Ultrasonics Sonochemistry 28 (2016) 150–160

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Investigation of TiO2 photocatalyst performance for decolorization in the

presence of hydrodynamic cavitation as hybrid AOP
Bhaskar Bethi a, S.H. Sonawane a,⇑, G.S. Rohit a, C.R. Holkar b, D.V. Pinjari b, B.A. Bhanvase c, A.B. Pandit b
a
Department of Chemical Engineering, National Institute of Technology, Warangal 506004, Telangana State, India
b
Chemical Engineering Department, Institute of Chemical Technology, Matunga, Mumbai, MS, India
c
Chemical Engineering Department, Laxminarayan Institute of Technology, RTM Nagpur University, Nagpur 440033, MS, India

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

Article history: In this article, an acoustic cavitation engineered novel approach for the synthesis of TiO2, cerium and Fe
Received 3 April 2015 doped TiO2 nanophotocatalysts is reported. The prepared TiO2, cerium and Fe doped TiO2 nanophotocat-
Received in revised form 9 July 2015 alysts were characterized by XRD and TEM analysis to evaluate its structure and morphology. Photo cat-
Accepted 9 July 2015
alytic performance of undoped TiO2 catalyst was investigated for the decolorization of crystal violet dye
Available online 10 July 2015
in aqueous solution at pH of 6.5 in the presence of hydro dynamic cavitation. Effect of catalyst doping
with Fe and Ce was also studied for the decolorization of crystal violet dye. The results shows that,
Keywords:
0.8% of Fe-doped TiO2 exhibits maximum photocatalytic activity in the decolorization study of crystal
Sonochemical synthesis
Nanophotocatalyst
violet dye due to the presence of Fe in the TiO2 and it may acts as a fenton reagent. Kinetic studies have
Hydrodynamic cavitation also been reported for the hybrid AOP (HAOP) that followed the pseudo first-order reaction kinetics.
Hybrid advanced oxidation process Ó 2015 Elsevier B.V. All rights reserved.
Waste water treatment

1. Introduction molecules to smaller molecules. For this application, advanced oxi-

dation processes (AOPs) have been employed and evaluated since
Dyes are having many applications in different industrial pro- the 20th century to degrade azo dyes from the wastewater.
cesses such as textile, printing, leather, paint, plastic, food, cosmet- Among AOPs, electrolysis and photo catalysis are extensively stud-
ics, and pharmaceutical industries [1]. Waste water discharge from ied [6]. AOPs involve the generation of hydroxyl radicals and com-
these industries containing high concentrations of dyes, high toxi- plete oxidization of such pollutants including dyes converted into
city and intense color causes serious problems on surrounding end products, such as CO2, H2O, etc. [7]. Recent literature has indi-
ecosystem [2]. Many treatment methods are available for the treat- cated that hybridization of different AOPs has been found to be
ment of above mentioned industrial wastewater, such as conven- more efficient for the wastewater treatment than individual oxida-
tional biological treatment (aerobic and anaerobic), adsorption, tion process [8,9].
coagulation and flocculation. The main drawbacks of these meth- Recently, hydrodynamic and acoustic cavitation has been
ods are not being able to completely degrade the dye molecules widely applied as an advanced oxidation technology along with
present in the waste water due to the complex and bio recalcitrant other AOPs for wastewater treatment as a hybrid treatment tech-
nature of the dye molecules. Azo dyes are known to as more nique [10–12]. When an aqueous solution is passed through a
non-biodegradable under aerobic biological conditions and these mechanical constriction, large pressure differentials are generated
dyes are converted to more hazardous intermediates under anaer- due to the change in flow geometry. If the pressure of the aqueous
obic conditions [3]. Some methods such as coagulation/flocculation solution at the constriction falls below the vapor pressure of the
and adsorption are physical treatment methods and these methods aqueous solution, cavities are formed, and grow and/or subse-
did not involve chemical transformation and therefore generally quently collapse on the recovery of pressure [13]. Sudden collapse
transport the waste components from one phase to another phase, of these cavities (occurring in microseconds) yields localized high
that leads to secondary waste pollutant on the environment [4,5]. temperatures and pressures. Water molecules under such extreme
Therefore, it is necessary to find an effective treatment technology conditions undergo thermal dissociation to form hydroxyl radicals,
for the degradation of the complex and non-biodegradable which are powerful oxidants for the complete mineralization of
many organic pollutants [14].

⇑ Corresponding author.
E-mail address: [email protected] (S.H. Sonawane).

http://dx.doi.org/10.1016/j.ultsonch.2015.07.008
1350-4177/Ó 2015 Elsevier B.V. All rights reserved.
 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160 151

Researchers have studied photocatalysis extensively among 5  10–5 mol/L, using nanoanatase TiO2 having anatase and rutile
other AOPs as a wastewater treatment method using nano sized phases in the ratio of 3:1 was shown the degradation rate greater
and micro sized photocatalysts with doping and/or in pure state. than 99.5% on UV illumination for 45 min. It was also confirmed in
Among many photocatalysts TiO2 has been widely studied the recent literature that ultrasound assisted synthesis of TiO2 has
because of its chemical inertness, strong oxidizing power, and shown the better decolorization performance than the conven-
long-term stability against photo and chemical corrosion, suitable tional synthesis technique [31]. The ultrasound assisted synthesis
band gap energy and electronic and optical properties [15–18]. The technique able to produce the very small size (nanometer range)
main drawbacks which are associated with the use of TiO2 in waste TiO2 particles having more specific surface area which is able to
water treatment are undesirable recombination of electrons and adsorb the large quantity of dye molecules on active sites of the
holes, and low efficiency under irradiation in the visible region catalyst leads to better decolorization.
[20,21]. Scientists are overcome this problem by extending the Some of the articles have reported the wastewater treatment
light absorption range of TiO2 from UV to visible light and to technique based on photocatalysis combined with cavitation tech-
improve the photocatalytic activity of TiO2 [22]. Dopants, such as nique as hybrid AOP. Very few articles were found on HC/UV and
transitional metals can be loaded on to TiO2 to minimize the HC/UV/TiO2 combination, for dyes decolorization and other organic
recombination of photo-generated electrons and photo-generated pollutants (pesticides, pharmaceutical compounds). Though litera-
holes and also shifts the excitation wavelength from the UV to ture reports are found on US/UV/TiO2 combination, but scale up of
the visible light spectrum [19–24]. In the past the researchers are waste water treatment using ultrasound cavitation is not effective
used the transition metals (Fe, Al, Ni, Cr, Co, W, V and Zr), metal solution [30]. It requires more energy compared to hydrodynamic
oxides (Fe2O3, Cr2O3, CoO2, MgO + CaO and SiO2), transition metal cavitation. It can possible to scale up the waste water treatment
ceramics (WO3, MoO3, Nb2O5, SnO2 and ZnO) and anionic com- using HC due to the production of more cavitation yield, less cost
pounds (C, N, and S) to dope TiO2 to improve its applicability of operation, cheap design. It was confirmed that HC is potentially
[25–28]. In the literature very few articles are reported the work suitable for scale up issues in waste water treatment based on cav-
on Ce doped TiO2 catalysts. They reported that the effect of Ce itation. Kalumuck [36] reported the degradation of p-nitrophenol
doped TiO2 catalysts are strongly depends on the various factors, in wastewater using hydrodynamic cavitation in a re-circulatory
such as the synthesis method and the cerium content [21,29,30]. pipe flow. It has been reported that the hydrodynamic cavitation
In this work, the reason for choosing dopants, such as transitional has shown about 20 times more rate of degradation compared to
metals was to improve its catalytic activity and to reduce the the ultrasonic horn and the oxidation efficiency is almost 25 times
recombination of photo-generated electrons and photo-generated more for the hydrodynamic cavitating jets. Sivakumar and Pandit
holes. Rauf [22] has given an overview on the photocatalytic degra- [37] studied the applicability of hydrodynamic cavitation for the
dation of azo dyes in the presence of TiO2 doped with selective degradation of Rhodamine B dye solution, they reported that
transition metals. Higher catalytic activity has been reported for hydrodynamic cavitation was much more energy efficient com-
the Ce doped TiO2 materials for photo-degradation of dyes and pared to acoustic cavitation. Hydrodynamic cavitation unit using
other pollutants. Cerium oxides have attracted much attention multiple hole orifice plates has been reported to give cavitational
due to the optical and catalytic properties associated with the yields (extent of degradation per unit energy supplied), which
redox pair of Ce3+/Ce4+. Cerium extends the photo response into are two times higher than the best acoustic cavitation device.
the visible region, this can lead to an increase in the charge sepa- Wang et al. [38] have studied the decolorization of an azo dye,
ration efficiency of surface electron–hole pairs. Earlier there are C.I. reactive red 2 (RR2) using TiO2 photocatalysis coupled with
many reports of Fe doping on TiO2 to improve its photo catalytic water jet cavitation. Bagal et al. [39] have studied the degradation
activity among a variety of transitional metals and also Fe on of diclofenac a pharmaceutical drug in wastewater samples using a
TiO2 acts as a Fenton reagent (Fe2+) has shown the better degrada- combined approach of hydrodynamic cavitation and heteroge-
tion performance of organic pollutants than other transition met- neous photocatalysis. They found that the degradation of diclofe-
als. Shirsath et al. [31] synthesized the titanium dioxide nac is about 95% with 76% reduction in TOC value. Although
nanoparticles doped with Fe and Ce using sonochemical approach. there are many studies reported in the literature on doped TiO2
They found that Ce doped TiO2 exhibits maximum photocatalytic with Fe and Ce as a photocatalysts for the degradation of various
activity followed by Fe-doped TiO2 and the least activity was for dyes, none of the studies to the best of our knowledge, have been
only TiO2 for the degradation of crystal violet (CV) dye. Narayana reported in the literature on combination of hydrodynamic cavita-
et al. [32] have synthesized the pure TiO2, Fe and Co doped photo- tion and doped photocatalysis. The novelty of this research is to
catalysts via sol–gel method. From the malachite green decoloriza- study the doped TiO2 photocatalysts with the combination of
tion study, they observed that Fe-doped TiO2 showed highest hydrodynamic cavitation for the treatment of dye waste water to
photocatalytic activity among the other two photocatalysts with know the effect of doped photocatalyst.
98% decolorization in 2 h. Ramirez et al. [33] have studied the pho- The present work reports the ultrasonic assisted synthesis of
tocatalytic degradation of acid orange 7 (AO7) using Ce-doped TiO2 TiO2, Fe-doped TiO2, Ce-doped TiO2 nanophotocatalysts. Prepared
slurry and employing solar irradiation. They have observed that photo catalysts have been used for the degradation of crystal violet
AO7 has shown higher decolorization when Ce content in the (CV) dye in the presence of hydrodynamic cavitation combined
TiO2 is about 1.0% (by weight) compared to TiO2. There is effect with photo catalysis.
of synthesis method on TiO2 structures and hence on photocat-
alytic activity. Anatase and rutile are two major phases are present
in TiO2. Composition of these phases varies from 20% to 80%. The 2. Materials and methods
anatase phase shows better degradation capability compared to
rutile phase of TiO2. Particle size, surface area, and their calcina- 2.1. Materials
tions temperature will also adversely affect on the photocatalytic
activity of TiO2. Andronic et al. [34] reported the synthesis of For the synthesis of pure TiO2, Fe–TiO2, and Ce–TiO2, chemicals
TiO2 by sol–gel method, the resultant TiO2 powder having 40% namely Titanium Tetra isopropoxide (TTIP) were obtained from
anatase and 60% rutile was shown the degradation of methyl Spectrochem Pvt. Ltd. Mumbai, India. Cerium nitrate and ferric
orange up to 37% in 30 min of UV irradiation. Samira et al. [35] nitrate were obtained from S.D. Fine Chemicals Ltd., Mumbai,
reported the crystal violet degradation of initial concentration: India. Sodium hydroxide, methanol and acetone were procured
152 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160

from Molychem Ltd., Mumbai, India. For the decolorization study, to time at a maximum wavelength ðkmax Þ of 590 nm. The
crystal violet dye (C25N3H30Cl) was procured from Sisco Research concentration of crystal violet dye was then calculated using the
Laboratories Pvt. Ltd. Mumbai, India. All the chemicals procured calibration curve prepared for crystal violet dye.
were of analytical grade and were used as obtained from the
supplier. 2.4. Synthesis of pure TiO2 and doped TiO2 nanophotocatalysts

2.2. Experimental setup In a typical synthesis procedure, sonochemical technique

[31,40] was used to prepare the pure TiO2 nanophotocatalyst.
The experimental setup of hydrodynamic cavitation coupled The synthesis procedure begins with 10 mL of titanium isopropox-
with photocatalytic reactor is shown in Fig. 1. This set up includes ide (TTIP) mixed with 2 mL acetone and 2 mL methanol in a
a tank of 5 L volume along with UV light assembly inside the tank. 250 mL beaker (ultrasound reactor). The reactor was placed in a
The setup is arranged in a closed loop manner, which includes a constant temperature bath and the sonication was carried in the
feed tank, positive displacement pump (power = 1.1 kW), pressure presence of ultrasonic irradiation using an ultrasonic horn
gauges and valves. Cooling jacket is provided to the feed tank in (Dakshin ultrasonic probe sonicator, 22 kHz operating frequency,
order to control temperature. Suction side of the pump is con- 130 W power supply). 50 mL sodium hydroxide solution was
nected to the bottom side of the feed tank and the discharge line added drop wise into the ultrasound reactor. During the addition
from the pump branches into two lines. The main line consists of of sodium hydroxide solution to the above mixture, a white precip-
a circular venturi and second line is the bypass line. In the present itate was formed. After the addition of 50 mL of sodium hydroxide
study, circular venturi with 2 mm throat diameter is used as a cav- solution, the mixture was further sonicated for 30 min. After
itating device. Geometrical dimensions of circular venturi are 30 min of irradiation the solution was kept undisturbed for settling
shown in Fig. 2. A bypass line is provided to control the flow of the precipitate. The resulting precipitate was filtered, dried and
through the main lines. Control valves and pressure gauges are calcined at 200 °C for 2 h.
provided at appropriate places to control the flow rate through Procedure used for the synthesis of pure TiO2 [31,40] has been
the lines containing the cavitating device (venturi) and to measure used for the synthesis of Fe-doped TiO2, and Ce-doped TiO2, includ-
the fluid pressures respectively. Alternatively, variable frequency ing the addition of ferric nitrate and cerium nitrate carried out
drive (VFD) is also provided to control the motor rpm such that individually for the synthesis of Fe doped TiO2 and Ce-doped
the flow through the main line can be controlled directly by chang- TiO2 nanophotocatalyst with molar ratios of 0.8 and 1.6 (mol%)
ing the number of piston stroke per minute of the positive dis- of Fe to TiO2 and Ce to TiO2 respectively. Schematic experimental
placement pump, while keeping bypass line closed. The material setup for the synthesis of undoped and doped TiO2 nanoparticles
of construction of the entire system except cavitating device is is shown in the Fig. 3. Typical method for the synthesis of
stainless steel (SS-316), whereas cavitating device, circular venturi Fe–TiO2 and Ce–TiO2 is shown in the Fig. 4. The same method
is made up of brass. Portable assembly, made up of quartz, contain- was adopted for the synthesis of Ce–TiO2 except the addition of
ing high pressure mercury vapor lamp (125 W) with cooling jacket, ferric nitrate, in the place of ferric nitrate; cerium nitrate was
is placed centrally in the feed tank for the UV–visible irradiation. added to synthesize Ce–TiO2 nanophotocatalyst.

2.3. Analytical procedure 2.5. Characterization

The crystal violet dye samples were collected for every interval Pure TiO2, Fe–TiO2, Ce–TiO2 nanophotocatalysts prepared
and analyzed using UV–Vis Spectrophotometer to observe a through acoustic cavitation technique was characterized by using
change in the absorbance value of crystal violet dye with respect powder X-ray diffractometer (Phillips PW 1800, range is 6–80°

Fig. 1. Hydrodynamic cavitation set up with UV–Vis photocatalysis system.

 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160 153

Fig. 2. Geometrical dimensions of cavitating device (circular venturi).

Fig. 3. Experimental setup for synthesis of undoped and doped TiO2 nanoparticles.

Fig. 4. Method for synthesis of Fe–TiO2.

154 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160

2h). The morphology and particle size of these three photocatalysts From the XRD patterns of pure TiO2, Fe–TiO2 and Ce–TiO2, the
were characterized by transmission electron microscopy (TEM, crystallite sizes of the synthesized TiO2, Fe–TiO2 and Ce–TiO2
H-7650 accelerating voltage of 120 kV). nanoparticles were estimated using Scherrer equation [43]:

kk
3. Results and discussion d¼ ð1Þ
bcos h

3.1. XRD analysis of doped and undoped TiO2 nanoparticles prepared where
by sonochemical method ‘d’ is crystallite size in nanometer,
‘k’ is shape factor constant, which is 0.89,
Powder X-ray diffraction (XRD) was used for identification of ‘b’ is the full width at half maximum (FWHM) in radian,
the particles size, crystal structures. TiO2 powder prepared by ‘k’ is the wave length of the X-ray which is 1.540598 nm for Cu
sonochemical approach and calcined at 200 °C was used in X-ray target Ka radiation and
powder diffraction (XRD) analysis to characterize the particles ‘h’ is the Bragg diffraction angle.
structure and crystal size. XRD pattern of ultrasonically prepared
TiO2 powder samples is shown in the Fig. 5. As observed from By using the above data the estimated crystalline sizes for pure
the XRD pattern of TiO2, the peaks are generated at 2h = 27.5°, TiO2, Fe–TiO2 and Ce–TiO2 are shown in Table 1. In detail, the ini-
30°, 42°, 48°, 54°, 62° and 72° confirms the TiO2 powder was tial observed peak at 2h = 27.5°, 27.8° and 26.5° for TiO2, Fe–TiO2,
predominantly crystalline in nature with anatase as a major phase. and Ce–TiO2 respectively and the full width of maximum intensity
Among the other peaks in XRD pattern of TiO2, the initial peaks for all three photocatalysts are 0.016711.
which are generated between the 2h range of 25–30° such as
27.5° and 30° are the prominent peaks with high intensity, 3.2. TEM analysis and particle size distribution of TiO2 and doped TiO2
which is used to determine crystallite size. These high intensity nanoparticles
peaks indicated that the crystalline phase of anatase TiO2 was
successfully formed. Transmission electron microscope (TEM) was used to study the
The XRD patterns of 0.8% Fe-doped TiO2 powder prepared by crystal structure, morphology, shapes and particle size. Figs. 6–8
sononochemical approach and calcined at 200 °C showed the main shows the typical transmission electron microscopic images of
peaks at 2h = 25.8°, 36.9°, 48.1°, 54.1° and 62.4°. These peaks are TiO2, 1.6 mol% of Fe–TiO2 and 1.6 mol% of Ce–TiO2 calcined at
corresponding to the anatase crystalline phase (which is photocat- 200 °C for 2 h. TEM images indicates that the particles of TiO2,
alytically active). The XRD pattern of Fe–TiO2 also showed the peak Fe-doped TiO2, and Ce–TiO2 are relatively uniform and are very
at 34.4°, the peak which is generated at this angle was assigned to small in size (<100 nm). It could be clearly interpreted that, the
the presence of Fe in hematite form in TiO2 [41,26]. Similarly the crystal growth formation has not occurred in the three photocata-
XRD patterns of Ce-doped TiO2 for 0.8% Fe–TiO2 showed the gener- lysts synthesized in this work and shows uniform doping of Fe and
ation of main peaks at 2h = 30°, 37.4°, 47.8°, 54.5° and 62.7° again Ce on TiO2. The main reason for the desegregation of crystals is due
related to the anatase crystalline phase. to the presence of ultrasonic irradiation while synthesis of photo-
It is also observed that the XRD patterns of Ce doped TiO2 catalysts. During the ultrasonic irradiation, number of micro jets
showed the presence of good intensity peaks at 30° and 30.6°. are formed due to the cavitational activity [31], these micro jets
These peaks intensity are assigned to cerium titanate – avoid the interaction between crystals which are formed during
Cex Ti1x O2 [21,42]. Thus, one can observe in the case of XRD synthesis and also breakdown the crystals into smaller size. This
pattern of ultrasonically prepared Ce doped TiO2 consists of peak phenomenon helps to reduce the agglomeration of particles hence
at 2h = 30°, this peak corresponding to the presence of cerium as the smaller and more uniform particles size and uniform shape
a separate cubic CeO2, or as cerium titanate in the TiO2 phase [31]. could be observed.
One can observe from the studies of TEM on pure TiO2, Fe–TiO2
and Ce–TiO2 prepared by various synthesis techniques reported in
the literature, tells that all the techniques other than ultrasonic
assisted synthesis result into the generation of enormous agglom-
erated crystalline phase, non-uniform and large crystalline sizes.

3.3. Decolorization of CV through HC alone

In a typical experimental procedure, 50 mg/L of crystal violet

(CV) dye were used for the preparation of 5 L crystal violet dye
stock solution. The following operating conditions such as constant
temperature (35 °C), constant pressure (5 kg/cm2 pump discharge
pressure to the cavitating device) and normal solution pH 6.5 were
used for the study of CV degradation. In this study, experiments
were carried out at pH of 6.5, which is the solution pH of the crystal
violet dye. A reason for keeping constant pH is reported as follows.

Table 1
Estimated crystalline sizes of photocatalysts prepared by sonochemical method.

Type of photocatalyst 2h b Particles size (nm)

Pure TiO2 27.5 0.016711 84.47
Fe-TiO2 27.8 0.016711 84.21
Fig. 5. XRD pattern of Ce-doped TiO2, Fe-doped TiO2 and undoped TiO2 powder Ce-TiO2 26.5 0.016711 84.32
prepared by sonochemical method [(A) TiO2, (B) Fe–TiO2, (C) Ce–TiO2].
 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160 155

Fig. 6. TEM image of pure TiO2.

Fig. 8. TEM image of 1.6 mol% of Ce doped-TiO2.

The crystal violet dye solution at different pH values shows dif-

ferent colors and unstable. But at pH 6.5 it has remains in a blue
violet color with an absorbance maximum at 590 nm, this is the
natural color state of the crystal violet dye. Angeloni et al. [37]
reported that at pH 1.0, the CV dye is yellow color with absorption
maxima at 420 nm and 620 nm and CV gradually changes its color
by increasing the acidity of the aqueous solution, being blue–green
at pH 2–5. The different colors are a result of the different charged
states of the dye molecule. In the yellow form, all three nitrogen
atoms carry a positive charge, of which two are protonated. At neu-
tral pH, both extra protons are lost to the solution, leaving only one
of the nitrogen atoms positive charged [37]. In alkaline solutions,
nucleophilic hydroxyl ions attack the electrophilic central carbon
to produce the colorless triphenylmethanol or carbinol form of
the dye. Suhail et al. [44] studied the effect of pH = 11 and
pH = 12 on crystal violet dye but they did not consider this pH
value because at pH = 11 turning color of crystal violet from violet Fig. 9. Identification of CV decolorization from UV–Vis absorption spectra analysis
to pale yellow, and this shows that the dye molecule structure is [HC alone].
convert from case of saline formula to OH within pH = 11 there-
fore, the dyes is deposited at the bottom reaction vessel at this
pH. The primary decolorization of synthetic waste water (crystal P2  Pv
CV ¼ ð2Þ
violet dye solution) in HC was performed by pumping of liquid 1
2
qv 20
solution through the cavitation device (circular venturi). Samples
were taken for every 30 min over the time span of 90 min of exper- where
iment and analyzed for the UV absorbance for finding out the per- P2 = fully recovered downstream pressure in kg/cm2.
centage decolorization of crystal violet dye in aqueous solution. Pv = vapor pressure of the dye solution in kg/cm2.
Fig. 9 shows the extent of CV decolorization from the analysis of q = density of the dye solution in kg/m3.
UV–Vis absorption spectra of crystal violet dye decolorization as v0 = velocity of the dye solution at the throat of the cavitating
a function of time. Concentration of CV decolorized in the presence constriction in m/s.
of HC alone as a function of time was shown in the Fig. 10. It has
been observed that crystal violet dye was decolorized up to 3.4. Effect of Fe–TiO2 on CV decolorization
45% when HC alone was alone used for 90 min.
The hydrodynamic characteristic of the cavitating device (circu- In a typical experimental study, UV photocatalysis has been
lar Venturi) has been studied by measuring the flow rate in main coupled with hydrodynamic cavitation (HC) to make a hybrid
line. The calculated CV for a circular venturi at an inlet pressure advanced oxidation process (HAOP) for studying the synergy of
of 5 kg/cm2 is 0.15 ðCV = 0.15) according to the following equation the decolorization of crystal violet dye solution. In a typical hybrid
[10,45]: AOP, 5 L of crystal violet dye solution consisting of 50 mg/L of dye
and 0.6 g/L of 0.8% Fe–TiO2 were used to study the decolorization
rate of crystal violet dye at it’s solution pH of 6.5. Samples were
taken, filtered and tested using the UV spectrophotometry, after
every 30 min interval in the total decolorization time of 90 min.
similar procedure was followed for 1.6% of Fe–TiO2 for finding
out the decolorization rate of crystal violet dye following HAOP.
It was observed that, 0.8% Fe–TiO2 showed the extent of decol-
orization to 98%. Whereas 1.6% of Fe–TiO2 showed the decoloriza-
tion of 85% in 90 min of treatment.
Shirsath et al. [31] reported that, as doping content of iron on
TiO2 increased from 0.4 mol% to 1.2 mol%, the photocatalytic activ-
ity of the Fe doped TiO2 increased but above 1.2 mol%, the photo-
catalytic activity of Fe doped TiO2 decreased with an increase in
the iron content. They also reported that small quantity of iron in
Fig. 7. TEM image of 1.6 mol% of Fe doped-TiO2. TiO2 is responsible for a reduction in the photo-generated hole–
156 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160

Fig. 10. Concentation of CV decolorized with respect to time [at pH = 6.5, inlet pressure = 5 bar, temperature = 35 °C, initial dye concentration 50 mg/L].

electron recombination rate. But at higher loadings, iron ions can photocatalyst having 0.6 g/L of catalysts loading were tried for
serve as recombination centers and the photocatalytic activity of the decolorization studies. All the remaining parameters such as
Fe doped TiO2 decreases. This phenomenon is also demonstrated pH, dye concentration, volume of dye solution, temperature and
in some of the earlier investigations [2,6,24]. The results obtained pressure are kept constant throughout the process and were same
with Fe doped TiO2 and HC work was also matches with the results as before. From the results, 0.8% Ce–TiO2 showed the decoloriza-
obtained by Shirsath et al. [31], in brief discussion, in this work tion of 84%. Whereas, 1.6% of Ce–TiO2 showed the decolorization
doping has been carried out between 0 and 1.6 mol% i.e. doping of 82%. It was observed that the Ce doped TiO2 did not show a sig-
with 0.8 and 1.6 mol% has been carried out. The doping of nificant effect on the degradation of crystal violet dye compared to
0.8 mol% gives the maximum decolorization of 98%, whereas the Fe doped TiO2. It has been observed that crystal violet dye
1.6 mol% shows the reduction in decolorization. Doping with decoloration increased as the Ce content increased in the
1.6 mol% shown in reduction in decolorization has been recon- Ce-doped TiO2 catalyst up to 1.0% i.e. 0.8% of Ce content. The
firmed from the results obtained by Shirsath et al. [31]. Thus, in increase in Ce loading may be attributed the photocatalytic activity
this study 0.8 mol% iron doping on TiO2 has been considered as of Ce doped TiO2 by trapping of electrons in cerium sites with their
the optimum doping concentration for the decolorization of crystal subsequent transfer to the absorbed O2 [30]. However, if the dop-
violet dye. ing of Ce amount is continued to increase from 1.0% to 3.0%, then
excess Ce dopant may introduce the indirect recombination of
3.5. Effect of Ce–TiO2 on CV decolorization electrons and holes to reduce the photocatalytic activity, leading
to a significant decrease in decolorization [25,30]. It has been
In this method, the prepared Ce–TiO2 nanophotocatalyst with observed that the degradation efficiency was higher when Ce con-
different doping percentages of 0.8% and 1.6% (Ce:TiO2 mol%) tent was below or equal to 1.0% in the TiO2 catalyst and achieved
was used for the decolorization studies of crystal violet dye. Each 84% color removal after 90 min of treatment. While, the

Fig. 11a. Percentage decolorization of CV dye in HC combined with pure TiO2 and Fe doped TiO2 [at pH = 6.5, inlet pressure = 5 bar, temperature = 35 °C, initial dye
concentration 50 mg/L].
 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160 157

Fig. 11b. Percentage decolorization of CV dye in photolytic and photocatalytic processes [at pH = 6.5, inlet pressure = 5 bar, temperature = 35 °C, initial dye concentration
50 mg/L].

Fig. 11c. Percentage decolorization of CV dye in HC combined with Ce–TiO2 [at pH = 6.5, inlet pressure = 5 bar, temperature = 35 °C, initial dye concentration 50 mg/L].

Fig. 12. Adsorption behavior of pure TiO2 as a function of time.

158 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160

decolorization efficiency was lower when Ce content was 1.6%, to carry out the actual experiments. Initially the crystal violet
achieved 82% of color removal at the same time. This effect has dye mixture was taken in a 1 L beaker and agitation was carried
been also observed in other reports [25, 30, and 31]. The results out with magnetic stirrer for 90 min in the dark environment to
obtained in this work was also matches with the results obtained establish the equilibrium adsorption characteristics of undoped
by the Ramirez et al. [33]. They have been studied the acid orange TiO2. With the above procedure a maximum of 9% of crystal violet
7 (AO7) decolorization using Ce doped TiO2 photocatalysts and dye was adsorbed on to the TiO2 (0.6 g/L loading) surface and
reported lower photocatalytic activity for Ce doped TiO2 than the adsorption equilibrium was obtained within 60 min of contact
pure TiO2. Hence, in this study 0.8 mol% of Ce doping on TiO2 has time. The equilibrium adsorption stage has been evaluated from
been considered as optimum loading concentration for decouriza- the Fig. 12 contains a plot of concentration of CV dye Vs time. It
tion of crystal violet dye. has been observed from Fig. 12 the adsorption behavior of undoped
TiO2 after 60 min has shows no reduction in concentration of the
3.6. Effect of undoped TiO2 on CV decolorization CV dye with extended time of contact.
Degradation of CV dye in photolytic process due to the genera-
To understand the effect of undoped TiO2, 0.6 g/L of undoped tion of hydroxyl radicals by the dissociation of water molecules
TiO2 were used for the decolorization of crystal violet dye at its under UV irradiations. During the photolytic process, crystal violet
normal pH (6.5) using HAOP. From the UV–Vis absorption spectra, dye decolorized up to 20%. Hence in photocatalytic process, the
it was observed that the crystal violet dye has been decolorized up generation of hydroxyl radicals is more as compared to photolytic
to 94% when TiO2 used along with HC. It has been observed that process, in this process, crystal violet dye has been decolorized up
the undoped TiO2 shown higher decolorization rate than 1.6% Fe– to 37.6%. It was observed that the maximum extent of decoloriza-
TiO2, Ce–TiO2 and 0.8% Ce–TiO2. However shows less decoloriza- tion of 94% was obtained using combined HC/UV + TiO2 process,
tion than 0.8% Fe–TiO2. Graphical representation of percentage whereas, 44.5% and 37.6% of decolorization was obtained in HC
decolorization of CV dye in various systems was shown in the and UV + TiO2 alone respectively. The extent of decolorization in
Fig. 11a–c. hybrid process has been attained due to generation of greater
hydroxyl radical compared to individual operating processes (HC
alone or UV + TiO2 alone).
3.7. Comparison of adsorption, photolytic, photo catalytic, HC+ photo
Synergetic effect of combined processes has been evaluated on
catalytic processes
the basis of reaction rate constant data of single and combined pro-
cess. The synergetic index of the HC combined with TiO2 photo-
Initially, a study on adsorption equilibrium for TiO2 surface has
catalysis has been calculated to evaluate the efficiency of the
been established in 1 L of crystal violet dye solution. Further, we
combined process of HC and TiO2 photocatalysis to compare with
have evaluated the time required for achieving the adsorption
individual process (HC and TiO2 photocatalysis alone). The syner-
equilibrium as well as the maximum amount of CV dye adsorbed
getic index (f) of HC combined with TiO2 photocatalysis has been
onto the TiO2 surface. This was attempted under agitation prior
calculated by using the following equation shows synergetic effect
of hybrid AOP:
Table 2
Reaction rate constants (k) of CV degradation in different systems [at pH = 6.5, inlet
kðHCþTiO2 photocatalysisÞ
f ðHCþTiO2 photocatalysisÞ ¼
pressure = 5 bar, temperature = 35 °C, initial dye concentration 50 mg/L]. kðHCÞ þ kðTiO2 photocatalysisÞ
Method k Value (min1) Synergetic coefficient 0:0275
¼
UV alone 0.0029 –
0:003 þ 0:0048
UV + TiO2 0.0048 – ¼ 3:52 ð3Þ
HC 0.003 –
HC + TiO2 0.0275 3.52
HC + TiO2 + 0.8% Fe 0.0332 – 3.8. Rate kinetics of CV decolorization
HC + TiO2 + 1.6% Fe 0.017 –
HC + TiO2 + 0.8% Ce 0.0289 –
HC + TiO2 + 1.6% Ce 0.0302 – The degradation of organic pollutants in hydrodynamic
cavitation will be occur by the generation of OH radicals and also

Fig. 13. Pseudo first order reaction kinetics of CV decolorization in HC and its combination with photocatalysis.
 B. Bethi et al. / Ultrasonics Sonochemistry 28 (2016) 150–160 159

Fig. 14. Pseudo first order reaction kinetics of CV decolorization in photolytic and photocatalysis.

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