Optical Materials 115 (2021) 111035

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Optical Materials
journal homepage: http://www.elsevier.com/locate/optmat

Research Article

Photocatalytic performances of ZnCr2O4 nanoparticles for cephalosporins

removal: Structural, optical and electrochemical properties
Y. Benrighi a, N. Nasrallah a, T. Chaabane a, **, V. Sivasankar b, *, A. Darchen c, O. Baaloudj a
a
Laboratory of Reaction Engineering, Faculty of Mechanical Engineering and Process Engineering, USTHB, BP 32, 16111, Algiers, Algeria
b
P.G. and Research Department of Chemistry, Pachaiyappa’s College (Affiliated to University of Madras), Chennai, 600 030, Tamil Nadu, India
c
UMR CNRS N_6226 Institut des Sciences Chimiques de Rennes, ENSCR, 11, Allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France

A R T I C L E I N F O A B S T R A C T

Keywords: The present contribution is about the synthesis of a composite photo-catalyst with remarkable activity and a
Spinel ZnCr2O4 narrow gap band to explore the possibility of using it for the removal of antibiotics in water. The synthesis of
Optical constants spinel ZnCr2O4 (ZCO) nanoparticles in pure phase by the combination of sol-gel methodology at 700 ◦ C was
Electrochemical properties
achieved. The identification and characterization were done using characterization studies such as X-ray
Photocatalysis
diffraction (XRD), Transmission Electron Microscope (TEM) and UV–Visible spectroscopy techniques. The
Antibiotics
illustration of spinel structure was done with the help of lattice constants using XRD data. The optical and
dielectric properties of ZCO were measured using the UV–Visible data. The photo-electrochemical property
revealed the flat band potential value of 0.3 VSCE which ascribes the n-type semiconductor. The photocatalytic
activity of ZCO nanoparticles under visible light source in degrading the three pharmaceutical products such as
Cefaclor (CFR), Cefuroxime (CFRM) and Cefixime (CFX) of 66.9%, 55.2% and 80.1% was also successfully
studied.

1. Introduction of antibiotics at high concentrations develops relatively higher selective

Water is very significant among various other natural resources [1]
and covers around 71% of the earth’s surface. However, its accessibility
by humans is about just 0.02% to the total freshwater of about 1.2% [2].
Potable water quality is a major concern [3–10]which becomes scarce to
the public across the world. Various compounds organic or inorganic
contaminants sully the water environment which includes pharmaceu­
tical compounds as one of the most hazardous contaminants [11]. An­
tibiotics and widely used [12] and extremely dangerous because their
environmental contamination can increase the aquatic toxicity [13].
Although there are many treatment methods developed for the
removal of contaminants they have pitfalls in degrading the antibiotic
molecules of wastewater and most predominantly the degradation
leading to by-products [14–16]. Cephalosporin belongs to the “pseu­
do-persistent type” of β-lactam antibiotics and being detected frequently
in the aquatic environments due to their wide antibacterial ability and
enormous clinical consumption. As a consequence of prolonged expo­
sure of bacteria to these types of antibiotics, selective proliferation of
resistant microorganisms is resulted [17–19]. Moreover, the discharge
pressure especially for the antibiotic-resistant bacteria which ultimately
aggravate the environmental systems. The inability of complete elimi­
nation of these antibiotics by usual biological treatments is reported by
many researchers [20]. Hence it becomes necessary to develop an effi­
cient technique to eliminate these hazardous pollutants. Over the last
decades, the interest towards the advanced oxidation process (AOPs) is
justified because it is an inexpensive, environmentally friendly and
sustainable alternative solution for the rapid degradation of
non-biodegradables in water sources [21–24]. Conspicuously, organic
products and pharmaceutical compounds undergo feasible degradation
thanks to the photocatalytic methods [25–31]. These methods are based
on semiconductors which are considered to be a special form of catalysts
that can be activated by photons from the sunlight [32]. In the synthesis
of semiconductors, zinc is one of the preferred materials. Besides, ZnO
has a proven record in its photocatalytic activity thanks to the remark­
able chemical stability and transparent ability towards light absorption.
However, its bandgap energy of 3.2 eV is the only problem for ZnO
materials [33,34]. In order to curtail the existing problems,
high-performance photo-catalysts exhibiting high optical properties

* Corresponding author.
** Corresponding author.
E-mail addresses: tfkchaabane@yahoo.fr (T. Chaabane), sivshri.20@gmail.com (V. Sivasankar).

https://doi.org/10.1016/j.optmat.2021.111035
Received 22 February 2021; Received in revised form 16 March 2021; Accepted 18 March 2021
Available online 3 April 2021
0925-3467/© 2021 Elsevier B.V. All rights reserved.
Y. Benrighi et al.
Fig. 1. XRD diffractogram with Rietveld refinement. Inset: the structural representation.
must be developed to achieve better results in the treatment of waste­
water [35]. As a prominent representative among semiconductors, zinc
chromate semiconductor with the chemical formula ZnCr2O4 (ZCO) has
attracted the attention of several research groups [36–41] thanks to its
very efficient photocatalytic activity, its narrow optical band gap of
about 1.8 eV [40] and highly visible-light activity which is suitable for
solar light. Inquisitively, there is a lack in the application of the
photo-catalytic ZCO nanoparticles in the treatment of pharmaceutical
wastewater and in particular no degradation study has been reported
using antibiotic compounds such as Cefaclor (CFR), Cefixime (CFX) and
Cefuroxime (CFRM). The present research is contributed on the syn­
thesis of ZnCr2O4 nanoparticles with remarkable photocatalytic activity
and narrow bandgap by sol-gel auto combustion method for the removal
of certain cephalosporin (CFR, CFX and CFRM) antibiotics from water by
photocatalytic degradation. The photo-catalytic ZCO nanoparticles were
characterized by XRD, TEM, DRS and electrochemical studies for com­
prehending the phase identification, surface morphology and opti­
cal/dielectric properties and semiconductor type respectively. A suitable
photo-degradation mechanism is also proposed in this paper.
2. Material and methods
Chemicals used in this study were zinc acetate 2 hydrate
[C4H6O4Zn⋅2H2O] (99% Riedel-de haen), chromium nitrate [Cr
(NO3)3⋅9H2O] (98% Biochem), Cefixime (CFX) C16H15N5O7S2, Cefaclor
(CFR) C15H14ClN3O4S and Cefuroxime (CFRM) C16H16N4O8S and poly­
vinylpyrrolidone (PVP) K30 were acquired from Pharmalliance phar­
maceutical company in Algeria. Chemicals such as ethanol, sodium
hydroxide, hydrochloric acid and nitric acid were supplied from Sigma
Aldrich, Algeria.
2.1. Synthesis of ZnCr2O4 nanoparticles
ZCO was synthesized using the sol-gel process. Molar ratio concen­
trations of zinc acetate dihydrate [C4H6O4Zn⋅2H2O] and chromium ni­
trate nano-hydrate [Cr(NO3)3⋅9H2O] in the ratio of 1:2 were used to
prepare the solution by dissolving independently in ethanol and an
additional 5 ml of 65% nitric acid was added to the solutions. Both so­
lutions were combined and heated at 50 ◦ C on a hot plate for 1 h after
complete solubilization. Then 50 ml of 15%w/w of poly­
vinylpyrrolidone (PVP K30) which serves as a complexing agent was
2
Optical Materials 115 (2021) 111035
added to the above reaction mixture. Then the solution was concen­
trated at 80◦ Cover 20 h by evaporation and it has become a black gel.
After an auto-combustion reaction occurred, the resulting gel was dried
at 200 ◦ C for 6 h and an amorphous powder (Xerogel) was obtained. The
obtained powder was crushed and calcined for 6 h at 750 ◦ C. Finally, the
calcined nanoparticles were characterized for their structure, optical
and electrochemical properties.
2.2. Characterization studies
The X-ray diffraction (XRD) was done using a Phillips PW 1730 and
using the Rietveld technique by the Maud software to calculate the
constructed crystals. Images of the nanoparticles were obtained on the
JEOL-24011BU Transmission Electron Microscope (TEM). The sample
was analyzed using a UV–visible diffuse reflection spectrum (DRS) of dry
pressed disk sample with the Cary 5000 UV–Visible spectrophotometer.
In the electrochemical analysis, the electrical contact was produced
using electrical cables and silver pigment on the back of the pellet fol­
lowed by covering the pellet with epoxy resin in a glass tube. Tri-
electrode analysis was carried out for the analysis (the working elec­
trode ZCO, with Platinum as the counter electrode and Ag/AgCl (4 M
KCl) as the reference electrode in NaSO4 (0.1 M) solution.
2.3. Photocatalytic degradation study
In order to test the photocatalytic efficiency, ZCO has opted for a
treatment application in water polluted by antibiotics that are not
biodegradable and have a high rate of danger to the environment. The
three antibiotics of the same class of cephalosporins such as Cefaclor
(CFR), Cefixime (CFX) and Cefuroxime (CFRM) were selected for the
application of photocatalytic degradation. The photocatalytic degrada­
tion of the pharmaceutical contaminants was carried out after opti­
mizing the parameters such as pH and dose of the catalyst. The optimal
conditions maintained at a temperature of 25 ◦ C during the photo-
catalytic reaction were pH 6, 1 g/L dose of the catalyst and an initial
concentration of 5 mg/L for each antibiotic solution. The antibiotic
samples were mixed and taken in a closed vessel in a dark condition for
120 min to maintain the equilibrium between adsorption and desorption
before irradiation. As a visible irradiation, a tungsten lamp (200 W)
produced by Osram was used and placed 10 cm away from the surface of
the solution. The solution temperature was held constant during all the
Y. Benrighi et al. Optical Materials 115 (2021) 111035

Table 1 are presented in Table 1. With the Debey-Scherer formula Eq. (2), the
Rietveld and space group parameters. crystallite size was estimated for the various peaks and it is between
Phase ZnCr2O4 28.63 nm and 40.23 nm.
Groupe space Fd-3m: 2 Kλ
D= (2)
a (Å) 8.333369 βcos(θ)
Atoms Atom X y z D is the regular phase crystallite (nm), K is the dimensionless (shape)
Zn 0.125000 0.125000 0.125000 factor (⁓0.9), β is the full width at the highest half of the phase (radian),
Cr 0.500000 0.500000 0.500000
β is the wavelength of the X-ray signal (nm), and a θ is the Braggs angle.
O 0.261978 0.261978 0.261978
V (Å3) 578.711187 The X-ray density was determined using the regular formula (Eq. (3))
R factors Rp 10.784023 [43,44].
Rexp 9.294538
Rwp 19.784046 ZM
ρ= (3)
Sig 2.12 NA V

NA is Avogadro’s number, M is the Molecular mass of ZCO (233.4012 g

photo-catalytic tests (25 ± 1 ◦ C) using a cooling system which is a
thermostatic bath connected reactor. An aliquot of 3 ml of the sample
was taken from the reaction mixture at intervals and then centrifuged for
10 min at a rate of 5000 rpm. The antibiotic concentrations of CFR
(λmax = 265 nm), CFX (λmax = 288 nm) and CRRM (λmax = 280 nm)
with reference to the maximum absorbance at the wavelength was
analyzed from the formula (Eq. (1)) using UV–Visible spectrophotom­
eter (OPTIZEN, UV - 3220UV).
CA − C(t)
Photodegradation% = × 100 (1)
CAd
CA (mg/L) is the initial antibiotic concentration following adsorption
and C (t) (mg/L) is the antibiotic concentration at time t. The pseudo-
first-order kinetic model was validated with the degradation kinetics
of antibiotics.
3. Results and discussion
3.1. Characterization of catalyst
3.1.1. Phase identification and structural investigation
To confirm the single phase of ZCO, an X-ray diffraction (XRD) was
recorded. Almost a single phase of ZCO was obtained at 700 ◦ C. Rietveld
refinement of the DRX has been performed with the method supplied by
Maud software. In Fig. 1, points and red lines respectively indicate the
experimental and theoretical results. All the peaks are narrow and
indicated the perfect crystallization of ZCO and the phase is indexed as a
cubic structure (space group Fd-3m: 2) in line with the JCPDS Card N◦
87-0028 [37,42]. The structural representation of ZCO is provided by
the Vista program (The inset in Fig. 1). All Rietveld refined parameters
mol− 1), Z is the count of model units in a single cell (Z = 8 [38]) and V is
the unit cell volume( 578.711187 Å ​ 3). The density of x-rays was found
to be 5.3596 g cm− 3.
Special surface area (SSA) measurements include important param­
eters such as particle size, structure and density. The particular surface
area of the ZCO catalyst was estimated by the Brunauer-Emmett-Teller
(BET) formula (Eq. (4)) [12].
6 × 103
S= (4)
Dp × ρ
Dp is the particle size, S is the specific surface area, and ρ is the density of
X-ray for ZCO 5.43 g cm− 3. SSA was calculated between 27.83 and
39.10 m2 g− 1 using this formula.
3.1.2. Morphology investigation
In order to analyze the particle size and morphology of the ZCO
powders, Transmission Electron Microscopy (TEM) technique was per­
formed. The TEM image (Fig. 2) contains accurate information about
nanoparticles’ size, form and size distribution. It is very explicable that
the catalyst was comprised of almost uniform type of particles (cubic in
shape) with diameters in the range of 30–40 nm which is well agreed
with DRX. Also, the image shows the existence of multiple aggregations
within the sample in the range of nanometers due to the ultrafine nature
of the ZCO powder.
3.1.3. Optical and dielectric properties
The optical characteristics of the ZnCr2O4 nanostructure were
investigated using the UV–Visible diffuse reflectance spectroscopy
(DRS) to explore the photo-catalytic activity of the ZCO semiconductor

Fig. 2. TEM images of ZCO.

3
Y. Benrighi et al.
Fig. 3. Tauc plot of UV-DRS spectrum for ZCO.
Fig. 4. Dependence of the dielectric parts as a function of the energy (hν).
under the visible light. The spectral distribution of T(λ) and R(λ) were
studied for ZCO in the wavelength range between 250 nm and 900 nm.
The bandgap energy (Eg ) is estimated by plotting the Tauc plot (Fig. 3).
The Tauc method is based on the assumption that the energy-dependent
absorption coefficient (α) which relies upon the energy of photon hυ,
expressed by the relation (Eq. (5)) [45,46]:
( )
(5)
1
(αhν)n = K hν − Eg
K is a proportionality constant, α is the coefficient of absorption and
the exponent n is a function of the nature of the transition (n = 2 direct
or 1/2 indirect transitions).
The bandgap energy (Eg ) of ZCO nanoparticles was obtained by the
extrapolation of the straight line with the x-axis. It was about 1.7 ± 0.1
eV in line with the grey color. This value is lower than that of TiO2 (3.2
eV) [33,34] and ZnO (3.37 eV) [47]. This value is also very closer to the
literature value of 1.8 eV [40]. The potential of the ZCO for the
photo-catalytic behaviour can be determined through the band gap
[48]. In pertinent to this the DR spectral characterization shows that the
ZCO catalyst has a significant effect on the band gap in the visible
region.
The dielectric complex constant (ϵ) contains the real (ϵr) and imag­
inary parts (ϵi) determined from UV–visible absorption spectra by
calculating the refractive index n(λ)and absorption index (extinction)
k(λ) using the Kramers-Kronig method set up on the accompanying
equations (Eqs. (6)–(8)) [48–51]:
4
Optical Materials 115 (2021) 111035
Fig. 5. The dielectric relaxation time τ as function of the energy hν, inset: εr as
function of λ2 .
εr (λ) = ​ n(λ)2 + K(λ)2 ; εi (λ) = 2 ​ n(λ)K(λ) (6)
where the extinction index k(λ) is calculated in terms of absorption α
with the next equation [49,51,52]:
α(ν)λ
K(λ) = ; α(ν) = α0 ehν/Eu (7)
4π
where λ, α(ν), α0 , h, Eu and n are wavelength, the absorption coefficient,
a constant, the Plank’s constant (6.63 × 10− 34 J/s), the Urbach energy
and the light frequency respectively.
And the refractive index n(λ) is measured from this formula [53–55]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( ) (
1 + R (λ ) + 4R ( λ ) − ( 1 − R ( λ ))2 K ( λ )2
n​ λ = (8)
1 − R (λ )
The dependence of the dielectric constants εr and εi on the energy
(hν) is shown in Fig. 4. The optical band gap (Eg ) value can be detailed
from this figure by extrapolating a direct line from the cross-point be­
tween both the arcs of the real and imaginary parts of the dielectric
value to the abscissa-axis [48], which is equal to about 1.66 eV. This
method gives the exact Eg value and it is in good line with the Tauc plot
of UV–visible that confirmed the band gap value.
The dielectric relaxation time τ confirms the value of the optical
band gap, Eg and also determines the limit of recombination of the
charge carrier and measured from this formula (Eqs. (9) and (10)) [41,
44,47]:
ε∞ − εr
|τ| = (9)
ωεi
where ε∞ is calculated with equation (10) [48] by drawing εr as function
of λ2 , as showing in the inset in Fig. 5.
εr = ε∞ − B ​ λ2 (10)
The dielectric relaxation time τ as a function of the energy (hν) is
represented in Fig. 5. The cross-point in the curve of dielectric relaxation
time at hν = 1.65 eV is attributed to the band-to-band absorption
because the maximum occurs at hν = Eg . This is in agreement with the
dielectric index gap values.
3.1.4. Electrochemical properties
The electrochemical characterization was performed in order to
better understand the semiconducting ability as well as the photo-
catalytic performance of ZCO. The cyclic voltammogram (CV) of ZCO
recorded in the Keithly system in connection to the potentiostat con
Y. Benrighi et al.
Fig. 6. (a) The cyclic voltammograms J (E) (b) Semi-logarithmic plot of ZCO plotted in NaSO4 (0.1 M) at a scan rate of 10 mV s− 1.
Table 2
Anodic and cathodic slope with the point of intercept from Tafel plot.
Ecorr(V) βa (v) βc (v) Icorr (mA/cm2)
− 0.3175 0.3360 − 0.302 0.0122
Fig. 7. The capacitance-potential characteristic (Mott-Schottky plot) of ZCO.
sisting of three electrodes could explain the semiconductor’s stability
and assess the specific potential of the redox couple. Fig. 6 (a) shows the
density potential traced in the dark, the decrease in current below ~ 0.4
V indicates the reduction of water into hydrogen while the current rises
over ~ 0.8 V is due to the evolution of oxygen. The large difference
between the anodic and cathodic peaks suggested the slow charge
transfer and represents a sluggish system by attributing the irreversible
mechanism [56,57]. Specific capacitance (Cs ) can be calculated using
cyclic voltammogram (CV) via electrochemical data by the following
expression (Eq. (11)):
∫
I.dV
Cs = (11)
V m ΔV
∫ be predicted such that the smaller the flat band potential, the higher are
where I.dV is the integrated area under the curve of CV, m (g) is the
mass of active material ZCO (1 g) on the electrode surface, ΔV is the
potential difference, V (mVs− 1 ) is the potential scan rates (10 mVs− 1).
Specific capacitance Cs was found around 3.43 × 10− 4 Fg− 1 .
The semi-logarithmic characteristic (Tafel) in Fig. 6 (b) gives an
exchange current density of 1.53 × 10− 4 mA cm− 2 and a potential of
0.32 V by confirming good electrochemical stability in a neutral
5
Optical Materials 115 (2021) 111035
Fig. 8. The EIS (Nyquist) diagram of ZCO, inset: equivalent electrical circuit.
medium. From the Tafel plot, we can determine the anodic slope βa (v)
and cathodic slope βc (v) which are presented with the point of intercept
in Table 2.
The photo-electrochemistry offers knowledge about the properties of
the semiconductor and the diagram of the energy band. The location of
electronic bands is critical and it could be reached by the understanding
of flat band potential Efb = (0.3 ​ V) which is estimated from the inter­
facial capacitance using the Mott-Schottky relation (Eq. (12)) [44]:
( )
C− 2 =
2
E − E −
kT
(12)
fb
εε0 A2 eND e
A is the surface area of the electrode, kT is the thermal energy, ε0 the
permittivity of free space [58] and ‘e’ be the charge of an electron. The
permittivity ε is determined from the dielectric measurement on sintered
pellet while the density of the holes ND = 2.064 × 1028 ​ cm− 3 is deter­
mined from the intercept with the abscissa axis and the slope of the
linear plot (C− 2 - E). The n-type semiconductor was explored by the
positive slope of dC− 2/dE. From the results of Mott – Schottky mea­
surements (Fig. 7) the photo – catalytic activity of the ZCO spinel could
the photonic efficiency and donor density of the photo-catalytic activity
[60]. Furthermore, the valence band (VB) and conduction band (CB) of
the photocatalyst can be estimated from the flat band.
The Electrochemical Impedance Spectroscopy (EIS) or Nyquist was
applied by a current or potential over a large frequency domain as
shown in Eq. (13). It allows bulk, grain boundaries and diffusion to be
quantified. The Nyquist diagram is the plot of (Zim vs Zreal ) [59]:
Y. Benrighi et al. Optical Materials 115 (2021) 111035

Table 3
Parameters of the equivalent electrical circuits with the chi-squared and weighted sum of squares.
Rs CPE-T CPE-P Wo-R Wo-T Wo-P Rp chi-squared weighted sum of squares

44.42 0.0009154 0.63082 529.3 87.34 0.1259 1E20 0.0002 0.00344

catalyst were used to provide a unified discussion on semiconductor

photo-catalysis as well as providing an insight into the relationship
among the band gap, flat band and the photo-catalyst itself. To confirm
the findings of those characterizations, the photocatalytic activity of
ZCO was explored under visible light by selecting three antibiotics of the
same class called cephalosporin viz., Cefaclor (CFR), Cefixime (CFX) and
Cefuroxime (CFRM). Prior to the photocatalytic degradation, the
photolysis of the three cephalosporin antibiotics did not achieve any
degradation and hence it was neglected. The degradation by ZCO photo-
catalyst under certain conditions such as pH of the cephalosporin solu­
tion and dose of the ZCO photo-catalyst were optimized respectively
with 6.0 and 1gL-1 with CFX antibiotics as detailed in sec 1.3. Based on
the optimized pH and dose amount of ZCO, the photocatalytic degra­
dation rate was determined and found to be constant after 180 min for
CFX, CFR and CFRM. The antibiotics such as CFX, CFR and CFRM with
the initial concentration of 5 mgL− 1 were degraded to the value of
80.1%, 66.9% and 55.2% respectively. The amount of CFX, CFR and
CRRM was found to be 4.01 mg, 3.34 mg and 2.76 mg respectively per
gram thanks to the photocatalytic activity of ZCO nanoparticles
(Fig. 9A). It is evident that the photocatalytic performance of ZCO varies
from one antibiotic compound to another with a difference in the
degradation efficiency in the range of 13.2–24.9%. The degradation
efficiency follows the order: CFX > CFR > CFRM and witnessed the
dependence of degradation rate with respect to the structure of the
compound.
The pseudo-first-order model [60] validation (Eq. (14)) in accor­
dance with the present degradation kinetics is confirmed from the R2
values as shown in Fig. 9B.
C
ln = − kobs (t) (14)
C0

where C and C0 are the concentrations (mgL− 1) of antibiotic compounds

Fig. 9. (a) Photodegradation of antibiotics using ZCO (b) pseudo-first-order
kinetic plot.
1 − 2q
Z = Q(jW)− n ; n = (13)
p characterizations. Also, the results affirm the ability of this photo-
‘n’is the homogeneity factor and Q is a frequency-independent
constant.
The data is fitted with the Zview program to an equal electric circuit.
Nyquist diagram (Fig. 8) illustrated the modeling outcome of the
equivalent electrical circuit which represents a half-circle connected to
the resistance of charge transition (Rs = 1 kΩ cm2) in series with a
Constant Phase Element CPE and Warburg Element WO , in parallel with
RP , the electrolyte solution. All properties of the equivalent electrical
circuits with the chi-squared and weighted sum of squares are presented
in Table 3.
3.2. Photo-catalytic efficiency of ZCO
The optical, dielectric and electrochemical characterizations of the
at time, t and t = 0. kobs is the constant called pseudo-first-order rate
constant expressed in sec− 1 and determined from the slope of the curve
drawn between ln CC0 and light irradiation time. The first-order - rate
constant was calculated to be 5.0 × 10− 3 sec− 1, 5.6 × 10− 3 s − 1 and 9.3
× 10− 3 s − 1 respectively for CFRM, CFR and CFX respectively. The rate
constant for the CFX degradation was found to be higher than that of
CFRM and CFR compounds. The maximum degradation percentage and
rate constant values were recorded for CFX in 3 h unlike CFR and CFRM
with moderate degradation percentage and lower rate constants than
CFX. So, these results can demonstrate that ZCO is able to perform in the
degradation of non-biodegradable antibiotics under visible irradiation,
which in line with the findings of the optical and electrochemical
catalyst for real wastewater treatment applications.
To draw the energy diagram of ZCO, the ZCO valence band and
conduction band (CB) energies are determined from the relationships
(Eqs. (15) and (16)):
ECB = 4.75 + eEfb + 0.059(pH − IP) − Ea (15)
EVB = ​ ECB − ​ Eg (16)
Ea is the activation energy (43 meV [40]). The expression 0.059 (pH - IP)
is neglected because its effect is very weak. After calculation, ECB and
EVB are equal to - 4.4 eV/0.35 V and - 6 eV/1.25 V respectively.
Generally, photocatalysts can usually attribute the photodegradation of
drug chemicals with various reaction pathways regulated by various
active species including OH* , O2 − * and h+ (hole) [25]. The generation of

6
Y. Benrighi et al.
Fig. 10. Energy diagram and Proposed mechanism for antibiotics degradation in the presence of ZCO nanoparticles.
O2 − * due to the reduction of surface - adsorbed O2 of ZCO is likely to take
place in the CB. Accordingly, in our precedent studies [11,12], both
holes and hydroxyl radicals were suggested to be active as oxidizing
agents and become responsible for the degradation of antibiotic com­
pounds. Wu et al. [61] reported that the possible photo-catalytic
degradation is mainly controlled by oxidation as a consequence of h+
and O2 − * rather than OH* . The mechanism as well as the energy diagram
constructed on the base of the photoelectrochemical characterization,
are explained in Fig. 10. The degradation mechanism of antibiotic under
light source is indicated by the following equations (Eq. (17)–(20)):
ZnCr2 O4 + hυ → ZnCr2 O4 * + e− + h+
H2 O + h+ → OH * + H +
O2 + e− → O2 − *
Antibiotic + O2 − * and OH * → CO2 + H2 O + degradation by products
4. Conclusion
Within the framework of our study, we successfully synthesized
ZnCr2O4 (ZCO) nanoparticles using the combination of sol-gel methods
for the removal of antibiotics in order to guarantee a clean and envi­
ronmentally friendly method of elimination of pharmaceutical com­
pounds. The ZCO nanoparticles were characterized for XRD, TEM and
DRS which confirmed the reliable multifarious applications. The cubic
structure with a space group Fd-3m was confirmed by Rietveld refine­
ment for ZCO catalyst using the DRX data. From the UV–Visible data, the
optical and dielectric constants were calculated such that the optical
band gap of 1.66 eV was verified. From the output of electrochemical
properties, the flat band potential of 0.3 VSCE was determined which
substantiated the behavior of n-type based semiconductors. The photo­
catalytic performance of ZCO corroborated its ability to degrade the
cephalosporin family of compounds viz., Cefixime, Cefaclor and Cefur­
oxime up to 80.1%, 66.9% and 55.2% respectively in 3 h. The study
detailed and confirmed that the spinel ZCO nanoparticles to be an
effective (photo) catalyst to degrade non - biodegradable compounds of
the cephalosporin family under visible light irradiation. This present
contribution is likely to be achievable in real wastewater treatment
applications.
Optical Materials 115 (2021) 111035
CRediT authorship contribution statement
Y. Benrighi: Investigation, Writing – original draft. N. Nasrallah:
Validation. T. Chaabane: Conceptualization. V. Sivasankar: Supervi­
sion. A. Darchen: Supervision. O. Baaloudj: Investigation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
(17) the work reported in this paper.
(18) Acknowledgment
(19) This work was financially supported by both the Faculties of Me­
chanical Engineering and Process Engineering Departments, USTHB,
(20) Algiers, Algeria.
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