Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

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

Mechanistic investigation in degradation mechanism of 5-Fluorouracil using

graphitic carbon nitride
⁎
G. Kumaravel Dinesh, Sankar Chakma
Department of Chemical Engineering, Indian Institute of Science Education and Research, Bhopal 462066, M.P., India

A R T I C LE I N FO A B S T R A C T

Keywords: The present study reports the synthesis of metal-free polymeric catalyst, graphitic carbon nitride (g-C3N4),
Graphitic carbon nitride through sonochemical method followed by thermal treatment. The synthesized g-C3N4 was characterized using
Fluorouracil XRD, DRS, FESEM, TGA, EDX, etc. and the characterization results revealed that it possesses medium band-gap
Mineralization energy, high thermal and chemical stability. The photo-activity of the catalyst was also evaluated using de-
Ultrasound
gradation of 5-Fluorouracil under different experimental conditions. The results revealed that the addition of
Wastewater
H2O2 during sonolysis process did not show any significant synergy. This is attributed to the low vapor pressure
of H2O2 that does not allow it to diffuse into the cavitation bubble to produce %OH radicals through sonolysis
process. Using sono-hybrid process, more than 90% degradation was seen within 5 min of treatment with a rate
constant of 3.95 × 10−2 s−1. In alkaline medium, 5-Fluorouracil degradation occurred through defluorination
and subsequently substitution of –OH group to the aromatic ring leading to formation of intermediates such as 2-
fluoro-3-oxopropanoic acid and urea. While sono-hybrid advanced oxidation processes (AOPs) helped towards
complete mineralization through formation of smaller molecular compounds such as maleic acids, lactic acids,
propanol, etc. On the other hand, the maximum synergy effect of ∼2.4 was seen for sonocatalysis process
followed by hybrid-AOPs of (US + g-C3N4 + H2O2 + UVC) with a synergy factor of ∼2.2. Also, the synthesized
catalyst exhibited the same catalytic activity even after 5 runs of sono-photocatalysis process for degradation of
5-Fluorouracil.

1. Introduction
In the last few decades, it has been reported that pharmaceutical,
cosmetics and personal care materials are becoming a new type of
emerging organic pollutants [1]. Several studies have also shown that
the occurrence of pharmaceutical drugs concentration in water bodies
has increased from parts per billion to parts per trillion [2–5]. The
pharmaceutical industries, hospitals and healthcare release a con-
siderable amount of highly toxic untreated metabolic compounds or
emerging organic pollutants consisting cytotoxic chemicals, heavy
metals, micro-organisms and radioactive elements which have adverse
cytostatic effect on microbial ecology [6,7]. The anthropogenic com-
pounds on exposure lead to communicable epidemic and endemic dis-
eases. Moreover, exposure to a very low dosage of such drugs may also
cause reproductive disorders. Antibiotic and chemotherapy drugs be-
long to emerging organic pollutants which are found in water and
considered to have carcinogenic, fetotoxic and mutagenic properties
[8]. The biodegradability of these recalcitrant pollutants is very low. In
fact, the chemotherapeutic drugs, a major group of alkylating agent,
once released from the human body transform into pharma logically
active metabolites end up in wastewater and affect the aquatic organ-
isms as well as human being. These unaltered and transformed meta-
bolite compounds or trace elements have been found in water from
nanogram to microgram per liter [9]. Thus, a new and efficient tech-
nique is always in research to treat these mutagenic compounds before
discharging into the land-field or river. As of now, several conventional
techniques have been developed to treat these cytotoxic compounds
and advanced oxidation processes (AOPs) are found to be the most
effective and efficient method for treating emerging organic pollutants.
The most popular AOPs include Fenton, photolysis, photocatalysis,
persulfate oxidation, ferrioxalate, etc. [10–13]. Among these techni-
ques, photocatalysis process is preferable due to reusability of the solid
catalysts in industrial applications. In photocatalysis process, semi-
conductors such as TiO2 and ZnO are widely used as catalyst for de-
gradation of carcinogenic organic pollutants from real wastewater [14].
It has also been observed that doping of transition metal into semi-
conductors helps to enhance the photo-activity of the catalysts through
generation of large quantity of free radicals – which promotes the

⁎
Corresponding author.
E-mail address: schakma@iiserb.ac.in (S. Chakma).

https://doi.org/10.1016/j.ultsonch.2018.09.032
Received 16 July 2018; Received in revised form 11 September 2018; Accepted 22 September 2018
1350-4177/ © 2018 Elsevier B.V. All rights reserved.

Please cite this article as: Dinesh, G.K., Ultrasonics - Sonochemistry, https://doi.org/10.1016/j.ultsonch.2018.09.032
G.K. Dinesh, S. Chakma
degradation of recalcitrant pollutants to a greater extent. However,
conventional photo-catalysts suffer relatively wide band-gap, faster
recombination nature of electron-hole pair (e– – h+), and proper utili-
zation of solar energy for enhancement of photocatalytic activity under
visible light [15]. Hence, it is very important to explore the different
types of photocatalysts to enhance the degradation efficiency of re-
calcitrant pollutants from wastewater by improving the photocatalytic
activity. Recently, graphitic carbon nitride (g-C3N4), a polymeric metal-
free material, has been reported to be a promising photocatalyst for
degradation of several organic pollutants [15,16]. Unlike the conven-
tional semiconductor, this polymeric metal-free catalyst consists of only
carbon, nitrogen, and a little bit of hydrogen [16]. The unique prop-
erties of g-C3N4 include great mesopore volume, high surface area, and
conjugated polymeric porous structure – for which it has drawn an
attention of researchers for application in photocatalysis process under
visible light [17–19]. Another advantage of g-C3N4 is that it can be
easily synthesized through polymerization of low cost and abundantly
available materials such as dicyandiamide, cyanamide, melamine, urea,
etc. In the last decades, researchers have also reported that simulta-
neous application of ultrasound with photocatalyst enhances process
efficiency. The principle phenomenon behind the enhanced degrada-
tion rate in sono-hybrid processes is the secondary effects of ultrasound,
i.e., cavitation, which has two major components physical and chemical
effects. Physical effect of cavitation is nothing but an intense mixing in
the medium due micro-turbulence, shock waves, and micro-streaming
[20]; while sonochemical effect generates several reactive species such
as %OH, HO2%, H2O2, etc. through transient collapse of cavitation bub-
bles and help to induce chemical reaction to degrade the organic mo-
lecules present in the bulk medium without producing any secondary
pollutants after the treatment [21].
In the present study, we have investigated the physical mechanism
of sono-photocatalysis process for degradation of cytostatic and cyto-
toxic drugs using g-C3N4. To study the sono-hybrid processes, g-C3N4
has been synthesized through sonochemical route followed by thermal
treatment used as photocatalyst. In order to investigate the degradation
mechanism, a cytostatic pharmaceutical drugs 5-Fluorouracil has been
chosen as model pollutants. The present study provides the insight in-
vestigation on the degradation of matrix organic pharmaceutical drugs
and effects of process variables such as catalyst loading, oxidant con-
centration, source of UV light irradiation and the possible degradation
pathway with the identification of intermediates. Thus, this study not
only reports the synthesis of metal-free polymeric catalyst but also
provide the information on degradation of pharmaceutical drugs using
g-C3N4 – which can be used as a framework for degradation of any
recalcitrant pollutants using sono-photocatalysis process.
2. Experimental section
2.1. Materials
5-Fluorouracil (99%) and Melamine (99%) have been procured
from Alfa Aesar and Sigma-Aldrich, respectively. The other chemicals
such as hydrogen peroxide (30%), ethanol (95%), sulphuric acid (98%),
and sodium hydroxide (97%) were procured from Merck India Ltd. and
used as received without any further purification. All experiments have
been conducted using ultra-pure water from Millipore water purifica-
tion system (Elix-3, Millipore, USA).
2.2. Synthesis of catalyst
The graphitic carbon nitride (g-C3N4) nanoparticles have been
synthesized using two different techniques, viz. direct pyrolytic method
and sonochemical route followed by thermal treatment. In a typical
experiment, 3.0 g of melamine was dissolved in 100 mL of ultra-pure
water at room temperature and allowed for pyrolytic treatment; while
in ultrasound-assisted synthesis, the solution was sonicated for 90 min
2
Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx
using a probe sonicator with a frequency of 20 kHz (Q-700, Q-Sonica) at
40% amplitude [22]. Then the solid particles were collected and wa-
shed with ethanol repeatedly to remove the water molecules and dried
for 60 min at 100 °C in hot air oven followed by calcination at 500 °C in
a muffle furnace for 30 min at a ramping rate of 20 °C/min. Finally, a
pale yellow colored powder was obtained and characterized using XRD,
FESEM, TGA, BET, DRS, etc. The samples synthesized with and without
ultrasound are denoted as MX and MUX, where X is the calcination
temperature in degree Celsius.
2.3. Method for degradation of drugs
The photocatalytic activity of the synthesized g-C3N4 was evaluated
through degradation of 5-Fluorouracil. All the experiments have been
conducted using either magnetic stirring or an ultrasound bath (S-15H,
Elmasonic) which operates at a frequency of 35 kHz and a power of
95 W. While the photo-assisted experiments have been carried out
under UV light irradiation. The UV tube was placed at the center of the
reaction beaker at a distance of 70 mm between the source of UV light
irradiation and the top surface of the reaction solution. All experiments
were conducted with an initial 5-Fluorouracil concentration of 30 mg/L
(0.23 mM) at different catalyst loading in the range of 0.01–0.10 g/L,
and H2O2. The pH of the reaction solution was adjusted using either
NaOH or H2SO4. A neutral pH was used for all reaction unless the pH is
mentioned.
In order to investigate the source of UV light irradiation, two dif-
ferent UV sources have been used (viz. UV-A and UV-C). The experi-
ments under UV-A irradiation were conducted using an 11 W tube
(Hong Kong Jie Meng International Lighting Ltd., Hong Kong) which
emits a light in the range of 300–400 nm with a maximum peak emis-
sion at 365 nm; while photo-degradation assisted with UV-C was stu-
died using a 9 W tube (Philips) that emits a light in the range of
200–300 nm with a maximum peak emission at 254 nm. All the ex-
periments were conducted at 25 ± 1 °C. In case of ultrasound-assisted
experiments, the rise in temperature during sonication was controlled
by circulating cold water from a refrigerated water bath (WBL-100,
MRC). The degradation of 5-Fluorouracil was monitored by with-
drawing samples from the reaction solution at regular interval of
10 min and filtered to separate the solid catalyst particles. The residual
concentration of drugs was analyzed using UV–visible spectro-
photometer (Lambda 365, Perkin Elmer). All the experiments were
conducted twice and the average value has been considered for plotting
the graphs.
In order to understand the chemical oxidation kinetics, a mathe-
matical expression can be derived for estimation of rate constant. Since
the •OH radical is the main oxidant which is responsible for degradation
of 5-Fluorouracil in the present study the reaction rate equation can be
written as follows:
dCFL
− α
= k CFL C∙βOH
dt (1)
where CFL is the concentration of 5-Fluorouracil at any point of time (t)
in mg/L, C ∙OH is the concentration of %OH at time (t), α and β are the
order of the reaction with respect to 5-Fluorouracil and %OH, and k is
the overall oxidation rate constant.
The stability of the %OH radicals is very short and it is difficult to be
determined. Hence, it is considered to constant at any given time.
Therefore, the Eq. (1) can be written as follows:
dCFL α
− = kobs CFL
dt (2)
where kobs is the pseudo first order rate constant of 5-Fluorouracil de-
gradation in s−1. The oxidation process initiated by %OH radicals can be
modeled as second order rate equation but first order with respect to
the individual concentration of %OH radicals and 5-Fluorouracil [23].
Therefore, the above equation (Eq. (2)) may be reduced to:
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

80

002
M500
MU500
100

o
US+600 C 60

002

% Reflectance
o
100

MS+600 C 40
002
100

o
Intensity (a.u.)

US+500 C
002

20

o
MS+500 C
121
100

0
100

002

200 300 400 500 600 700 800 900

111

o Wavelength (nm)
121
110

US+400 C
(A)
100

121
100

002
111

o
3.5
121
110

MS+400 C
233

M500
3.0 MU500
10 20 30 40 50 60 70 80
2.5

2 degree)
1/2
2.0
Fig. 1. XRD patterns of g-C3N4 calcined at different temperature after synthesis (eV) Melem
1/2

with and without ultrasound. 1.5

(h F(R))

1.0
dCFL
− = kobs CFL
dt (3)
0.5 2.66 eV
Now, if we integrate the above equation (Eq. (3)) with the following
0.0
conditions: at time = 0, CFL = C0, FL and at time = t, CFL =Ct , FL , the 2.60 eV 2.75 eV 3.65 eV
final expression can be obtained as below. 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0

Ct , FL ⎞ h (eV)
ln ⎛⎜ ⎟ = −k obs t

⎝ C0, FL ⎠ (4) (B)

Finally, the experimental data was fitted to the above equation to Fig. 2. (A) Diffuse reflectance spectra, and (B) Estimated band-gap energy of
determine the rate constants. The plotting of time (t) vs. ln(Ct , FL/ C0, FL) synthesized g-C3N4 catalyst.
yields a straight line – from where the value of kobs can be estimated as
the slope of the fitted line.
in the range of 25.26–79.34 nm for the sample synthesized without
ultrasound. In case of the sample synthesized under ultrasound irra-
3. Characterization of graphitic carbon nitride diation, the average particle size was in the range of 23.25–57.19 nm.
From hereafter, the samples synthesized with and without ultrasound
3.1. XRD analysis are denoted as M500 and MU500, respectively.

The XRD pattern of the g-C3N4 was performed in the 2θ range of

10–90° using PANalytical Bragg-Brentano diffractometer (PleaseCheck
radiation, λ = 1.5406 Å) and the results are shown in Fig. 1. The ap-
pearance of two peaks at PleaseCheck value of 13.15° and 27.7° are
widely accepted as the g-C3N4 tri-s-triazine building block. The peak
indexed at 27.7° with a lattice plane of (0 0 2) indicates the character-
istic stacking peak of aromatic compounds – which is attributed to
stacking of tri-s-triazine aromatic system where the electron has stronger
inter-layer binding [24]. The peak indexed at 13.15° corresponds to the
lattice plane of (1 0 0) also supports the stacking of tri-s-triazine aro-
matic electron system. As the pyrolysis temperature was increased be-
yond 400 °C, the peaks of tri-s-triazine are reduced/disappeared for both
the samples synthesized with and without ultrasound. This essentially
confirms the formation of regular stacking of C-N monolayers at (0 0 2)
planar direction. The samples synthesized through ultrasound followed
by pyrolysis process showed high-intensity peaks at (0 0 2) compared to
the samples synthesized through the conventional method as seen from
the XRD analysis data. This essentially indicates that ultrasound influ-
ences to enhance the crystallinity of the materials. The mean size of the
particles has been determined using Scherrer equation and found to be
3.2. Optical properties
The optical properties of g-C3N4 synthesized through pyrolytic
process and ultrasound followed by thermal treatment have been re-
corded using diffuse reflectance spectra (DRS) and depicted in Fig. 2.
The result showed a red shift of the spectra in case of ultrasound. The
band-gap energy of the samples was determined using the Kubelka-
Munk function. The calculated band-gap energy of the sample was
2.66 eV synthesized through pyrolytic treatment; while, the band-gap
energy for the sample synthesized using ultrasound followed by thermal
treatment was found to be 2.60 eV. A similar observation on reduced
band-gap energy was also reported by Dillip et al. and Ong et al.
[25,26]. The reduction in band-gap is attributed to the extension of
electron delocalization in aromatic sheets due to bathochromic-shift
effect [27]. Thus, increases the absorptivity of visible light and en-
hances the photo-activity in degradation process under solar light.

3
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

3.3. Particle size distribution and zeta potential measurement material. The major weight loss occurred after ∼550 °C for both the
samples and ∼98% weight loss was observed at 725 °C and 660 °C for
The particles size distribution was performed using Delsa™ Nano C the samples M500 and MU500, respectively. This could be the result of
(Beckman Coulter) particle size analyzer and the results are depicted in converting the carbon nitride polymer into C and N containing gases.
Fig. S1 (Supplementary Information). According to the particle size From the TGA results, we can conclude that the synthesized g-C3N4 is
distribution analysis, the particles are distributed in the diameter range highly thermally stable due to the presence of heptazine-base units
of ∼0.1–10 µm and ∼0.16–3 µm for the samples synthesized in absent [29].
and presence of ultrasound. To study the surface charges, the Zeta
potential measurements have been conducted at neutral pH in water. It 3.6. Surface morphology and elemental study
was found that the particle surface of the sample M500 has a negative
charge of −23.09 mV relating to the stable and monodispersed nega- The surface morphology and elemental analysis of the g-C3N4 have
tive electrostatic repulsions between NeC]N bonds [28]. This value analyzed using field emission scanning electron microscopy (FESEM)
was increased to −21.66 mV in case of the sample synthesized via ul- and energy-dispersive X-ray (EDX) spectroscopy (Ultra Plus, Zeiss,
trasound followed by thermal treatment technique. The negative sur- Germany). The analysis results of the samples are depicted in Fig. S3
face charges essentially indicate that the catalysts possess a great affi- (Supplementary Information). The SEM images showed that it was
nity towards electron transfer under ultraviolet light [28]. composed of large particles with the formation of typical stacked la-
mellar layers of g-C3N4. The g-C3N4 consists of free flow mesoporous
3.4. BET surface area analysis particles, which can be due to the presence of melem units. EDX ana-
lysis revealed that the synthesized g-C3N4 consists of carbon and ni-
The BET specific surface areas (Belsorp-MR6, MicrotracBEL) of the trogen only.
synthesized g-C3N4 have been analyzed from nitrogen adsorption and
desorption isotherms by nitrogen multilayer adsorption measured as a 4. Results and discussion of 5-Fluorouracil degradation
function of relative pressure (Ps/P0) in the range of 0.05–0.2. The iso-
therms and the pore size distribution of the samples (M500 and MU500) In order to investigate the photocatalytic activity of the synthesized
are shown in Fig. 3. The BET analysis revealed that the sample syn- g-C3N4, degradation experiments have been carried out using 5-
thesized with ultrasound (MU500) exhibits mesoporous structure with a Fluorouracil as a model emerging pharmaceutical pollutants and the
surface area of 5.599 m2/g; while the sample synthesized with con- experimental results conducted under different experimental conditions
ventional method (M500) showed a microporous structure with a are presented in Table 1. Moreover, prior to the oxidative degradation
comparatively lower surface area of 1.848 m2/g. This could be attrib- experiment, we have also studied adsorption process with vigorous
uted to the physical effects of ultrasound which reduces the size of the stirring at 600 rpm of the reaction solution with g-C3N4 to confirm the
particles; thus increases the total BET surface area. Also, the results reduction of the drugs is due to the oxidation process and not by the
showed that the ultrasound-assisted g-C3N4 has 2 folds higher pore adsorption process. Experiments were conducted with an initial drug
volume (0.1482 m3/g) than the g-C3N4 synthesized through pyrolytic concentration of 30 mg/L (0.23 mM) and catalyst amount of 0.10g/L.
treatment (0.0739 m3/g). The results of the adsorption and sono-photocatalysis process of the
drug are shown in Fig. S4 (Supplementary Information).
3.5. Thermogravimetric analysis (TGA)
4.1. Effect of the irradiation source
Thermogravimetric analysis (TGA 4000, Perkin Elmer) was per-
formed to determine the thermal stability of the g-C3N4 samples and the In sono-photolysis process, it is essential to study the process
results are depicted in Fig. S2 (Supplementary Information). The results parameters such as power of ultrasound, source of UV light irradiation,
showed that both M500 and MU500 are highly thermal stable with concentration of oxidant, reaction pH of the solution, etc. Therefore, the
slight differences in thermal oxidation behavior between M500 and experiments were conducted under various conditions and the results
MU500. The weight loss up to 500 °C is mainly due to the deliverance of are shown in Fig. 4. The maximum degradation of 9%, 6% and 16%
volatile components and H2O molecules absorbed on the surface of the were obtained under the irradiation of ultrasound, UV-A light
(300–400 nm) and UV-C light (200–300 nm), respectively. The
100

M500 Table 1
MU500 Summary of experimental results of 5-Fluorouracil degradation.
Volume adsorbed at STP (cm /g)

80
Experimental category η% k (s−1) R2
3

1.56 × 10−3
0.0007 0.12
1. US alone 8.94 ± 1.30 0.952
60
2.89 × 10−3
0.0006

M500
0.10
MU500
2. MS + UVC 15.90 ± 1.60 0.964
3.34 × 10−3
0.0005
7. US + UVC 18.17 ± 2.20 0.921
Por e volume ( cm /g-nm )
/g-nm)

0.08

1.08 × 10−3
0.0004
3

4. MS + H2O2 6.28 ± 0.28 0.945

3
Pore volume (cm

0.06

1.57 × 10−3
0.0003
40 0.04
5. US + H2O2 8.98 ± 0.50 0.906
3.05 × 10−3
0.0002
6. MS + H2O2 + UVC 16.70 ± 1.09 0.972
5.05 × 10−3
0.0001 0.02
8. US + H2O2 + UVC 26.14 ± 0.37 0.950
5.33 × 10−3
0.0000
0 2 4 6 8 10
0.00
0 10 20 30 40 50
9. US + g-C3N4 27.39 ± 1.78 0.944
20
7.70 × 10−3
Pore diameter (nm) Pore diameter (nm)
10. MS + g-C3N4 + UVC 36.98 ± 0.89 0.926
11. US + g-C3N4 + UVC 64.14 ± 2.89 1.71 × 10−2 0.988
12. MS + g-C3N4 + H2O2 48.32 ± 3.21 1.10 × 10−2 0.991
0 13. US + g-C3N4 + H2O2 60.38 ± 0.59 1.54 × 10−2 0.953
14. MS + g-C3N4 + H2O2 + UVC 78.84 ± 2.89 2.59 × 10−2 0.954
0.0 0.2 0.4 0.6 0.8 1.0
15. US + g-C3N4 + H2O2 + UVC 90.65 ± 2.64 3.95 × 10−2 0.959
Relative pressure (P/P0)
Note: US – Ultrasound treatment, MS – mechanical stirring, UVC – ultraviolet
Fig. 3. BET surface area and BJH pore size distribution of g-C3N4 synthesized light C (200–300 nm), g-C3N4 – graphitic carbon nitride, η – degradation effi-
with and without ultrasound. ciency (%), k – pseudo 1st order rate constant (s−1), R2 – regression co-efficient.

4
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

20 50
US US
UV-A MS+UVC
UV-C 40 MS+UVA
Degradation of Fluorouracil (%)

Degradation of Fluorouracil (%)

15

30

10

20

5
10

0
0
0 10 20 30 40 50 60 2 4 6 8 10 12
Time (min) Initial solution pH

Fig. 4. Effect of irradiating source on degradation. Fig. 5. Effect of initial solution pH on Fluorouracil degradation.

degradation under ultrasound irradiation is mainly due to chemical 4.2. Effect of solution pH
effect of cavitation, known as sonochemical effect, which generates
several reactive species (such as %H, %O, %OH, PleaseCheck , H2O2) at the The pH of the medium has direct influence in degradation process of
time of transient collapse of cavitation bubbles in aqueous phase organic pollutant from wastewater irrespective of treatment type
[30–32]. While, the degradation of 5-Fluorouracil under UV light ir- whether it is physical, chemical or biological process. Therefore, the
radiation could be explained on the basis of oxidation process occurred initial solution pH is considered to be a key operating parameter which
in the presence of reactive species (%OH, %H, %O, PleaseCheck , influences the degradation efficiency or rate constant of any chemical
PleaseCheck etc.) generated through excitation and ionization of water reaction. It has a significant effect on the degree of ionization of the
molecules as described below, where PleaseCheck denotes the incident pharmaceutical drugs, activity of oxidants used during treatment,
photon energy [33–35]: properties of the catalyst and activities of the reactive species [37].
Hence, in order to investigate the effect of solution pH on drug de-
H2 O+ hυ → H2 O∗ gradation under different techniques, experiments were conducted at
−
H2 O→ H2 O+ + eaq different pH and the results are presented in Fig. 5. From the experi-
mental results, it can be observed that the degradation efficiency is not
Moreover, it is difficult to predict the destiny of the excited water significant at neutral and in acidic conditions. This is because of high
molecule (H2O*). But most likely this molecule relaxes to ground state stability of the compound at neutral and strong acidic aqueous medium
or dissociate as given below: as it is not ionized in acidic medium and independent of pH below 7
H2 O∗ → ∙ H+ ∙OH [38,39].
On the other hand, the degradation efficiency was increased in al-
Whereas, the ionized water molecule (H2O+) associates into hy- kaline condition above neutral pH with increasing the pH value in all
dronium ion (H3O+) through the reaction: categories. The maximum degradation efficiencies of 37%, 22% and
H2 O+ + H2 O→ H3 O+ + ∙OH 41% have been achieved under ultrasound irradiation, UV-A and UV-C;
respectively. The augmentation in degradation efficiency of 5-
On the other hand, the free electron either recombines with hy- Fluorouracil is mainly due to the oxidation process as described earlier
dronium ion or water molecule in the bulk solution through dissociative and hydrolytic process. In alkaline hydrolytic process, 5-Fluorouracil
electron attachment to form %H radicals in the reaction solution [33]. undergoes a series of reaction with intermediates such as urea, fluoride,
−
eaq + H3 O+ → ∙ H+ H2 O aldehyde, etc. [39]. Legay et al. have investigated the hydrolytic de-
gradation process of 5-Fluorouracil thoroughly using nuclear magnetic
−
eaq + H2 O→ OH− + ∙H resonance spectroscopy and proposed the possible degradation pathway
as shown in Fig. 6 [39]. In alkaline medium, degradation of 5-Fluor-
Also, the presence of dissolved oxygen can help in generation of
ouracil follows stereoselective hydration of C5-C6 double bond leading
other alternative radicals through the following reactions which are
to 5,6-dihydro-5-fluoro-6-hydroxyuracil with cis- and trans-stereo-
also responsible for degradation of recalcitrant organic pollutants
isomers. In the second step, it involves either defluorination or cleavage
[33,36].
of N3-C4 bond resulting in formation of diastereoisomeric acids which
−
eaq + O2 → O∙−
2 subsequently breakdown resulting in the release of 2-fluoro-3-ox-
opropanoic acid and urea; and finally, fluoroacetaldehyde and CO2.
∙ H+ O2 → HO∙2 Also, the detail degradation mechanism of 5-Fluorouracil under sono-
∙ H+ O2 → ∙ O+ ∙OH hybrid process is given in Section 4.8.

Now, comparing the degradation results obtained under UV-A and

UV-C light irradiation, it can be seen that the degradation efficiency
under UV-C more pronounced. This could be attributed to the photon
energy which varies from 3.10 to 3.94 eV for UV-A and 4.43 to 12.4 eV
for UV-C. Hence, strong photon energy irradiated from UV-C source
either generates highly reactive radicals or directly hit the 5-
Fluorouracil molecule resulting in higher rate of degradation.
4.3. Effect of catalyst loading
In order to investigate the effect of catalyst loading on degradation
process, the experiments were conducted with different catalyst loading
in the range of 0.01–0.10 g/L with an initial 5-Fluorouracil concentra-
tion of 30 mg/L (0.23 mM) at neutral pH with a total treatment time of

5
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

F
6
5 1 NH
4 2
3
O N O
H

OH- / H2O

HO H
HO H HO H
F
H
F
6 6
6 1 NH H 5 1 NH
F 5 1 NH 5
4 2
4 2 4 2 3
3 3
-
O O N O
O N O N O H
H H
D2
D1

- F OH-
OH- - F
H
HO H
HO H F
HO
H
6
5 1 NH 6
6 NH H 5 1 NH
F 5 1 4 2 4
3 COO- 3
2
4 2
COO- 3 O N O
H H2N O
H2N O
D3
D4 D5

NH2 F OH

H2N
+
O O
D6
O D7

O
CO2 +
F
D8
Fig. 6. The possible hydrolytic degradation pathway of Fluorouracil. D1 and D2: cis- and trans-5,6-dihydro-5-fluoro-6-hydroxyuracil, D3: 5-hydroxyuracil, D4 and
D5: 2-fluoro-3-hydroxy-ureidopropanoic acid (diastereoisomers), D6: urea, D7: 2-fluoro-3-oxopropanoic acid, D8: fluoroacetaldehyde.

60 min. The results are depicted in Fig. 7. The results revealed that the
rate of degradation was increased with the catalyst loading in the re-
action solution. When the catalyst dosage was increased 10 times, i.e.,
0.01 g/L to 0.10 g/L, the degradation efficiency was increased from
20% to 27% under ultrasound irradiation. A similar trend was also
observed for the experiments conducted under UV-A and UV-C light
irradiation. However, the highest degradation efficiency was obtained
with 0.075 g/L catalyst loading under both UV-A and UV-C light irra-
diation. The corresponding values were 25% and 36% under UV-A and
UV-C light irradiation, respectively. But, reduced degradation efficiency
was seen when the catalyst dosage was increased from 0.075 to 0.1 g/L.
The above results could be explained as follows:
(i) Under ultrasound irradiation, the addition of catalyst or solid par-
ticles increases the number of cavitation bubbles in the system. The
presence of catalyst particles in reaction solution facilitates addi-
tional nucleation sites that cause the formation of more cavitation
bubbles in the medium due to the surface roughness of the catalyst
[40–43]. It results in diminishing the cavitation threshold and en-
hances the cavitational phenomenon; thus increases the

6
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

30 50

US
UV-C
25 UV-A
40

Degradation of Fluorouracil (%)

Degradation of Fluorouracil (%)

20

30
15

20
10
0.010 g/L
0.025 g/L
5 0.050 g/L 10
0.075 g/L
0.100 g/L
0
0
0 10 20 30 40 50 60
4 mM 12 mM 20 mM 28 mM 36 mM 44 mM 48 mM
Time (min)
H2O2 Concentration
(A)
Fig. 8. Effect of H2O2 concentration on degradation of Fluorouracil under
various activation techniques.
30

sonophysical and sonochemical effects of cavitation resulting

25 higher degradation efficiency.
(ii) On the other hand, increasing the amount of catalyst addition into
Degradation of Fluorouracil (%)

the reaction solution increases the number of %OH radical produc-

20
tion by facilitating more surfaces where radicals are generated. But
at higher concentration of catalyst, the degradation efficiency was
15 decreased due to the low penetrability of ultraviolet light through
the reaction solution [44]. Hence, screening effect due to the high
concentration of catalyst in the reaction solution bound the electron
10
excitation during photocatalysis oxidation process edging the de-
0.010 g/L gradation efficiency to a certain level.
0.025 g/L
5 0.050 g/L
0.075 g/L 4.4. Effect of oxidant concentration
0.100 g/L
0
0 10 20 30 40 50 60 In hydroxyl radical based AOPs, it is necessary to study the con-
Time (min)
centration of oxidant in the reaction solution as it influences the oxi-
dative degradation process directly by scavenging the %OH radical. In
(B)
order to investigate the effect of H2O2 concentration, the experiments
were conducted with different concentration (viz. 4–48 mM) and the
40 results are depicted in Fig. 8. Comparing the results obtained under
ultrasound and ultraviolet light irradiation, it can be seen that the
augmentation of 5-Fluorouracil degradation under ultrasound is not
significant even after the addition of H2O2 which could be due to the
Degradation of Fluorouracil (%)

30
weak oxidant. Also, the low vapor pressure of H2O2 does not allow it to
evaporate into the cavitation bubble to enhance the •OH radical pro-
duction. In case of degradation under ultraviolet light irradiation, the
20 rate of degradation of 5-Fluorouracil was increased with H2O2 con-
centration and the maximum was obtained ∼42% at 36 mM H2O2
under UV-C light irradiation. As the concentration of the oxidant was
increased beyond this value, the degradation was reduced gradually
10 0.010 g/L due to scavenging effect of •OH radicals by excess H2O2 in the reaction
0.025 g/L
0.050 g/L
mixture as follows [10,45]:
0.075 g/L
H2 O2 + ∙OH → H2 O+ HO∙2
0.100 g/L
0
0 10 20 30 40 50 60 HO∙2 + ∙OH → H2 O+ O2
Time (min) Comparing the degradation results between UV-A and UV-C, the
(C) highest degradation was seen for UV-C light irradiation. This augmen-
tation in degradation rate can be described on the basis of molar ex-
Fig. 7. Effect of catalyst loading on degradation of Fluorouracil under (A) so-
nocatalytic process, (B) conventional photocatalysis process using UV-A, and tinction coefficient (ε ) of H2O2 and the photon energy of ultraviolet
(C) conventional photocatalysis process using UV-C. light as described in the previous section. The molar extinction coeffi-
cient of H2O2 is ∼19.6 L/mole.cm at 253.7 nm (UV-C) which is ap-
proximately two thousand times higher than the molar extinction
coefficient of H2O2 at 360 nm (∼0.01 L/mole.cm). Therefore, the

7
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

30 40
MS + H2O2
US + H2O2
25 US + UVA
US + UVC
Degradation of Fluorouracil (%)

Degradation of Fluorouracil (%)

US + UVA + H2O2 30
US + UVC + H2O2
20

15 20

10

10 0.010 g/L
0.025 g/L
5
0.050 g/L
0.075 g/L
0.100 g/L
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min)
Time (min)
(A) (B)

70 100

60
Degradation of fluorouracil (%) 80
Degradation of Fluorouracil (%)

50

60
40

30 40
MS + g-C3N4 + H2O2
US + g-C3N4 + H2O2
20
0.010 g/L MS + g-C3N4 + H2O2 + UV A
0.025 g/L 20
US + g-C3N4 + H2O2 + UV A
0.050 g/L
10 MS + g-C3N4 + H2O2 + UV C
0.075 g/L
US + g-C3N4 + H2O2 + UV C
0.100 g/L
0
0 0 10 20 30 40 50 60
0 10 20 30 40 50 60
Time (min) Time (min)

(C) (D)
Fig. 9. (A) Effect of oxidant on degradation added either externally or generated in-situ through cavitation, (B) Sono-photocatalysis degradation of Fluorouracil at
different catalyst loading under UV-A, (C) Sono-photocatalysis degradation of Fluorouracil at different catalyst loading under UV-C, (D) Degradation study under
different hybrid processes. [H2O2] = 4 mM, g-C3N4 = 0.075 g/L, Fluorouracil = 30 mg/L, pH = 6.8.

absorptivity of H2O2 is high in UV-C range that helps to generate more
number of %OH radical in the reaction; and hence augmented de-
gradation efficiency under UV-C light irradiation.
4.5. Sono-hybrid degradation
Simultaneous application of more than single AOPs leads toward
complete degradation/mineralization. Moreover, the time taken for
complete mineralization also reduces significantly when hybrid AOPs
are used for degradation of recalcitrant pollutants. In order to in-
vestigate the effect of hybrid-AOPs on drug degradation, the experi-
ments were conducted under various experimental conditions and the
results are shown in Fig. 9. The salient observations of the experimental
results obtained under various categories are as follows:
(i) Addition of H2O2 to the reaction mixture does not show any sig-
nificant degradation in presence and absence of ultrasound as seen
from Fig. 9A. This is due to low oxidation potential of H2O2. Also,
the low vapor pressure of H2O2 does not allow to diffuse into the
cavitation bubble to produce reactive %OH radicals, which reflected
in the less degradation efficiency of 5-Fluorouracil.
(ii) When the sonolysis process was performed in the presence of UV-A
and UV-C, the maximum degradation was observed with
(US + UV-C) category. This is again attributed to the high molar
absorptivity of H2O2 in UV-C light which promotes the degradation
by generating more %OH radicals from in-situ generated H2O2
through cavitation. Addition of H2O2 externally in these two ca-
tegories, viz. (US + UV-A) and (US + UV-C), the degradation is
more pronounced but level-off the degradation after 40 min of
treatment time. This limitation of degradation could be again ex-
plained on the basis of scavenging effect of %OH radical by in-situ
generated excess H2O2 in the reaction solution during sonolysis.
(iii) Almost same degradation efficiency was seen for the catalyst
loading of 0.075 and 0.10 g/L when conducted under ultrasound
and UV-A light irradiation (Fig. 9B and C), but higher than the
degradation percentage obtained with conventional photocatalysis
process under UV-A light. Comparing the sono-photocatalysis re-
sults obtained under UV-A and UV-C, an extended degradation was
seen for sono-photocatalysis process under UV-C light irradiation.
The enhancement in degradation of 5-Fluorouracil is basically dual
effects of AOPs, viz. photocatalysis and photolysis. In the category
of sono-photocatalysis with UV-C, the in-situ generated H2O2

8
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

70
through cavitation is exposed to UV-C light with high absorptivity
and produces more %OH radicals which react with organic mole-
60
cule and degrade them at the faster kinetic rate.
(iv) Finally, the experiments were conducted with hybrid-AOPs where

Degradation of Fluorouracil (%)

50
the oxidant H2O2 was activated either single, dual or triple acti-
vation techniques, viz. g-C3N4, (g-C3N4 + US), (g-C3N4 + UV-A/ 40
UV-C + US). The results are shown in Fig. 9D. The results revealed
that g-C3N4 alone or ultrasound combined with g-C3N4 could not 30
activate the H2O2 to produce reactive species which reflected in
less degradation efficiency of 5-Fluorouracil. But when the de- 20
gradation experiments were conducted with (US + g- st
1 Run
nd
2 Run
C3N4 + H2O2) in the presence of either UV-A or UV-C, it showed a 10 rd
3 Run
th
4 Run
positive synergy effect and the maximum degradation of 90% was th
5 Run
0
achieved under the category of (US + g-C3N4 + H2O2 + UV-C),
where sonocatalysis, photolysis and photocatalysis are employed 0 30 60 90 120 150 180 210 240 270 300
Time (min)
together. The synergy effect is discussed in details in the next
section. Fig. 11. Reusability of the catalyst g-C3N4 for sono-photocatalysis process.
pH = 6.8, g-C3N4 = 0.075 g/L, Fluorouracil = 30 mg/L, frequency = 37 kHz,
temperature = ∼25 °C.
4.6. Synergism

The synergy effect must be investigated in order to optimize the cost
of the process, especially when more than one AOP is employed si-
multaneously. Most of the time, it was reported that the combination of
two or more techniques enhances the process efficiency, but in some
cases, this statement is not absolutely correct. From our earlier studies,
it was found that a negative synergy is also possible when more than
one AOPs are applied together [31,46,47]. Therefore, it is important to
explore the possible synergy effect in hybrid-AOPs for degradation of
recalcitrant pollutants. In order to estimate the synergy effect of com-
bined or hybrid processes, the following co-relation was used:
(khybrid - AOPs ) − (k sum total of individual - AOPs )
Synergy factor =
(k sum total of individual - AOPs )
The estimated synergy factor is shown in Fig. 10. It can be observed
that the highest synergism of ∼2.4 was seen for sonolysis when catalyst
particles were added to the reaction mixture; while the addition of
H2O2 in sonolysis process did not show any enhancement due to the
insignificant production of %OH radicals as described in the earlier
section. However, the category where H2O2 was added externally in
sonocatalysis process showed a positive synergy factor of 1.4 (Category
E) which is equivent to the synergy factor calculated for hybrid-AOP of
(photolysis + photocatalysis) (Category F). The highest combination of
inividual AOPs where sonolysis, photolysis and photocatalysis (Cate-
gory G) were performed simultaneously showed a synergy factor of
∼2.2.
4.7. Reusability of photocatalyst
The catalyst stability and reusability are considered to be essential
factors for practical applications. In the present study, the catalyst
stability and reusability have been evaluated by using the same catalyst
for five successive sono-photocatalysis experimental runs. After each
run, the catalyst was separated and washed repeatedly with ultra-pure
water and ethanol followed by drying in a hot air oven at 100 °C for
30 min. Then fresh degradation experiments of 5-Fluorouracil have
been performed using the treated and dried catalyst under the same
experimental condition, i.e. 5-Fluorouracil concentration = 30 mg/L,
pH = 6.8, reaction volume = 100 mL and total treatment
time = 60 min. The results are presented in Fig. 11. The experimental
results revealed that the photocatalytic activity of g-C3N4 for the de-
gradation of 5-Fluorouracil under the same experimental conditions
give approximately the same degradation efficiency. This essentially
indicates that the catalyst possesses high structural stability giving
more than same degradation efficiency for the five successive con-
tinuous degradation runs. Therefore, the catalyst was rich with tightly
bound electrons rich surface having hydrophilic terminating groups
with ease separation. Thus, the mesoporous g-C3N4 can be used as a
reusable catalyst with same catalytic activity for practical applications.

3.0 4.8. Identification of degradation intermediates

A: US + g-C3N4 A 2.416
B 0.847
B: US + g-C3N4 + UVC C 0.004
2.5 C: US + H2O2 D 0.096
In order to determine the degradation intermediates of 5-
D: US + H2O2 + UVC E 1.405 Fluorouracil formed during the sono-photocatalysis reaction, the sam-
F 1.41
E: US + g-C3N4 + H2O2 G 2.211 ples have been analyzed to detect the by-products using a Bruker
2.0 F: MS + g-C3N4 + H2O2 + UVC microTOF-Q II (QTO201G003) high-resolution mass spectrometer
Synergy Factor

G: US + g-C3N4 + H2O2 + UVC

equipped with water’s UPLC (A11UPD6228). The representative mass
1.5 spectrum of sample collected from sono-photocatalysis process is shown
in Fig. S5 (Supplementary Information). The identified m/z data has
been used to propose the plausible degradation mechanism of 5-
1.0
Fluorouracil by %OH radicals generated through sono-photocatalysis
process. In AOPs, it is well reported that the 5-fluorinated aromatic
0.5 compounds loss the fluorine atom and open the aromatic ring through
hydroxylation of the compound during the oxidation [48]. The de-
gradation of 5-Fluorouracil occurred through attacking of C-F bond by
0.0
A B C D E F G
highly reactive %OH radical resulting in defluorination and subse-
Experimental Category quently substitution of –OH group to the aromatic ring as shown in the
Fig. 12. The similar degradation by-products identified in the present
Fig. 10. Estimated synergy factor calculated based on the hybrid and individual study have also been reported by numerous studies [48–51]. However,
AOPs. we have also identified small molecular compounds such as maleic

9
G.K. Dinesh, S. Chakma Ultrasonics - Sonochemistry xxx (xxxx) xxx–xxx

F
NH
m/z: 130.02
[M+H]+: 131.027
O N O
H

O O
O

F HO
F
NH NH
NH

HO N O HO N O
O N O H
H H
m/z: 146.01 m/z: 144.02
m/z: 146.01 [M+H]+: 145.051
O O
O

HO OH HO
HO
N NH
NH2

OH
HO N O HO N O
HO N O H
H
m/z: 162.03 m/z: 160.01 OH
+
[M+H] : 163.061
m/z: 160.01

O
HO
OH

O HO OH m/z: 61.06
m/z: 90.03 [M+H]+: 61.041
m/z: 116.01
[M+H]+: 91.041
OH [M+H]+: 117.057
Fig. 12. The plausible sono-photocatalysis degradation pathway for Fluorouracil.

acids, lactic acids, propanol, etc. which further degrade to inorganic
compounds, CO2 and H2O.
5. Conclusion
The present study investigated the synthesis of g-C3N4 and its
characterization including catalytic activity for the treatment of phar-
maceutical effluents. The characterization results showed that in-
creasing the calcination temperature helped the formation of g-C3N4
phase; while the sample synthesized in the presence of ultrasound fol-
lowed by thermal treatment showed low impurities and low band-gap
energy of 2.60 eV indicating easy transport of electrons. Thus, increases
the degradation of drug by producing more %OH radicals in the reaction
solution for reaction with drug molecules. Moreover, ultrasound also
helped to increase the specific BET surface area. The adsorption and
degradation results revealed that the degradation is mainly due to the
oxidation process. It was also observed that the degradation is more
effective under UV-C light irradiation compare to UV-A light irradiation
due to formation of reaction species (%OH, %H, %O, O∙− ∙
2 , HO2 etc.)
through excitation and ionization of water molecules. Also, the reaction
solution pH played a key role for 5-Fluorouracil degradation. Under
alkaline condition, 5-Fluorouracil degradation occurred through hy-
drolytic process leading to formation of intermediates such as 2-fluoro-
3-oxopropanoic acid and urea. While sono-hybrid AOPs helped towards
complete mineralization through formation of smaller molecular com-
pounds such as maleic acids, lactic acids, propanol, etc. On the other
hand, the maximum synergy effect of ∼2.4 was seen for sonocatalysis
process followed by hybrid-AOPs of (US + g-C3N4 + H2O2 + UVC)
with synergy factor of ∼2.2.
Acknowledgement
This work is financially supported by Science and Engineering
Research Board (SERB), Govt. of India (ECR/2016/000669 and PDF/
2017/000259). The authors of the paper also acknowledge the analy-
tical facilities provided by Central Instrumentation Facility at IISER
Bhopal and Dr. A.K. Koner for stimulating discussion and his valuable
suggestion in this work. The authors are also thankful to the anonymous

10
G.K. Dinesh, S. Chakma
referees for their meticulous assessment of the manuscript and con-
structive criticism.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ultsonch.2018.09.032.
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