Materials Letters 101 (2013) 93–95

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

Metal-organic framework as a template for synthesis of magnetic CoFe2O4

nanocomposites for phenol degradation
Feng-Xiang Qin a, Shao-Yi Jia a, Yong Liu b, Xu Han c,d, Hai-Tao Ren a, Wei-Wei Zhang a,
Jing-Wei Hou e, Song-Hai Wu a,n
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin, PR China
b
School of Chemistry & Chemical Engineering, Tianjin University of Technology, Tianjin, PR China
c
State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin, PR China
d
School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin, PR China
e
Petrochemical Research Institute of PetroChina, Beijing, PR China

ar t ic l e i nf o a b s t r a c t

Article history: This paper presents a facile strategy for preparing magnetic CoFe2O4 nanocomposites using a metal-
Received 25 January 2013 organic framework (MOF) as both template and precursor for the first time. In this approach, cobalt
Accepted 16 March 2013 nitrate hexahydrate as a second precursor was immobilized into the pores of MOF by incipient wetness
Available online 25 March 2013
impregnation. Then, magnetic CoFe2O4 nanocomposites were produced under several calcined condi-
Keywords: tions in air. Interestingly, the as-obtained nanocomposites still kept the morphology of MOF. The
Metal-organic framework composition of nanocomposites varied with the molar ratio of Fe/Co. The structure, morphology and
Magnetic materials magnetic behavior of the nanocomposites were characterized by powder X-ray diffraction (XRD),
Nanocomposites scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). The as synthesized
Phenol degradation
magnetic nanomaterials showed relatively high catalytic performance for oxidation degradation of
phenol using potassium peroxymonosulfate (PMS) as oxidant.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction capacity has been prepared using a zeolite-type metal-organic

The application of magnetic particles in solving environmental
problems has received considerable attention in recent years. The
spinel cobalt ferrite as a kind of typical magnetic material has
attracted intensive attention due to its high coercivity, moderate
saturation magnetization, fine mechanical and chemical stability.
Its magnetic properties are bound up with the morphology,
dimension, and crystallinity of the nanocrystals [1]. Many efforts
were made to prepare CoFe2O4 crystals with various nanostruc-
tures. There are many approaches for the synthesis of such spinel
cobalt ferrite, but the templating method allows more control over
its structures and properties [2]. Porous metal-organic frameworks
(MOFs), which exhibit high specific surface area, well-defined
structure and chemical tunability, can be used as templates in
the synthesis of nanoporous carbon and metallic nanoparticles [3–5].
Novel ZnO-based nanostructured architectures were successfully
synthesized via simple heat treatment of MOF-5 under different
atmospheric conditions [4]. Nanoporous carbon material with an
unexpectedly high surface area and considerable hydrogen storage
n
Corresponding author. Tel.: þ86 022 87401961.
E-mail address: songhaiwu@gmail.com (S.-H. Wu).
framework (ZIF-8) as both a precursor and a template [5].
Phenols and their derivatives are considered as the important
pollutants since they are harmful to organisms even at very low
concentration. The most effective techniques to degrade organic
compounds are advanced oxidation processes (AOPs) which are
based on the generation of reactive species, such as hydroxyl
radicals and sulfate radicals [6]. Heterogeneous photocatalysis has
been widely used technique for phenol degradation [7–9]. Fenton
reaction involving hydrogen peroxide and Fe ion has also been
extremely popular. However, it has a major disadvantage of
requiring a low pH (∼3). In order to eliminate the drawback of
Fenton reagent, sulfate radical produced by sulfate based oxidant
was recently investigated [10]. In the presence of peroxymono-
sulfate (PMS), the spinel CoFe2O4 can be used as heterogeneous
catalyst for pollutant degradation and can be easily recovered
under external magnetic field [11,12].
To the best of our knowledge, there is no report about synthesis
of magnetic particles based on MOF-template method. Here we
report the synthesis of α-Fe2O3/CoFe2O4, Co3O4/CoFe2O4, α-Fe2O3/
Co3O4/CoFe2O4 nanocomposites using Fe-containing MOF
(MIL100-Fe) as a template for the first time. The nanocomposites
exhibited excellent catalytic performance for phenol oxidation
degradation in aqueous solution using PMS as oxidant.

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.03.085
94 F.-X. Qin et al. / Materials Letters 101 (2013) 93–95
2. Experimental
Materials preparation: MIL100-Fe was synthesized according to
Horcajada et al. [13]. In a typical synthesis of nanocomposites, 300 mg
MIL100-Fe was dispersed in 15 mL ethanol and 290 mg Co
(NO)2  6H2O were dissolved in 5 mL ethanol (molar ratio of Fe/Co as
1:1). Then Co solution was added dropwise to MIL100-Fe solution at
room temperature with vigorous stirring for 24 h. The mixed ethanol
solution was evaporated at 80 1C for 4 h. The obtained solid was then
calcined at different temperatures (400 1C, 500 1C or 600 1C) for 4 h.
Materials with different Fe/Co molar (2:1 and 1:2) were obtained via
similar process. The materials were designated as MIL100-Fe-x:y-z,
where x:y denotes the molar ratio of Fe/Co and z denotes the heating
temperature.
Materials characterization: The surface morphologies of the
nanocomposites were examined by a field emission scanning
electron microscope (FE-SEM, JEOL JSM-6700F). Powder X-ray
diffraction patterns were collected using Cu-Kα radiation on
Fig. 1. XRD patterns of the materials obtained under different conditions.
(1) MIL100-Fe; (2) MIL100-Fe-500; (3) MIL100-Fe-1:1-400; (4) MIL100-Fe-1:1-
500; (5) MIL100-Fe-1:1-600; (6) MIL100-Fe-1:1-700; (7) MIL100-Fe-2:1–700; and
(8) MIL100-Fe-1:2-700.
Fig. 2. SEM of the materials obtained under different conditions. (a) MIL100-Fe-500; (b) MIL100-Fe-1:1-400; (c) MIL100-Fe-2:1-400; (d) MIL100-Fe-1:1-500; (e) MIL100-Fe-
1:1-600; and (f) MIL100-Fe-1:1-700.
Rigaku D/max 2200/PC diffractometer (Rigaku Corporation, Japan).
Magnetic characterization was conducted on a vibrating sample
magnetometer (VSM, LDJ, 9600-1) at 300 K.
Catalytic properties measurement: To study the catalytic oxida-
tion degradation of phenol, 0.2 g PMS was added to 50 mL 50 mg/L
phenol solution. Then, 10 mg catalysts were added to initiate the
reaction. The reaction was carried on for 120 min and stirred at
room temperature. Phenol concentrations were determined by
means of 4-aminoantipyrine (4-AAP) spectrophotometric method
using a UV1700 visible spectrophotometer at 510 nm [14]. For the
recycle test of the catalysts, after each run, the catalysts were
separated by magnet and thoroughly washed with deionized
water, then dried in vacuum oven at 80 1C for 6 h.
3. Results and discussion
Fig. 1 depicts XRD patterns of the as-prepared materials under
different conditions. Only α-Fe2O3 (JCPDS 33-0664) phase were
observed after calcination of MIL100-Fe at 500 1C. The result
illustrates that the pore structure of MIL100-Fe was completely
destroyed. All the other materials showed intensive peaks
Fig. 3. Magnetic hysteresis of the materials at T ¼ 300 K.
 F.-X. Qin et al. / Materials Letters 101 (2013) 93–95
Fig. 4. Phenol oxidation degradation using nanocomposites as catalysts. (a) Degradation with different materials; and (b) degradation in consecutive runs using the recycled
catalysts.
attributed to CoFe2O4 (JCPDS 03-0864) phase. The peaks become
sharper and more intense as the temperature increases from
400 1C to 700 1C. The average grain size of the CoFe2O4 phase
was determined by fitting the (311) peak in the XRD pattern, using
the Scherrer formula. The result shows that the size of the CoFe2O4
particle was 6.7, 15.5, 28.8 and 37.9 nm, which keeps the same
trend with the SEM results (Fig. 2). Materials obtained at 400 1C
and 500 1C were composed of obvious CoFe2O4 phase, subcrystal-
line α-Fe2O3 and subcrystalline Co3O4 (JCPDF 43-1003). MIL100-
Fe-1:1-600 also indicates the co-existence of CoFe2O4, α-Fe2O3 and
Co3O4. MIL100-Fe-1:1-700 was composed of single pure CoFe2O4
phase. MIL100-Fe-2:1-700 showed intensive peaks attributed
to CoFe2O4 and α-Fe2O3, while MIL100-Fe-1:2-700 indicates the
co-existence of CoFe2O4 and Co3O4.
SEM results were shown in Fig. 2. Although Fig. 2(a) indicates
that the morphology of MIL100-Fe was integrated, the lattice
structure was completely destroyed (Fig. 1-(2)) under the pyrolysis
process. After the cobalt ions were introduced into cavities and
channels of MIL100-Fe, CoFe2O4 spherical particles formed at its
secondary building units (SBU). The mean particle sizes of CoFe2O4
in nanocomposites obtained at 400 1C, 500 1C, 600 1C and 700 1C
were 31, 44, 50 and 55 nm respectively according to the random
statistical results from SEM patterns. The spherical CoFe2O4
particles in MIL100-Fe-2:1-400 were unconspicuous. The reason
may be that subcrystalline CoFe2O4 and α-Fe2O3 nanoparticles
formed at 400 1C. Moreover, as the calcination temperature
increased, monodispersed CoFe2O4 particles emerged and further
increased the interspace between each CoFe2O4 particle.
The magnetization–magnetic field (M–H) hysteresis loops of
the nanocomposites obtained at different temperatures were
shown in Fig. 3. The results indicate that all the nanocomposites
are magnetic. The saturation magnetization (Ms) of MIL100-Fe-
1:1-400 and MIL100-Fe-1:1-500 is 15.97 emu/g and 27.87 emu/g,
respectively. It may be due to the bigger size of magnetic particles
in MIL100-Fe-1:1-500. And the remanent magnetization (Mr) and
magnetic coercive field (Hc) change according to the temperature.
Higher temperature leads to higher remanent magnetization and
higher magnetic coercive field. Moreover, molar ratio of Fe/Co also
affects the saturation magnetization (data not shown).
The application of magnetic nanoparticles in the phenol degra-
dation was also studied. As is shown in Fig. 4(a), after 120 min of
degradation, the phenol concentration was reduced by 97.6%,
98.4%, 95.4%, 95.0%, 75.2% and 94.9%. The regenerated catalysts
exhibited good performance and stability (Fig. 4(b)). Phenol can
95
still be completely degraded within 120 min in all three runs
except MIL100-Fe-1:2-700. The reason may be that Fe(III) has a
promotion effect on the regeneration of Co(II)–OH complexes,
which is the rate-limiting step for Co(II)-mediated PMS activation
process, while Co3O4 has been demonstrated inferior in this
process [15]. However, MIL100-Fe-1:2-700 was composed of
Co3O4 and CoFe2O4 while none of Fe(III).
4. Conclusions
In summary, magnetic α-Fe2O3/Co3O4/CoFe2O4, α-Fe2O3/CoFe2O4
and Co3O4/CoFe2O4 nanocomposites can be prepared using MIL100-
Fe as a template by a simple and facile calcining process. The as-
prepared nanocomposites exhibited magnetic properties and promis-
ing performance for phenol oxidation degradation using PMS as
oxidant. The strategy presented in this work may be extended to the
preparation of other metal oxides and nanocomposites.
Acknowledgments
This study was supported by the National Natural Science
Foundation of China (Nos. 41003040; 41201487), the Natural
Science Foundation of Tianjin (No. 10JCYBJC06000) and the Pro-
gram of Introducing Talents of Discipline to Universities (B06006).
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