Journal of Alloys and Compounds 564 (2013) 55–62

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Journal of Alloys and Compounds

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Synthesis of ZnFe2O4/ZnO nanocomposites immobilized on graphene with

enhanced photocatalytic activity under solar light irradiation
Lin Sun a,b, Rong Shao a,⇑, Lanqin Tang a,⇑, Zhidong Chen b
a
College of Chemical and Biological Engineering, Yancheng Institute of Technology, 9 Yingbin Avenue, Yancheng 224051, PR China
b
Institute of Petrochemical Technology, Changzhou University, Changzhou 213164, PR China

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

Article history: Magnetically recyclable ZnFe2O4/ZnO nanocomposites immobilized on different content of graphene
Received 4 January 2013 with favorable photocatalytic activity under solar light irradiation were successfully prepared on the
Received in revised form 16 February 2013 basis of an ultrasound aided solution method. The molar ratio of ZnFe2O4 to ZnO and the content of
Accepted 21 February 2013
graphene could be controlled by adjusting the amount of zinc salts and graphene oxide dispersions.
Available online 6 March 2013
The most excellent photocatalytic activity under solar light irradiation was displayed when the molar
ratio of ZnFe2O4 to ZnO was 0.1 and the weight ratio of graphene to ZnFe2O4/ZnO was 0.04. Furthermore,
Keywords:
the presence of magnetical ZnFe2O4 will facilitate the recycling process of photocatalyst nanoparticles.
ZnFe2O4/ZnO
Nanocomposite
Ó 2013 Elsevier B.V. All rights reserved.
Graphene
Photocatalysis

1. Introduction nanocomposites such as SnO2–ZnO [11], ZnO/CdS [12], ZnO/In2O3

Environmental problems such as air pollution, soil contamina-
tion, especially refractory wastewater produced by some noxious
organics, have aroused much attention in the area of environmen-
tal remediation [1]. Over past few decades, nano-semiconductor
photocatalysts offer an extremely convenient route for eliminating
the crisis of water pollution inasmuch as various organic pollutants
can be easily degraded under UV or solar light irradiation in the
presence of photocatalysts [2–4].
Nano zinc oxide (ZnO) with features of high activity, chemical
stability, morphology controllable preparation, and environmental
friendly has been widely used as photocatalysts [5]. Unfortunately,
ZnO has a wide bandgap of 3.2 eV, which is unfavorable for absorp-
tion and utilization of visible light region of solar light. Namely
light with shorter wavelength (below 385 nm) can be employed
to drive ZnO to generate electron–hole pairs [6,7]. It is well known
that the major hindrance for enhancing photocatalytic efficiency of
pure semiconductor photocatalysts is the fast recombination of
photogenerated electron–hole pairs [8,9]. One of effective strate-
gies to address this problem is to prepare semiconductor nanocom-
posites, which will facilitate the charge migration [10]. Especially,
the combination of P-type semiconductor and N-type semiconduc-
tor, as well as non-mental doping semiconductors will improve the
photocatalytic activity significantly. In recent years, some
researchers have devoted to this area and many semiconductor
⇑ Corresponding authors. Tel./fax: +86 515 8829 8615.
E-mail addresses: sr@ycit.cn (R. Shao), sulisky00@126.com (L. Tang).
[13], NiO/ZnO [14], Cu2O/ZnO [15], and N doped Cu2O [16] have
been successfully synthesized.
At the same time, it is noteworthy that some spinel materials,
including ZnFe2O4, are a class of semiconductors with narrow
bandgaps. These semiconductors exhibit characteristics of excel-
lent visible-light response, good photochemical stability, as well
as favorable magnetism [17,18]. Although these materials with
such superior properties open up a promising gate for applications
in photocatalysis oxidation, they are seldom used as photocatalysts
independently due to the lower valence band potential and poor
property in photoelectric conversion [19]. Based on the fundamen-
tal theory of photocatalysis, it is not difficult to envisage that an-
other profitable pathway to improve the photocatalytic activity is
looking for some supporting medium with outstanding electric
conductivity. Photoinduced electrons can be transferred rapidly
by conductive supporters, simultaneous leaving more positive
holes, so as to remarkably enhance the photocatalytic efficiency
[20]. Among various conducting materials, carbon material, espe-
cially two-dimensional (2D) graphene which was first obtained
by Geim et al., has been received extensively concern for use in
the area of photocatalysis [21–24].
Recently, hot semiconducting materials have aroused many
interests [25–27]. It had been reported that the ZnFe2O4/TiO2
nanomaterial could be served as photocatalyst and modified elec-
trode [28–30]. However, the preparation process usually involved
high temperatures or some complicated fabricating methods,
which would limit the production in a large scale. Meanwhile,
the photocatalytic activity of ZnFe2O4/TiO2 nanocomposite under

0925-8388/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.02.147
56 L. Sun et al. / Journal of Alloys and Compounds 564 (2013) 55–62

solar light irradiation was also restrained [31]. On the other hand,
some researchers also had conducted a series of investigations on
the ferrite–graphene-based magnetical photocatalysts with visi-
ble-light-response, such as ZnFe2O4/graphene [32], NiFe2O4/graph-
ene [33], and CoFe2O4/graphene [34]. Unfortunately, in the absence
of H2O2, the composite photocatalysts exhibited inferior photocat-
alytic activity under solar light irradiation. Namely H2O2 played
crucial roles in the photocatalysis oxidation but it was considered
as introduced contaminant to some extent.
Therefore, from views of protecting the environment, enhancing
the photocatalytic activity and improving the visible light absorp-
tion region of solar light spectrum, the conjugation between semi-
conductor nanocomposites and graphene seems tremendously
meaningful. In the present work, we selected the nanocomposite
of P-type ZnFe2O4 and N-type ZnO as photocatalyst, successfully
synthesized ZnFe2O4/ZnO nanocomposites immobilized on graph-
ene and investigated their photocatalytic activity under solar light
irradiation, including the effects of ZnFe2O4 content and graphene
content on the photocatalytic efficiency. The molar ratio of ZnFe2O4
to ZnO could be adjusted easily because of the growth-tunable of
ZnO. On the other hand, the excellent photocatalytic activity of
the novel material was exhibited without any assisted reagents.
The formation of ZnFe2O4/ZnO nanocomposites as well as the pres-
ence of graphene efficiently facilitated the charge transfer and im-
proved the photocatalytic reactivity under solar light irradiation.
Meanwhile, the existence of magnetic ZnFe2O4 nanoparticles pro-
vided a convenient route for recycling the photocatalyst by an
external magnetic field. The prepared samples were characterized
by X-ray diffraction (XRD), scanning electron microscopy (SEM),
transmission electron microscopy (TEM), energy-dispersive X-ray
spectroscopy (EDS), UV–vis diffuse reflectance spectra (UV–vis
DRS), fourier transform infrared (FT-IR) and X-ray photoelectron
spectroscopy (XPS). Photochemical experiments of the obtained
samples were carried out by choosing methylene blue (MB) as a
model target under UV and solar light irradiation. To our best
knowledge, the novel composite material had never been reported
previously.
2. Experimental
2.1. Materials
of the above suspension. After reaction at 80 °C for 5 h, the ZnFe2O4/ZnO nanocom-
posite was finally obtained. The optimum molar ratio of ZnFe2O4 to ZnO had been
investigated in literature [32]. The sample prepared under optimum condition
was labeled with MZ-1 and was chosen as raw material for the preparation of
ZnFe2O4/ZnO nanocomposites immobilized on graphene.
2.4. Preparation of ZnFe2O4/ZnO nanocomposites immobilized on graphene
20 mL of of prepared GO dispersions was transferred into 180 mL of distilled
water containing 0.4 g of sample MZ-1. The suspension was ultrasonic agitated
for 10 min (120 W, 40 KHz) and then mechanically stirred for 24 h at room temper-
ature. After that, 200 lL of ammonia and 38 lL of 80 wt% hydrazine hydrate were
added, reacting at 95 °C for 1 h. The obtained precipitate was collected by a magnet
and washed with distilled water thoroughly and dried in vacuum oven at 40 °C. The
sample was designated as MZG(4%). Similarly, samples with different graphene
content were also prepared. For comparison, bare ZnFe2O4 and bare ZnO immobi-
lized on graphene were obtained using the same preparing method. The detailed
information was presented in Table 1.
2.5. Photochemical experiments
Photocatalytic activity of the obtained samples was evaluated at a photochem-
ical reaction apparatus, the schematic diagram was shown in Fig. 1. A 500 W xenon
lamp (the wavelength distribution was similar to that of solar light) was used as the
light source. For each experiment, 70 mg of photocatalyst was dispersed in 500 mL
of 10 mg/mL of MB aqueous solution, Prior to the irradiation, the suspension was
magnetically stirred in the dark for 30 min to ensure the adsorption/desorption
equilibrium of MB solution with the photocatalyst. 5 mL of the aliquots were sam-
pled and analyzed by recording variations in the absorption band (663 nm) in the
UV–vis spectra of MB.
2.6. Characterization
X-ray diffraction (XRD) patterns were recorded on a DX2700 diffractometer
using Cu Ka radiation (k = 0.154056 nm) at 40 kV and 35 mA in the range of 2h va-
lue between 5° and 80°. The morphology and grain size of the obtained products
Table 1
Summarized sample designations of ZnFe2O4/ZnO immobilized on graphene with
different mass ratio of GO to ZnFe2O4/ZnO nanocomposites.
Constituent of Mass ratio of GO to ZnFe2O4/ZnO Lable
photocatalysts (%)
ZnFe2O4 4 MG(4%)
ZnO 4 ZG(4%)
ZnFe2O4 + ZnO(MZ-1) 2 MZG(2%)
ZnFe2O4 + ZnO(MZ-1) 4 MZG(4%)
ZnFe2O4 + ZnO(MZ-1) 6 MZG(6%)

All chemicals and reagents were of analytical purity and used as received with-
out further purification. Distilled water was used throughout.

2.2. Preparation of graphene oxide (GO) dispersions

The detailed fabrication process of GO dispersions has been described in re-

ported literature [35]. In a typical synthesis, 2.00 g of flake graphite, 2.00 g of NaNO3
and 96 mL of concentrated H2SO4 were mixed and magnetically stirred in an ice
bath. Then, 12.00 g of KMnO4 was gradually added to the above mixture. The
formed pasty suspension was first stirred at nearly 0 °C for 90 min and then at
35 °C for 2 h. After that, 80 mL of distilled water and 10 mL of 30 wt% H2O2 were
added dropwise to the mixture with continuous stirring. The mixture solution
was vigorously agitated for another 10 min and then centrifuged at a high speed
of 14 000 rpm, the collected graphite oxide was washed with distilled water until
pH = 7. The exfoliation process of graphite oxide was carried out in a mild ultrasonic
environment (80 W, 5 min), and the formed suspension after ultrasonic treatment
was centrifuged for 5 min at a relatively low speed of 5000 rpm. GO, namely the
supernatant was obtained. Moreover, the concentration of GO suspension was
determined by the method of weighing, and the resultant concentration of GO
was 0.8 mg/mL.

2.3. Synthesis of ZnFe2O4/ZnO nanocomposites

The preparing procedure of ZnFe2O4/ZnO nanocomposites was according to our

previous study [36]. Briefly, at first, pure ZnFe2O4 nanoparticles were synthesized
via a hydrothermal method accompany with Zn(NO3)26H2O and Fe(NO3)39H2O
as the main salts. Then, a certain amount of pure ZnFe2O4 nanoparticles and
Zn(NO3)26H2O were dispersed in 110 mL of ethanol, the mixture was ultrasonic
agitated for several minutes. KOH ethanol solution was used to adjust the pH value Fig. 1. Schematic diagram of photocatalytic apparatus.
 L. Sun et al. / Journal of Alloys and Compounds 564 (2013) 55–62 57

were characterized with scanning electron microscopy (SEM, JSM-7500F). Trans-

(A) mission electron microscopy (TEM). Energy-dispersive spectroscopy (EDS) using a
(002)
FEI Tecnai G20 was utilized to have a further acknowledgment of the microstruc-
tures and chemical composition of the products. Fourier transform infrared (FT-
IR) spectra was measured by the KBr pellet method with a NEXUS-670 analyzer.
Intensity (a.u.)

Surface electronic states were analyzed by X-ray photoelectron spectroscopy

(XPS, ESCALABMKLL). UV–vis diffuse reflectance spectra were measured at room
temperature in the 250–800 nm wavelength using an UV–vis spectrometer (UV-
2450). Magnetic property of the sample was measured using a superconduction
(a)
quantum interference device (SQUID, MPMS-XL-7).
(b)

(004)
(c) 3. Results and discussion

10 20 30 40 50 60 3.1. XRD analysis

2θ (degree)
Fig. 2A shows the XRD pattern of graphene (a), graphene oxide
(b), and nature graphite (c), respectively. The peak located at 26.4°
(B) • • ZnO
and 55.3° is corresponded to the (0 0 2) and (0 0 4) facet of graphite
♣ ZnFe 2 O4
accordingly. The characteristic diffraction peak of exfoliated GO is
•
• ♣ observed at 11.3°. Meanwhile, 0.78 nm of interlay space (d-spac-
♣ ing) of GO (2h = 11.3°) is significantly larger than that of nature
♣
Intensity (a.u.)

• graphite (0.34 nm, 2h = 26.4°), which confirms the introduction of

♣ •
♣ ♣ ♣ (d) oxygen-containing functional groups [37]. The graphene sheet
exhibits a broad diffraction peak located at about 24°, and the cor-
responding interlay spacing value is 0.37 nm. The lower d-spacing
(e) value compared with GO (0.78 nm) well illuminates the reduction
of graphene oxide after treatment with hydrazine hydrate for 1 h.
The typical XRD pattern of MZG(4%) (d), MZ-1 (e), and pure
(f)
ZnFe2O4 NPs (f) is presented in Fig. 2B, respectively. Peaks centered
20 30 40 50 60 70 80 at 30°, 35°, 43°, 54°, 57°, and 62° in pattern f can be indexed to
2θ (degree) (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0) crystal planes of cu-
bic spinel ZnFe2O4, and the corresponding positions are also de-
Fig. 2. XRD patterns of (a) graphene, (b) graphene oxide, (c) nature graphite, (d) tected in pattern d and e. Moreover, the diffraction peaks of 32°,
MZG(4%), (e) MZ-1, and (f) pure ZnFe2O4 NPs, respectively. 34°, 36°, 48°, 69°, and 77° in pattern d and e are corresponded to

(A) (B)

(C) 10.28%
Cu 16.34%
O
C Fe
Intensity (a.u.)

Atomic % Zn
1.27%
7.83%
64.28%
C
Zn
Cu
Zn
O
Fe Cu Zn

2 4 6 8 10
Energy (KeV)

Fig. 3. (A) SEM image of pure ZnFe2O4 nanoparticles, (B) TEM image of MZG(4%), and (C) EDS spectrum of MZ-1.
58 L. Sun et al. / Journal of Alloys and Compounds 564 (2013) 55–62

(1 0 0), (0 0 2), (1 0 1), (1 0 2), (2 0 1) and (2 0 2) of ZnO with hexago- nanoparticles, and the sphere-like NPs with a diameter of 10–
nal wurtzite structure. It is interesting to find that no obvious dif- 20 nm. Fig. 3b is the TEM image of MZG(4%). As shown in Fig. 3b,
ferences are displayed in XRD patterns of sample MZ-1 and the size of the grain is 20–30 nm, which is larger than bare ZnFe2-
MZG(4%), and the broad peak of graphene is not detected, which O4 observed in Fig. 3a, implying the combination of ZnFe2O4 and
is probably ascribed to the low amount and relatively low diffrac- ZnO NPs. Meanwhile, the 2D graphene layer can be confirmed dis-
tion intensity of graphene [22]. tinctly (the arrow directions), indicating the successful formation
of ZnFe2O4/ZnO nanocomposites immobilized on graphene.
3.2. SEM, TEM and EDS Fig. 3c shows the results of EDS analysis of sample MZ-1. The peaks
of Fe, Zn, O elements are detected (The peaks of Cu and C elements
Fig. 3a shows a typical SEM image of pure ZnFe2O4. It is clearly come from the supporting TEM grid). Furthermore, the mass ratio
illustrated that the pure ZnFe2O4 sample is constructed with lots of of Fe to Zn is 0.16, which is close to the expected value of 0.18.

(A) (B) Zn 2p
Zn 2p

Survey
2p3/2
Zn 2p

Intensity (a.u.)
Intensity (a.u.)

2p1/2
Zn LMM
O 1s
Fe 2p
O KLL

C 1s

Fe 3p
Zn 3s

Zn 3d

1200 1000 800 600 400 200 0 1050 1045 1040 1035 1030 1025 1020
Binding Energy (eV) Binding Energy (eV)

(C) Fe 2p (D) H2O

O 1s
Intensity (a.u.)

2p3/2
Intensity (a.u.)

2p1/2
2p3/2 Zn-O

C-O-C

730 725 720 715 710 705 538 536 534 532 530 528 526
Binding Energy (eV) Binding Energy (eV)

(E) C 1s (F) 160

C=C 140
(b)
120
C-C
% Transmittance
Intensity (a.u.)

100
(a)
80
1580

60
C=O
1723
3400

1630

40
1370

20
1060

0
4000 3500 3000 2500 2000 1500 1000
290 288 286 284 282
Binding Energy (eV) Wavenumbers (cm-1)

Fig. 4. XPS and FT-IR spectrums of MZG(4%): (A) the whole XPS spectra; (B) Zn 2p region; (C) Fe 2p region; (D) O 1s region; (E) C 1s region, and (F) FT-IR spectrums of (a)
graphene oxide, and (b) graphene.
 L. Sun et al. / Journal of Alloys and Compounds 564 (2013) 55–62
3.3. XPS and FT-IR
In order to investigate the surface chemical compositions and
valance state of the obtained samples, X-ray photoelectron spec-
troscopy (XPS) analysis is employed, and the corresponding results
are shown in Fig. 4A–E. Fig. 4A exhibits the survey XPS spectra for
the representative ZnFe2O4/ZnO nanocomposites immobilized on
graphene of MZG(4%). Elements of Zn, Fe, O, and C are observed
in the whole XPS spectra, and no any other elements can be de-
tected, which is consistent with the EDS results. In Fig. 4B, two
peaks centered at 1044.4 eV and 1021.4 eV (no obvious shifts can
be found when compared with pure ZnFe2O4) are assigned to Zn
2p1/2 and Zn 2p3/2, respectively, implying that Zn element exists
mainly in the form of Zn2+ chemical state on the sample surface
[38,39]. The main peaks of Fe 2p1/2 and 2p3/2 are observed at
725.1 eV and 711.6 eV, respectively. Furthermore, a satellite peak
of the Fe 2p3/2 also can be detected at the position of 719.1 eV,
which is well agreement with the reported value for Fe3+ com-
pounds [40,41]. Fig. 4D shows four main peaks of O 1s with the
binding energy of 533.7 eV, 531.9 eV and 530.2 eV, which is as-
signed to the CAO bond in the form of CAOAC occurred in graph-
ene sheets, adsorbed water, and ZnAO bonds in both ZnO and
ZnFe2O4, respectively [42,43]. The peaks of C 1s are found at
288.5 eV, 285.3 eV, and 284.5 eV in Fig. 4E, which is attributed to
the C@O bond, CAC bond and C@C bond, respectively. It is clearly
seen that the intensity of oxygenated functional group (C@O) is
obviously lower than that of CAC and C@C, demonstrating a well
reduction of graphene oxide after treatment with hydrazine
(A)
MZ-1
Absorbance (a.u.)
MZG(4%)
ZnO
300 400
Wavelength (nm)
(B) 1.0
0.8
(αhν)2 (eV)2
pure ZnO
0.6
0.4
0.2
3.18 eV
0.0
3.0 3.2 3.4
hν (eV)
Fig. 5. UV–vis absorption spectra (A) and plots of (ahm)2 versus photo energy (hm) (B and C) of pure ZnO, sample MZ-1, and sample MZG(4%).
59
hydrate [32]. Moreover, for sample MZG(4%), no obvious peak
shifts can be observed in all Zn 2p region, Fe 2p region and O 1s re-
gion when compared with those of pure ZnFe2O4 and sample MZ-1
(which are shown in Supporting Information), implying none of
new chemical bonds formed during the preparation procedure.
The structures of exfoliated graphene oxide and graphene have
also been confirmed by FT-IR (as shown in Fig. 4F). Fig. 4Fa is the
FT-IR spectra of graphene oxide, the peaks centered at
3400 cm1, 1723 cm1, 1630 cm1, 1370 cm1, and 1060 cm1
are attributed to OAH stretching vibrations of adsorbed water,
C@O stretching vibrations of carboxyl or carbonyl groups, OAH
deformation vibrations of COOH groups, OAH deformation vibra-
tions of tertiary CAOH, and CAO stretching vibrations of epoxy
groups, respectively [44–46]. After treatment with hydrazine hy-
drate at 95 °C for 1 h, it is interesting to note that the peaks of
1723 cm1, 1630 cm1, and 1370 cm1 that presented at graphene
oxide spectrum disappeared, the peak centered at 1630 cm1 also
has a sharp decrease in intensity (as shown in Fig. 4Fb). Mean-
while, a new peak occurred at 1580 cm1, which is ascribed to
the skeletal vibration of the graphene sheets [47]. Therefore, the
formation of graphene oxide and the reduction of graphene oxide
also have been confirmed by FT-IR results, which is coincide with
the XRD and XPS analysis.
3.4. UV–vis diffuse reflection spectrum
The optical properties of synthesized samples were then inves-
tigated by UV–vis absorption spectrum. As shown in Fig. 5A, the
500 600 700 800
(C)
1.4
1.2 MZ-1
(αhν) 2 (eV)2
1.0
MZG(4%)
1.79 eV
0.8 1.91 eV
1.5 2.0 2.5
hν (eV)
60 L. Sun et al. / Journal of Alloys and Compounds 564 (2013) 55–62

absorption edge for sample Z-1 is near 400 nm, which can be as-
signed to the intrinsic band gap adsorption of ZnO [48]. However,
the absorption edge for sample MZ-1 and sample MZG(4%) is
determined to be around 780 nm. Compared to the pure ZnO sam-
ple, after doping with ZnFe2O4, the absorption band has no struc-
tures such as shoulders and possesses relatively steep edges,
implying that the absorption in the visible light region is not due
to the surface states but induced by an intrinsic band transition
[19]. Thus will significantly facilitate the photocatalytic procedure
under solar light irradiation. Furthermore, plots of (ahm)2 versus
photo energy (hm) are illustrated in Fig. 5B and C, the band gap
for pure Z-1, MZ-1, MZG(4%) is 3.18 eV, 1.79 eV and 1.91 eV,
respectively, which is consistent with the discussion above.
3.5. Photocatalytic activity and magnetic property
The results of photochemical experiments of ZnFe2O4/ZnO
immobilized on graphene under solar light irradiation are shown
in Fig. 6A. It is clearly demonstrated that MZG(4%) exhibits the
highest photocatalytic activity among all the samples. The reactiv-
ity order is MZG(4%) > MZG(6%) > MZG(2%) > ZG(4%) > MG(4%).
Moreover, it is interesting to find that with the amount of GO
increasing, the photocatalytic activity of photocatalysts with dif-
ferent graphene content increases firstly and then decreases. When
the mass ratio of GO to MZ-1 reaches the critical value of 4%, the
photocatalyst displays the highest activity. Fig. 6B shows the vari-
ances in the absorbance of MB with MZG(4%) as photocatalysts
under solar light irradiation, and depicts the photocatalytic effi-
ciency of MZG(4%) explicitly. After irradiation for 100 min, the
decoloration of MB aqueous solution is almost completely (the in-
set in Fig 6B). For a better understanding of the photocatalytic
activity of synthesized photocatalysts, the kinetic model is dis-
cussed. It is received that kinetics for photocatalysis can be de-
scribed in terms of Langmuir–Hinshelwood (L–H) model when
the initial concentration of target is relatively lower, and the for-
mula can be expressed by the following equation [49].
C0
In ¼ Kt
C
where C0 is the initial concentration of MB, C is the current con-
centration of MB, and K is the apparent first-order rate constant.
Fig. 6C reveals that the plot of (In C0/C) and solar light irradiation
time (t) is approximate linear. The apparent first-order constant
is determined as 0.0330, 0.0116, 0.0101, 0.00588, 0.00313 for
MZG(4%), (b) MZG(6%), (c) MZG(2%), (d) ZG(4%), and (e) MG(4%),
respectively. Particularly, it is considered that the reaction rate of
MZG(4%) increases over 5–10 times compared with ZG(4%) and
MG(4%). The results of photochemical experiments (Fig. 6A) well
confirm that graphene sheets play a crucial role for enhancing
the photocatalytic reactivity of ZnFe2O4/ZnO nanocomposites,
that’s mainly ascribed to the excellent electric conductivity of 2D
graphene. Also, neither of the two constitutions of ZnFe2O4 and
ZnO can be excluded, namely ZnFe2O4, ZnO and graphene are all
necessary in the enhanced photocatalytic procedures [50,51].

(A) 0.8
663 nm
1.0
(a) 0.7

0.8 0.6 0 min

0.5 20 min
(b)
Absorbance

0.6 40 min
0.4
C/C0

(c) (pH=7)
60 min
0.4 0.3
80 min
(d)
0.2 100 min
Light OFF

(e)
Light ON

0.2
0.1

0.0 (f) 0.0

-20 0 20 40 60 80 100 120 400 500 600 700 800

Solar light irradiation time (min) Wavelength (nm)

(C) 5
(a) k=0.0330
4
(b) k=0.0116 (a)

(c) k=0.0101
3
In (C0/C)

(d) k=0.00588
(e) k=0.00313
2

(b)
1
(c)
(d)
(e)
0

0 20 40 60 80 100 120
Time (min)

Fig. 6. (A) Photocatalytic degradation of MB under solar light irradiation with (a) blank (no catalysts), (b) MG(4%), (c) ZG(4%), (d) MZG(2%), (e) MZG(6%), and (f) MZG(4%) as
photocatalyst, respectively. (B) Absorption spectra of MB solution taken at different irradiation time using MZG(4%) as photocatalyst. (C) Kinetic linear simulation curves of
MB degradation with different samples: (a) MZG(4%), (b) MZG(6%), (c) MZG(2%),(d) ZG(4%), and (e) MG(4%).
 L. Sun et al. / Journal of Alloys and Compounds 564 (2013) 55–62
Fig. 7. Schematic diagram showing charge generation and transfer with solar light
irradiation causing the degradation the MB solution.
However, when the amount of graphene reaches the maximum,
the photocatalytic activity will be dramatically suppressed (curve
h in Fig. 6A) due to the shortage of photocatalysts. In our prepara-
tion process, the highest photocatalytic activity under solar light
irradiation is observed when the mass ratio of rGO to ZnFe2O4/
ZnO composite is fixed at 4%.
On the basis of above experimental results and detailed analy-
sis, a possible photocatalysis mechanism is proposed and eluci-
dated schematically in Fig. 7. The electrons in full valence band
(VB) of ZnFe2O4 and ZnO will be excited to the empty conduction
band (CB) separately under solar light irradiation, leaving an equal
number of holes with positive charge in corresponding positions.
Meanwhile, the presence of ZnFe2O4 will favor the utilization of
visible light region due to its narrow band gap, so as to increasing
the photocatalytic activity under visible light irradiation [17].
Moreover, the difference of band structures between ZnFe2O4 and
traditional photocatalysts such as TiO2 and ZnO will facilitate the
photoinduced electrons transfer from the CB of ZnFe2O4 to the CB
of ZnO and holes migrate from the VB of ZnO to the VB of ZnFe2O4,
respectively [17,52]. Furthermore, the CB potential of ZnO
(4.05 eV vs. vaccum) and graphene sheet (work function:
4.42 eV) are also beneficial for the electrons transfer from the
CB of ZnO to graphene layers [53,54]. These processes will effi-
ciently hinder the recombination of photogenerated electron–hole
pairs and considerably enhance the photocatalytic activity under
UV or solar light irradiation. Afterward, the generated electrons
will act with O2 to yield superoxide radical anion O 2 and the
8
Magnetization (emu/g)
4 Yancheng Institute of Technology under Grant number
0 ince with no. AE201122.
-4
-8
-20000 -10000 0 10000
Magnetic field (Oe)
Fig. 8. The room temperature M–H loop for MZG(4%); Inset: digital images of
MZG(4%) dispersed in water with the (A) absence of external magnetic field (B) and
presence of external magnetic field.
61
formed O2 ions will further react with H2O, producing hydroxyl
radical OH, which possess strong oxidation ability and can destroy
dye molecules completely [55]. The mechanism is proposed in
terms of the following formulas:
sunlight þ
ðZnFe2 O4 =ZnOÞ þ hm ƒƒƒƒ! ZnFe2 O4 ðh Þ þ ZnOðe Þ
ZnOðe Þ þ graphene ! ZnO þ grapheneðe Þ
e þ O2 ! O
2

O 
2 þ H2 O ! HO2 þ OH
HO2 þ H2 O ! H2 O2 þ OH
H2 O2 ! 2OH
þ
h þ OH ! OH
2OH þ dye ! H2 O þ CO2
The room temperature magnetic hysteresis loop of MZG(4%)
shows a paramagnetic behavior with a maximum magnetization
of around 8 emu/g at 20 kOe (as given in Fig. 8). Moreover, the
magnetization curve and demagnetization curve are correspon-
dence, no hysteresis phenomenon is observed, and the remanent
magnetization and coercivity are equal to zero. Although the mag-
netization is not too high, the composite photocatalyst still can be
conveniently separated by an external applied magnetic field (the
inset in Fig. 8).
4. Conclusions
The present study outlined facile solution-based methods with
several steps to fabricate magnetically ZnFe2O4/ZnO nanocompos-
ites immobilized on graphene sheets. The usage amount of graph-
ene, which played crucial role for the photodegradation of MB
under solar light irradiation, could be easily controlled by adjusting
the amount of graphene oxide dispersions. The narrow bandgap of
ZnFe2O4 NPs and the excellent electron transfer ability of graphene
sheets were both in favor of the photocatalysis procedure. The
highest photocatalytic activity under solar light irradiation was
displayed when the mass ratio of GO to the ZnFe2O4/ZnO compos-
ite was set as 0.04. Furthermore, the novel photocatalyst could be
conveniently separated and recycled by an external magnetic field
due to its high magnetism.
Acknowledgements
This work was supported by The Talents Introduction Project of
XKR2011008, and the research fund of Key Laboratory for Ad-
vanced Technology in Environmental Protection of Jiangsu Prov-
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jallcom.2013.
02.147.
20000
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