Environmental Science and Pollution Research (2022) 29:25486–25495

https://doi.org/10.1007/s11356-021-17077-2

RESEARCH ARTICLE

Efficient photocatalytic degradation of metronidazole from aqueous

solutions using Co/g‑C3N4/Fe3O4 nanocomposite under visible light
irradiation
Mojtaba Yeganeh1,2 · Hamid Reza Sobhi3 · Ali Esrafili1,2

Received: 16 August 2021 / Accepted: 12 October 2021 / Published online: 29 November 2021
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2021

Abstract
Herein, the efficient degradation of a highly consumed antibiotic known as metronidazole (MNZ) in aqueous solutions using
Co/g-C3N4/Fe3O4 nanocomposite under visible light irradiation was accomplished. Initially, the photocatalyst (Co/g-C3N4/
Fe3O4) was synthesized by a simple hydrothermal method and then characterized by several analytical techniques, namely
EDS, SEM, XRD, UV–vis DRS, and FTIR. The efficiency of the synthesized photocatalyst with regard to the degradation
of the studied antibiotic (MNZ) under visible light irradiation was fully evaluated. The influential operational parameters
affecting the efficiency of the degradation process such as pH (2–10), nanocomposite dosage (0.2–1 g/L), MNZ concentration
(5–20 mg/L), and irradiation time (0–80 min) were optimized. The results revealed that the maximum degradation efficiency
for MNZ was obtained under the following conditions: irradiation time of 60 min, pH = 8, MNZ concentration of 5 mg/L, and
photocatalyst dosage of 0.7 g/L. In addition, the degradation of MNZ followed the pseudo-first-order kinetic model. The best
rate constant (k) value was determined to be 0.0102 ­min−1 with the correlation coefficient (R2) of 0.992. According to the
results of the quenching tests, it was found out that hydroxyl radicals (OH°) were the main species responsible for the MNZ
degradation. Furthermore, the applied photocatalyst (Co/g-C3N4/Fe3O4) exhibited a high level of recovery and stability after
five cycles of reuse. Co/g-C3N4/Fe3O4/Vis system exhibited an excellent performance in the treatment of wastewater and
real water samples. Finally, it was concluded that the synthesized nanocomposite could be potentially used as a promising
and suitable photocatalyst in the degradation of other antibiotics.

Keywords Co/g-C3N4/Fe3O4 · Visible light · Photocatalytic · Metronidazole · Antibiotics

Introduction Various types of antibiotics can end up in the environment

through different ways including the production process,
Antibiotics have been extensively applied for the cure of disposal of expired drugs, and sludge utilization (Husain
diseases of livestock and human beings worldwide. In fact, Khan et al. 2020; Luo et al. 2020). In addition, majority
the residues of antibiotics in the environment pose a great of antibiotics are not simply prone to degradation resulting
threat to the ecosystem and human health (Peng et al. 2019). in tipping the balance of the entire ecosystem (Chen et al.
2018; McBean 2019).
Metronidazole (MNZ) is widely used for the treatment of
Responsible Editor: Sami Rtimi
infectious diseases in both humans and animals (Wang et al.
* Ali Esrafili 2016). MNZ can affect humans and the ecological environ-
[email protected] ment due to its high solubility and low biodegradability in
1 water (González-Pleiter et al. 2013; Zhou et al. 2018).
Department of Environmental Health Engineering, School
of Public Health, Iran University of Medical Sciences, The conventional treatment processes, which are cur-
Tehran, Iran rently used for the treatment and removal of antibiotics,
2
Research Center for Environmental Health Technology, Iran seem not to be highly effective on the account of the fact that
University of Medical Sciences, Tehran, Iran they are associated with incomplete degradation and genera-
3
Department of Chemistry, Payame Noor University, Tehran, tion of secondary toxic pollutants (Al Aukidy et al. 2012;
Iran Drzewicz et al. 2004; Khan et al. 2020b). So far, a number of
Environmental Science and Pollution Research (2022) 29:25486–25495 25487

treatment methods such as nanofiltration membranes (Pronk was then applied for the degradation of MNZ under visible
et al. 2006), electrodialysis (Pronk et al. 2007), biodegrada- light irradiation. Then, the influential parameters affecting
tion (Pan et al. 2018), adsorption (Sarker et al. 2017), and the degradation process were separately optimized. The
advanced oxidation (Yin et al. 2018) have been employed kinetics, impact of scavengers, and the mechanism of MNZ
to effectively remove antibiotics from contaminated water degradation were all investigated as well. Finally, Co/g-
media. Nevertheless, the major problems associated with C3N4/Fe3O4/Vis system exhibited an excellent performance
these methods are high consumption of energy, high cost, in the treatment of wastewater and real water samples.
and low mineralization efficiency (Abdili et al. 2017, Gos-
wami and O'Haire 2016).
Amongst the abovementioned methods, advanced oxida- Materials and methods
tion processes (AOPs) have been considered one of the most
effective methods for the degradation of antibiotics mainly Chemicals
owing to the unique feature of the production of highly
reactive oxidizing agents like hydroxyl radicals (Khan et al. All chemicals used in this study were of analytical grade.
2020a, Wan and Wang 2016). Additionally, the degrada- MNZ ­( C 6 H 9 N 3 O 3 ), sulfuric acid ­(H 2 SO 4 ), melamine
tion of several antibiotics, namely ciprofloxacin (Mou et al. ­(C3H6N6), ­FeCl3.6H2O, ­FeCl2.4H2O, hydrochloric acid
2019), metronidazole (Bahareh and Habibi 2019), gemiflox- (HCl), ammonia (­ NH4OH), cobalt phosphate (­ Co3 ­(PO4)2),
acin (Gholami et al. 2020), sulfonamides (Wu et al. 2019), sodium hydroxide (NaOH), methanol ­(CH3OH), and ethanol
and sulfacetamide (Guo et al. 2020), by various photocata- ­(C2H5OH) were all purchased from Merck Company and
lytic methods has been vastly reported in the literature. applied with no further purification.
Recently, a number of catalysts such as T ­ iO2, ZnO/TiO2,
MgO, and ­ZnSeO3/g-C3N4 have been used in photocatalyst Synthesis of Co/g‑C3N4/Fe3O4
processes (Ahmadifard et al. 2019; Moorthy et al. 2020;
Sraw et al. 2020; Topkaya et al. 2014). Graphene (G) and Initially, g-C3N4 nanoparticles were fabricated by direct
graphene oxide (GO), both considered catalyst, have exhib- heat treatment of melamine at 550 °C for 2 h under a gen-
ited a high level of efficiency with regard to the degradation tle stream of nitrogen gas (Kumar et  al. 2013b). Co/g-
of organic matters in the photocatalytic processes prob- C3N4/Fe3O4 nanocomposite catalyst was then synthesized
ably due to the formation of strong π-π interactions with by a hydrothermal method. For the preparation of Co/g-
aromatic structures (Ghodsi et al. 2020). Carbon graphite C3N4/Fe3O4 nanocomposite, the following procedure was
nitride (g-C3N4) is a typical of metal-free polymer semicon- implemented:
ductor material which has a relatively large band gap energy Initially, 125 mg of ­C3N4 g nanoparticles was poured into
to absorb visible light. It also has unique characteristics 500 mL of ethanol/water (1:2, v/v) followed by a 5-h sonica-
including environmental compatibility and biaxial structure tion at room temperature. Then, 1.838 g of F ­ eCl3·6H2O and
(Kumar et al. 2013a). However, the separation and recovery 0.703 g of ­FeCl2.4H2O were dissolved separately in 20 mL
of g-C3N4 from effluents samples is very difficult. As a rem- of distilled water (DI-water) and subsequently introduced to
edy, magnetic properties have been integrated within the the g-C3N4 solution. The resulting mixture was agitated for
structure of g-C3N4. ­Fe3O4 nanoparticles have attracted a 30 min at 80 °C followed by a gentle addition of 10 mL of
lot of attention due to their magnetic properties resulting in ammonia ­(NH4OH) while vigorously shaking. The produced
their vast applications in the various systems with regard to g-C3N4/Fe3O4 nanoparticles were washed twice with DI-
the separation and recovery of catalyst from aqueous media water and ethanol and subsequently dried at 80 °C (Kumar
(Alizadeh et al. 2019). On the other hand, grafting the metal/ et al. 2013b). Finally, ­Co3(PO4)2 solution (10%, w/v) was
metal oxides of Cd, Au, and Ag on the surface of semicon- slowly mingled with as-prepared g-C3N4/Fe3O4 nanoparti-
ductors can present a better photocatalytic efficiency under cles. The resulting mix was stirred for 24 h and then dried
light irradiation (Duan et al. 2016; Zhou et al. 2010). ­Co3O4, at 150 °C and washed three times with distilled water and
designated as a P-type semiconductor, has a unique electron ethanol (Zhou et al. 2010).
configuration which reduces the recombination of electrons/
holes enhancing the photocatalyst efficiency (He et al. 2018; Characterization
Zhou et al. 2010).
In the present work, g-C3N4/Fe3O4/Co nanocomposite In order to identify the morphological structure of the
was successfully synthesized by a simple hydrothermal synthesized nanocomposite, a number of analyses such as
method. The prepared photocatalyst was characterized by XRD, FTIR, SEM, EDS, VSM, and DRS were individu-
several analytical techniques such as EDS, SEM, XRD, ally employed. In brief, identification of the phase structure
UV–vis DRS, and FTIR. The synthesized nanocomposite was made by XRD analysis, while useful information about
25488 Environmental Science and Pollution Research (2022) 29:25486–25495

the chemical bonds of the nanocomposite was obtained by is observed which is in agreement with the file (JCPDS No.
FTIR and EDX spectrometers. The morphology and micro- 0867–10). In addition, the obtained results are in agreement
structure were examined by SEM instrument. Respective with the report by Zhu et al. (Zhu et al. 2019). It is note-
magnetic and optical properties of the prepared catalyst were worthy that the average crystal size for Co/g-C3N4/Fe3O4
evaluated by VSM and DRS techniques. nanocomposite was determined to be about 36 nm. Finally,
the results obtained in this study are consistent with those of
Analytical procedures the report by Wen-Da Oh et al. (Oh et al. 2018).

As-prepared Co/g-C3N4/Fe3O4 nanocomposite was applied FTIR analysis

as the catalyst for the degradation of MNZ under visible
light using a 300 W tungsten lamp at room temperature. A In order to learn useful information about the chemical
700-mL glass vessel containing 500 mL of aqueous sam- structure of Co/g-C3N4/Fe3O4 nanocomposite, FTIR analy-
ple of MNZ was used to conduct the experimental tests. sis was performed within the range of 400–4000 ­cm−1. Fig-
The impacts of various factors such as MNZ concentration ure 1b illustrates the spectra obtained for g-C3N4, g-C3N4/
(5–20 mg/L), catalyst dosage (0.2–1.0 g/L), pH (2–10), and Fe 3O 4 and Co/g-C 3N 4/Fe 3O 4, respectively. Within the
reaction time (0–80 min) on the efficiency MNZ degradation g-C3N4 spectrum, a sharp band indexed at 808 ­cm−1 corre-
were thoroughly evaluated and then the optimized conditions sponds to the vibrational bending of the triazine rings. The
were established. absorption peaks located in the range of 1200–1600 ­cm−1
The catalyst was collected using an external magnet from are most likely to refer to the stretching heterocyclic bands
solution, and the quantitative levels of degradation for MNZ of C-N/C = N. The peaks shown in 1241, 1318, 1425, and
were monitored and measured by a HPLC instrument (Cecil 1635 ­cm−1 are related to the C-N bonds of the aromatic ring.
4100, England) equipped with a UV–visible detector (CE The wide peak at 3100–3400 ­cm−1 can be attributed to the
4900) set at 318 nm. The mobile phase consisted of water/ vibration of N–H and O–H bonds which are probably associ-
acetonitrile (80:20%) running under a flow rate of 1.0 mL/ ated with the amine groups and adsorbed water molecules.
min. The removal percentage (R%) of MNZ was calculated
using the following equation: VSM analysis

C0 − Ct In a further related analysis, VSM was implemented to

Removal(%) = × 100
C0 determine the magnetic properties of the nanocomposite.
As depicted in Fig. 1c, due to the presence of ­Fe3O4 in the
where C0 and Ct are the respective initial and given-time nanocomposite structure, a favorable magnetic property was
concentrations of MNZ (mg/L). observed within the range of − 30 to 30 emu/g. This finding
is in agreement and consistent with the report by Kumar
et al. (Kumar et al. 2018) and Musavi et al. (Mousavi and
Results and discussion Habibi-Yangjeh 2018).

Characterization of photocatalyst SEM and EDS analysis

XRD analysis SEM analysis was used for the recognition of the morphol-
ogy of the synthesized catalyst (Co/g-C3N4/Fe3O4). SEM
XRD analysis was applied to determine both the phase mor- images of Co/g-C3N4/Fe3O4 are shown in Fig.  2a. The
phology and the crystalline structure of the nanocomposite. images confirm the irregular plane structure featuring the
Figure 1a represents the spectra in relation to the structure moderate aggregation of the particles with a relatively wide
of g-C3N4, g-C3N4/Fe3O4 and Co/g-C3N4/Fe3O4 nanocom- range of size (5–50 nm). Furthermore, the results of EDS
posites. g-C3N4 is indexed with the two peaks at 13.6 and analysis were used to identify the composition of the ele-
27.3°, which correspond to the planes of (100) and (002) and ments within the structure of Co/g-C3N4/Fe3O4 nanocom-
refer to the tri-S-triazine structure (JCPDS, 87–15-26). The posite. As shown in Fig. 2b, it was demonstrated that the
peaks shown at 35.5, 43.2, 57.3, and 62.62° are attributed synthesis of the studied nanocomposite catalyst was properly
to the crystalline structure of ­Fe3O4 which is in line with the accomplished.
0033–75 code. The peaks in the g-C3N4 /Fe3O4 spectrum According to the SEM findings, it was revealed that the
are related to the tetrahedral magnetic structures which are Co particles had a regular shape within the surface of the
consistent with the file (JCPDS No. 0629–10). Within the nanocomposite. In addition, the EDS analysis clearly shed
nanocomposite spectrum, the monophasic crystal structure light on the presence of the elements involved as well as their
Environmental Science and Pollution Research (2022) 29:25486–25495 25489

(b)
(a)

Transmittance %
Intensity

g-C3N4
g-C3N4/Fe3O4 g-C3N4
Co/g-C3N4/Fe3O4 g-C3N4/Fe3O4
Co/g-C3N4/Fe3O4

10 20 30 40 50 60 70 4000 3500 3000 2500 2000 1500 1000 500

Angel (2theta) Wavenumber (cm )-1

Fig. 1  a XRD patterns, b FTIR spectra, and c VSM magnetization curves of the as-prepared catalyst

ratios in the chemical structure of catalyst. The elements of the optical properties of the nanocomposite. According to
C, O, Fe, and Co were identified in the structure of the nano- the results shown in Fig. 2c, the maximum absorption band
composite with the percent ratios of 11.6, 61.6, 14.95, and was recorded within the range of UV light (300–350 nm),
11.77%, respectively. The results obtained are also consistent which is thought to be responsible for the excitation of the
with the results reported by Song et al. (2018). band gap of the nanocomposite. The absorption peak in the
UV range is most likely attributed to the conjugated π-π
DRS analysis electrons in the 1,3,5-triazine structure. This result is in line
with the report by Aziz Habibi-Yangjeh et al. (2019).
DRS analysis is founded on the basis of irradiation of light
to the surface of an unknown powder sample and the subse- Effect of key factors on MNZ degradation
quent measurement of the diffusion reflectance against that by Co/g‑C3N4/Fe3O4
of a standard sample. By measuring the reflectance, the opti-
cal properties of the sample can be evaluated. The results Effect of initial pH
of DRS analysis for g-C3N4, g-C3N4/Fe3O4 and Co/g-C3N4/
Fe3O4 are presented in Fig. 2c. It is clear-cut that pH plays a key role in the performance
Band gap energy in semiconductors plays a major role of a photocatalytic degradation process. Thus, the effect
in their photocatalytic activity. To test the capability of the of pH on the degradation efficiency of MNZ was examined
nanocomposite for the absorption of light radiation and for- within the range of 2–10, while other influential param-
mation of electron–hole pairs, the UV–vis DRS technique eters including MNZ concentration and the catalyst dosage
was implemented. DRS analysis was also used to determine were kept unchanged at the respective levels of 10 mg/L
25490 Environmental Science and Pollution Research (2022) 29:25486–25495

1.2
(c)

1.0

0.8
Absorbance

0.6

0.4
g-C3N4
0.2 g-C3N4/Fe3O4
Co/g-C3N4/Fe3O4

0.0
200 300 400 500 600 700

Wavelenght (nm)

Fig. 2  a SEM images, b EDS, and c UV–vis spectra of as-prepared catalyst

and 0.2 g/L (Fig. 3). As depicted in Fig. 3, the degrada- Effect of nanocomposite dosage
tion of MNZ at pH 2, 4, 6, 8, and 10 was determined to
be 46.2, 54.6, 65.1, 81.7, and 72.9%, respectively. As can The impact of various amounts of Co/g-C 3 N 4 /Fe 3 O 4
be deduced, by increasing the pH values up to 8, the level nanocomposite (catalyst) on the degradation efficiency of
of degradation for MNZ improved and afterward slowly MNZ was studied in the range of 0.2 to 1.0 g/L, while the
dropped. Therefore, the maximum photocatalytic effi- rest of conditions were kept unchanged (pH 8 and initial
ciency for MNZ was achieved at pH 8. MNZ concentration 10 mg/L) (Fig. 4). As can be easily
This may be explained by the fact that at this notable pH deducted, with an increase in the dosage of the catalyst
value, due to the presence of ­OH− ions, a higher genera- (from 0.2 to 0.7 g/L), the corresponding degradation effi-
tion of OH• is anticipated. It means that more ­OH− ions ciencies for MNZ improved, while a further rise in the
will be available on the catalyst surface resulting in higher level of catalyst dosage (from 0.7 to 1.0 g/L) led to a small
degradation efficiency for MNZ (Zangiabadi et al. 2020, drop in the degradation efficiency. This could be reasoned
2019). All in all, the optimum pH 8 was selected for the by the fact that by increasing the dosage of nanocomposite,
subsequent experiments. more and more accessible sites would be available for the
Environmental Science and Pollution Research (2022) 29:25486–25495 25491

Effect of initial concentration of MNZ

80

The effect of initial concentration of MNZ on the degrada-

tion process was examined within the range of 5–20 mg/L.
Degradation efficiency (%)

60
It is evident that the efficiency of degradation was remark-
ably reduced with an increase in the initial concentration of
MNZ (Fig. 5). As can be seen, the degradation efficiency of
40
MNZ sharply dropped from 98.3 to 73.4% by increasing the
concentration of MNZ from 5 to 20 mg/L applying the irra-
PH=2 diation time of 60 min. This is justified by the fact that with
20 PH=4
PH=6 the rise in the concentration of MNZ, the number of active
PH=8 sites of the nanocomposite occupied by MNZ molecules
PH=10 decreased, and as a result, a substantial fall in the photo-
0
0 20 40 60 80
catalytic activity is observed. Moreover, further intermediate
products are generated which consume the reactive species
Time (min)
in the process, leading to a fall in the efficiency of degrada-
tion (Ahmed et al. 2011; Jamila et al. 2020). In a report on
Fig. 3  The effect of initial pH on photodegradation of MNZ (0.2 g/L
the photocatalytic degradation of MNZ using ZnO/Fe2O3/
catalyst and MNZ concentration = 10 mg/L)
clinoptilolite, the degradation efficiency fell from 93 to 63%
as MNZ concentration was elevated from 1 to 100 mg/L
100 (Davari et al. 2021).

MNZ degradation under various systems

80
Degradation efficiency (%)

A number of control experiments were conducted to learn

60 more about the contribution of each individual component
involving in the photodegradation process. To do this, the
contribution level of each individual component in the degra-
40
dation of MNZ was determined. For this reason, five different
0.2 g/L components, namely lone visible light, visible light/g-C3N4,
0.5 g/L
20 0.7 g/L
visible light/g-C3N4/Fe3O4, visible light/Co/g-C3N4/Fe3O4,
1 g/L and lone Co/g-C3N4/Fe3O4, were implemented under the
optimal stablished conditions and the contact time of 60 min.
0
0 20 40 60 80
Time (min) 100

Fig. 4  The effect of the catalyst dosage on the efficiency of MNZ

Degradation efficiency (%)

80
degradation (pH = 8, MNZ concentration = 10 mg/L)

60
adsorption of MNZ molecules, leading to a higher rate of
degradation (Mohammadzadeh Kakhki and Ahsani 2020).
In contrast, a further rise in the amount of the catalyst 40
could trigger the events like agglomeration and turbidity, 5 mg/L
which prevent the light penetrating into the solution (Lau 10 mg/L
20 mg/L
and Augustine 2019). In a study by Bashiri et al. (Bashiri 20

et al. 2020), the nanocomposite of F

­ e3O4/rGO/TiO2 within
the range of 0.25 to 1.25 g/L was applied for the degrada- 0
tion of MNZ. They concluded that with an elevation of the 0 20 40 60 80
catalyst dosage from 0.25 to 0.75 g/L, the corresponding Time (min)
degradation efficiency increased.
Fig. 5  Effect of initial concentration of MNZ on the photocatalytic
degradation of MNZ (pH = 8 and Dosage = 0.7 g/L)
25492 Environmental Science and Pollution Research (2022) 29:25486–25495

As can be seen in Fig. S1, the degradation efficiency of MNZ observed in Fig. 6, the degradation efficiency of MNZ was
was ranked as follows: lone Co/g-C3N4/Fe3O4 (12.6%) and determined to be 98.3% in the absence of any scavengers,
lone visible light (23.4%), visible light/g-C3N4 (45.2%), vis- while the corresponding values were dropped to 41.35, 93.1,
ible light/g-C3N4/Fe3O4 (62.7%), and visible light/Co/g-C3N4/ and 87.3% once TB, AO, and BQ were used, respectively.
Fe3O4 (98.3%). The results obtained clearly demonstrate that Compared to h­ + and O ­ 2°−, the results confirm that OH° plays
the synergetic effect arising from the combination of visible a significant role in the current photodegradation process.
light irradiation and the nanocomposite highly facilitated the
degradation process (Ghodsi et al. 2020). Photocatalytic mechanism

Recovery and reusability of Co/g‑C3N4/Fe3O4 Generally, the application of UV/Vis irradiation can trig-
ger the activation of a nanocomposite catalyst to produce
The recyclability and sustainability of the catalyst is one of a number of active radicals (e.g., hydroxyl, superoxide),
the important factors in practical applications. Therefore, the which are the main responsible for improving the efficiency
recovery of Co/g-C3N4/Fe3O4 in the degradation of MNZ was of the degradation process. As a result of UV/Vis irradiation,
evaluated within five cycles under the optimum stablished the electrons are transferred from the valance band (VB) to
conditions (catalyst dosage = 0.7 g/L, pH = 8, MNZ concen- the conduction band (CB) of the catalyst-producing elec-
tration = 5 mg/L, and contact time = 60 min) (Fig. S2). Upon tron–hole ­(e−/h+) pairs. The photo-excited electrons in the
completion of each cycle, the catalyst was magnetically sepa- CB of the catalyst (− 1.3 eV, Vs. NHE) can be transferred
rated from the reaction solution, washed with proper amounts to the CB of the metal used (+ 0.8 eV, Vs. NHE) due to the
of DI-water and ethanol, and finally dried at 80 °C. Then, the reduction of the potential values (Wen et al. 2017; Zhang
degradation efficiency of MNZ was measured. As depicted in et al. 2016). The transferred electrons can be effectively
Fig. S2, a small level of reduction (5.7%) in the degradation stored within the Co metal, lowering the risk of (Wood et al.
efficiency for MNZ was observed after the fifth cycle com- 2001) ­e−/h+ recombination and facilitating the separation
pared to the first one. This result is clearly indicative of high of ­e−/h+ pairs in the catalyst. At this stage, the separated
stability of Co/g-C3N4/Fe3O4. It is noted that a good catalyst electrons can be captured by dissolved oxygen, which acts
recyclability using Z­ nFe2O4@methyl cellulose in the photo- as an electron receptor, leading to the production of super-
degradation of MNZ was also observed by Tamaddon et al. oxide ­(O2●) radicals. Co metal can be also stimulated by the
(2020).

Investigation of photocatalytic degradation kinetics 100

98.3
93.1
In order to properly describe a kinetic pattern for the degrada- 87.3
80
Degradation efficiency (%)

tion of MNZ, a set of experiments were considered and per-

formed under the optimum conditions established earlier on
(pH 8, MNZ concentration 5 mg/L, and nanocomposite dosage 60
0.7 g/L), and the results were tabulated in Table 1. According
to the results obtained, the degradation of MNZ fits best to the
pseudo-first-order model. 40 41.35

Effect of scavengers 20

In order to assess the impact of the role of scavengers in the

photodegradation process, three commonly used scavengers, 0
No scavenger TB AO BQ
namely tert-butanol (TB), ammonium oxalate (AO), and ben-
zoquinone (BQ), were employed acting as the respective scav-
Fig. 6  The photocatalytic activity of Co/g-C3N4/Fe3O4 in the pres-
engers of superoxide radicals (OH°), holes ­(h+), and hydroxyl ence of different scavengers (pH = 8, dosage = 0.7 g/L, MNZ concen-
radicals ­(O2°−) (Eswar et al. 2015; Liu et al. 2017). As can be tration = 5 mg/L, time = 60 min)

Table 1  Kinetic parameters Zero-order First-order Pseudo-first-order Second-order

obtained for the photocatalytic
2 2 2
degradation of MNZ k R k R k R k R2

0.0691 0.813 0.054 0.831 0.0102 0.992 0.0732 0.881

Environmental Science and Pollution Research (2022) 29:25486–25495 25493

effect of the local surface plasmon and stimulate the produc- ions, TDS (total dissolved solids), and organic compounds
tion of electrons leading to the production of ­O2● from the in the real samples, all of which could compete with MNZ to
dissolved oxygen molecules. Superoxide radicals ­(O2●) can react with the free radicals leading to a decrease in the effi-
degrade and decompose water to produce strong secondary ciency of degradation. All things considered, the Co/g-C3N4/
oxidizing radicals such as hydroxyl radicals (­ OH●) which Fe3O4/Vis system exhibited an appropriate efficiency in the
are stronger oxidizing agents than the superoxide radicals treatment of complicated real water samples. Therefore, the
­(O2●) (Yang et al. 2017; Zhang et al. 2017). In addition, system could be efficiently used for the degradation of MNZ
hydrogen peroxide ­(H2O2) can be generated by superoxide in various complicated water samples.
radicals ­(O2●), which subsequently reacts with the electrons
­(e−) and holes ­(h+) to produce hydroxyl radicals (­ OH●). As
discussed and confirmed earlier, the degradation of MNZ is Conclusions
under the control of hydroxyl radicals (­ OH●). This implies
that the ­OH● radicals are highly likely to attack and subse- In this study, the efficient degradation of metronidazole
quently degrade MNZ. (MNZ) from aqueous solutions using Co/g-C3N4/Fe3O4
nanocomposite under visible light irradiation was accom-
Performance of Co/g‑C3N4/Fe3O4/Vis system in real samples plished. The photocatalyst (Co/g-C3N4/Fe3O4) was initially
prepared by a simple hydrothermal method and then charac-
The applicability of the current photocatalyst system (Co/g- terized by several analytical techniques, namely EDS, SEM,
C3N4/Fe3O4/Vis) for the degradation of MNZ in four dif- XRD, UV–vis DRS, and FTIR. The best photocatalytic deg-
ferent real samples, namely surface runoff, tap water, raw radation efficiency (98.3%) for MNZ was achieved under
wastewater, and secondary sedimentation effluent, was the optimal conditions and irradiation time of 60 min. The
evaluated. The characteristics of the samples are listed results showed that the degradation efficiency of MNZ was
in Table  S1. All the samples underwent the optimum slightly decreased (5.7%) after five cycles of reuse. Further-
experimental conditions stablished (pH = 8, catalyst dos- more, the degradation of MNZ followed the pseudo-first-
age = 0.7  g/L, MNZ concentration = 5  mg/L, irradiation order kinetic model. Experiments regarding the scavengers
time = 60 min), and their corresponding degradation results showed that hydroxyl radicals (OH°) play a significant role
were illustrated in Fig. 7. As can be seen, the performance of in the degradation process. The current Co/g-C3N4/Fe3O4/
Co/g-C3N4/Fe3O4/Vis system (in terms of degradation effi- Vis system exhibited an excellent performance in the treat-
ciency) for DI-water, tap water, surface runoff, treated, and ment of several complicated water samples. Finally, accord-
raw wastewater was determined to be 98.3, 92.1, 85.5, 88.7, ing to the obtained results, it is concluded that Co/g-C3N4/
and 56.1%, respectively. The reduction in the MNZ degrada- Fe3O4 photocatalyst could be considered a promising and
tion efficiency can be due to the presence a wide variety of suitable catalyst in the photocatalytic degradation of MNZ
owing to easy recovery and high catalytic activity.
100
Supplementary Information  The online version contains supplemen-
.3

tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 11356-0​ 21-1​ 7077-2.
98

.1
92

.7
Degradation efficiency (%)

88

80
.5
85

Author contribution  Mojtaba Yeganeh: Investigation/writing original

draft, formal analysis methodology. Hamid Reza Sobhi: Conceptualiza-
60 tion, writing-reviewing and editing. Ali Esrafili: Visualization, writing
original draft/review and editing, supervision.
.1
56

40
Funding  The authors would like to gratefully appreciate the Iran Uni-
versity of Medical Sciences for the provision of financial supports
20 (Grant No. 99-3-61-20007).

Data availability  All data generated or analyzed during this study are
0
included in this published article.
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Declarations 
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Ethics approval  Not applicable.

Fig. 7  Performance and capability of Co/g-C3N4/Fe3O4/Vis sys-
tem for MNZ degradation in real samples under optimum condi- Consent to participate  Not applicable.
tions (pH = 8, dosage = 0.7  g/L, MNZ concentration = 5  mg/L,
time = 60 min) Consent for publication  Not applicable.
25494 Environmental Science and Pollution Research (2022) 29:25486–25495

Competing interests  The authors declare no competing interests. organisms: implications for environmental risk assessment. Water
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