Accepted Manuscript

Title: Synthesis of ZnFe2 O4 nanoparticles for photocatalytic

removal of toluene from gas phase in the annular reactor

Author: Habib Mehrizadeh Aligholi Niaei Hui-Hsin Tseng

Dariush Salari Alireza Khataee

PII: S1010-6030(16)30145-9
DOI: http://dx.doi.org/doi:10.1016/j.jphotochem.2016.08.028
Reference: JPC 10342

To appear in: Journal of Photochemistry and Photobiology A: Chemistry

Received date: 29-2-2016

Revised date: 13-7-2016
Accepted date: 28-8-2016

Please cite this article as: Habib Mehrizadeh, Aligholi Niaei, Hui-Hsin Tseng, Dariush
Salari, Alireza Khataee, Synthesis of ZnFe2O4 nanoparticles for photocatalytic removal
of toluene from gas phase in the annular reactor, Journal of Photochemistry and
Photobiology A: Chemistry http://dx.doi.org/10.1016/j.jphotochem.2016.08.028

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 Synthesis of ZnFe2O4 nanoparticles for photocatalytic removal of
toluene from gas phase in the annular reactor

Habib Mehrizadeha,b,1, Aligholi Niaeia,2, Hui-Hsin Tsengc,3, Dariush Salarib,*, Alireza

Khataeed,e,4

a
Research Laboratory of Reactor and Catalyst, Faculty of Chemical Engineering, University of
Tabriz, Tabriz, Iran
b
Research Laboratory of Petroleum Technology, Faculty of Chemistry, University of Tabriz,
Tabriz, Iran
c
School of Occupational Safety and Health, Chung Shan Medical University, Taichung, 402,
Taiwan, ROC
d
Research Laboratory of Advanced Water and Wastewater Treatment, Faculty of Chemistry,
University of Tabriz, Tabriz, Iran
e
Department of Nanotechnology, Near East University, 99138 Nicosia, North Cyprus, Mersin
10, Turkey

* Corresponding authors:

Tel.: +98 413 3393149;

Fax: +98 413 3340191;

E–mail address: dariush_salari@yahoo.com

1
h_mehrizade@yahoo.com
2
aniaei@tabrizu.ac.ir
3
hhtseng@csmu.edu.tw
4
a_khataee@tabrizu.ac.ir

1
Graphical abstract

2
Research Highlights:

- Synthesize the mesoporous ZnFe2O4 spinel nanoparticles by sol-gel auto combustion method.

- Photocatalytic removal of toluene as a deputy of VOCs pollutant in the annular batch

photoreactor.

- Study the photocatalytic activity of prepared ZnFe2O4 in the UV and Visible irradiation.

- Investigation the effective parameters on the photocatalytic removal of toluene.

- Comparison of photocatalytic activity of prepared nanoparticles with ZnO and TiO2

nanophotocatalysts

3
Abstract
Spinel type mesoporous ZnFe2O4 nanoparticles were synthesized by sol-gel auto combustion

method and characterized by XRD, FE-SEM, DRS and BET. XRD pattern of prepared

nanocrystals showed that ZnFe2O4 spinel formed in cubic structure and the mean crystallite size

was 25 nm. FE-SEM image showed that prepared particles were in nanoscale with low

aggregation and porous structure. From DRS results, the optical band gap was calculated about

1.87 eV. From BET analysis, specific surface area of prepared nanoparticles was obtained 39

m2/g. The prepared nanoparticles application was studied on the removal of toluene from gas

phase by photocatalytic process under UV and visible irradiation in the annular photoreactor.

The prepared nanoparticles were capable to remove about 60% of toluene with 900 ppmv

concentration. The prepared nanoparticles had more efficiency than commercial ZnO and TiO2

nanoparticles in the photocatalytic removal of toluene. The operational parameters such as initial

concentration of pollutant, catalyst loading, photoreactor humidity and light intensity were

studied.

Keywords: Nanocatalyst; Mixed Metal Oxides; Semiconductors; Photoreactor; Air Pollutants.

4
1. Introduction

Volatile organic compounds (VOCs) are the main air pollutants in the urban areas, which

significantly impact on the human health and chemistry of atmosphere [1, 2]. These compounds

extensively used in domestic activities and industrial processes and lead to creation of pollutant

in the water and air [3]. The impact of VOCs on the human and ecosystem health are

considerable as decreasing the air quality, formation of photochemical smog, stratospheric ozone

depletion and the greenhouse effect [4, 5]. Benzene, toluene, ethylbenzene, and xylene (BTEX)

are an important group of aromatic VOCs that used widely in the industry [6].With the matter of

global warming owing to the greenhouse effect, the treatment of atmospheric emission, including

VOCs, has become an ecological and economic priority [7]. VOCs can be treated by several

methods, including destructive (incineration, biofiltration and catalytic oxidation) and

nondestructive (absorption, adsorption, condensation and membrane filtration) processes [8].

Photocatalytic removals of VOCs exhibit a successful pathway for elimination of air pollutants

and get huge interest in pollution control [9]. Particularly, photocatalytic degradation of VOCs is

gaining more interest because of harmful impact of VOCs on the human and environment [10].

Today extensive efforts have been made in the development of effective photocatalyst for the

elimination of organic pollutants [11]. Zinc ferrite (ZnFe2O4), as a stable spinel-type (AB2O4)

mixed metal oxide semiconductor, which has been widely used in many fields such as pigment,

catalyst and specially used as an effective visible light photocatalyst for degradation of pollutant

due to its relatively small band gap, tunable band edge by modulating grain size and good

photochemical stability [12-15]. Nanostructure ZnFe2O4 because of its visible light response and

stability against photoanodic corrosion is a potentially useful solar energy material for the

photochemical processes [16]. Nanoscale materials have been demonstrated to present high

5
surface activity due to the high percentage of surface atoms [11]. Nanoscale metal oxides have

been synthesized by different methods such as sol-gel, chemical co-precipitation, hydrothermal

and so on [17]. The sol-gel process because of the excellent control over chemistry,

homogeneity, purity, and crystalline phase is considerable among these techniques [18]. A part

of the solution combustion method is Citrate-Nitrate Auto-combustion synthesis (CNA), which is

similar to pechini process and can be described as a “sol-gel combustion method”. The fuel in

CAN synthesis is citric acid and metal nitrates are used as the metal and oxidant source [19]. The

CAN synthesis method is the appropriate option to prepare reproducible and optimum

nanostructure materials [17].

In this research, ZnFe2O4 nanosemiconductor was prepared by citrate nitrate auto combustion

sol-gel process and characterized by XRD, SEM, DRS and BET. Synthesized nanoparticles

immobilized on the aluminum foils by electrophoretic method. Prepared nanoparticles were used

as a photocatalyst for removal of toluene as a deputy of VOCs pollutant under different UV and

visible irradiation in the self-designed annular photoreactor. The operational parameters that

effected photocatalytic removal such as pollution concentration, catalyst amount, irradiation type

and humidity were investigated.

2. Material and methods

2.1. Materials

Zn(NO3)2.6H2O, Fe(NO3)3.6H2O, citric acid (C6H8O7.H2O), commercial ZnO and TiO2

nanopowder, toluene, NaOH, ethanol and acetylaceton were purchased from Merck Co. The

aluminum foils with 70 micrometer thickness were purchased from Payvan Company, Iran.

6
2.2. ZnFe2O4 nanoparticles preparation

ZnFe2O4 nanoparticles were synthesized by citrate-nitrate auto-combustion synthesis (CNA)

method. Zn(NO3)2 and Fe(NO3)3 were dissolved in100 mL distillated water by 1:2 molar ratio of

them and homogenized using a magnetic stirrer at 70˚C. An appropriate amount of citric acid

was added into above solution and the temperature was justified at 90°C to evaporate the water.

A polycondensation reaction between nitrate ions and citric acid carried out during the

dehydration process and caused the formation of gel. When the gel was formed, the temperature

was raised to 200°C to burn the organic contents and the reaction products converted into the

brownish powder. The prepared powder was calcinated at 700°C and cooled slowly to room

temperature and stored for applications.

2.3. Immobilization of prepared ZnFe2O4 on the aluminum foils

The prepared ZnFe2O4 nanoparticles were immobilized on the aluminum foils by

electrophoretic deposition (EPD) process. The aluminum foils were selected because of their

flexibility and capability to take an annular shape similar to the wall of the reactor and pretreated

by polishing. Prepared nanocrystalline powders of ZnFe2O4 were dispersed in ethanol and

acetylacetone and before electrophoretic deposition process; the suspension was stirred for 1 h

and then ultrasonicated for 30 min and put in the container for electrophoresis. During the EPD

process, a plate of aluminum foil as the anode and the pretreatment foils of aluminum as the

cathode were immersed in the container of ZnFe2O4 suspension. The immobilization of ZnFe2O4

on the aluminum foils was occurred by applying DC electric field at 30V. After finishing the

immobilization process, the residual solvent on the immobilized sheets was removed by

evaporation at ambient temperature in the air for 10 h. For more treatment of immobilized

ZnFe2O4 film, the immobilized plates sintered at 350◦C for 1 h.

7
2.4. Photocatalytic removal process of toluene

Photocatalytic removal process was studied in the annular batch photoreactor with the total

volume of 1500 cm3. The 36 W Florescent or 8W UV lamp (Philips, UV-C, The Netherlands)

vertically was inserted in the quartz tube at the center of the photoreactor and the temperature of

photoreactor was controlled by air stream inside the quartz tube. The aluminum foils containing

immobilized ZnFe2O4 nanoparticles were installed in the internal side of the outer wall of

photoreactor. To achieve homogenous dispersion of gaseous molecules and effective mass

transfer in the reactor the stirrer rotation was adjusted on the optimum amount (1200 rpm). The

humidity and temperature of the photoreactor were recorded by thermohygrometer (TFA, Kat.

Nr. 30. 5013, Germany), which its sensor was installed in the photoreactor.

Photocatalytic removal study was done by injecting a known quantity of toluene into the

reactor and stirred for 30 min to vaporize and reach to equilibrium with known concentration.

Photocatalytic removal process of toluene was initiated by lighting on the UV lamp and sampling

from the reactor during irradiation time at the appropriate intervals. Quantitative analysis of

toluene samples in the gas phase were determined by gas chromatography using GC (Shimadzu,

GC-2010 Plus, Japan) that was equipped with a CBP5 column and connected to flame ionization

detector (FID). Photocatalytic removal performance was studied by calculating the degree of

photocatalytic removal efficiency of toluene (X) as a function of irradiation time according to the

following equation:

𝐶0 − 𝐶𝑡
𝑋= (1)
𝐶0

where Co is the initial concentration of toluene and Ct is the remaining concentration of toluene

at any intervals in the photoreactor.

8
2.5. Characterization of synthesized ZnFe2O4 nanoparticles

The average crystalline size and the crystalline phase of synthesized ZnFe2O4 nanoparticles

were determined by X-ray diffraction (XRD) pattern. The XRD analysis was recorded by X-ray

powder diffractometer (Philips, PW1830, The Netherlands) for 2θ over 4-70º, with Cu Kα (λ =

1.5406 Aº) radiation and accelerating voltage of 40 kV at room temperature. The morphology

and size of prepared particles and also immobilized powder on the aluminum foil were

determined by Field Emission Scanning Electron Microscopy (FE-SEM) (JEOL, JSM-6700F,

Japan). The optical band gap of synthesized ZnFe2O4 nanoparticles was determined through

recording of UV-Vis DRS in the wavelength range 500-800 nm by UV-Vis spectrophotometer

(Hitachi, U-3900, Japan). The specific surface area and other surface properties were determined

through BET analysis by a BET Sorptometer (PMI, BET-201-AEL, USA). The nitrogen was

used as the adsorbent and the sample out gassed to 20 micron vacuum at 120ºC.

3. Results and discussion

3.1. Characterization of synthesized ZnFe2O4 nanoparticles

Fig. 1 shows the XRD pattern of synthesized ZnFe2O4 nanoparticles. Strong peaks at 18.3,

28.9, 35.3, 37.1, 43, 53.2, 56.8, 62.3º correspond to the cubic phase of prepared ZnFe2O4

nanocrystlas. From Debye-Scherer formula [20] the mean crystalline size of prepared particles

were calculated about 25 nm.

Fig. 1.

Fig. 2a shows the FE-SEM image of prepared ZnFe2O4 particles. From the FE-SEM image

low aggregation of particles and porous structures of prepared catalyst in the nanoscale is

observed. The porous structure cause to improve the light harvesting by prepared nanoparticles
9
and also porous structures have a great ability to capture protons efficiently [21-23]. Fig. 2b

shows the surface image of immobilized ZnFe2O4 nanopowder on the aluminum foil. From the

Fig. 2b the smooth and homogeneous coating of ZnFe2O4 particles were obtained on the

aluminum foil.

Fig. 2.

Fig. 3a shows the UV-Vis diffuse reflectance spectrums of prepared ZnFe2O4 nanoparticles

and the absorption edge for the prepared sample was observed around 665 nm. From the DRS by

using the Tauc relation (Eq. 2), the optical band gap energy for prepared nanoparticles has been

calculated about 1.87 eV [24].

αhυ = A(hυ – Eg)n (2)

According to Tauc relation (Eq. 2), α is the absorption coefficient, hυ is the photon energy, Eg is

the optical band gap energy, n for direct band gap semiconductors is equal to 1/2 and A is a

constant. The plotted graph of (αhυ)2 vs. hυ (Fig. 3b) were used to calculate the optical band gap

energy and from extrapolation of the straight line to (αhυ)2=0 axis, the optical band gap energy

for synthesized nanoparticles were obtained 1.87 eV [24, 25].

Fig. 3.

Fig. 4a shows the nitrogen adsorption isotherm of prepared nanoparticles, and from the

literature this kind of adsorption could be classified as a typical Type III isotherm. From the

Fig.4a, multi-point BET analysis with 22 points was used to calculate the BET specific surface-

area of prepared ZnFe2O4 nanoparticles and the specific surface area of prepared nanoparticles

were calculated about 39 m2/g. Fig. 4b shows the pore-size distribution of the prepared ZnFe2O4

nanoparticles that was obtained from the adsorption isotherms based on the Barett-Joyner-

10
Halenda (BJH) model and from this figure the most probable pore sizes were 1.75nm. In

addition, from BJH model average pore diameter, pore volume and porosity were obtained 4.86

nm, 0.0452 cm3/g and 4.52% respectively and prepared ZnFe2O4 nanoparticles can be

categorized as the mesoporous material [26, 27].

Fig. 4.

3.2. ZnFe2O4 nanoparticles and irradiation effect on the photocatalytic removal of

toluene

The effects of the presence of synthesized ZnFe2O4 nanoparticles, UV and visible irradiation

on the removal efficiency of toluene are shown in Fig. 5. The results show that the photocatalytic

removal efficiency of toluene was negligible in the absence of ZnFe2O4 nanopowder plate

(photolysis) and UV light (adsorption). The observed high photocatalytic removal efficiency in

the presence of both ZnFe2O4 nanopowders plate and UV or visible irradiation (UV or

Visible/ZnFe2O4 process) is mainly because of photocatalytic activity of ZnFe2O4 nanoparticles.

In the presence of UV or visible light with sufficient energy, photo excitation of catalyst particles

caused the creation of electron-hole pairs and the highly reduction potentials of these excited

electrons caused to create hydroxyl radicals. Hydroxyl radicals and also created the positive

holes caused the destruction of pollutant as shown in equation 3-13 [25, 28-31].

ZnFe2O4 + hυ → ZnFe2O4 (h+VB) + ZnFe2O4 (e−CB) (3)

O2 + ZnFe2O4 (e−CB) → O2•− (4)

O2•− + H+ → HO2• (5)

HO2• +O2•− → HO2- + O2 (6)

11
 2HO2• → O2 + H2O2 (7)

H2O2 + hυ → 2 OH• (8)

H2O2 + e−CB → OH− + OH• (9)

C6H5CH3 + OH• → C6H5CH2• →→ C6H5COOH → C6H6 →→ CO2 (10)

C6H5CH3 + OH•→ HO(C6H4)CH3 →→ HO(C6H4)COOH → C6H5OH →→ CO2 (11)

C6H5CH3 + h+VB →C6H5CH2• →→ C6H5COOH → C6H6 →→ CO2 (12)

C6H5CH3 + h+VB → C6H4•CH3 →→ CH2CHCOCH3 + CH3COCHO →→ CO2 (13)

Fig. 5.

3.3. Initial toluene concentration effect on the photocatalytic removal of toluene

The effect of various initial toluene concentrations on the photocatalytic removal efficiency

were investigated from 300 to 3200ppmv and illustrated in Fig. 6. The results show that,

increasing the toluene concentration from 300 to 900 ppmv cause to increase the photocatalytic

removal efficiency, but increasing the concentration above 900 ppmv cause to decrease the

removal efficiency. This finding is related to kinetic effect and blocking the active sites. At the

first stage increasing the concentration causes to increase the amount of molecules reaching the

catalyst surface and this cause to increase removal efficiency. But increasing the concentration

more than 900 ppmv causes the adsorption of more toluene molecules on the photocatalyst

surface and these molecules will block more active sites on the catalyst surface and lead to

reduce the hydroxyl radical generation on the photocatalyst surface. This phenomenon causes to

12
reduce the production of active species on the photocatalyst surface and leads to the decrease of

photocatalytic removal efficiency of toluene at higher concentration [32, 33].

Fig. 6.

3.4. ZnFe2O4 dosage effect on the photocatalytic removal of toluene

Catalyst amount is a main factor in the initial rate of photocatalytic degradation of pollutant

and increasing the catalyst loading proportionally increases the initial rate of photocatalytic

process [34]. To study the effect of ZnFe2O4 loading amount, by changing the number of

uniformly ZnFe2O4 immobilized plates in the photoreactor their amount was varied. Fig.7

illustrates the photocatalytic removal efficiency of toluene in the different amount of nano

photocatalyst loading from 0 to 60 mg. As shown in Fig. 7, increasing the amount of ZnFe2O4

nanoparticles causes to increase the photocatalytic removal efficiency. This observation can be

interpreted by increasing the number of active radicals, because increasing the photocatalyst

amount causes to increase the number of active sites on the photocatalyst surface and this

increases the photocatalytic removal efficiency by increasing the generation of more active

species for photocatalytic activity [35].

Fig. 7.

3.5. The effect of light intensity and type on the photocatalytic removal of toluene

Photocatalytic reaction rate largely depends on the radiation absorption on the photocatalyst

and increasing the light intensity leads to the increase in the photocatalytic decomposition rate

[36]. Not only the intensity of the radiation has an effect on degradation rate of photocatalytic

activity but also the wavelength of irradiated light is one of the main factors of the system’s

13
efficiency [37]. The impact of irradiation intensity on the photocatalytic removal performance of

toluene has been investigated by changing the light sources with different power and different

irradiation wavelength from UV to Visible. The impact of light power on the photocatalytic

removal performance of toluene is illustrated in Fig. 8. For both of UV and Visible sources,

increasing the light power cause to increase the photocatalytic removal. However the removal

efficiency of UV lamps is more than visible, but the removal efficiency in the visible light is also

considerable and this is because of the small band gap of prepared ZnFe2O4 nanoparticles.

Required photons for excitation of electrons from the valence band to the conduction band of

photocatalyst were generated by irradiation and increasing the light power causes more photons

to reach on the surface of the catalyst and this leads to produce more active species that promote

photocatalytic performance [38-40].

Fig. 8.

3.6. Initial relative humidity effect on the removal of toluene

In the photocatalytic elimination of gaseous organic compounds, water vapor quantity is

important because the water molecules are the source of hydroxyl radicals and reduction of water

content causes to decrease hydroxyl radical production on the surface of the catalyst and leads to

the decrease of photocatalytic performance [41]. The effect of humidity of photoreactor on the

photocatalytic removal of toluene based on Relative Humidity (RH) of photoreactor is shown in

Fig. 9. As shown in Fig. 9, initially increasing the relative humidity causes to decreases of

removal efficiency, but increasing further humidity causes to increase photocatalytic removal

efficiency. This finding might be closely related to interaction on the surface of photocatalyst

between toluene and water molecules. The impact of water vapor in the gas phase photocatalytic

14
elimination depends on the type of pollutants and their concentration and also humidity [42]. In

the absence of water vapor or low RH, the reaction is mainly initiated by the created holes on the

surface of photocatalyst (equations 12 and 13) via electron transfer from toluene to photocatalyst,

but in the presence of water molecules, hydroxyl radicals (equations 10 and 11) also take part in

the photocatalytic removal of pollutant [31]. The competitive adsorption between toluene and

water molecules on the surface of photocatalyst, and the covering of active sites of the

photocatalyst surface by water molecules causes this phenomenon to occur. At the initial stage

increasing the humidity causes to destroy the water vapor equilibrium in the system and leads to

increase the water molecules adsorption on the catalyst surface, but this amount cannot create

sufficient hydroxyl radicals to promote the photocatalytic reaction. Therefore, at the initial stage

increasing the water molecules adsorption on the catalyst surface causes to decrease the

photocatalytic elimination reaction on the catalyst [42, 43]. At the high quantity of water vapor

in the photoreactor, hydroxyl radical production overcomes the adsorption effect of water, thus at

high humidity in the photoreactor, increasing the hydroxyl radicals production leads to the high

photocatalytic removal efficiency [41, 44].

Fig. 9.

3.7. Comparison of photocatalytic activity of prepared ZnFe2O4 and commercial

TiO2 and ZnO nanoparticles

Fig. 10 shows the results of photocatalytic removal efficiency of toluene using equal amounts

of prepared ZnFe2O4 and commercial ZnO and TiO2 nanoparticles at the same condition. The

results indicate that photocatalytic process using prepared ZnFe2O4 nanoparticles has more

removal efficiency than commercial ZnO and TiO2 nanoparticles. This may be attributed to

15
mixed metal oxide structure of ZnFe2O4 that reduces recombination and also the small band-gap

of ZnFe2O4 [12]. Also the porous structure of ZnFe2O4 can harvest illuminated light very well

and cause to improve photocatalytic activity on the toluene removal [21, 23]. The surface area of

prepared ZnFe2O4, commercial TiO2 and ZnO are 39, 10 and 3.3 m2/g respectively [45, 46].

Fig. 10.

4. Conclusions

ZnFe2O4 nanoparticles with mesoporous morphology and average crystalline size of 25 nm

were synthesized successfully by sol-gel auto-combustion method with optical band gab of 1.87

eV. Prepared ZnFe2O4 nanoparticles able to photocatalytically remove toluene from the gas

phase by UV and visible /ZnFe2O4 process and photocatalytic removal efficiency of toluene was

negligible when ZnFe2O4 nanopowder and light was used on their own. Degree of photocatalytic

removal of toluene by UV/ZnFe2O4 process was affected by the initial concentration of pollutant,

catalyst amount, illumination power and relative humidity of photoreactor. Increasing the

catalyst loading and light intensity cause to increase the photocatalytic removal efficiency, but

for increasing the initial concentration of toluene after an optimum, decreasing in removal

efficiency was observed. For humidity after a decrease in removal efficiency, increasing was

observed. Synthesized ZnFe2O4 spinel nanoparticles had higher photocatalytic performance than

commercial TiO2 and ZnO nanoparticles.

Acknowledgements

The authors sincerely thank the University of Tabriz (Iran) for providing the support.

References

16
[1] X. Xie, M. Shao, Y. Liu, S. Lu, C.-C. Chang, Z.-M. Chen, Estimate of initial isoprene
contribution to ozone formation potential in Beijing, China, Atmospheric Environment, 42
(2008) 6000-6010.
[2] A. Jun-lin, W. Yue-si, W. Fang-kun, Z. Bin, Characterizations of volatile organic compounds
during high ozone episodes in Beijing, China, Environmental monitoring and assessment,
184 (2012) 1879-1889.
[3] S.B. Kim, H.T. Hwang, S.C. Hong, Photocatalytic degradation of volatile organic compounds
at the gas–solid interface of a TiO2 photocatalyst, Chemosphere, 48 (2002) 437-444.
[4] M. Ulman, Z.a. Chilmonczyk, Volatile Organic Compounds - Components,
Sources,Determination - A Review, Chem. Anal. (Warsaw), 52 (2007) 173-200.
[5] M. Ras, R. Marcé, F. Borrull, Volatile organic compounds in air at urban and industrial areas
in the Tarragona region by thermal desorption and gas chromatography–mass spectrometry,
Environmental monitoring and assessment, 161 (2010) 389-402.
[6] P. Baltrėnas, E. Baltrėnaitė, V. Šerevičienė, P. Pereira, Atmospheric BTEX concentrations in
the vicinity of the crude oil refinery of the Baltic region, Environmental monitoring and
assessment, 182 (2011) 115-127.
[7] G. Darracq, A. Couvert, C. Couriol, A. Amrane, P. Le Cloirec, Removal of Hydrophobic
Volatile Organic Compounds in an Integrated Process Coupling Absorption and
Biodegradation—Selection of an Organic Liquid Phase, Water Air Soil Pollut, 223 (2012)
4969-4997.
[8] F.I. Khan, A. Kr. Ghoshal, Removal of Volatile Organic Compounds from polluted air,
Journal of Loss Prevention in the Process Industries, 13 (2000) 527-545.
[9] M. Tokumura, R. Nakajima, H.T. Znad, Y. Kawase, Chemical absorption process for
degradation of VOC gas using heterogeneous gas–liquid photocatalytic oxidation: Toluene
degradation by photo-Fenton reaction, Chemosphere, 73 (2008) 768-775.
[10] K. Demeestere, A.D. Visscher, J. Dewulf, M.V. Leeuwen, H.V. Langenhove, A new kinetic
model for titanium dioxide mediated heterogeneous photocatalytic degradation of
trichloroethylene in gas-phase, Applied Catalysis B: Environmental, 54 (2004) 261-274.
[11] G.-Y. Zhang, Y.-Q. Sun, D.-Z. Gao, Y.-Y. Xu, Quasi-cube ZnFe2O4 nanocrystals:
Hydrothermal synthesis and photocatalytic activity with TiO2 (Degussa P25) as
nanocomposite, Materials Research Bulletin, 45 (2010) 755-760.
[12] L. Han, X. Zhou, L. Wan, Y. Deng, S. Zhan, Synthesis of ZnFe2O4 nanoplates by succinic
acid-assisted hydrothermal route and their photocatalytic degradation of rhodamine B under
visible light, Journal of Environmental Chemical Engineering, 2 (2014) 123-130.
[13] X. Cao, L. Gu, X. Lan, C. Zhao, D. Yao, W. Sheng, Spinel ZnFe2O4 nanoplates embedded
with Ag clusters: Preparation, characterization, and photocatalytic application, Materials
Chemistry and Physics, 106 (2007) 175-180.

17
[14] N.M. Mahmoodi, Zinc ferrite nanoparticle as a magnetic catalyst: Synthesis and dye
degradation, Materials Research Bulletin, 48 (2013) 4255-4260.
[15] Y. Hou, X.-Y. Li, Q.-D. Zhao, X. Quan, G.-H. Chen, Electrochemical Method for Synthesis
of a ZnFe2O4/TiO2 Composite Nanotube Array Modified Electrode with Enhanced
Photoelectrochemical Activity, Advanced Functional Materials, 20 (2010) 2165-2174.
[16] Z.-h. Yuan, L.-d. Zhang, Synthesis, characterization and photocatalytic activity of
ZnFeO/TiO nanocomposite, Journal of Materials Chemistry, 11 (2001) 1265-1268.
[17] Z. Seeley, Y.J. Choi, S. Bose, Citrate–nitrate synthesis of nano-structured titanium dioxide
ceramics for gas sensors, Sensors and Actuators B: Chemical, 140 (2009) 98-103.
[18] A.R. Phani, S. Santucci, Structural characterization of nickel titanium oxide synthesized by
sol–gel spin coating technique, Thin Solid Films, 396 (2001) 1-4.
[19] F. Deganello, G. Marcì, G. Deganello, Citrate–nitrate auto-combustion synthesis of
perovskite-type nanopowders: A systematic approach, Journal of the European Ceramic
Society, 29 (2009) 439-450.
[20] A.R. Khataee, V. Vatanpour, A.R. Amani Ghadim, Decolorization of C.I. Acid Blue 9
solution by UV/Nano-TiO2, Fenton, Fenton-like, electro-Fenton and electrocoagulation
processes: A comparative study, Journal of Hazardous Materials, 161 (2009) 1225-1233.
[21] A. Ibhadon, P. Fitzpatrick, Heterogeneous Photocatalysis: Recent Advances and
Applications, Catalysts, 3 (2013) 189.
[22] A.O. Ibhadon, G.M. Greenway, Y. Yue, P. Falaras, D. Tsoukleris, The photocatalytic
activity of TiO2 foam and surface modified binary oxide titania nanoparticles, Journal of
Photochemistry and Photobiology A: Chemistry, 197 (2008) 321-328.
[23] L.-x. Pang, X.-y. Wang, X.-d. Tang, Enhanced photocatalytic performance of porous TiO2
nanobelts with phase junctions, Solid State Sciences, 39 (2015) 29-33.
[24] K.V. Anand, M.K. Chinnu, R.M. Kumar, R. Mohan, R. Jayavel, Formation of zinc sulfide
nanoparticles in HMTA matrix, Applied Surface Science, 255 (2009) 8879-8882.
[25] M. Wang, L. Sun, J. Cai, P. Huang, Y. Su, C. Lin, A facile hydrothermal deposition of
ZnFe2O4 nanoparticles on TiO2 nanotube arrays for enhanced visible light photocatalytic
activity, Journal of Materials Chemistry A, 1 (2013) 12082-12087.
[26] T. Xie, L. Xu, C. Liu, Y. Wang, Magnetic composite ZnFe2O4/SrFe12O19: Preparation,
characterization, and photocatalytic activity under visible light, Applied Surface Science,
273 (2013) 684-691.
[27] M.M. Rahman, S.B. Khan, H.M. Marwani, A.M. Asiri, SnO2–TiO2 nanocomposites as new
adsorbent for efficient removal of La(III) ions from aqueous solutions, Journal of the Taiwan
Institute of Chemical Engineers, 45 (2014) 1964-1974.

18
[28] K.-H. Wang, J.-M. Jehng, Y.-H. Hsieh, C.-Y. Chang, The reaction pathway for the
heterogeneous photocatalysis of trichloroethylene in gas phase, Journal of Hazardous
Materials, 90 (2002) 63-75.
[29] S. Brosillon, L. Lhomme, C. Vallet, A. Bouzaza, D. Wolbert, Gas phase photocatalysis and
liquid phase photocatalysis: Interdependence and influence of substrate concentration and
photon flow on degradation reaction kinetics, Applied Catalysis B: Environmental, 78
(2008) 232-241.
[30] S. Aber, H. Mehrizade, A.R. Khataee, Preparation of ZnS nanocrystal and investigation of
its photocatalytic activity in removal of C.I. acid blue 9 from contaminated water,
Desalination and Water Treatment, 28 (2011) 92-96.
[31] M. Sleiman, P. Conchon, C. Ferronato, J.-M. Chovelon, Photocatalytic oxidation of toluene
at indoor air levels (ppbv): Towards a better assessment of conversion, reaction
intermediates and mineralization, Applied Catalysis B: Environmental, 86 (2009) 159-165.
[32] R.K. Nath, M.F.M. Zain, A.A.H. Kadhum, A.B.M.A. Kaish, An investigation of LiNbO3
photocatalyst coating on concrete surface for improving indoor air quality, Construction and
Building Materials, 54 (2014) 348-353.
[33] J.-L. Shie, C.-Y. Pai, Photodegradation Kinetics of Toluene in Indoor Air at Different
Humidities Using UVA, UVC and UVLED Light Sources in the Presence of Silver Titanium
Dioxide, Indoor and Built Environment, (2010).
[34] U.I. Gaya, A.H. Abdullah, Heterogeneous photocatalytic degradation of organic
contaminants over titanium dioxide: A review of fundamentals, progress and problems,
Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 9 (2008) 1-12.
[35] C. Sarantopoulos, E. Puzenat, C. Guillard, J.-M. Herrmann, A.N. Gleizes, F. Maury,
Microfibrous TiO2 supported photocatalysts prepared by metal-organic chemical vapor
infiltration for indoor air and waste water purification, Applied Catalysis B: Environmental,
91 (2009) 225-233.
[36] W.H. Ching, M. Leung, D.Y.C. Leung, Solar photocatalytic degradation of gaseous
formaldehyde by sol–gel TiO2 thin film for enhancement of indoor air quality, Solar Energy,
77 (2004) 129-135.
[37] L. Lin, Y. Chai, B. Zhao, W. Wei, D. He, B. He, T. Qunwei, Photocatalytic oxidation for
degradation of VOCs, Journal of Inorganic Chemistry, 3 (2013) 14-25.
[38] W.-K. Jo, H.-J. Kang, LED Irradiation of a Photocatalyst for Benzene, Toluene, Ethyl
benzene, and Xylene Decomposition, Chinese Journal of Catalysis, 33 (2012) 1672-1680.
[39] W.K. Jo, H.J. Kang, Photocatalytic performance of cylindrical reactor inserted with UV
light-emitting-diodes for purification of low-level toxic volatile organic compounds, Applied
Surface Science, 259 (2012) 657-663.

19
[40] N. Daneshvar, D. Salari, A.R. Khataee, Photocatalytic degradation of azo dye acid red 14 in
water: investigation of the effect of operational parameters, Journal of Photochemistry and
Photobiology A: Chemistry, 157 (2003) 111-116.
[41] T.M. Twesme, D.T. Tompkins, M.A. Anderson, T.W. Root, Photocatalytic oxidation of low
molecular weight alkanes: Observations with ZrO2–TiO2 supported thin films, Applied
Catalysis B: Environmental, 64 (2006) 153-160.
[42] A.K. Boulamanti, C.J. Philippopoulos, Photocatalytic degradation of C5–C7 alkanes in the
gas–phase, Atmospheric Environment, 43 (2009) 3168-3174.
[43] M. Zhang, T. An, J. Fu, G. Sheng, X. Wang, X. Hu, X. Ding, Photocatalytic degradation of
mixed gaseous carbonyl compounds at low level on adsorptive TiO2/SiO2 photocatalyst
using a fluidized bed reactor, Chemosphere, 64 (2006) 423-431.
[44] J.-F. Wu, C.-H. Hung, C.-S. Yuan, Kinetic modeling of promotion and inhibition of
temperature on photocatalytic degradation of benzene vapor, Journal of Photochemistry and
Photobiology A: Chemistry, 170 (2005) 299-306.
[45] G. Marcı,̀ M. Addamo, V. Augugliaro, S. Coluccia, E. Garcıá -López, V. Loddo, G. Martra,
L. Palmisano, M. Schiavello, Photocatalytic oxidation of toluene on irradiated TiO2:
comparison of degradation performance in humidified air, in water and in water containing a
zwitterionic surfactant, Journal of Photochemistry and Photobiology A: Chemistry, 160
(2003) 105-114.
[46] U.I. Gaya, A.H. Abdullah, M.Z. Hussein, Z. Zainal, Photocatalytic removal of 2,4,6-
trichlorophenol from water exploiting commercial ZnO powder, Desalination, 263 (2010)
176-182.

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Figure captions
Fig. 1. XRD pattern of prepared ZnFe2O4 nanocrystals.

Fig. 2. a) FE-SEM image of prepared ZnFe2O4 nanoparticles b) immobilized ZnFe2O4

nanoparticles on the aluminum foil.

Fig. 3. a) UV- Vis DRS of synthesized ZnFe2O4 nanoparticles b) Plot of (αhυ)2 as a function of

hυ for determination of Eg.

Fig. 4. a) Nitrogen adsorption isotherms for prepared ZnFe2O4 (Inset: Multi-point BET analysis

plot based on the surface area of ZnFe2O4 at different nitrogen loadings)

b) Pore size distribution based on BJH model for prepared ZnFe2O4 nanoparticles.

Fig. 5. ZnFe2O4 nanoparticles and light effect on the photocatalytic removal of toluene

[Toluene]o = 900 ppmv; [ZnFe2O4] = 60 mg and RH = 10%.

Fig. 6. Effect of initial toluene concentration on the photocatalytic removal efficiency

[Toluene]o = 300-3200 ppmv; [ZnFe2O4] = 60 mg and RH = 10%.

Fig. 7. Effect of ZnFe2O4 dosage on the photocatalytic removal of toluene

[Toluene]o = 900 ppmv; [ZnFe2O4] = 0-60 mg and RH = 10%.

Fig. 8. Light power and type effect on the photocatalytic removal efficiency of toluene

[Toluene]o = 900 ppmv; [ZnFe2O4] = 60 mg and RH = 10%.

Fig. 9. Effect of reactor humidity on the photocatalytic removal of toluene

[Toluene]o = 900 ppmv; [ZnFe2O4] = 60 mg and RH = 10-75%.

Fig. 10. Comparison of ZnFe2O4 photocatalytic efficiency by commercial ZnO & TiO2

nanoparticles

[Toluene]o = 900 ppmv; [Photocatalysts] = 60 mg; RH = 10% and 8 W UV Light.

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Fig. 1.

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Fig. 2.

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Fig. 3.

24
Fig. 4.

25
Fig. 5.

26
Fig. 6.

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Fig. 7.

28
Fig. 8.

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Fig. 9.

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Fig. 10.

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