Ceramics International 43 (2017) 1290–1297

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Photo-Fenton degradation of organic pollutants using a zinc oxide

decorated iron oxide/reduced graphene oxide nanocomposite
crossmark
⁎
Devi Prashad Ojhaa, Mahesh Kumar Joshib,c, Han Joo Kima,d,
a
Department of Convergence Technology Engineering, Chonbuk National University, Jeonju 561-756, Republic of Korea
b
Department of Bionanosystem Engineering, Chonbuk National University, Jeonju 561-756, Republic of Korea
c
Department of Chemistry, Tri-Chandra Multiple Campus, Tribhuvan University, Kathmandu, Nepal
d
Eco-friendly Machine Parts Design Center, Chonbuk National University, Jeonju 561-756, Republic of Korea

A R T I C L E I N F O A BS T RAC T

Keywords: Herein, we report a magnetically-separable tertiary composite, zinc oxide-decorated iron oxide deposited
Photo-Fenton reduced graphene oxide (ZnO-Fe3O4/rGO), as a heterogeneous catalyst for photo-Fenton degradation of organic
Methylene blue (MB) pollutants in aqueous media under ambient conditions. In this study, zinc oxide nanoparticles were
Photodegradation hydrothermally deposited on the surface of Fe3O4/GO composite that was synthesized by a solvothermal
Fe3O4 nanospheres
process. The physicochemical properties of the as–synthesized composite were explored using scanning electron
Hydrothermal
microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform
Reduced Graphene oxide (rGO)
infrared spectroscopy (FTIR), and photoluminescence (PL) studies. The as-prepared catalyst showed superior
stability and, due to the presence of the magnetic Fe3O4 nanospheres, could be conveniently separated from the
reaction system with an external magnet for reuse. The as-synthesized, ZnO-Fe3O4/rGO composite exhibited
superior catalytic activity for the degradation of azo-dye compared to pristine ZnO, ZnO/Fe3O4, Fe3O4, and
Fe3O4/GO. These results revealed the synergistic effects between the different components of the catalyst and
confirmed the rapid redox reaction between Fe2+ and Fe3+. It was also observed that this catalytic behavior
could be reproduced in consecutive experiments without a considerable decrease in efficiency. All of these
merits indicate that the composite catalyst is a promising candidate for the degradation of organic compounds
under visible light in environmental remediation applications.

1. Introduction Fe2++ H2O2 → Fe3+ + OH− + •OH (1)

Highly-reactive hydroxyl radicals degrade dyes into smaller mole-

The presence of recalcitrant organic compounds, which are often
toxic and non-biodegradable in wastewater, has led to serious environ-
mental pollution [1–3]. Sizable amounts of colored chemical com-
pounds are released into the environment during the dying processes of
the textile, leather goods, industrial paint, food, plastics, and cosmetics
industries [4]. Remediation of such chemicals via photo-chemical
processes is already recognized as a superior strategy compared to
conventional treatment technologies [5–7]. This technique is primarily
based on the generation of powerful oxidizing hydroxyl (•OH) radicals
by either i) direct photolysis of H2O2, ii) light-induced heterogeneous
photo-Fenton-type reactions, or iii) other heterojunction photolysis
techniques [7–10]. The Fenton process is cost effective, environmen-
tally friendly, and increasingly used for wastewater treatment [11–13].
This process involves a simple reaction between H2O2 and ferrous salts
in an aqueous solution at ambient conditions to generate •OH radicals
[14]:
cules such as CO2 and H2O. The Fe species can be recycled via Eq. (2):
Fe3+ + H2O2 → Fe2+ + HO2− + H+ (2)
Despite being a chemically efficient process for the removal of
organic pollutants, the Fenton reaction slows appreciably due to the
slow conversion of ferric ions to ferrous salts (Eq. 2). Furthermore, the
Fenton reaction produces substantial amounts of iron sludge due to the
loss of iron ions, limiting its application for wastewater treatment.
Secondly, hydroxyl radicals are consumed by hydrogen peroxide due to
the radical scavenging of hydrogen peroxide. The narrow pH range
(pH < 3) also limits the activity of the overall process [15–17].
Principally, the reactions that enhance the rate of conversion of Fe
(III) back to Fe (II) increase the rate of the Fenton reaction. In the
presence of UV irradiation, the heterogeneous photo-Fenton process
boosts the regeneration of ferrous ions and produces hydroxyl radicals

⁎
Corresponding author.
E-mail address: khanjoo@jbnu.ac.kr (H.J. Kim).

http://dx.doi.org/10.1016/j.ceramint.2016.10.079
Received 11 September 2016; Received in revised form 11 October 2016; Accepted 12 October 2016
Available online 13 October 2016
0272-8842/ © 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
D.P. Ojha et al.
[18,19]:
Fe 3+
+ H2O + hv → Fe
2+
+ •OH + H +
(3)
Among the various iron salts, magnetite (Fe3O4) nanoparticles are
considered to be promising compounds for photocatalysis due to their
unique magnetic, electric, and catalytic properties; biocompatibility;
and low toxicity [20]. However, nano-scale magnetite particles easily
aggregate to form larger particles, which reduce the specific surface
area and dispersibility and limit the catalytic activity [21]. Several
studies have attempted to enhance the conversion rate between Fe2+
and Fe3+ when these materials are used as Fenton catalysts [22]. Yang
et al. [23] hybridized Fe3O4 with TiO2 to boost the conversion between
Fe3+ and Fe2+. Additionally, Xu et al. [24] employed CeO2 to enhance
the efficiency of Fe3O4 in the Fenton system. In another study, Zubir
et al. [25] synthesized a GO-Fe3O4 nanocomposite as a heterogeneous
photo-Fenton catalyst and found that loading up to 10 wt% GO was
beneficial for intercalating GO within Fe3O4 nanoparticles, resulting in
a higher surface area and excellent catalytic efficiency.
Considering factors like cost, abundance in nature, biocompatibil-
ity, and oxidative nature, ZnO NPs are considered to be the best
alternative to TiO2 NPs [26]. ZnO can exhibit comparable or superior
properties as an ideal photocatalyst. Owing to their significant chemi-
cal, optical, and electrical properties, ZnO NPs have been widely used
in gas sensors, solar cells, and electrochromic devices, in addition to
photocatalytic and antibacterial applications [26]. Therefore, in this
study, we attempt to synthesize a photo-Fenton catalyst by hybridizing
ZnO with Fe3O4. UV–visible light can excite electrons from the valence
band (VB) to the conduction band (CB) to generate electron-hole pairs
in ZnO. The photoexcited electrons can be quickly transported to Fe3+,
accelerating the redox transformation between Fe3+ and Fe2+ [27].
Meanwhile, the simultaneously-generated holes can also react with
H2O to produce highly-oxidative hydroxyl radicals. The as-generated
radicals, together with the holes, can mineralize the organic pollutants
nonselectively [28]. Therefore, hybridizing ZnO with Fe3O4 can en-
hance the Fenton efficiency of Fe3O4 NPs. However, the photo-induced
electron-hole pairs in ZnO suffer from high recombination rates,
causing the reactivity of the electron-hole pairs to rapidly diminish.
In order to solve this problem, an effective interlayer of graphene can
be introduced [29]. The interlayer of graphene not only reduces the
recombination of photoelectrons, but also can strengthen the electron
transport between ZnO and Fe3O4. Therefore, construction of a ternary
Fenton catalyst with Fe3O4 and ZnO using graphene as a support
material could be a facile strategy. The advantages of this design can be
summarized as follows. When ZnO is combined with graphene, the
electrons in the valance band of ZnO can be excited to the conduction
band under the irradiation of visible light. The existence of graphene
will prolong the lifetime of the photoexcited electron-hole pairs [30],
thereby increasing the possibility of successful electron transfer from
ZnO to the Fe3+/Fe2+ redox pair [31]. Additionally, the presence of
various oxygen-containing groups on graphene, such as carboxyl,
epoxides, and alcohols, imbue graphene with its excellent adsorption
capacity, which helps to remove organic pollutants [32].
In this work, we synthesized an in-situ ZnO-decorated Fe3O4/rGO
photo-Fenton composite for rapid degradation of organic pollutants.
The degradation efficiency, stability, and magnetic performance of the
composite were evaluated. The composite catalyst possesses great
potential for photo-driven destruction of organic compounds.
2. Experimental
2.1. Materials
Zinc acetate dehydrate Zn(NO3)2·2H2O, potassium permanganate
(KMnO4), sulfuric acid (H2SO4), hydrogen peroxide (H2O2), ethylene
glycol (EG), anhydrous ferric chloride (FeCl3), anhydrous sodium
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Ceramics International 43 (2017) 1290–1297
acetate (NaAc), trisodium citrate, (3-aminopropyl)trimethoxysilane
(APTMS), isopropyl alcohol, methylene blue (MB), and graphite
(average particle diameter 0.20 mm) were purchased from Sigma
Aldrich and used without further purification.
2.2. Preparation of GO
Graphite oxide was prepared using a modified Hummer's method
[33]. Briefly, 125 mL of concentrated sulfuric acid and 5 g of the
graphite powder were deposited into a 500 mL, three–necked, round-
bottom flask. Solid potassium permanganate (17.5g) was slowly added
at 0 °C, and the mixture was stirred for 3 h at 35 °C. The as-prepared
mixture was diluted by adding a sufficient amount of distilled water in a
0 °C ice bath·H2O2 (30 vol%) was added until the gas bubbles
disappeared. The as-obtained product was centrifuged and washed
several times with deionized water and vacuum dried at 70 °C for 2
days.
2.3. Preparation of the Fe3O4/GO nanocomposite
Fe3O4 nanospheres were prepared by the solvothermal method
using a procedure reported in the literature [34]. In a typical process,
1.299 g of FeCl3, 0.5 g of trisodium citrate, and 2.0 g of NaAc were
dissolved in 40 mL of ethylene glycol under magnetic stirring. The
homogeneous yellow solution was then transferred into a 100 mL,
Teflon-lined, stainless-steel autoclave; heated at 200 °C for 10 h; and
cooled to room temperature. The as-obtained black product was
washed with ethanol and distilled water, respectively. Then, 0.5 g of
the as-prepared Fe3O4 spheres was dispersed in an isopropyl alcohol
solution by ultrasonication (30 min). Afterward, 0.5 mL of APTMS was
added to the above mixture and refluxed at 80 °C for 24 h. The product
was thoroughly washed by ethanol and then dried in a vacuum oven.
Later, 100 mL of the APTMS-modified Fe3O4 (5 mg/mL) aqueous
solution was mixed with 150 mL of GO (0.5 mg/mL) for about
30 min under mechanical agitation to obtain the Fe3O4/GO nano-
spheres.
2.4. Preparation of ZnO-Fe3O4/rGO nanocomposites
30 mg of the as-prepared Fe3O4/GO composite particles was
dispersed in 50 mL of ethanol (ultrasonication, 30 min), and 0.46 g
of a zinc acetate solution was slowly dropped into the mixture. The
solution pH was maintained at 11 and continuously agitated for
30 min. Later, the mixture was transferred into a 100 mL, Teflon-
lined, stainless-steel autoclave and heated at 180 °C for 4 h. The end
product was rinsed several times with ethanol and distilled water,
respectively. After drying at 70 °C under vacuum, a ternary composite
with ZnO nanoparticles decorated on the surface of rGO-supported
Fe3O4 spheres was obtained.
2.5. Photo-Fenton degradation of methylene blue
The photo-Fenton activity of the as-prepared catalysts was evalu-
ated by analyzing the photodegradation of MB in an aqueous solution
under visible irradiation. For the degradation of MB, 20 mg of the as-
prepared catalyst was added into a 100 mL photoreactor containing
50 mL of an aqueous solution of 10 mg/L MB. A 300 W Xe lamp with a
UV cut-off filter ( < 420 nm, Oriel) and a water filter (IR cut-off) were
used as the light source. The pH of the reaction mixture was
maintained at 7. The suspension was sufficiently stirred for 30 min in
the dark to reach adsorption-desorption equilibrium between the
catalysts and MB. Before illumination under visible light,
30 µm H2O2 was added to the mixed solution, and the lamp was
turned on to initiate the photodegradation reaction. At a given time
interval, 1 mL aliquot of the solution was withdrawn, centrifuged, and
filtered out, and its absorbance was measured. The concentration of the
D.P. Ojha et al.
remnant MB was determined by recording the absorbance of the
supernatant at 664 nm by UV–vis spectroscopy.
2.6. Physicochemical characterization
The surface morphology and structure of the as-prepared catalysts
were examined by field-emission scanning electron microscopy (FE-
SEM, S-7400, Hitachi, Japan) and transmission electron microscopy
(TEM, JEM-2200, JEOL, Japan, 200 kV). TEM samples were prepared
by suspending the particles in anhydrous ethyl alcohol, collecting them
on a carbon-coated copper grid, and drying them at room temperature.
Powder X-ray diffraction (XRD, Rigaku, Cu Kα λ=1.540 Ao, 30 kV,
40 mA) patterns were recorded to verify the crystalline structure of the
different samples. Fourier transform infrared (FT-IR) spectra of the
different samples were recorded with an ABB Bomen MB 100 spectro-
meter (Bomen, Canada). The UV–vis spectra of the MB solutions were
recorded on a UV–vis spectrometer (UNICO UV-2102PC) at room
temperature. The photoluminescence (PL) spectra were measured by a
Perkin Elmer instrument to confirm the photoconductivity of the
samples.
3. Result and discussion
3.1. Physicochemical properties of the nanocomposite
The shape and size of the as-synthesized catalysts were examined
using FE-SEM and TEM. Fig. 1 shows the representative FE-SEM
images of the different samples. The Fe3O4 nanospheres (synthesized
by a solvothermal method) were uniform with an average size of
200 nm. The FE-SEM image of the GO/Fe3O4 nanocomposite (Fig. 1b)
shows that the Fe3O4 NPs were well-dispersed on the thin-layered, 2D
GO sheets; these particles maintained their particle size distribution
Fig. 1. SEM image of different samples: (a) Fe3O4 nanospheres, (b) Fe3O4/GO, (c) ZnO-Fe3O4/rGO nanocomposite and (d) EDS spectra of the nanocomposite.
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and morphology, which is important for effective electron transfer
between Fe3O4 and the graphene sheet [35]. Furthermore, the flat, 2D,
sheet-like morphology of GO provides additional area for the effective
adsorption of the pollutants. The FE-SEM image of the ZnO-Fe3O4/
rGO ternary nanocomposite in Fig. 1c clearly shows that ZnO NPs were
well attached to the surface of the Fe3O4, and the shape and size of the
Fe3O4 nanospheres were well preserved in the ZnO-Fe3O4/rGO nano-
composite. EDS analysis shows the presence C, Zn, O, and Fe in the
nanocomposite which supports the presence of ZnO and Fe3O4 on the
graphene sheet.
The TEM and HRTEM images in Fig. 2 provide further insight into
the morphology and surface properties of the as-prepared samples. The
particle size of Fe3O4 (Fig. 2a) was approximately 200 nm, which is
consistent with the SEM images. Fig. 2c shows a low-magnification
TEM micrograph of the as-prepared ZnO-Fe3O4/rGO nanocomposite,
in which Fe3O4 nanospheres and ZnO particles are successfully
deposited over the very thin-layered 2D graphene sheet. The corre-
sponding HRTEM image (Fig. 2d) confirms the existence of Fe3O4 and
ZnO crystal lattices (lattice spacing =0.25 nm (belonging to the (311)
plane of Fe3O4) and 0.26 nm (belonging to the (001) plane of ZnO)).
The existence of diffraction rings in the SAED pattern in Fig. 2b
suggests the polycrystalline nature of Fe3O4, which is composed of
several smaller nanoparticles [36]. It can be seen that Fe3O4 and ZnO
nanoparticles are well attached on graphene sheet. Hydrothermal
treatment might have changed the graphene oxide to reduced-gra-
phene oxide [37] and the large number of functionalities present in
rGO might have provided sufficient nucleation site for ZnO and Fe3O4
crystal growth [38]. Further, as shown in Energy dispersive X-ray
(EDX) mappings (Fig. 3) of the ZnO-Fe3O4/rGO nanocomposite
confirmed the distribution C, Zn, Fe, and O in as prepared nanocom-
posite.
XRD patterns of as-synthesized Fe3O4, Fe3O4/GO, and ZnO-Fe3O4/
D.P. Ojha et al.
Fig. 2. TEM image of different samples: (a) Fe3O4, (c) ZnO-Fe3O4/rGO, (d) HR-TEM image of Fe3O4 and ZnO from the nanocomposite, and (b) SAED Pattern of polycrystalline Fe3O4
nanosphere.
rGO are shown in Fig. 4. The diffraction peaks of Fe3O4(Fig. 4a) at
2θ (18.1°, 30.2°, 35.4°, 43.3°, 53.4°, 57.1°, and 62.7°), which corre-
spond to miller indices of (111), (220), (311), (400), (422), (511), and
(440), respectively, are in accordance with the Fe3O4 PDF data (JCPDS
file no. 19–0629). The position and relative intensity of all of the
diffraction peaks matched well with the characteristic peaks of crystal-
line magnetite [39]. No diffraction peaks related to the carbon were
detected after modifying Fe3O4 by GO, implying that the reduced
graphene oxide sheets were completely exfoliated due to the loading of
sufficient NPs on their surfaces (Fig. 4b). This result might be due to
the presence of magnetite, which reduces the aggregation of graphene
sheets to form more monolayer graphene, subsequently leading to
weaker carbon peaks. Furthermore, the overwhelmingly strong signals
of iron oxide might have diminished/hidden the weak carbon peaks in
the XRD pattern [40]. The as-synthesized ZnO- Fe3O4/rGO (Fig. 4c)
exhibited additional diffraction peaks corresponding to the crystalline
wurtzite hexagonal phase structure of ZnO at 2θ at 31.35, 34.25, 36.08,
47.42, 56.39, 62.7, 66.29, 67.82, and 69.04°; these peaks can be
assigned to the (100), (002), (101), (102), (110), (103), (200), (112),
and (201) facets, respectively (JCPDS card 75–1526). These results
confirmed the in situ synthesis of ZnO NPs on the surface of the as-
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synthesized Fe3O4/GO composite.
Additionally, the molecular structures of different samples as well
as the reduction of GO to rGO was also investigated by FT-IR
spectroscopy. Fig. 5 displays the IR spectra of the different samples.
The IR band of GO at 1725 cm−1 corresponds to ν (C˭O), the peak at
1553 cm−1 corresponds to aromatic ν (C˭C), and the peak at 1215 cm−1
is assigned to epoxy ν (C-O) [38]. The IR bands of pristine Fe3O4
(Fig. 5b) showed a broad peak located at 3396 cm−1 and a sharp peak
at 1585 cm−1; these can be assigned to the H-O-H stretching and the
bending vibration of the free or adsorbed water, respectively.
Furthermore, the broad absorption band at 555 cm−1 is assigned to
the γ (Fe-O) stretching vibration in the tetrahedral site, and another
band beginning at 633 cm−1 is due to the γ (Fe-O) torsional vibration
mode of Fe in the octahedral site of magnetite [41]. GO-modified Fe3O4
showed a new small band at 1723 cm−1, which can be indexed to the
C˭O vibration of GO. The broadening of the IR band at 3396 cm−1 for
the Fe3O4/GO is due to the O–H bond vibration of GO as well as to
moisture absorbed by the composite. The absorption band of Fe3O4 at
1585 cm−1 was broadened compared to that of pristine Fe3O4, which
may be due to the overlapping of the GO band at 1570 cm−1. This result
revealed the successful assembly of Fe3O4 nanospheres on the GO sheet
D.P. Ojha et al. Ceramics International 43 (2017) 1290–1297

Fig. 3. EDX elemental mapping images of C, Zn, Fe, and O in the ZnO-Fe3O4/rGO nanocomposite.

Fig. 4. XRD Patterns of different samples: (a) Fe3O4, (b) Fe3O4/GO, (c) ZnO-Fe3O4/
rGO.
Fig. 5. FT-IR spectra of different samples: (a) ZnO, (b) Fe3O4, (c) Fe3O4/GO, and (d)
−1 ZnO-Fe3O4/rGO.
(Fig. 5c). The absorption band at 860 cm is attributed to the
overlapping of the absorption band at 906 cm−1 of Fe3O4.
The PL emission intensity is related to the recombination of excited
Furthermore, a new peak at 1201 cm−1, which appeared after the
electrons and holes; decreased emission intensity indicates a decrease
addition of GO, is slightly shifted compared to that of the original GO
in recombination rate [44]. Therefore, the PL spectra of different
[42]. The intensity of the IR peaks corresponding to the oxygen
samples were evaluated to understand the recombination rates of
functional groups was decreased in the ZnO-Fe3O4/rGO nanocompo-
electrons-holes and to elucidate the trapping, migration, and transfer
site [Fig. 5d], revealing the reduction GO into the rGO via hydro-
of charge carriers. The PL spectra (Fig. 6) of different samples clearly
thermal treatment [43].
show that the emission intensity of Fe3O4 nanospheres decreased upon

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D.P. Ojha et al.
Fig. 6. PL spectra of different samples: (a) Fe3O4, (b) Fe3O4/GO, and (c) ZnO-Fe3O4/
rGO.
Fig. 7. Photo-Fenton degradation of MB by different samples.
combination with GO. Furthermore, the incorporation of ZnO onto the
Fe3O4/GO composite significantly decreased the PL intensity, suggest-
ing enhanced photocatalytic activity. The decrease in PL intensity of the
composite indicates that the rate of recombination between photo-
generated electrons and holes decreased, which is beneficial for the
photocatalytic process. The lowest emission intensity of the ZnO-
Fe3O4/rGO composite indicates its highest photocatalytic efficiency.
This quenching of PL intensity in the ternary hybrid is attributed to the
improved transformation of photoexcited electrons. This transforma-
tion might have been caused by the photoexcited electrons transferred
from ZnO to the rGO sheet via the semiconductor–carbon heterojunc-
tion [45]. These findings suggest that rGO can act as a recombination
inhibitor, thereby trapping the photogenerated electrons from the
semiconductor.
3.2. Photo-Fenton degradation activities of ZnO-Fe3O4/rGO
The photocatalytic activities of the as-prepared composites were
evaluated by monitoring the discoloration of methylene blue (MB)
under visible-light irradiation (λ≥420 nm). The concentration of MB
was recorded by measuring the absorbance at 664 nm, which is the
characteristic wavelength of MB [46]. The amounts of as-prepared
composites, initial concentration of MB, amount of H2O2, solution pH,
and solution volume were kept same in all of the experiments. The
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concentration of the dyes was analyzed using a UV–vis spectrophot-
ometer. The following equation was used to account for the degrada-
tion rate [47]:
C
Degradation efficiency (%)=1 − Co ×100%Here, C0 is the initial concen-
tration, and C is the concentration of remnant MB after irradiation for
time (t).
Fig. 7 shows the photo–Fenton efficiency of the different samples
toward organic dye degradation. The degradation process was rapid in
the beginning when Fe3O4 was used as the catalyst. However, the
reaction rate decreased after 20 min, which can be attributed to the
consumption of most of the ferrous ions that were present in Fe3O4 at
the first stage; the regeneration of ferrous (Fe+2) ions from ferric (Fe+3)
ions is slow compared to the consumption of ferrous ions [48–51]. The
Fe3O4/GO (Fig. 7) composite showed a slightly higher degradation rate
compared to the Fe3O4 NPs. The GO present in the composite might
have increased the concentration gradient at the nanocomposite sur-
face and accelerated the reaction between hydroxyl radicals and the
pollutants. Several studies have reported the affinity of rGO toward
organic pollutant adsorption [52,53]. Similarly, combining rGO with
ZnO can decrease the band gap of ZnO, thereby extending the solar
light absorption of ZnO in the visible range [30]. For the ZnO-Fe3O4/
rGO nanocomposite sample it took about 150 min to remove ~~97% of
the MB dye from aqueous solution under visible light irradiation
whereas Fe3O4/GO could only decompose about 45% of the total MB
concentration. Thus, in ZnO-Fe3O4/rGO, the electrons in the valance
band of ZnO can be excited into the conduction band of ZnO under the
irradiation of visible light; these can be successfully transported to the
Fe3+/Fe2+ redox pair in Fe3O4 through the graphene interlayer. Thus,
the interlayer rGO might have prolonged the lifetime of the photo-
excited electron-hole pairs, contributing to the higher catalytic activity
[54,55]. Overall, with visible irradiation, the electron transfer between
the ferric ions and the ferrous ions is accelerated, thereby promoting
the continuous generation of •OH radicals [56]. These resulting •OH
radicals are responsible for the degradation of MB. Fig. 8 illustrates the
proposed mechanism of the synergistic effect of photo-Fenton and
photocatalytic reaction as described above.
Recovery and recyclability are important aspects of eco-friendly
catalysts for water treatment. The recyclability of the as-synthesized
photo-Fenton catalyst is expressed in Fig. 9a. This reveals that the
catalytic reduction efficiency of the as-synthesized composite was
almost the same after five successive reactions. This result suggests
that the magnetically-recoverable ZnO-Fe3O4/rGO catalyst was neither
deactivated nor poisoned during the catalytic and separation processes.
The interlayer of graphene might have blended with ZnO and Fe3O4 to
provide sufficient stability. Magnetic-based catalysts can be easily
recovered from the reaction system by magnetic separation. Fig. 9b
shows the excellent recovery of the as-synthesized catalyst from the
reaction system using a magnet. The reusability of ZnO-Fe3O4/rGO
nanocomposites was evaluated by performing five successive cyclic
tests under similar reaction conditions, as mentioned above.
4. Conclusions
In the present study, a photo-Fenton-type tertiary nanocomposite
was synthesized by in situ deposition of ZnO nanoparticles on the
surface of the Fe3O4/GO composite. The as-synthesized composite
showed enhanced photo-Fenton degradation of an organic dye. The
superior efficiency of the as-synthesized nanocomposite is attributed to
the synergistic effect of the components of the nanoparticles. The
incorporation of rGO provided sufficient sites for the adsorption of MB,
thereby enhancing the catalytic degradation. Additionally, ZnO pro-
vided active electron-hole pairs, contributing to the successful transfer
of electrons from ZnO to the Fe3+/Fe2+ redox pair, thereby enhancing
the performance of the photo–Fenton system. The as-synthesized
composite displayed excellent stability and recycling performance,
D.P. Ojha et al.
Fig. 8. Suggested mechanism for the photo-Fenton degradation of MB by ZnO-Fe3O4/rGO nanocomposite.
Fig. 9. (a) Catalytic reusability of ZnO-Fe3O4/rGO nanocomposite up to 4 cycles, (b) Digital image showing magnetic separation of catalyst from the reaction system.
which was attributed to the magnetic properties of Fe3O4. The
presented photo-Fenton reagent synthesis protocol is an efficient, less
toxic and low-cost method that can be used to produce unique
nanocomposites.
Acknowledgements
This paper was supported by the research fundsof newly appointed
professors at Chonbuk National University in 2015 and by a grant from
the Korean Ministry of Education, Science, and Technology (MEST)
(project No. 2014-R1A1A2009068) provided by the National Research
Foundation (NRF) (Project No. 2014-R1A1A2009068). We would also
like to thank the staff at the Center for Chonbuk University Research
Facility (CURF) for analyzing the FE-SEM, XRD, and TEM data.
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