 2.82  10
2, 7.85  10
2, and 4.30  10
1 min
1,
respectively. Typical results for ln k were showed in Fig. 2 as a func-
tion of the resident time with temperature. Four different temper-
atures (30 °C, 40 °C, 50 °C and 60 °C) were applied and a linear
dependence was observed at each temperature, indicating the
decomposition of H2O2 in the presence of ZIF-67 followed the
first-order kinetics. The rate coefficients are 4.30  10
1,
7.84  10
1, 1.31, and 3.47 min
1, individually, which was higher
than that of cobalt salts and complexes [15]. Compared with the
Fig. 2. (a) Decomposition of hydrogen peroxide with various catalysts; (b) kinetics of decomposition of hydrogen peroxide (20 mM) catalyzed by ZIF-67 at different
concentrations at 25 °C, pH 7.0; (c) kinetics of decomposition of hydrogen peroxide (20 mM) catalyzed by ZIF-67 (300 lg/mL) at different temperatures; (d) Arrhenius plots of
ln k as a function of inverse temperature for ZIF-67.
smooth surface of ZIF-67, the formed crumpled surface could
increase the surface area of the catalysts, speeding up the reaction.
In the lower temperature, the size effect may be more obviously. As
the synthesized ZIF-67 having a broad size distribution, the devia-
tions in the lower temperature were larger than in higher
temperature.
A temperature-dependent decay rate can be analysed by the
standard Arrhenius equation and the activation energy can be cal-
culated correspondingly. The activation energy was proportional to
the slope of the lines through the data of Fig. 2d. The activation
energy of decomposition of H2O2 by ZIF-67 was 37 kJ mol
1, lower
than reported cobalt complexes and metal oxides, supporting the
experimental result. Furthermore, the observed activation energy
of 37 kJ mol
1 was less than the 210 kJ mol
1 for cleavage of the
O–O bond in H2O2, indicating the involvement of ZIF-67 in the
decomposition reaction [19].
In ZIF-67, cobalt atom is bridged with four nitrogen atoms by
coordination bonds to form an octahedral geometry. It is reported
that Co(PHOPD)2 complex has two electrons in the eg orbitals and
hence the ligand field stabilisation energy (LFSE) is not very high
[15]. The hydrogen peroxide decomposition reaction is therefore
expected to be relatively faster. In this work, ZIF-67 has a similar
structure to that of Co(PHOPD)2 complex. Inspired by this, a simpli-
fied decomposition mechanism was proposed. Organic ligands
could provide coordination bonds and crystal field, similar to
PHOPD. Cobalt centers act as the catalytic center. Firstly, H2O2 is
coordinated with cobalt atom in the ZIF-67 [20]. The H2O2 is depro-
tonated to form OOH
, which will be deoccupied from coordina-
tion site and formed O2 (see Fig. 3).
 W. Chen et al. / Materials Letters 239 (2019) 94–97
Fig. 3. Scheme of decomposition of hydrogen peroxide by ZIF-67 crystals.
4. Conclusion
ZIF-67 crystals were synthesized and used as catalysts for the
decomposition of H2O2 in aqueous solution. A fast decomposition
of hydrogen peroxide could be observed by the naked eyes after
adding H2O2 to the ZIF-67 solution. After the reaction, a crumpled
surface was observed in the crystals. First-order kinetics were fol-
lowed for the decomposition reaction. From the Arrhenius equa-
tion, the activation energy was calculated to be 37 kJ mol
1.
Based on the obtained results, a simplified reaction mechanism
was proposed.
Acknowledgements
This work was financially supported in part by grants from the
National Natural Science Foundation of China (Nos. 31470956,
51861145307, 31661143030 and 31700859), the Doctoral Fund
of Education Ministry of China (No. 2018M633524).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matlet.2018.12.064.
97
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