ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 12, pp. 2044−2049.

© Pleiades Publishing, Ltd., 2015.

VARIOUS TECHNOLOGICAL
PROCESSES

Photocatalytic Degradation of Diclofenac Sodium

in Aqueous Solution Using N, S, and C-doped ZnO1
M. Giahi

Department of Chemistry, Lahijan Branch, Islamic Azad University, Lahijan, Iran

e-mail: m.giahi@liau.ac.ir; giahi_m@yahoo.com

Received November 14, 2015

Abstract—In this investigation photocatalytic degradation of diclofenac sodium as drug pollutants was studied.
N, S, and C-doped ZnO particles were supported from thiourea and zinc sulfate via a precipitation method and
characterized by X-ray diffraction (XRD) together with X-ray photoelectron spectroscopy (XPS). The degrada-
tion was studied under different conditions including concentrations of catalyst and drug, initial pH value, and
presence of electron acceptor. The results showed that photocatalytic degradation of drug was strongly influenced
by these parameters. Therefore, the best conditions for the photocatalytic degradation of diclofenac sodium were
obtained. The optimum concentrations of N, S, C-doped ZnO was found to be 0.44 g L–1. The photodegradation
efficiency of the drug decreased with an increase in its initial concentration of diclofenac sodium. In acidic solu-
tions, photocatalytic degradation efficiency was higher than in alkaline solutions. The photodegradation efficiency
of diclofenac sodium was accelerated by addition of a small amount of K2S2O8 and H2O2.
DOI: 10.1134/S10704272150120228

INTRODUCTION low cost, and nontoxicity. Recently, some groups have

Diclofenac, as one of the most popular antiphlogistics,
is produced in great quantities. Nowadays this drug is
ubiquitously present in the aquatic environment due to
its resistance to biodegradation. For that reason numerous
drugs and their metabolites are ubiquitously present in
the aquatic environment. Regional studies, e.g., on the
German rivers Elbe and Saale [1, 2], and international
studies in the USA and Great Britain [3, 4] confirm the
increase of pharmaceutical compounds in water due to the
incomplete removal of these substances during the pas-
sage through sewage treatment plants [5]. Photocatalysis
is an advanced technology for the degradation of toxic
and nonbiodegradable compounds to carbon dioxide and
inorganic constituents using semiconductors as catalysts
[6]. Large band gap semiconducting particles are being
investigated as catalysts for photodegradation of drugs
and organic contaminants in water. Among many semi-
conductors applied; titanium dioxide is the most widely
employed photocatalytic semiconducting materials
because of its chemical inertness, nonphotocorrosion,
1 The text was submitted by the author in English.
demonstrated that doping with a non-metal impurity
can provide an effective modification of the electronic
structure of TiO2 and thereby narrowing the band gap
[7–15]. ZnO is a promising semiconductor material for
advanced applications due to its unique chemical and
physical properties, environmental stability, and low
cost as compared to other binary nanosize metal oxides
[16]. The energy levels for the conduction and valence
bands, and the electron affinity of zinc oxide are similar
to those of TiO2, making ZnO a suitable candidate as a
semiconductor material for photocatalysis. It is also an-
ticipated that nanostructured ZnO can become a versatile
alternative to TiO2 since some researchers [17–19, 23]
have mentioned that zinc oxide is much more efficient
than titanium dioxide, particularly for photocatalytic
degradations of azo dyes [17], pulp wastewaters [18], and
phenols [23] under UV irradiation. Modification of ZnO
photocatalysts involves doping with non-metal elements
that results in a desired band-gap narrowing and an en-
hancement in the photocatalytic efficiency under daylight
induced. This technique opens up a new possibility for the
development of solar or daylight induced photocatalytic
materials [19, 20–22]. In the present work N, S, C-doped

2044
 PHOTOCATALYTIC DEGRADATION OF DICLOFENAC SODIUM
C/S
7000
6000
5000
4000
3000
2000
1000
0
5 15 25 35
Fig. 1. XRD pattern of N, S, and C-doped ZnO.
ZnO particles were synthesized at 800°C. Photocatalytic
activity was determined by means of degradation of di-
clofenac sodium under UV light irradiation.
EXPERIMENTAL
Preparation of catalyst. All chemicals used in this
study were reagent-grade and were used without further
purification. The method employed for the synthesis of
N, S, C-doped ZnO in this work was similar to that re-
ported elsewhere [24].
The N, S, C-doped ZnO catalyst was prepared as
follows: 4.75 g thiourea was mixed with 11.12 g zinc
sulfate in 500 mL distillated water. The solution was then
stirred for 3 h until completely dissolved. The solution
was later treated with an ammonia solution (28%) for pH
to reach 7. The resulting solution was stirred for another
2 h. Precipitated product was separated from the solution,
and dried at 100°C for 24 h. The obtained product was
ground and calcined at 800°C for 3 h with a heating rate
of 5 °C min–1.
Characterization. The X-ray diffraction (XRD) patterns
were obtained on an X-ray diffractometer (type HZG41B-
PC) using CuKα irradiation, α = 0.15406 nm; accelerating
voltage of 40 kV; scanning speed of 2° min–1 and scan-
ning angle of 10–90°. The average crystallite sizes of
N, S, C-doped ZnO were determined according to the
Scherrer equation using the full-width half-maximum data
of each phase after correcting the instrumental broaden-
ing. X-ray photoelectron spectra (XPS) were recorded
on a Kratos Axis Ultra DLD XPS system. The amounts
of the dopants in the modified ZnO were determined by
an elemental analyzer.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 12 2015
2045
45 55 65 75 85 2θ
Photocatalytic reaction. The photodegradation stud-
ies were carried out in a batch reactor system. The setup
consisted of a UV chamber made of MDF having dimen-
sions (68 × 50 × 43 cm) and 2 × 18 mercury vapor lamp
(Philips), fitted on the top of the chamber. An exhaust fan
was fitted on the side wall of the chamber to maintain a
constant temperature. The reactor was a cylindrical quartz
flask with a diameter of 2 cm and 5 cm height.
Procedure. In a 50 mL flask, 25 mL of the drug solu-
tion with appropriate concentration was placed and the pH
was measured. A known amount of N, S, C-doped ZnO
nanopowder was added to the drug and oxidant (K2S2O8)
and the mixture was irradiated with the UV lamp. The
aqueous suspension was magnetically stirred throughout
the experiment and 5 mL samples were withdrawn on
regular time intervals and centrifuged. Absorbance of the
supernatant solution was then measured. The quantitative
estimation of the drug was carried out using a UV-Vis
spectrophotometer (Model Jenway 6405) at λmax = 275 nm.
The degree of photodegradation (X) as a function of time is
given by: X = (C0 – C)/C0, where C0 is the initial concen-
tration of drug and C, the concentration of drug at time t.
RESULTS AND DISCUSSION
Characterization of N, S, C-doped ZnO. Figure 1
shows the XRD pattern of the N, S, C-doped ZnO sample.
At 800°C crystallization is complete. However, ZnO and
ZnS are suspected to appear in the samples because the
diffraction peaks at 2θ = 31.8°(100), 34.5°(002), and
36.3°(101), attributed to the former. Some of the other
peaks are mainly suspected to the result from S- and
OH-containing compounds like Zn2(OH)2SO4 [24]. The
ZnO crystal is in the hexagonal wurtzite phase. Average
2046 GIAHI

CPS which was in good agreement with the value (40.8 nm)
14000 calculated from XRD pattern using the Scherrer equation
(as shown in Fig. 1).

Zn2p
Zn2p
10500 Effect of catalyst concentration. A series of experi-
ments were carried out using different concentrations of

OKLL
N, S, C-doped ZnO (0.12 to 0.6 g L–1) to establish the

O1s
ZnLMM
7000 effect of photocatalyst loading and to avoid unnecessary
excessive photocatalyst. It was observed that as the
concentration of the photocatalyst increased from 0.12 to
S1s

3500
Zn3s

0.44 g L–1, the photodegradation efficiency of diclofenac

Zn3p

S2s
O2s

sodium increased rapidly from 51.1% to 98.2%. Then

0 S2p S2p
0 200 400 600 800 1000 1200
Binding energy, eV
Fig. 2. XPS image of nanocrystalline N, S, and C-doped ZnO.
Average of particle: 43
35 nm
Fig. 3. TEM image of nanocrystalline N, S, and C-doped ZnO.
particle size was determined using the Scherrer equation.
The sizes were found to be 40.8 nm.
Figure 2 shows the XPS spectra of the N, S, C-doped
ZnO. The XPS survey showed the presence of N, S and
C atoms. The percentage of N, S, and C in the nanopow-
der components was determined as 2.17, 2.07, 57.1,
respectively.
The microstructure of the N, S, C-doped ZnO powders
was further studied by TEM. Figure 3 shows the TEM
image of the N, S, C-doped ZnO powders. It can be ob-
served from Fig. 3 that the nanocrystallite appeared in an
agglomerated status, and mesoporous structures without
a long-range order. The size of the primary particles,
estimated from the TEM image was about 43 ± 2 nm,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 12 2015
the efficiency decreased slightly when the amount of N,
S, C-doped ZnO was above 0.44 g L–1. It is believed
that the increase in the number of N, S, C-doped ZnO
particles will increase the number of both photons and
diclofenac sodium molecules absorbed. Therefore, the
degradation efficiency can be enhanced with increasing
N, S, C-doped ZnO concentration due to the increase in
total surface area available for contaminant adsorption.
A further increase of the catalyst concentration beyond
0.44 g L–1 may cause light scattering and screening
effects. The excessive N, S, C-doped ZnO dosage leads
to opacity of the suspension, which prevents from the
solution being illuminated. The scattering and screening
effects reduce the specific activity of the catalyst [25]. At
high catalyst concentration, particle aggregation may also
reduce the catalytic activity [26]. So, the photodegradation
efficiency of diclofenac sodium decreases. In this study,
the optimum amount of catalyst was found to be 0.44 g L–1
for the degradation of diclofenac sodium.
Effect of initial concentration. The influence of
initial drug concentration on degradation was examined
in the range 10–50 mg L–1 at 0.44 g L–1 catalyst loading
and H2O2 (1 mM) under UV irradiation. A representative
concentration-time profile is shown in Fig. 5. The rate
of photodegradation of the drug decreased at higher
concentrations. With increasing the amounts of drug,
more drug molecules were adsorbed on the surface of
the photocatalyst and the active sites of the catalysts were
also reduced. Therefore, with increasing occupied sites of
catalyst surface, generation of hydroxyl radicals will be
decreased. On the other hand, increasing concentration of
drug can lead to decreasing the number of photons arrived
to the surface of catalysts. By increasing the intensity of
light adsorbed by molecules of drug, the excitation of
photocatalyst particles by photons will be reduced leading
to diminished photodegradation efficiency [27].
Effect of initial pH value. The pH value of the
different wastewater is different, and it influences
 PHOTOCATALYTIC DEGRADATION OF DICLOFENAC SODIUM 2047

120 100 1
2 3
100 5 90
6 4
80 7 80
Degradation, %

Degradation, %
3
2
60 4 70 5
1

40 60

20 50

0
30 60 90 120 30 60 90 120
Irradiation time, min Irradiation time, min
Fig. 4. Effect of catalyst concentration. Conditions: diclofenac Fig. 5. Effect of of initial surfactant concentration. Conditions:
sodium 20 mg L–1, H2O2 1 mM, pH = 6.0, irradiation time 2 h, N, S, and C-doped ZnO 0.44 g L–1, H2O2 = 1 mM, pH = 6.0,
Vt 25 mL. Catalyst concentration, g L–1: (1) 0.12, (2) 0.2, Irradiation time 4 h, Vt 25 mL. UV irradiation, ppm: (1) 10,
(3) 0.28, (4) 0.36, (5) 0.44, (6) 0.52, (7) 0.6. (2) 20, (3) 30, (4) 40, (5) 50.

100
the photocatalytic reactions for degradation of the
pollutants. Similarly, the pH plays an important role 90
Degradation, %

in the degradation of diclofenac sodium. The effect of 80

the initial pH value on the photodegradation efficiency
of diclofenac sodium is shown in Fig. 6. In all cases,
the maximum degradation efficiency was obtained in
acidic pH 6.0 for diclofenac sodium. In the presence of
N, S, C-doped ZnO and in pH 6.0, degradation efficiency
was 98.2% was obtained. The interpretation of pH
effects on the photocatalytic process is a very difficult
task because of its multiple roles such as electrostatic
interactions between the semiconductor surface, solvent
molecules, substrate and charged radicals formed
during the progress of reaction [27]. The pH influences
adsorption and dissociation of substrate, catalyst surface
charge, oxidation potential of the valence band, and other
physicochemical properties of the system. Therefore, pH
of the solution is an important parameter in performing
the reaction on the surface of semiconductor particles.
In acidic solutions, photodegradation efficiency was
higher than in alkaline solutions. This is because
photodecomposition of N, S, C-doped ZnO takes place
in acidic and neutral solutions.
Effect of electron acceptors. One possible way
to increase the reaction rate would be to increase the
concentration of OH• radicals because these species are
widely considered to be promoters of photocatalytic
degradation. Addition of other powerful oxidizing species,
such as hydrogen peroxide and potassium peroxydisulfate,
70
60
50
40
2 4 6 8 10 12
pH
Fig. 6. Effect of initial pH value. Conditions: diclofenac sodium
20 mg L–1, N, S, and C-doped ZnO 0.44 g L–1, H2O2 1 mM,
irradiation time 2 h, Vt 25 mL.
to N, S, C-doped ZnO suspensions is a well-known and
extensively studied procedure and, in many cases, leads
to an acceleration of the rate of the photodegradation.
The degradation rate for the decomposition of diclofenac
sodium in the presence of H2O2 and K2S2O8 is shown in
Fig. 6. According to this figure, in the presence of K2S2O8
(1 mM) the photodegradation efficiency of diclofenac
sodium increases from 86.1 to 93.2%. The enhancement
of reaction rate is due to the inhibition of electron-hole
recombination and production of other oxidizing species,
namely, sulphate radical anion [Eq. (1)]. The sulphate
radical anion SO 4•– may react with photogenerated
electron and with water molecule producing hydroxyl
radical [Eqs. (2)–(4)]. The sulphate radical anion (SO4•–)

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 12 2015

2048 GIAHI

120 is due to the fact that hydrogen peroxide could increase

the concentration of OH radical, by inhibiting the elec-
100 3 tron hole recombination. H2O2 is considered to have two
2
functions in the process of photocatalytic degradation. It
Degradation, %

80 1
accepts a photogenerated electron from the conduction
60 band and, thus, promotes the charge separation:

40 H2O2 + e− → OH− + OH• (5)

20 and it also forms OH• radicals according to [28–30]:

0
30 60 90
Irradiation time, min
Fig. 7. Effect of electron acceptors. Conditions: diclofenac
sodium 20 mg L–1, N, S, and C-doped ZnO 0.44 g L–1, pH =
6.0, irradiation time 2 h, V t 25 mL. (1) ZnO,C,N,S/UV,
(2) ZnO,C,N,S/UV/H2O2 (1 mM), (3) ZnO,C,N,S/UV/K2S2O8
(1 mM).
is also a very strong oxidant. This radical anion also
participates in the degradation process.
S2O82− + e− → SO42− + SO4•−
SO4•− + H2O → SO42− + OH• + H+,
SO4•− + RH → SO42− + Int1,
SO4•− + Int1 → … → SO42− + CO2,
where Int1 symbolized the first reaction intermediates
partially transformed until the total mineralization.
Figure 7 shows that the presence of H2O2 increases
the rate of degradation compared to other kinds. Addition
of H2O2 (1 mM), rapidly increases the photodegradation
efficiency of diclofenac sodium from 86.1 to 98.2%. This
120 H2O2 + O2•− → OH− + OH• + O2. (6)
The table show that this work has some good param-
eters in the comparison with other work the same area
in literature. Present work has a good efficiency and
irradiation time.
CONCLUSIONS
Highly photoactive mesoporous N, S, C-doped
ZnO photocatalysts can be successfully prepared.
Crystallization of ZnO is greatly suppressed due to
(1) N, S, C-dopants. An appropriate amount of dopants can
(2) reduce the recombination of e−–h+ pairs and raise the
photocatalytic activity under UV irradiation. The opti-
(3)
mal degradation conditions of diclofenac sodium are:
(4) 0.44 g L–1 N, S, C-doped ZnO, pH 6.0, 1 mM H2O2, and
concentration of LABS 20 mg L–1. After 4 h irradiation,
about 98.2% removal of drug was achieved [31–36].
ACKNOWLEDGMENTS
The financial support provided by the Islamic Azad
University Lahijan is greatly acknowledged.

The comparison of this work with some other work the same area in literature
UV or visible Irradiation
Photocatalyst Pollutant Degradation, % Reference
light time, min
ZnO Ethyl violet (EV) UV 300 99.4 31
Nb-doped ZnO Indigo Carmine Dye UV 300 97.4 32
Cu2O-doped ZnO Methyl orange (MO) Visible 180 73.0 33
Cr, N-doped ZnO Thymol blue(TB) UV 180 78.5 34
Visible 180 98.9 34
Pure ZnO Malachite green (MG) Visible 120 80.0 35
N-doped ZnO Malachite green (MG) Visible 90 98.0 35
N, S, C-doped ZnO Acid orange 7 (AO7) UV 120 70.9 36
N, S, C-doped ZnO Diclofenac Sodium UV 240 98.2 In this work

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 88 No. 12 2015

 PHOTOCATALYTIC DEGRADATION OF DICLOFENAC SODIUM
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