Journal of Industrial and Engineering Chemistry 20 (2014) 68–73

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Nanostructure composite ZnFe2O4–FeFe2O4–ZnO immobilized on

glass: Photocatalytic activity for degradation of an azo textile dye F3B
Mohammad Hossein Habibi *, Amir Hossein Habibi
Nanotechnology Laboratory, Department of Chemistry, University of Isfahan, Isfahan 81746-73441, Islamic Republic of Iran

A R T I C L E I N F O A B S T R A C T

Article history: An efficient and scalable one-pot synthetic method to prepare nanostructure composite of ZnFe2O4–
Received 25 February 2013 FeFe2O4–ZnO (ZFZ) has been investigated. This method is based on thermal decomposition of iron(III)
Accepted 9 April 2013 acetate and zinc acetate in monoethanolamine (MEA) as a capping agent. Moreover, thermogravimetric
Available online 9 May 2013
analysis (TG-DTG) was performed to determine the temperature at which the decomposition and
oxidation of the chelating agents took place. ZFZ was immobilized on glass using doctor blade method
Keywords: and calcinated at different temperatures. The properties of the ZFZ nanocomposite have been examined
ZnFe2O4–FeFe2O4–ZnO
by different techniques, such as X-ray diffraction (XRD), field emission scanning electron microscopy
Nanostructure
Doctor blade
(FESEM) and diffuse reflectance (DRS). FESEM shows that nanocomposite is monocrystallines and a
Reactive Red 195 narrow dispersion in size of 48 nm. XRD confirms that the prepared nanocomposite is composed of
franklinite, ZnFe2O4 (54%), magnetite, FeFe2O4 (8%) and wurtzite, ZnO (48%). Photocatalytic activity of
ZFZ immobilized on glass was carried out by choosing an azo textile dye, Reactive Red 195 (F3B) as a
model pollutant under UV irradiation with homemade photocatalytic apparatus and the results
indicated that ZFZ exhibited good photocatalytic activity.
ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction nanostructure composite ZnFe2O4–FeFe2O4–ZnO immobilized on

Azo textile dyes are the main chemical class of dyes due to their
stability and the range of colors available compared to natural
dyes. More than 60% of all textile dyes contains azo dyes which
making them the largest group of synthetic colorants released into
the environment [1–3]. Nanostructure zinc oxide with a large
exciton binding energy and wide band gap has received growing
interest in the application of photocatalysis [4–8]. Nanostructure
zinc oxides show more advantages than titanium dioxide with
lower cost and higher quantum yields [9–12]. Nanoparticles of
photocatalysts must be separated and reused after application
which may encounter technological problems [13]. The immobili-
zation of nano-size photocatalyst overcomes the difficulties in
separation and recycle of photocatalyst [14–18]. There are some
reports on immobilization of the nano-size photocatalysts on
different supports but the problem is lower efficiency of the
immobilized photocatalyst compared with nanoparticles suspen-
sions [19–24]. This can be done by application of nanostructured
photocatalyst with more active sites, higher surface-to-volume
ratio and less electron–hole recombination is needed [25–27].
However, to our best knowledge, there are no report about the
glass and their use as photocatalyst for degradation of an azo
textile dye F3B. In continuation of our research in semiconductor
metal oxide thin film [6,28–30], in the present work, we report for
the first time the preparation and characterization of nanostruc-
ture composite ZnFe2O4–FeFe2O4–ZnO immobilized on glass. The
nanostructure coating was characterized in detail by means of
XRD, SEM and DRS. We have applied the coatings for photocatalytic
decoloration of a textile dye (F3B) (Fig. 1) as an aquatic
environmental pollutant.
2. Experimental
2.1. Materials
Borosilicate glass was used as a support of the ZnFe2O4–
FeFe2O4–ZnO (ZFZ) nanocomposite. Zinc acetate dihydrate,
Zn(CH3COO)2
2H2O, iron(III) acetate, Fe(CH3COO)2, monoetha-
nolamine and isopropanol were used without any further
purification. Double-distilled water was used in all the experi-
ments.
2.2. Preparation of ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite

* Corresponding author. Tel.: +98 311 7932707; fax: +98 311 6689732. To the solution of isopropyl alcohol, 30 ml as a solvent,
E-mail addresses: habibi@chem.ui.ac.ir, mhhabibi@yahoo.com (M.H. Habibi). monoethanolamine, 0.63 ml as a complexing agent, zinc acetate

1226-086X/$ – see front matter ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.04.025
 M.H. Habibi, A.H. Habibi / Journal of Industrial and Engineering Chemistry 20 (2014) 68–73
Fig. 1. Chemical structure of Reactive Red 195 (F3B) as a textile dye.
dihydrate, Zn(CH3COO)22
H2O (2.304 g), was added while stirring
at 60 8C for 1 h to achieve a transparent solution (Sol A). Iron(III)
acetate, Fe(CH3COO)3 (1.826 g) was dissolved in the mixture of
isopropyl alcohol, 30 ml and monoethanolamine, 0.63 ml while
stirring at 60 8C for 1 h (Sol B). Sol A was added to Sol B with
continuous stirring for 10 min at room temperature and aged for 2
days. The solution was heated to 80 8C with formation of a gel.
Dried gel was annealed at 700 8C to obtain the ZnFe2O4–FeFe2O4–
ZnO (ZFZ) nanocomposite. A schematic diagram of the process is
presented in Fig. 2.
2.3. Preparation of ZnFe2O4–FeFe2O4–ZnO paste (ZFZP)
ZnFe2O4–FeFe2O4–ZnO powders (0.60 g) was grinded in a
mortar with 1 mL of acetic acid at 5 min. Double distilled water
(1 mL) was added with stirring for 1 min (5 times). Ethanol (1 mL)
was added and stirred for 1 min (15 times). Ethanol (2.5 mL) was
added and grinded in the mortar for 1 min (6 times). The paste was
Fig. 2. Flow chart for preparation ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite
paste.
69
Fig. 3. Absorption spectra of F3B taken at different photocatalytic degradation
times using ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite coated on glass as
photocatalysts.
transferred to a 300 mL beaker with addition of 100 mL ethanol.
The sample was sonicated for 1 min. Terpineol (20 mg) was added
and the paste solution was sonicated. A solution of ethyl cellulose
in ethanol was sonicated the solvent was evaporated in a rotary
evaporator. It was found that ZnFe2O4–FeFe2O4–ZnO/ethyl cellu-
lose/terpineol paste is helpful to increase the powder loading and
make it possible to produce ZnFe2O4–FeFe2O4–ZnO films with
higher surface uniformity and particle density after sintering
process.
2.4. Coating of ZnFe2O4–FeFe2O4–ZnO paste on glass by doctor blade
(ZFZPC)
The paste was coated on a glass slide by doctor blade method
and the thin film annealed at 550 8C for 2 h. Microscope slides were
carefully cleaned by ethanol and dried in an oven. ZnFe2O4–
FeFe2O4–ZnO paste immobilized on glass substrates were fabri-
cated using the doctor blade method [31,32]. The area of the
ZnFe2O4–FeFe2O4–ZnO coated glass was 11.25 cm2, length 7.5 cm
and width 1.5 cm. The ZFZPC coated glass was air dried, annealed
at 550 8C and cooled [33,34].
2.5. Characterization
The thermoanalytical measurements (TG-DTG) study for the
thermal decomposition of precursors were carried out with a using
a Mettler TA4000 system from 20 to 700 8C at a heating rate of
5 8C min 1. ZnFe2O4–FeFe2O4–ZnO paste on glass by doctor blade
was characterized by XRD analysis using X-ray diffractometer (D8
Advance, BRUKER) in the diffraction angle range 2u = 20–608, using
Cu Ka radiation. The crystallite size D of the sample was estimated
using the Scherer’s equation, (0.9l)/(b cos u), by measuring the
line broadening of main intensity peak, where l is the wavelength
of Cu Ka radiation, b is the full width at half-maximum, and u is the
brag’s angle. Field emission scanning electron microscopy (FE-
SEM, Hitachi, model S-4160) was used to observe the surface
morphology of the ZnFe2O4 photocatalyst. Diffuse reflectance
spectra (DRS) were collected with a V-670, JASCO spectrophotom-
eter and transformed to the absorption spectra according to the
Tach relationship. FT-IR absorption spectra of selected samples
were obtained using KBr disks on a FT-IR 6300. A UV-Spectropho-
tometer (Varian Cary 500 Scan) was used to measure F3B azo
textile dye concentrations at various time intervals during the
reactions at wavelength 563 nm (Fig. 3).
70 M.H. Habibi, A.H. Habibi / Journal of Industrial and Engineering Chemistry 20 (2014) 68–73
Fig. 4. Photooxidation set up (a) oxygen cylinder; (b) power supply; (c) lamps; (d)
photoreactor with aluminum foil as reflector for a full irradiate of catalyst; (e) fan;
(f) magnetic stirrer; (g) 2 l Pyrex beaker; (h) photooxidation cell; (i) water
thermostat Haake model F-122.
2.6. Experimental procedure for photocatalytic degradation of F3B azo
textile dye
The experiments were conducted under a 250 W Hg lamp
placed 5 cm above the solutions using a Petri Dish with 20 ml of
F3B azo textile dye and the ZnFe2O4–FeFe2O4–ZnO paste coated on
glass slide using by doctor blade method. Three milliliter dye
solution about was withdrawn periodically to monitor the
absorbance spectra. The degradation process of Reactive Red 2
was monitored by the absorbance at 563 nm. The UV light was
turned off during the absorbance monitoring process. Aqueous
solution was poured into the testing container (Fig. 4).
3. Results and discussion
3.1. Characterization of ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite
3.1.1. Thermogravimetric analysis
TG-DTG curves of synthesized ZFZ nanocomposite are shown in
Fig. 5. The TG curve exhibits two distinct weight loss steps. The first
weight loss step in the peak temperature of 250 8C, arises due to
Fig. 5. TG-DTG of ZnFe2O4–FeFe2O4–ZnO dried sol.
the loss of residual moisture in the powder. The second weight loss
step in the peak temperature of 350 8C is associated with the
combustion of acetates. A small weight loss was observed about
640 8C, implying the presence of nanocomposite oxides.
3.1.2. XRD analysis
The crystal structure of the ZnFe2O4–FeFe2O4–ZnO (ZFZ)
nanocomposite has been analyzed via X-ray powder diffraction
measurements. Diffraction patterns show the characteristic Bragg
peaks expected for ZnFe2O4, FeFe2O4 and ZnO. The calculated cell
parameters are in agreement with the typical value for the ferrite
spinels and zinc oxide wurtzite. The sizes of the nanoparticles
synthesized were calculated by the Debye–Schrerrer formula using
the diffraction patterns, being the diameter similar with those
calculated by analyzing FESEM images. Fig. 6a shows the XRD
patterns of ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite sample
annealed at 500 8C. The detected diffraction peaks could be
attributed to the characteristic peaks of ZnFe2O4 (31.7%), FeFe2O4
(13.8%) and ZnO (54.5%) (Table 1). This composition ratio was
supported by EDS measurements. The peaks centered at 31.78,
34.48, 36.28 and 47.58 in Fig. 6a are corresponded to (1 0 0), (0 0 2),
(1 0 1) and (1 0 2) of zinc oxide with the hexagonal wurtzite
structure (space group: P63mc), respectively [4,35]. The diffraction
patterns in Fig. 6a show characteristic peak for FeFe2O4 at 43.1
(4 0 0) [36]. This finding indicates that the composite consists of
FeFe2O4 crystals with spinel structures [36–38]. The diffraction
peaks (2 2 0), (3 1 1), (4 0 0), (5 1 1) and (4 4 0) at 2u of 30.18, 348,
438, 568, and 628 in the XRD spectra are corresponding to ZnFe2O4
franklinite phase respectively [39,40]. Fig. 6b shows the XRD
patterns of ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite sample
annealed at 600 8C. The detected diffraction peaks could be
attributed to the characteristic peaks of ZnFe2O4 (50.2%), FeFe2O4
(11.0%) and ZnO (38.9%). Fig. 6c shows the XRD patterns of
ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite sample annealed at
700 8C. The detected diffraction peaks could be attributed to the
characteristic peaks of ZnFe2O4 (54.2%), FeFe2O4 (7.3%) and ZnO
(38.6%). The results from the XRD spectra in Fig. 6a–c showed that
the increase of annealing temperature increases the amounts of
ZnFe2O4 phase.
3.1.3. Morphology characterization
Fig. 7 shows the typical FESEM image of ZnFe2O4–FeFe2O4–ZnO
(ZFZ) nanocomposite. With an average size of the sphere-like and
square-like nanoparticles around 46 nm, close to the XRD analysis
[41–43].
3.1.4. Diffuse reflectance (DRS) spectroscopic analysis for
determination of band gap
A Tauc plot is used to determine the band gap of ZnFe2O4–
FeFe2O4–ZnO (ZFZ) nanocomposite. A Tauc plot shows the quantity
hn (the energy of the light) on the abscissa and the quantity (ahv)n
on the ordinate, where a is the absorption coefficient of the
material and n = 2 for indirect allowed transitions [44–46]. The
band gap of ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite is shown
in Fig. 8. The energy band gap of films was found to be 2.07 eV.
Fig. 9 shows the band gaps obtained for ZnFe2O4–FeFe2O4–ZnO
(ZFZ) nanocomposite using Kubelka–Munk plot [47].
3.2. Photocatalytic degradation of F3B azo textile dye using ZnFe2O4–
FeFe2O4–ZnO (ZFZ) nanocomposite coated on glass by doctor blade
(ZFZPC)
The photocatalytic activity of ZnFe2O4–FeFe2O4–ZnO (ZFZ)
nanocomposite coated on glass is evaluated by choosing azo
textile dye, Reactive Red 195 (F3B) as a model and the results are
presented in Fig. 10. The F3B degradation kinetics data were
 M.H. Habibi, A.H. Habibi / Journal of Industrial and Engineering Chemistry 20 (2014) 68–73 71

Fig. 6. (a) XRD patterns for the ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite annealed at 500 8C. (b) XRD patterns for the ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite
annealed at 600 8C. (c) XRD patterns for the ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite annealed at 700 8C.

Table 1 examined using a first-order reaction kinetics. The first order rate
Effect of annealing temperature on relative intensities of different phases found in
constant k is obtained by plotting ln(C0/Ct) vs. time (min). As
the XRD analysis using zinc acetate and iron acetate.
shown, the effect of light on increasing decolorization rate of the
Mol. ratio Temp. (8C) ZnO ZnFe2O4 FeFe2O4 azo textile of F3B is evident and the decolorization percentages
(%, w/w) (%, w/w) (%, w/w)
under light conditions are found to be about 60%. The light-induced
1:1 500 54.5 31.7 13.8 decolorization of azo textile of F3B on the ZnFe2O4–FeFe2O4–ZnO
1:1 600 38.9 50.2 11.0 particles is contributed to the following possible mechanism. The
1:1 700 38.6 54.2 7.2
rate of valence electrons excited to the conduction band, occurring

Fig. 7. FESEM image of ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite annealed at

700 8C. Fig. 8. Tauc plot ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite annealed at 700 8C.
72 M.H. Habibi, A.H. Habibi / Journal of Industrial and Engineering Chemistry 20 (2014) 68–73
Fig. 9. Munk plot ZnFe2O4–FeFe2O4–ZnO (ZFZ) nanocomposite annealed at 700 8C.
Fig. 10. ln C0/Ct vs. time for photocatalytic degradation of an azo textile dye,
Reactive Red 195 (F3B) as a model pollutant under UV irradiation using ZnFe2O4–
FeFe2O4–ZnO paste on glass by doctor blade (ZFZPC) immobilized on glass.
at the ZnFe2O4–FeFe2O4–ZnO particles surface, is accelerated by
irradiation. The photo-generated holes are scavenged by azo textile
of F3B. A photolysis test was conducted in the presence of Reactive
Red 2 (F3B) without ZnFe2O4–FeFe2O4–ZnO paste coated on glass
slide as photocatalysts but with the UV lamp turned on. The direct
photolysis of Reactive Red 2 (F3B) by UVC, UVA and 250 W Hg
lamps was negligible. The UV applied alone was not sufficient
without the presence of the photocatalysts for the oxidation of
Reactive Red 2. Photodegradation of Reactive Red 2 (F3B) with
UVA, UVC and 250 W Hg lamps with ZnFe2O4–FeFe2O4–ZnO paste
coated on glass slide are compared. The photoactivity with UVC
and UVA using ZnFe2O4–FeFe2O4–ZnO paste coated on glass slide
are very close. However, using 250 W Hg lamp the photoactivity
was slightly higher due to higher intensity.
4. Conclusions
Nanostructure composite of ZnFe2O4–FeFe2O4–ZnO (ZFZ) was
prepared using thermal decomposition of iron(III) acetate and
zinc acetate. ZFZ composite was immobilized on glass using
doctor blade method. The properties of the ZFZ nanocomposite
was examined by XRD, FESEM and DRS. XRD confirms that the
prepared nanocomposite is composed of franklinite, ZnFe2O4
(54%), magnetite, FeFe2O4 (8%) and wurtzite, ZnO (48%). Photo-
catalytic activity of ZFZ immobilized on glass was carried out by
choosing an azo textile dye, Reactive Red 195 (F3B) as a model
pollutant under UV irradiation with homemade photocatalytic
apparatus and the results indicated that ZFZ exhibited good
photocatalytic activity.
Acknowledgment
The authors wish to thank the University of Isfahan for
financially supporting this work.
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