Ultrasonics Sonochemistry 21 (2014) 1797–1804

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

Sonocatalytic and sonophotocatalytic degradation of rhodamine 6G

containing wastewaters
Nileema B. Bokhale a, Snehal D. Bomble a, Rachana R. Dalbhanjan a, Deepika D. Mahale a, Shruti P. Hinge a,
Barnali S. Banerjee a, Ashish V. Mohod a,⇑, Parag R. Gogate b,⇑
a
Department of Chemical Engineering, AISSMS College of Engineering, Kennedy Road, Near RTO, Pune 411001, India
b
Chemical Engineering Department, Institute of Chemical Technology, Matunga, Mumbai 400019, India

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

Article history: The present work deals with degradation of aqueous solution of Rhodamine 6G (Rh 6G) using sonocata-
Received 28 October 2013 lytic and sonophotocatalytic treatment schemes based on the use of cupric oxide (CuO) and titanium
Received in revised form 13 March 2014 dioxide (TiO2) as the solid catalysts. Experiments have been carried out at the operating capacity of 2 L
Accepted 22 March 2014
and constant initial pH of 12.5. The effect of catalyst loading on the sonochemical degradation has been
Available online 1 April 2014
investigated by varying the loading over the range of 1.5–4.5 g/L. It has been observed that the maximum
degradation of 52.2% was obtained at an optimum concentration of CuO as 1.5 g/L whereas for TiO2 max-
Keywords:
imum degradation was observed as 51.2% at a loading of 4 g/L over similar treatment period. Studies with
Sonolysis
Photocatalysis
presence of radical scavengers such as methanol (CH3OH) and n-butanol (C4H9OH) indicated lower
Rhodamine 6G degradation extents of degradation confirming the dominance of radical mechanism. The combined approach of ultra-
Intensification sound, solid catalyst and scavengers has also been investigated at optimum loadings to simulate real con-
Radical scavengers ditions. The optimal solid loading was used for studies involving oxidation using UV irradiations where
COD removal 26.4% and 28.9% of degradation was achieved at optimal loading of CuO and TiO2, respectively. Studies
using combination of UV and US irradiations have also been carried out using the optimal concentration
of the catalysts. It has been observed that maximum degradation of 63.3% is achieved using combined US
and UV with TiO2 (4 g/L) as the photocatalyst. Overall it can be said that the combined processes give
higher extent of degradation as compared to the individual processes based on US or UV irradiations.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction the oxygen levels drastically leading to severe problems with the
ecosystem. Even a very small amount of dye in water is visible
With ever increasing human requirements, newer and more and impedes light penetration and thus reduces the photosynthe-
toxic chemical species are being developed and possibly dis- sis process of the aquatic plants, affecting their growth and also de-
charged in the effluent streams. Various industries are responsible creases the gas solubility, interfering with the natural system [1].
for contributing such chemicals into the environment. Among all Wastewater containing dye is poisonous, carcinogenic and terato-
the industries, textile and dying industries contribute the major genic to human beings. Therefore, it becomes utmost important to
portion of overall water pollution. Till date, more than 100,000 develop efficient removal approaches and disposal methods for
dyes are commercially available. It is observed that, typically two stable dyes. The efficacy of the conventional methods, especially
tons of dye is required for dying 25 tons of fiber and very less quan- the most commonly used biological oxidation schemes, can be
tity of the dye is actually attached to the fabric leaving most of the lower for the dye wastewater treatment due to the presence of
chemicals into the effluent streams. These discharged effluents can molecules refractory to the micro-organisms in the wastewater
be colored especially due to the residual dyes and can give obnox- streams. Also, the treatment times with chemical/biological meth-
ious color to the natural water sources due to possible mixing, if ods may be quite high and total mineralization may not be possible
not treated properly. The mixing of colored effluents can change especially for a complex effluent stream containing a mixture of
pollutants in high concentration and thus, there is a need to devel-
op treatment schemes based on the use of advanced techniques,
⇑ Corresponding authors. Tel.: +91 8600047170 (A.V. Mohod). Tel.:+91 22
which can operate either individually or in combination with the
33612024; fax: +91 22 33611020 (P.R. Gogate).
E-mail addresses: [email protected] (A.V. Mohod), pr.gogate@
conventional methods to meet the stringent environmental regula-
ictmumbai.edu.in (P.R. Gogate). tions [2]. Advanced oxidation processes (AOP) or in general the

http://dx.doi.org/10.1016/j.ultsonch.2014.03.022
1350-4177/Ó 2014 Elsevier B.V. All rights reserved.
1798 N.B. Bokhale et al. / Ultrasonics Sonochemistry 21 (2014) 1797–1804

methods based on the generation of hydroxyl radicals can be one of

the promising approaches for treatment of refractory materials [3].
Some of the AOP, which have shown considerable promise for
wastewater treatment applications, include Fenton chemistry and
photocatalytic oxidation [4–6]. Cavitation which also generates hy-
droxyl radicals and hot spots can be effectively applied for the
treatment of wastewater. However, it has been observed that none
of the methods can be used individually in wastewater treatment
applications due to substantially lower efficiencies especially for
the complex effluent streams and higher costs of operation and Fig. 1. Chemical structure of rhodamine 6G (Rh 6G).
usually a combination of different AOPs has been found to be more
efficient for wastewater treatment [7–12].
The objective of this work is to investigate the degradation of a the analytical reagent grade were obtained from Merck Specialties
commercial basic dye Rhodamine 6G using sonochemical reactors Pvt. Ltd., Mumbai. All the chemicals were used as received from the
and its combination with UV irradiation based photocatalytic oxi- supplier without any treatment.
dation. Studies have also been carried out to understand the
dependency of degradation on the extent of free radicals. The nov- 2.2. Experimental methodology
elty of the work is established due to the fact that even though the
toxicity of Rhodamine 6G is well established, not many studies In a typical run for the optimization studies, ultrasonic bath
have been directed towards understanding the degradation of Rho- having maximum capacity of 3 L has been used with an operating
damine 6G using sonophotocatalytic oxidation. In the earlier work volume of 2 L. The ultrasonic bath provided with three transducers
[13], we demonstrated the process optimization and process inten- placed at the bottom of the reactor having a fixed operating fre-
sification studies for decolorization of Rh 6G using individual sono- quency of 50 kHz was procured from Medica Instrument Mfg. Co.
chemical degradation concentrating on the effect of various Pune, India. The maximum power rating of the equipment was
parameters like initial concentration, pH, H2O2 and additives like 170 W. The ultrasonic bath was made up of stainless steel and
CCl4 and air. The present work is the continuation of the work on had dimensions of 25.5 cm along the length, 16 cm along the width
developing cavitation based hybrid treatment strategies for effec- and 5 cm along the height. Calorimetric study was carried out for
tive removal of Rhodamine 6G and concentrates on different ap- the sonochemical reactor to quantify the energy efficiency of the
proaches based on sonophotocatalytic oxidation. Ultrasonic bath reactor. Energy efficiency i.e. fraction of the total supplied electri-
of capacity 3 L has been used as source of ultrasound whereas pas- cal energy actually dissipated into the system (based on calorimet-
sage of UV irradiations have been achieved using a simple UV tube. ric measurements) has been estimated as a function of the volume
The two catalysts used are the TiO2 and CuO at various loading of the reaction mixture (over the range 0.5–3 L) with an aim of
whereas the effect of additives (methanol and n-butanol) on the quantifying the zone of influence of the ultrasonic irradiations
quantum of radicals has also been investigated for understanding [14]. Based on the obtained results, 2 L operating capacity has been
the mechanism of degradation of Rh 6G. It is important to note chosen and was kept constant throughout the experiments. The ac-
here that ultrasound based treatment approach might not be able tual power dissipated in the system was observed to be 31 W giv-
to provide a complete solution in actual effluent treatment plants ing an energy efficiency of approximately 18%. For experiments
but would be useful as a pretreatment to the biological oxidation related to UV irradiations, UV lamp was procured from Philips
which is very important considering the biorefractory nature of India Pvt. Ltd., Mumbai (Model PL-S) with a power rating of 9 W.
the dyes. The initial concentration of Rh 6G solution was fixed at 10 ppm
Rhodamine 6G having molecular formula C28H31N2O3Cl has a for all the experiments based on the studies presented in our ear-
dark reddish purple color and is highly toxic in nature. The pres- lier work with varying initial concentrations [13]. Experiments
ence of Rh 6G may cause long term adverse effects in the aquatic were performed at pH 12.5, which resulted from dissolution of
environment. Such water pollution may not damage our health Rh 6G in distilled water and subsequent adjustment by addition
immediately but can be harmful after long term exposure. Some of 1 N NaOH. The effect of different additives was investigated over
of the toxins in industrial waste may only have a mild effect the concentration range of 1.5–4.5 g/L. Samples were withdrawn
whereas other can be fatal as they can cause immune suppression, from the solution and the concentration of dye was determined
reproductive failure or acute poisoning. Thus, the removal of pollu- using a UV–VIS spectrophotometer (Chemito Spectrascan UV
tants from industrial aqueous effluents is an important practical 2600 double beam) at wavelength of k = 523 nm [15].
problem.
3. Results and discussion

2. Materials and methods 3.1. Effect of cupric oxide loading

2.1. Materials Ultrasonic degradation of Rh 6G was investigated in the pres-

ence of different concentrations of cupric oxide ranging from 1.5
Rhodamine 6G was procured from Merck Specialties Pvt. Ltd., to 4.5 g/L and the obtained results have been given in the Fig. 2.
Mumbai, India. Rhodamine 6G is also commonly known as Rh It has been observed from the figure that the extent of degradation
6G, R6G, CI Pigment Red 81, CI Pigment Red 169, and CI 45160 was significantly higher (almost six times) in the presence of CuO
where CI is color index. Fig. 1 gives the chemical structure of at a loading of 1.5 g/L of CuO, which can be attributed to the fact
R6G. The initial pH of the solution was adjusted to the optimized that addition of solid particles provides additional nuclei which
value of 12.5 [13] using 1N NaOH. Aqueous solutions containing promote the cavitational activity [16]. In the presence of solid par-
0.01 g/l (10 ppm) R6G dye were prepared using demineralized ticles, an additional phase is available to increase the cavitational
water, freshly prepared in the laboratory. Titanium dioxide (TiO2) activity by allowing more bubbles to form and grow into the active
was obtained from Fischer Scientific, Navi Mumbai, India whereas cavitation bubbles. At the solid–liquid interface, the tensile
cupric oxide (CuO), methanol (CH3OH) and n-butanol (C4H9OH) of strength is lower than at the bulk solution. Solids also provide
 N.B. Bokhale et al. / Ultrasonics Sonochemistry 21 (2014) 1797–1804 1799

60 (16.8%) at 0.1 g/L of TiO2 loading as compared to that in the ab-

sence of catalyst (10.2%). The observed trends can be attributed
50 to the fact that the number of nuclei increases as a result of intro-
Extent of degradation, %

duction of heterogeneous surface and the extent of interfacial cav-

40 itation also increases with the quantity of the catalyst. The rate of
degradation of the organic compound is proportional to the
30
CuO amount of OH and H present in the reaction mixture and the pres-
ence of TiO2 catalyst enhances the dissociation reaction of H2O
20
thereby increasing the number of free radicals generated [21].
Thus, sonication of Rh 6G using TiO2 particles leads to an increase
10
in the surface area and the maximum extent of degradation as
51.23% was observed at 0.4 g/L loading of TiO2. The results are con-
0
0 1 2 3 4 5 sistent with the earlier results of Kubo et al. [22], who have shown
Catalyst loading, g/L that the degradation efficiency of sonochemical reactors increases
in the presence of TiO2 particles and, also the rate constant for deg-
Fig. 2. Effect of CuO on Rh 6G degradation using US (pH = 12.5; concentra- radation of phenol increases with an increase in the loading of TiO2
tion = 10 ppm; catalyst loading 1.5–4.5 g/L). particles. Similar observations were also reported in earlier work
additional cavitation nuclei as they entrap gases in their crevices [23] where degradation of formic acid has been investigated in a
and introduce heterogeneity in the medium [17]. It is important multiple frequency sonochemical reactor. The use of TiO2 particles
to note here that an increase in the solid content beyond loading for intensification of cavitational activity and hence the production
of 1.5 g/L however resulted in a marginal decrease in the extent of hydroxyl radicals is recommended particularly in the case of
of degradation which can be explained on the basis of enhanced wastewater treatment applications where synergistic effects of
contribution of scattering effects and attenuation of incident sound sonochemistry and photocatalytic oxidation can be utilized for
energy by the solid particles. Thus it is important to select a opti- intensification of oxidation [24–25].
mized loading of the solids to get the desired beneficial effects. It It would be worthwhile to compare the obtained trends for the
should be essentially noted here that the particle size distribution effect of CuO and TiO2 particles on the extent of degradation. In the
and shape of solid particles would have an effect on the intensifi- case of CuO, the mechanism of intensification is by virtue of surface
cation of cavitational activity and the optimum loading as the sur- cavitation and some catalytic action on the dissociation of hydro-
face area and hence the degree of surface cavitation leading to gen peroxide formed due to the recombination of the hydroxyl rad-
enhanced number of cavitating bubbles or the scattering effects icals. These two mechanisms ensure continuous production of
[18] would be dependent on the size of the particles and surface hydroxyl radicals leading to enhanced degradation of the dye mol-
characteristics. ecules. In the case of TiO2 particles, the mechanism is by surface
Similar results have been reported by Guo et al. [5] for the deg- cavitation as well as some catalytic action on the formation of hy-
radation of 2,4-dinitrophenol (initial concentration of 20 mg/L) droxyl radicals [13–15] which results into localized higher concen-
where enhanced degradation was observed in the presence of cup- tration of hydroxyl radicals leading to dominant recombination
ric oxide till optimized loadings. Our earlier work [19] also illus- reaction rather than effective utilization by the dye molecules.
trates the existence of optium loading of CuO for obtaining the Due to these effects the extent of intensification is somewhat lower
maximum hydroxyl radical generation. as compared to the use of CuO. To understand the effect of particle
size and specific area of the solid particles on the extent of surface
cavitation occurring in the system, analysis of the samples of CuO
3.2. Effect of titanium oxide loading and TiO2 has been performed using scanning electron microscope
(SEM). The SEM images (Fig. 4) shows that the TiO2 particles ap-
The effect of the presence of TiO2 particles at various loadings pears to be finer and more crystalline as compared to the CuO,
over the range of 1.5–4.5 g/L on the decolorization of Rh 6G using which can possibly give more surface cavitation. However, surface
ultrasonic bath has been illustrated by Fig. 3. It has been observed cavitation is not the controlling mechanism in both these additives
that the extent of decolorization increased with an increase in the as explained earlier and the dissociation of formed hydrogen per-
amount of catalyst. Shirgaonkar and Pandit [20] have also reported oxide back to hydroxyl radicals appear to be marginally more dom-
that the extent of degradation of tricholrophenol was higher inating resulting into higher extents of degradation for the use of
CuO. Due to the finer nature of particles, it is also expected that
the particles will be well dispersed in the liquid medium due to
60 the effects of acoustic streaming and associated mixing and
hence the dominance of scattering effects is not observed in the
50
case of use of TiO2. Also the tendency of formation of agglomerates
Extent of degradation, %

in the case of CuO gives more scattering effects which gives opti-
40
mum loading at lower concentration of the CuO as compared to
TiO2. Overall, it should be noted that the addition of solid catalyst
30
TiO2 gives multiple effects in terms of surface cavitation, scattering of
20 incident sound waves as well as catalytic action in terms of en-
hanced formation of hydroxyl radicals and the final end result on
10 the extent of degradation would be dependent on the net result
of these counteracting effects.
0
0 1 2 3 4 5
3.3. Effect of methanol addition
Catalyst loading, g/L

Fig. 3. Effect of TiO2 on Rh 6G degradation using US (pH = 12.5; concentra- The effect of methanol addition on the extent of degradation
tion = 10 ppm; catalyst loading 1.5–4.5 g/L). was investigated at constant operating volume of 2 L for different
1800 N.B. Bokhale et al. / Ultrasonics Sonochemistry 21 (2014) 1797–1804

Fig. 4. SEM images of TiO2 and CuO particles.

loading of methanol (1.5–4.5 ml/L) and the obtained results have 6G have been depicted in Fig. 6. It can be observed from the figure
been given in Fig. 5. It has been observed that as the concentration that the extent of degradation augmented initially till an optimum
of methanol increases, the extent of degradation also increases. It loading beyond which a decrease in the extent of degradation was
can be seen that the extent of degradation is higher at higher load- observed for a further increase in the loading of n-butanol. The
ing i.e. 4.5 ml/ L as compared to the lower loading of methanol maximum extent of degradation as 22% was obtained with the
(1.5 ml/L). The addition of methanol can create CH2OH radicals in addition of 1.5 ml/L of n-butanol. The detrimental effect of higher
the system which can play a role in abstraction of H radicals from concentration of n-butanol can be explained by competitive hydro-
the system [26–28] making the OH radicals available for the de- xyl radical reactions with Rh 6G and n-butanol [29]. The obtained
sired reaction of dye degradation to a greater extent. Presence of result shows that hydroxyl radical plays an important role in son-
methanol can also have a scavenging action on the hydroxyl radi- olytic degradation of Rh 6G and presence of strong scavenging ac-
cals but the higher volatility of methanol ensures quick production tion results in detrimental effects. It is also important to note here
of CH2OH radicals which play a positive role. The obtained results that due to lower volatility of the n-butanol as compared to meth-
confirm that the scavenging action is not the main factor in decid- anol, the production of radicals for abstraction of H is reduced and
ing the sonolysis of Rh 6G. also larger presence in the bulk leads to a dominant scavenging ac-
tion on the hydroxyl radicals. The overall result is that the compet-
itive reactions of OH with alcohols leads to the consumption of the
3.4. Effect of n-butanol addition hydroxyl radicals by undesired reaction leading to reduced dye
degradation.
To understand the exact role of hydroxyl radical as the primary An increase in the extent of degradation at lower concentration
oxidant, sonolysis of Rh 6G in the aqueous solution was carried out of alcohol can also be explained on the basis of action of alcohols in
in the presence of strong radical scavenger such as n-butanol as altering the bubble concentration. Riesz et al. [12] reported that OH
compared to the possible scavenging action of methanol. Different radicals are produced inside the bubble or at the bubble-water
experiments were performed to understand the effect of n-butanol interface of stable cavitation bubbles. The generation of radicals
at various loadings over the range of 1.5–4.5 ml/L. The obtained re- in the sonication may be closely related to the characteristics of
sults for the effect of n-butanol on the extent of degradation of Rh

30
25

25
Extent of degradation, %

20
Extent of degradation, %

20

15
15
Methanol n-butanol
10
10

5 5

0 0
0 1 2 3 4 5 0 1 2 3 4 5
Methanol loading, ml/L n-butanol loading, ml/L

Fig. 5. Effect of methanol on Rh 6G degradation using US (pH = 12.5; Fig. 6. Effect of n-butanol on Rh 6G degradation using US (pH = 12.5;
concentration = 10 ppm; catalyst loading 1.5 and 4.5 ml/L). concentration = 10 ppm; catalyst loading 1.5–4.5 g/L).
 N.B. Bokhale et al. / Ultrasonics Sonochemistry 21 (2014) 1797–1804 1801

Table 1 70
Maximum extent of degradation of Rh 6G at optimum loadings of additives.
60
Sr. no. Additive Optimized loading Extent of degradation (%)

Extent of degradaon, %
1 TiO2 4.0 g/L 51.2 50
US+CuO
2 CuO 1.5 g/L 59.2
40 US alone
3 Methanol 4.5 ml/L 28.8
4 n-Butanol 1.5 ml/L 26.1 UV + CuO
30
UV alone

20 US+UV+CuO
US+UV alone
cavitation bubbles. Because of the transient characteristics of bub- 10
bles at 50 kHz, the possibility for the recombination reaction be-
tween OH and H radical increases due to the longer expansion 0
US+CuO US alone UV + CuO UV alone US+UV+CuO US+UV
period of bubble at lower frequency (50 kHz) [30]. This implies that alone
the transportation of OH radicals to the interface of bubble-solu-
tion will become difficult at lower ultrasonic frequency (50 kHz). Fig. 7. Variation in the extent of degradation of Rh 6G with or without CuO catalyst
under different modes of operations (pH = 12.5; concentration = 10 ppm).
The addition of alcohol in sonication with low frequency can pre-
vent the coalescence of bubbles by adsorption onto the surface of
bubble, resulting in an increase in the number of active bubbles 70
[31–34]. Due to the enhanced active bubbles, the extent of cavita-
tional intensity increases leading to an overall increase in the ex- 60
tent of degradation. It is also expected that the contribution of

Extent of degradaon, %
methanol to enhancing the number of active bubbles will be higher 50

due to higher effect on the stability of cavitation bubbles and hence US+TiO2
40
higher extents of degradation are obtained in the presence of US alone
methanol as compared to n-butanol. 30 UV+ TiO2
A summary of the maximum extents of degradation obtained by UV alone
using different heterogeneous catalysts (CuO, TiO2) and other addi- 20
US+UV+ TiO2
tives such as methanol and n-butanol based on the use of ultra- US+UV alone
10
sonic method have been given in Table 1 which confirm the
maximum degradation obtained for the sonocatalytic approach of 0
US + CuO.

4. Sonophotocatalytic degradation
Fig. 8. Variation in the extent of degradation of Rh 6G with or without TiO2 catalyst
under different modes of operations (pH = 12.5; concentration = 10 ppm).
4.1. Effect of combination studies at optimal CuO (1.5 g/l) loadings

Initially, degradation of Rh 6G was studied using ultrasound and compared to US + catalyst but does not yield the additive effect.
ultraviolet irradiation alone to quantify the extent of degradation It is interesting to note here that the combined treatment based
using basic approaches. It has been observed that degradation of on the use of CuO catalyst did not result in synergistic results. It
Rh 6G was possible up to certain limiting value and it enhanced is important to note that the synergistic results will be obtained
in the presence of CuO for both the irradiations, though significant mostly where the reduced efficiency of photocatalyst attributed
effect was observed for the ultrasonic irradiations as compared to to the adsorption of contaminants on the surface resulting in the
the ultraviolet irradiation. At pH 12.5 and using optimum catalyst blocking of the active sites is dominant [38]. Overall it can be said
loading of CuO, it has been observed that the kinetic rate constant that it is just better to operate under the sonocatalytic mode as
followed the order of US + Catalyst (7.0 min 1) > UV + Catalyst compared to the sonophotocatalytic mode of operation. In the case
(2.2 min 1). The maximum degradation of 52.8% is obtained for of combined operation of sonophotocatalysis, the extent of COD re-
the combined operation of US and optimal CuO after 180 min of moval was 84% in the same treatment period.
treatment due to the enhanced formation of hydroxyl radicals
(OH), and hydroperoxyl radicals (O2H) leading to a increase in 4.2. Effect of combination studies at optimal TiO2 (4 g/l) loadings
the rates of reactions with Rh 6G in the bulk solution or at the
interface between the bubbles and the liquid phase [35,36]. The ex- Experiments were also carried out to compare the efficacy of
tent of degradation was found to be 26.4% for the UV treatment in sonocatalysis (US + TiO2), photocatalysis (UV + TiO2) and sonop-
the presence of CuO as catalyst after 180 min of reaction time. hotocatalysis (US + UV + TiO2). Initially, the degradation of Rh 6G
Murugandham and Swaminathan [37] investigated the effect of (10 ppm initial concentration) was investigated using individual
catalyst loading on the degradation of RY 14 azo dye with initial operations i.e. sonochemical and photocatalytic oxidation. The
concentration of 5  10 4 mol/l and reported that the maximum solution was sonicated for 180 min and the extent of degradation
(91.3%) extent of decolorization was obtained in presence of cata- was found to be 51.2% as shown in Fig. 8. Similarly, the extent of
lyst i.e. TiO2 particles. It can be also established in the present work degradation was found to be 28.9% for the photocatalytic oxida-
that under specific conditions i.e. with optimal catalyst, sonocata- tion. In the case of combined approach, 63.3% degradation was
lytic approach have better efficacy as compared to the combination achieved. Also, it has been observed that the maximum COD re-
of ultraviolet irradiation with the catalyst. moval (89%) was obtained by using combined approach of TiO2
The extent of degradation for combined approach of US + UV (Table 2). Thus, it can be said that the combination of US and UV
and CuO catalyst was 60.8% after 180 min reaction time. The re- irradiations have better efficacy as compared to the ultrasonic irra-
sults for the combination approach have been depicted in Fig. 7 diations and UV irradiations alone for the case of TiO2 as the
and it can be seen that the extent of degradation is increased as catalyst, though it is not resulting in any synergistic effects.
1802 N.B. Bokhale et al. / Ultrasonics Sonochemistry 21 (2014) 1797–1804

Table 2 46.9% when the experiments were carried out with optimal meth-
Maximum extent of degradation of Rh 6G using combination of both irradiation. anol loading i.e. 4.5 ml/L in the presence of UV irradiation. This can
Sr. no. Studies Extent of degradation (%) % Removal of COD be attributed to the fact that the enhancement of Rh 6G removal
1 US + UV + TiO2 63.3 89 percent in this case is due to interaction of photons of a proper en-
2 US + UV + CuO 60.8 84 ergy level with the molecules of chemical species present in the
3 US + UV + Methanol 34.0 63 solution, with or without the presence of the catalyst [42–44].
4 US + UV + Butanol 40.0 76 Stock et al. [43] have reported similar results about enhanced effi-
cacy of UV irradiations in degradation of Naphthol Blue black (NBB)
as compared to ultrasound.
Fig. 9 shows the degradation spectrum of Rh 6G using combination Further, the rate of degradation of Rh 6G with optimized con-
of both irradiations along with catalyst TiO2 at different treatment centration of n-butanol i.e. 1.5 ml/L followed the order of US/UV/
times, which also confirms effective removal of the dye using the n-butanol > US/n-butanol > UV/n-butanol. Fig. 11 gives the results
combination approach. It is important to note here that the syner- obtained for the combination approach of optimal n-butanol with
gistic effects are likely to observed only where there is a possibility US and UV. As seen in the figure, the effect in the present work was
of blocking of the active sites by the pollutant or its intermediate not much pronounced since only 40.9% degradation was obtained
degradation products resulting in a substantial decrease in the with combination of US and UV radiation as against 26.0% and
quantum of free radicals generated in the system and hence the 37.2% using US and UV individually. It has been observed that
rates of degradation with an increase in the treatment time. The re- operation using UV alone and combined approaches results in al-
sults obtained in the present work establish that such mechanism most similar percentage of removal of Rh 6G. Table 2 shows that
does not exist and hence possible increase in the extent of degra- maximum percentage degradation and percentage removal of
dation would be due to enhanced generation of hydroxyl radicals COD obtained using combination mode irradiation whereas all
and its subsequent utilization by pollutant molecules to a limited the kinetic rate constant along with percentage degradation are
extent [38–41]. Sonolysis can also increase the photocatalytic reac- summarized in Table 3. Manousaki et al. [44] and Dai et al. [45],
tion rate by increasing the catalytic activity of the semiconductor demonstrated that butanol quenches hydroxyl radicals, reducing
catalyst. This could occur through the size reduction of photocata- rate of degradation.
lyst particles consequent to particle deagregation, leading to an in-
crease in the surface area and hence enhanced catalytic 4.4. Effect of combination of radical promoters and scavengers
performance. Other effects induced by US, such as acceleration of
the mass transfer between the solution phase and the photocata- To understand the exact role of solid catalyst and scavengers,
lyst surface and continuous cleaning of the catalyst by acoustic experiments were carried out at optimal catalyst loadings as
cavitation, might also have some role in increasing the photocata- 1.5 g/L of CuO, 4 g/L of TiO2 and optimal loadings of radical scav-
lytic degradation rates. engers as 4.5 ml/L of methanol and 1.5 ml of n-butanol. The ob-
tained trends for degradation of Rh 6G using combined approach
4.3. Effect of combination studies at optimal alcohol (methanol and n- of solid catalysts and scavengers have been depicted in Fig. 12. It
butanol) loading can be seen from figure that using the combination of solid catalyst
and radical scavengers along with ultrasound marginally affects
To verify reaction pathway and effects of radical scavenger, the extent of degradation. The extent of degradation is higher for
experiments were carried out using methanol and n-butanol in the combined approach of CuO with alcohols as against only CuO
combination with US and UV. Fig. 10 shows the extent of degrada- though definitely additive effect is not seen. Similar result was also
tion of Rh 6G with or without methanol additive using individual seen for the combination of optimal TiO2 and additives. It has also
operation of irradiation and combination mode. It can be observed been found that the extent of degradation of Rh 6G using combined
from the figure that maximum extent of degradation of Rh 6G was optimal TiO2 and additives is less than combined optimal CuO and

Fig. 9. Spectrum of degradation of Rh 6G with TiO2 catalyst combined with US and UV (pH = 12.5; concentration = 10 ppm).
 N.B. Bokhale et al. / Ultrasonics Sonochemistry 21 (2014) 1797–1804 1803

50 Table 3
Kinetic rate constant for all studies with percentage degradation of Rh 6G.
45
S.N. Studies Rate constant, Degradation
40 k  103 (min 1) (%)
Extent of degrdaon, %

35 1 1.5 g/L CuO + US 7.0 52.8

2 3 g/L CuO + US 3.9 42.4
30
US+ methanol 3 4.5 g/L CuO + US 2.8 42.2
25 US alone
4 1.5 g/L CuO + UV 2.2 26.4
5 1.5 g/L CuO + US + UV 8.4 60.8
20 UV+methanol 6 1 g/L TiO2 + US 0.7 07.4
15 UV alone 7 2 g/L TiO2 + US 6.7 43.3
8 3 g/L TiO2 + US 4.0 39.1
10 US+UV+methanol
9 4 g/L TiO2 + US 6.8 51.2
US+UV alone 10 4 g/L TiO2 + UV 2.6 28.9
5
11 4 g/L TiO2 + US + UV 8.9 63.3
0 12 4 g/L TiO2 + UV 2.6 28.9
13 1.5 ml/L Methanol + US 1.1 18.4
14 3 ml/L Methanol + US 1.2 20.7
15 4.5 ml/L Methanol + US 1.1 23.7
16 4.5 ml/L Methanol + UV 4.1 46.9
17 4.5 ml/L Methanol + US + UV 2.6 34.0
Fig. 10. Variation in the extent of degradation of Rh 6G with or without methanol 18 1.5 ml/L n-butanol + US 2.3 26.0
additive under different modes of operations (pH = 12.5; concentration = 10 ppm). 19 3 ml/L n-butanol + US 1.4 17.1
20 4.5 ml/L n-butanol + US 0.3 11.9
21 1.5 ml/L n-butanol + UV 3.5 37.2
22 1.5 ml/L n-butanol + US + UV 0.9 12.3
23 10 ppm Rh 6G + US 0.4 07.7
45
24 10 ppm Rh 6G + UV 0.9 00.8
40 25 10 ppm Rh 6G + US + UV 1.2 12.3
26 US + Optimal CuO + Optimal methanol 8.5 67.0
35 27 US + Optimal CuO + Optimal n-butanol 9.5 70.07
Extent of degradaon, %

28 US + Optimal TiO2 + Optimal methanol 7.4 53.39

30
29 US + Optimal TiO2 + Optimal n-butanol 1.2 22.04
25 US+n-butanol

US alone
20
UV+n-butanol
15
UV alone
10 80
US+UV+n-butanol

5 US+UV alone 70

0 60
Extent of Degradaon, %

50
CuO + methanol

40 CuO + n-butanol

TiO2 + methanol
30
Fig. 11. Variation in the extent of degradation of Rh 6G with or without n-butanol TiO2 + n-butanol

additive under different modes of operations (pH = 12.5; concentration = 10 ppm). 20

10

additives, which can be attributed to dissociative action on hydro- 0

gen peroxide which tries to decrease the effect of the scavenging CuO + methanol CuO + n-butanol TiO2 + methanol TiO2 + n-butanol
action induced by alcohols.
Fig. 12. Variation in the extent of degradation of Rh 6G using optimal catalyst and
additives (pH = 12.5; concentration = 10 ppm).
5. Conclusions

The present work has shown that Rh 6G as a basic dye can be using combination mode (US + UV) with TiO2 (4 g/L). The work has
effectively removed by using combinations of ultrasound irradia- clearly established the suitability of combined approach as a pre-
tion and UV irradiations. It can be concluded that for effective deg- treatment to dye containing wastewaters wherein the further
radation of Rh 6G, use of catalyst is vital. For individual operation treatment may be achieved more effectively by the biological
of two modes of irradiation, sonolysis has more efficiency as com- oxidation.
pared to photolysis. Based on the optimization studies for the ef-
fect of additives, it can be concluded that beneficial effects have
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