Environ Sci Pollut Res (2014) 21:7296–7306
DOI 10.1007/s11356-014-2645-x
RESEARCH ARTICLE
Facile synthesis of magnetic ZnFe2O4–reduced graphene oxide
hybrid and its photo-Fenton-like behavior under visible iradiation
Yunjin Yao & Jiacheng Qin & Yunmu Cai & Fengyu Wei &
Fang Lu & Shaobin Wang
Received: 13 November 2013 / Accepted: 10 February 2014 / Published online: 26 February 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract A magnetic ZnFe2O4–reduced graphene oxide
(rGO) hybrid was successfully developed as a heterogeneous
catalyst for photo-Fenton-like decolorization of various dyes
using peroxymonosulfate (PMS) as an oxidant under visible
light irradiation. Through an in situ chemical deposition and
reduction, ZnFe2O4 nanoparticles (NPs) with an average size
of 23.7 nm were anchored uniformly on rGO sheets to form a
ZnFe2O4–rGO hybrid. The catalytic activities in oxidative
decomposition of organic dyes were evaluated. The reaction
kinetics, effect of ion species and strength, catalytic stability,
degradation mechanism, as well as the roles of ZnFe2O4 and
graphene were also studied. ZnFe2O4–rGO showed to be a
promising photocatalyst with magnetism for the oxidative
degradation of aqueous organic pollutants and simple separa-
tion. The combination of ZnFe2O4 NPs with graphene sheets
leads to a much higher catalytic activity than pure ZnFe2O4.
Graphene acted as not only a support and stabilizer for
ZnFe2O4 to prevent them from aggregation, largely improving
the charge separation in the hybrid material, but also a catalyst
for activating PMS to produce sulfate radicals at the same
Responsible editor: Angeles Blanco
Y. Yao (*) : J. Qin : Y. Cai : F. Wei : F. Lu
Anhui Key Laboratory of Controllable Chemical Reaction and
Material Chemical Engineering, School of Chemical Engineering,
Hefei University of Technology, Tunxi Road 193, Hefei 230009,
China
e-mail: yaoyunjin@gmail.com
Y. Yao
State Key Laboratory of Materials-Oriented Chemical Engineering,
Nanjing University of Technology, Nanjing 210009, China
S. Wang (*)
Department of Chemical Engineering, Curtin University,
G.P.O. Box U1987, Perth, WA 6845, Australia
e-mail: shaobin.wang@curtin.edu.au
time. The ZnFe2O4–rGO hybrid exhibited stable performance
without losing activity after five successive runs.
Keywords ZnFe2O4 . Graphene . Magnetic separation .
Dye . Fenton . Peroxymonosulfate
Introduction
Organic dyes are one of the largest groups of pollutants
discharged into wastewater from textile, dyeing and other
industrial processes. Conventional treatment technologies are
ineffective for removing dyes because many dye compounds
are highly resistant to conventional physical, chemical, and
biological treatments (Nidheesh et al. 2013; Wols and
Hofman-Caris 2012; Yu et al. 2012). To deal with the emer-
gent issue with efficient ways of wastewater treatment, ad-
vanced oxidation processes (AOPs) including catalytic wet air
oxidation, Fenton oxidation, photocatalytic oxidation, and
electrocatalytic oxidation, have been developed and exten-
sively studied (Hu et al. 2013; Nidheesh et al. 2013; Zhou
et al. 2013). One of the most potent AOPs is photo-Fenton
oxidation because it can achieve high reaction yields with low
treatment costs, mainly due to the use of sustainable solar light
as a photon source. Photo-Fenton can produce hydroxyl rad-
icals (•OH) by homogeneous photocatalysis with Fe(II/III),
UV−Vis light, and H2O2 (Wang and Chu 2012). However, one
of its main drawbacks is the need to work at a pH lower than 3
because Fe(III) hydroxides tend to precipitate at higher pHs
(Klamerth et al. 2012; Yuan et al. 2011b).
During the past years, sulfate radical (SO−•
4 ) generated from
a peroxymonosulfate (PMS; Oxone) oxidant with heating, UV
irradiation, transition metals or alkaline activation is attracted
increasing research interests as a candidate to •OH for the
degradation of recalcitrant organic pollutants (Guan et al.
2013; Khan et al. 2013; Wang and Chu 2011; Zhang et al.
Environ Sci Pollut Res (2014) 21:7296–7306
2013). PMS, a type of (bi)sulfite, has a higher oxidizing
potential (1.82 V) than H2O2 (1.76 V), and is an inexpensive
and environmentally friendly oxidant in several different ap-
plications, especially, in the decomposition of aromatic pol-
lutants in water (Sun et al. 2009; Yao et al. 2013b). Recently,
many studies related to the activation of PMS have focused on
transition metals, among which Co(II) and supported cobalt
oxide catalysts were found to be the best activators (Chan and
Chu 2009; Chen et al. 2008; Yao et al. 2013a; Zhang et al.
2010). Although these catalysts are still effective in initiating
sulfate radical generation from PMS, concerns about leaching
of potentially carcinogenic metal ions from the solid phase is a
major limitation for practical application in water treatment.
Therefore, it remains a challenge to develop a new technology
to efficiently produce by activating PMS.
As is well known, many spinel-type oxides have been
found to have visible-light-driven photoactivity. Among them,
spinel ZnFe2O4 with a relatively narrow band gap of 1.9 eV
has drawn particular attention in the conversion of solar ener-
gy, photocatalysis, and photochemical hydrogen production
from water, because of its visible-light response, good photo-
chemical stability, and low cost (Fu and Wang 2011).
Moreover, ZnFe2O4 is a magnetic semiconductor and there-
fore, ZnFe2O4-based catalysts can be recovered from the
solution after the reaction using a magnet without any loss
of their own magnetic properties. Over the past few years,
more attention has been paid to morphology-controlled syn-
thesis of ZnFe 2 O 4 , and ZnFe 2 O 4 -based composite
photocatalysts including TiO2–ZnFe2O4 (Hou et al. 2010;
Zhang et al. 2012b), ZnO–ZnFe2O4 (Sun et al. 2013),
MWCNT–ZnFe2O4 (Sui et al. 2012), and so forth. However,
low-cost fabrication of ZnFe2O4-based photocatalysts with
superior photocatalytic efficiency remains a great challenge.
Carbon-supported noble metals have been widely investi-
gated as catalysts, and the literature results demonstrate that
control of nanostructures of supported hybrids is a key factor
(Jung et al. 2013). Compared to other carbon matrices such as
graphite, carbon black, and carbon nanotubes, graphene is
emerging as one of the most appealing carbon materials and
has proven to be a promising candidate for the fabrication of
visible-light-responsive photocatalytic composites. It has been
suggested that graphene may tailor the size and morphology
of photocatalysts. Additionally, its conductive properties can
also retard the recombination of photogenerated electron−hole
pairs, consequently resulting in an enhancement in photocat-
alytic activity (Zhang et al. 2008). Since graphene can exhibit
enhanced performance, it has become a priority for re-
searchers to prepare graphene-based hybrids with ZnO (Li
and Cao 2011; Zhang et al. 2012a), TiO2 (Pan et al. 2012;
Perera et al. 2012), Ag3PO4 (Yang et al. 2013) and NiFe2O4
(Fu et al. 2012), etc. Fu and Wang (2011) reported the syn-
thesis of ZnFe2O4–graphene composites as a catalyst for
photoelectrochemical degradation of methylene blue using
7297
H2O2 as an oxidant under visible light irradiation. In our
previous work, hybridization of conjugative π structure mate-
rial with a metal oxide has been used to fabricate highly
efficient catalysts, such as Mn3O4–graphene (Yao et al.
2013b), Co3O4–graphene (Yao et al. 2012b), CoFe2O4–
graphene (Yao et al. 2012c), and Co(OH)2–graphene (Yao
et al. 2013a). However, to our best knowledge, little work
has been done in photo-Fenton-like catalytic reactions of
ZnFe2O4–graphene hybrids for the heterogeneous activation
of PMS under visible light irradiation.
Herein, in this work, we predominantly focus on the syn-
thesis of magnetic ZnFe2O4−reduced graphene oxide (rGO)
hybrids and, specifically, their application toward the photo-
Fenton-like degradation of several organic dyes by PMS
under visible light irradiation. The physical and chemical
characterizations of ZnFe2O4–rGO hybrids were conducted,
and the performance in heterogeneous reaction was evaluated.
The reaction kinetics, ion strength, material stability, degrada-
tion mechanism, as well as the roles of ZnFe2O4 and graphene
were comprehensively studied. The as-synthesized ZnFe2O4–
rGO hybrids exhibit remarkably enhanced visible light
photoactivity toward organics degradation as compared to
the original ZnFe2O4. The origin accounting for the improved
photoactivity and the underlying reaction mechanism have
been studied in terms of a series of characterization and
controlled experiments.
Materials and methods
Synthesis of ZnFe2O4–rGO hybrids
Graphite oxides (GO) were generated by oxidation of graphite
powder under acidic conditions according to the modified
Hummers method as described in our previous works
(Bradder et al. 2011; Hartono et al. 2009; Yao et al. 2012a).
In a typical synthesis of ZnFe2O4–rGO hybrids, 0.6 g of GO
was well dispersed in 250 ml of distilled water, and then the
dispersion was ultrasonicated for 60 min to be exfoliated GO.
Later, 2.01 g of iron (III) nitrate nonahydrate
(Fe(NO3)3•9H2O) and 0.74 g of zinc nitrate hexahydrate
(Zn(NO3)2•6H2O) were dissolved in 20 ml of distilled water.
The molar ratio of Fe3+ and Zn2+ was 2:1, which is accurately
controlled to be the theoretic molar ratio in the zinc ferrite
magnetite molecule. Then, the above aqueous solution was
added into the GO aqueous suspension under vigorous mag-
netic stirring for 1 h to ensure the electrostatically driven
assembly of positively charged Fe3+ and Zn2+ on the surface
of negatively charged GO sheets. In addition, NH3 aqueous
solution (28 %) was added in a dropwise manner to the above
mixture to make solution pH>10, followed by stirring of 1 h.
Subsequently, 10 ml of hydrazine hydrate were added to the
above solution and the temperature of the solution was raised
7298
to 80 °C with constant stirring for 4 h. ZnFe2O4–rGO hybrids
were obtained by the direct collection of the precipitates using
centrifugation, washed several times with absolute ethanol,
and dried at 60 °C in vacuum overnight. For a comparison,
bare ZnFe2O4 NPs and rGO were also prepared as in the
above procedure but without adding GO or mixture of
Fe(NO3)3•9H2O and Zn(NO3)2•6H2O (Chandra et al. 2010;
Li et al. 2011). All the products were stored in a desiccator for
further experiments.
Catalyst characterization
The morphologies of as-synthesized samples were examined
by field emission scanning electron microscopy (FESEM)
(Zeiss Neon 40EsB FIBSEM), and transmission electron mi-
croscopy (TEM) (JEOL 2011 TEM) equipped with an energy-
dispersive X-ray spectrometer (EDS). For TEM, a suspension
of ZnFe2O4–rGO hybrids in ethanol was drop-casted onto
carbon-coated copper grids and dried under ambient condi-
tions. X-ray diffraction (XRD) patterns of the powders were
collected on a Bruker D8 Advance X-ray diffractometer (Cu
Kα radiation, λ=1.5418 Å) in a 2θ range from 5° to 70° at
room temperature. Raman spectra were performed on a Dilor
Labram model 1B dispersive Raman spectrometer using the
helium–neon laser at 632.8 nm. Thermogravimetric analysis
(TGA) and differential thermal analysis (DTA) of samples
were carried out on a Perkin-Elmer Diamond TG/DTA ther-
mal analyzer in argon or air at a rate of 100 ml/min. X-ray
photoelectron spectroscopy (XPS) was conducted using an
ESCALAB250 spectrometer equipped with a
monochromatized Al Kα source. The Brunauer–Emmett–
Teller (BET) surface area was determined by a
Quantachrome NOVA 1200 Sorptomatic apparatus at liquid
N2 temperature. The corresponding BET surface area of the
ZnFe2O4–rGO hybrids is found to be 168.5 m2 g−1, which is
about two times as high as that of the ZnFe2O4 catalyst
(80.5 m2 g−1).
Catalyst performance
Orange II (4-(2-hydroxy-1-naphthylazo) benzenesulfonic ac-
id) was used as a model azo dye. The photo-Fenton-like
reactions of various catalysts in the solution were carried out
at room temperature in a closed system using a 500-W xenon
lamp (λ>420 nm) placed in an inner irradiation-type 200 ml
Pyrex reaction cell cooled by circulated water. The incident
photon flux of the lamp used in all experiments was found to
be about 1.59×10–6 Einstein l−1 s−1 by a radiometer (model
FZ-A; Photoelectric Instrument Factory of Beijing Normal
University, China) (Rojas et al. 2010; Yang and Luan 2012).
In a typical experiment, ZnFe2O4–rGO (20 mg) powder was
added into Orange II (20 mg/l, 100 ml) solution under vigor-
ous stirring. Prior to visible light exposure, the suspension was
Environ Sci Pollut Res (2014) 21:7296–7306
aged in the dark in 30 min to equilibrate the adsorption and
desorption of dye molecules. After stirring for 30 min, PMS
(100 mg) was added into the above mixing solution and simul-
taneously, the suspension solution was irradiated under visible
light condition. The reactions were carried out for various time
and water samples taken at different time intervals (1.0 ml) (up
to 150 min) were immediately filtered (0.8 μm) to remove
essentially the catalyst solids. Then, 1.0 ml of methanol was
added to quench the HSO−5 residuals. The quantity of Orange II
in solution was determined by measuring the UV−Vis absorp-
tion intensity at 484 nm, the main absorption peak of the dye.
For the ZnFe2O4–rGO/PMS/Vis process, five different
sodium salts (NaCl, NaNO 3 , Na 2 CO 3 , NaHCO 3
and CH3COONa) at 0.05 M placed in Orange II aqueous
solution were tested to investigate the effect of the anions on
the degradation of pollutants. In addition, the effect of varying
dosages of Cl– ranged from 0 to 0.5 M, was also examined.
ZnFe2O4–rGO was further used for the degradation of the
different organic dyes (Methyl orange, Methyl violet,
Methylene blue, and Rhodamine B) under the similar condi-
tions. To evaluate the stability of ZnFe2O4–rGO hybrids, the
catalyst was gathered after the completion of the reaction,
washed, dried under vacuum, and reused in a fresh solution
of Orange II under visible light.
Results and discussion
Catalyst characterization
FESEM and TEM images were collected for bare ZnFe2O4
NPs and ZnFe2O4–rGO hybrids, as shown in Fig. 1. The bare
ZnFe2O4 NPs show as spherical particles, but are severely
aggregated together (Fig. 1a). In comparison, the size of the
ZnFe2O4 NPs in ZnFe2O4–rGO is around 24 nm (Fig. 1b).
This suggests that the intimate interaction between bare
ZnFe2O4 NPs and hierarchic flexible graphene sheets drasti-
cally limits the agglomeration of the crystalline ZnFe2O4 NPs
to some extents. TEM images (Fig. 1c, d) further reveal the
intimate hybrid structure of catalysts: ZnFe2O4 NPs are de-
posited on the surface of the large rGO sheets. Both the edge
of rGO and the nanostructure of ZnFe2O4 NPs are clearly
observable in the higher magnification TEM image. It is worth
noting that effective catalytic activity is expected to be asso-
ciated with high surface area of the active catalytic sites.
Based on the TEM images, it could be confirmed an intimate
interaction between the ZnFe2O4 NPs and the graphene sheets
and such a combination enables fast electron transport through
the ZnFe2O4 NPs to the graphene, guaranteeing efficient
chemical performance (Li et al. 2012a, b). EDS confirms the
formation of ZnFe2O4–rGO hybrid, where only Zn, Fe, O, and
C elements on the rGO sheets can be detected with Cu and Si
peaks emanating from the TEM grid (see the inset of Fig. 1d).
Environ Sci Pollut Res (2014) 21:7296–7306
Fig. 1 a SEM image of bare a b
ZnFe2O4. b–d SEM and TEM
images with different
magnifications of ZnFe2O4–rGO
hybrid. Inset: EDS of the hybrid
100 nm
c d
XRD pattern of ZnFe2O4–rGO hybrid is shown in Fig. 2a,
together with as-prepared bare ZnFe2O4 NPs. It is obviously
seen that almost all the diffraction peaks can be assigned to
spinel-type ZnFe2O4 (JCPDS 22-1012). The peaks at 2θ
values of 18.3°, 30.1°, 35.3°, 43.0°, 53.5°, 56.3°, and 62.4°
can be indexed to (111), (220), (311), (400), (422), (511) and
(440) crystal planes of spinel ZnFe2O4, respectively (Fu and
Wang 2011). The ZnFe2O4–rGO hybrid exhibits the similar
diffraction peaks to those of ZnFe2O4 NPs. However, com-
pared to pure ZnFe2O4 (Fig. 2a), a weak and broad character-
istic peak on ZnFe2O4–rGO appears at 2θ of 24.5–27.5°,
which can be indexed to the disorderedly stacked graphene
sheets (002) (Li et al. 2012a, b; Wang et al. 2012). In both
samples, no impurities were detected in the XRD patterns,
confirming the high purity of the products. These results
indicate that the as-synthesized hybrid consists of disorderedly
stacked graphene and crystalline ZnFe2O4 NPs. The grain size
of the pure ZnFe2O4 was calculated to be about 27.0 nm based
on the Scherrer equation, which is larger than that of the
ZnFe2O4–rGO sample (23.7 nm). These indicate the rGO
sheets in the reaction suspensions could affect the crystalliza-
tion behavior of the ZnFe2O4 NPs.
The presence of ZnFe2O4–rGO is further supported by
Raman spectroscopy, as shown in Fig. 2b. The two peaks at
1317 cm−1 (D peak) and 1569 cm−1 (G peak) are attributed to
graphene. Besides, the two dimensional (2D) band at
2,674 cm−1 is also seen, which is further indicative of the
existence of monolayer graphene in the hybrids (Fu et al.
2012). All the peaks in the 100–1,000 cm−1 region can be
ascribed to the spinel ZnFe2O4 phase. In general, the ID/IG
7299
200 nm
graphene
ZnFe2O4
intensity ratio is a measure of disorder degree and average size
of the sp2 domains in graphite materials. The ID/IG ratio for
ZnFe2O4–rGO is 0.90, which implies the presence of local-
ized sp3 defects within the sp2 carbon network in the rGO
sheets (Bai et al. 2012, 2013).
The thermal decomposition of ZnFe2O4–rGO hybrid has
been studied by TG-DTA under air and argon flow, as shown
in Fig. 2c. Two distinct weight losses were observed on TGA
profile in air atmosphere at temperatures of 20–120 °C and
250–600 °C, respectively, which corresponded to the losses of
the adsorbed water and the burnt-out of graphene, respective-
ly. In addition, a strong exothermic peak (512.7 °C) was
observed in the DTA. However, in argon flow, ZnFe2O4–
rGO hybrids show much higher thermal stability with a grad-
ual weight loss up to 800 °C, and no abrupt weight loss and an
exothermal peak can be observed. This is consistent with the
thermal behavior of graphene itself in argon atmosphere as
reported in the literature (Ji et al. 2011). According to the mass
loss in ZnFe2O4–rGO, about 60.0 wt.% of metal oxide depos-
ited on the surface of graphene.
A critical issue for a series of spinel compounds under
highly oxidizing conditions is oxidation of metal species
(Hong et al. 2012). The oxidation may lead to microphase
separation and deactivation of the catalysts. Thus, confirma-
tion of the surface conditions of each component after the
reaction is necessary. The change on the surface of ZnFe2O4–
rGO hybrids before and after photocatalytic reaction was
measured by XPS, which was performed in the Fe 2p, Zn
2p, O 1 s, and C 1 s energy regions. The binding energy of
each element was corrected using the C 1 s peak from residual
7300
Fig. 2 a XRD patterns of
ZnFe2O4 and ZnFe2O4–rGO
hybrid. b The Raman spectra of
ZnFe2O4–rGO. c TG-DTA curves
of ZnFe2O4–rGO hybrid at air
and argon atmosphere
carbon (284.8 eV). In the survey region (0–1,000 eV), carbon,
iron, and oxygen were detected (Fig. 3a). In Fig. 3b, two peaks
centered at 1,045 and 1,022 eV (no obvious shifts can be
found before and after the reaction) 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 (Sun et al. 2013). The similar intensity ratios of the
main peaks for the two samples indicate that the surface
conditions were the same even after the photocatalytic reac-
tion was performed under highly oxidizing conditions.
Figure 3c displays the XPS spectrum of the Fe 2p3/2 peak at
712.08 eV with a weak satellite peak at 725.78 eV for
ZnFe2O4 before the reaction and at 712.18 eV with a weak
satellite peak at 725.78 eV after the reaction. Although the
main Fe 2p3/2 peak from the sample after the reaction was
slightly shifted in the direction of higher binding energy, the
similarity of the peak shapes between the main and satellite
peaks in the two samples indicate that there was no change in
the valence state of Fe3+. The C 1 s peak located at 284.8 eV is
related to the graphitic carbon in graphene (Fig. 3a). These
results are in good agreement with the XRD and Raman
studies.
O 1 s patterns of XPS were also measured, as shown in
Fig. 3d. The O 1 s peaks at about 529.9−530.3 eV correspond
to the lattice oxygen OI for ZnFe2O4 catalysts, and another
component at about 531.5 eV belongs to the chemisorbed
oxygen OII bonded with C atoms in graphene. The
chemisorbed oxygen on the ZnFe2O4–rGO catalyst surface
Environ Sci Pollut Res (2014) 21:7296–7306
is the most active oxygen, which plays an important role in the
oxidation reaction (Xu and Wang 2012). The peak at 531.5 eV
changed after the reaction, suggesting that oxidation in the
Fenton-like reaction favored the formation of graphene ox-
ides. The little changes in the surface conditions of ZnFe2O4–
rGO hybrids before and after the reaction were supported by
the XPS analysis. Thus, ZnFe2O4–rGO hybrids are highly
robust even during the photocatalytic reaction.
Catalytic evaluation
To investigate visible light photodegradation activities of
ZnFe2O4–rGO hybrids, Orange II was firstly used as a repre-
sentative organic dye for test. In the tests of the catalytic
activity, a series of heterogeneous Fenton-like reactions and
photolysis were carried out for comparison. Figure 4a presents
the decolorization efficiency of Orange II as a function of time
under different reaction systems.
As shown in Fig. 4, the photodegradation rates of Orange II
using different catalysts decreased in the following order:
ZnFe2O4–rGO/PMS/Vis > ZnFe2O4–rGO/PMS > ZnFe2O4–
rGO/Vis, and ZnFe2O4–rGO/PMS/Vis > ZnFe2O4/PMS/Vis >
ZnFe2O4/Vis > PMS/Vis. The Orange II concentration was
almost constant during visible light irradiation without any
catalysts and PMS, which confirmed the photostability of the
dye in photolysis. Without PMS, the decolorization due to
ZnFe2O4–rGO or ZnFe2O4 photocatalysis was slow after
adsorption–desorption equilibrium, indicating that ZnFe2O4–
Environ Sci Pollut Res (2014) 21:7296–7306 7301

Fig. 3 XPS spectra of ZnFe2O4–

rGO hybrids before and after the
reaction in the a survey scan; b Zn
2p region; c Fe 2p d O 1 s energy
regions

rGO and ZnFe2O4 could not lead to significant degradation of
Orange II. Without a catalyst, 22 % of Orange II was degraded
at PMS/visible light. It is worthwhile to note that in the
presence of PMS, ZnFe2O4–rGO hybrids exhibited the
highest catalytic activity: 100 % of Orange II was degraded
by the ZnFe2O4–rGO within 150 min. The color of Orange II
solution gradually diminished upon SO−• 4 in the presence of
ZnFe2O4–rGO hybrids, indicating that catalysis destroyed the
chromophoric structure of the dye.
For the ZnFe2O4/PMS/Vis system, Orange II concentration
firstly decreases up to a reaction time of 30 min, which is
ascribed to adsorption process. When PMS was added and
visible light was switched on, desorption and
photodegradation occurred synchronously. Orange II concen-
tration increases with a maximum at about 40 min, which is
attributed to desorption process as the leading role. Finally, the
concentration decreases again because of the
photodegradation process. The photocatalytic activity of pure

Fig. 4 a Orange II degradation

under different conditions. b UV–
vis spectral changes for Orange II
degradation with ZnFe2O4–rGO/
PMS/Vis system. Inset: the
magnetic separation property of
ZnFe2O4–rGO hybrids. (Reaction
conditions: [Orange II]=20 mg/l,
[PMS]=0.5 g/l, [catalyst]=0.1 g/l,
T=25 °C)
7302
ZnFe2O4 was lower, giving 81.5 % Orange II removal under
the same conditions. This phenomenon showed that the
ZnFe2O4–rGO catalyst catalyzed decomposition of Orange
II at approximate rate to the ZnFe2O4 and rGO photocatalyzed
decomposition of Orange II, indicating that the introduced
PMS and visible light accelerated reactions by oxide catalysis
and photocatalysis, respectively. Therefore, combination of
ZnFe2O4 and graphene results in a synergistic effect in cata-
lytic activity, thereby enhancing the relative rates of mass
transfer and chemical reaction at reactive sites, which is similar
to that of ZnFe2O4–rGO/H2O2/Vis system (Sun et al. 2013).
To understand and clarify the changes in molecular struc-
ture of Orange II due to photodegradation using ZnFe2O4–
rGO under visible light irradiation, representative UV–Vis
spectral changes in the dye solution as a function of irradiation
time were observed (Fig. 4b). One main band at maximum
absorption of 484 nm, corresponds to the n–p* transition of
the azo form, and the another band at 310 nm is attributed to
the p–p* transition of the naphthalene ring (Long et al. 2012;
Wang et al. 2011). It can be clearly seen that, after 150 min of
irradiation time and onward, the visible band disappeared,
which might be due to the fragmentation of the azo links by
oxidation. In addition to this rapid decolorization effect, the
decay of the absorbance at 310 nm was considered an evi-
dence of aromatic fragment in the dye molecule and its inter-
mediates (Riaz et al. 2013). As indicated in the “Introduction”
section, ZnFe2O4 possesses remarkable magnetic properties,
which account for its good performance in magnetic separa-
tion using an external magnet (inset of Fig. 4b).
ZnFe2O4–rGO was further used for the degradation of the
different organic dyes under similar conditions (Fig. 5). A
lower photocatalytic degradation rate was observed for
Orange II compared to other dyes. The photocatalytic degra-
dation rates of the dyes follow the order: Methyl orange >
Methyl violet > Methylene blue > Rhodamine B > Orange II.
Fig. 5 Photodegradation of various dyes in the presence of ZnFe2O4–
rGO/PMS under visible light irradiation. (Reaction conditions: [dye]=
20 mg/l, [PMS]=0.5 g/l, [catalyst]=0.1 g/l, T=25 °C)
Environ Sci Pollut Res (2014) 21:7296–7306
The results indicate that almost all the organic pollutants could
be degraded within 150 min in the ZnFe2O4–rGO/PMS/Vis
system, indicating the excellent catalytic performance of
ZnFe2O4–rGO towards the oxidation of organic pollutants.
In this study, we also examined the effect of several anions
such as Cl−, NO−3 , CO32−, CH3COO– and HCO3−, because the
salts are usually found in waste streams, on the decolorization
of Orange II. In Fig. 6a, a series of tests at varying dosages of
Cl− ion in ZnFe2O4–rGO/PMS/Vis system were also present-
ed, and it was found that the presence of Cl− ion could
improve the removal performance and increase the reaction
rate of the decolorizarion process. In the absence of salt, 95 %
of Orange II decolorization was achieved at 150 min in the
ZnFe2O4–rGO oxidative process, while 95 % of Orange II
removal only needed 35 min at [NaCl]=0.5 M. On the other
hand, another series of tests with different anions were com-
pared (Fig. 6b). In the presence of salts, the rapid and efficient
decolorization of Orange II was shown to follow the order:
CO32− > HCO3− > Cl− > CH3COO− > NO−3 . It is well known
that two possible effects of inorganic ions on the photocata-
lytic reactions may occur, (1) changing the ionic strength of
reaction medium and (2) inhibition of catalytic activity of the
photocatalyst (Behnajady et al. 2012). Some researchers have
previously reported that CO32−, HCO3−, Cl− and CH3COO−
ions had inhibitory effects on the photocatalytic activity of
the AOPs via different radical-related reaction mechanisms
(Chan and Chu 2009; Gu et al. 2012; Huang et al. 2009; Yuan
et al. 2011a). According to Eqs. 1–6, these ions are scavenger
for SO−•4 radicals.
−
SO−•
4 þ Cl →SO4 þ Cl•
2−
ð1Þ
Cl• þ Cl − →Cl −•
2 ð2Þ
SO−• −
4 þ HCO3 →SO4 þ HCO3 •
2−
ð3Þ
HCO3 •→H þ þ CO−•
3 ð4Þ
SO−• 2− 2− −•
4 þ CO3 →SO4 þ CO3 ð5Þ
SO−• −
4 þ CH 3 COO →SO4 þ CH 3 COO•
2−
ð6Þ
However, in this research, these ions showed their enhanc-
ing effects, suggesting the inhibitory effect of ions can be
neglected and increasing of Orange II removal efficiency with
increasing Cl− initial concentration can be related to increas-
ing of ionic strength of solution (Behnajady et al. 2012).
Figure 6 shows that Orange II adsorption on ZnFe2O4–rGO
is significantly enhanced at the presence of inorganic ions and
that high ionic strength increases the dye adsorption, resulting
in stronger surface reaction between adsorbed dye and
Environ Sci Pollut Res (2014) 21:7296–7306
Fig. 6 a Different amount of
chloride and b various anions
effect on the degradation of
Orange II. (Reaction conditions:
[Orange II]=20 mg/l, [PMS]=
0.5 g/l, [catalyst]=0.1 g/l, T=
25 °C)
radicals. Yuan et al. (2011a) reported a dual effect of chloride
(i.e., inhibitory and accelerating effects) on azo dye degrada-
tion in Co/PMS AOP and found that high concentrations of
chloride (>5 mM) can significantly enhance dye decoloriza-
tion, which is similar to what we observed in this investigation.
Stability and reusability of ZnFe2O4–rGO catalysts
Compared with the photocatalytic activity, the stability is very
important for recycling of catalysts based on their importance
for practical application. In this work, to investigate the pho-
tocatalytic stability of ZnFe2O4–rGO hybrids in the recycled
process, five cycles of Orange II photodegradation were con-
ducted. Figure 7 shows that there is no obvious reduction in the
photocatalytic degradation efficiency after five repeated cycles,
which indicated the possibility of using the catalyst for a longer
operation time. Furthermore, XPS measurements showed the
similar structure of the catalyst before and after the reaction
(Fig. 3). Therefore, ZnFe2O4–rGO hybrid has an excellent
long-term stability and can be reused without loss of catalytic
activity for the degradation of organic pollutants in water.
Fig. 7 Recycled performances in the presence of ZnFe2O4–rGO hybrids
for photodegradation of Orange II dye. (Reaction conditions: [Orange
II]=20 mg/l, [PMS]=0.5 g/l, [catalyst]=0.1 g/l, T=25 °C)
7303
Role of ZnFe2O4 and rGO
According to the above results, it is evident that the positive
synergistic effects of ZnFe2O4 and graphene were responsible
for the efficient generation and separation process under vis-
ible light excitation. Figure 8 illustrates the photoelectron
transfer mechanism for the ZnFe2O4–rGO hybrids under vis-
ible light irradiation. ZnFe2O4 with narrow band gap energy
(1.9 eV) could be easily excited by visible light with energy
less than 2.95 eV (λ>420 nm) and induced the generation of
electron–hole pairs (Eq. 7). Since the conduction band (CB) of
graphene lay in more positive level than that of the ZnFe2O4
CB, the photoelectrons were collected from ZnFe2O4 and
transferred across the interface of the heterostructure to the
surface of the graphene framework (Eqs. 8–9). The electrons
then traveled along the graphene, leaving the photogenerated
holes in the valence band of ZnFe2O4. In such a way, the
photoinduced electron–hole pairs were effectively separated.
Meanwhile, some photogenerated holes reacted directly with
the surface-adsorbed Orange II molecules to produce (Orange
II)●+. Furthermore, the reactive (Orange II)●+ radical trans-
formed into H2O and CO2 (Eq. 10) at the same time, The SO−• 4
and •OH are also formed by photolytic activation of PMS
(Eq. 11) (Chan and Chu 2009).
Fig. 8 Mechanism for Orange II degradation by ZnFe2O4–rGO/PMS/
Vis system
7304
Based on the above experimental results, it was found that
the ZnFe2O4–rGO hybrid exhibited a high photocatalytic activ-
ity in the degradation of several contaminants. Its photocatalytic
activity is improved compared with that of the pure ZnFe2O4
sample. The improved photocatalytic performance of
ZnFe2O4–rGO hybrid can be ascribed to its composite struc-
ture. Firstly, high-surface-area rGO sheets offer more active
adsorption sites and photocatalytic reaction sites for organic
pollutants, which improved photocatalytic activity. Secondly,
because of the presence of conductive rGO sheets, hybrid can
serve as an effective acceptor of the photoexcited electrons;
hence, the photogenerated CB electrons of ZnFe2O4 can be
easily transferred to rGO framework by which the lifetime of
photogenerated electrons is significantly improved. The trans-
portation and mobility of electrons on rGO sheets are very rapid
in the specific π conjugated structure; thus, the efficient electron
transfer from ZnFe2O4 to rGO sheets keeps electrons away
from the ZnFe2O4. More photogenerated electrons and holes
are produced by continuously working in this way, effectively
suppressing the charge recombination and improving the pho-
tocatalytic activity, which suggests a better stability and recy-
clability of ZnFe2O4–rGO composites in the photocatalytic
process. Thirdly, graphene is not only a support, but also a
catalyst for activating PMS to produce SO−• 4 , which has been
reported in other literature (Peng et al. 2013; Sun et al. 2012).
Finally, Orange II is broken down mainly by the primary
radicals, SO−•4 , which play a key role in degradation process
(Eq. 12). These results demonstrate that ZnFe2O4–rGO be-
haves as an efficient material in utilizing solar energy for the
photodecomposition of pollutants. According to the above
analysis, the reaction mechanism for the degradation of
Orange II is shown as follows:
ZnFe2 O4 þ hv→ZnFe2 O4 ðh þ eÞ ð7Þ
ZnFe2 O4 ðeÞ þ graphene→grapheneðeÞ ð8Þ
grapheneðeÞ þ HSO−5 →SO−•
4 þ OH −
ð9Þ
ZnFe2 O4 ðhÞ þ Orange II→ðOrange II Þ•þ →CO2 þ H 2 O
ð10Þ
HSO−5 þ hv→SO−•
4 þ •OH ð11Þ
SO•−
4 þ Orange II→½…many steps…Š→CO2 þ H 2 O ð12Þ
Conclusion
Magnetic ZnFe2O4–rGO hybrids were prepared under basic
conditions, characterized by FESEM, TEM, EDS, XRD,
Environ Sci Pollut Res (2014) 21:7296–7306
Raman, TGA and XPS techniques and used for the degrada-
tion of various dyes in aqueous solutions. TEM observations
indicate that ZnFe2O4 NPs with an average size of 23.7 nm
anchored uniformly on the rGO sheets to form ZnFe2O4–rGO
hybrids. The as-prepared ZnFe2O4–rGO sample exhibited
excellent photo-Fenton-like activities and magnetic property
for easy separation as well as the durability on the elimination
of the organic pollutants under visible light irradiation, main-
taining high activities after five repeated uses. The photocat-
alytic activity of ZnFe2O4–rGO for the degradation of Orange
II was evidently improved compared to that of the pure
ZnFe2O4 under the same conditions, which is attributed to
the roles of rGO in NPs dispersion and activation of PMS. A
possible mechanism for its enhanced photocatalytic activity
was proposed, which is ascribed to the improved charge
separation and faster charge transfer in the composite material.
ZnFe2O4–rGO hybrids also exhibited high activity in the
presence of various salts, and are thus believed to be effective
catalytic materials for environmental applications.
Acknowledgments The support by the Anhui Provincial Natural Sci-
ence Foundation (No. 1308085MB21), the National Natural Science
Foundation of China (Grant 51372062), Technology Foundation for
Selected Overseas Chinese Scholar of Anhui Province (NO.
2013AHST0415), the State Key Laboratory of Materials-Oriented Chem-
ical Engineering (NO. KL13-12), the Fundamental Research Funds for
the Central Universities (NO. 2012HGQC0010), and the Project Spon-
sored by the Scientific Research Foundation for the Returned Overseas
Chinese Scholars, State Education Ministry are gratefully acknowledged.
The support from Australian Research Council for DP110103699 is also
acknowledged.
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