Chemical Engineering Journal 417 (2021) 129225

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Peroxymonosulfate activation through LED-induced ZnFe2O4 for

levofloxacin degradation
Yiwen Zhong a, Kaimin Shih d, Zenghui Diao c, Gang Song a, Minhua Su a, Li’an Hou a,
Diyun Chen a, Lingjun Kong a, b, *
a
Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources, School of Environmental Science and Engineering, Guangzhou University,
Guangzhou, 510006, China
b
Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, School of Environmental Science and Engineering, Institute of Environmental Health
and Pollution Control, Guangdong University of Technology, Guangzhou, 510006, China
c
School of Environmental Science and Engineering, Zhongkai University of Agriculture and Engineering, Guangzhou 510225, China
d
Department of Civil Engineering, The University of Hong Kong, Pokfulam Road, Hong Kong, China

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

Keywords: Recently, a lot of attentions were paid on sulfate (SO-4∙) and hydroxyl (∙OH) radicals-based advanced oxidation
ZnFe2O4 processes in degradation of fluoroquinolone antibiotic due to their favorable oxidation potential. This work
Peroxymonosulfate reported an integrated peroxymonosulfate (PMS) activation process by coupling ZnFe2O4 (ZFO) with energy-
Levofloxacin
saving LED for degradation and defluorination of levofloxacin (LEV). The LEV degradation efficiency reached
LED
88.52 % within 180 min in the ZFO-500/LED/PMS system, which was higher than those of other activation
systems. Both SO-4∙ and ∙OH were generated in the integrated ZFO-500/LED/PMS system by the photo-generated
electrons and holes activation of PMS under the LED irradiation. The recombination of photo-generated electrons
and holes was reduced. Plenty of ∙O–2 and 1O2 were produced contributing to LEV degradation. The possible
degradation pathways and mechanisms were proposed. This study presented a promising LED-assisted PMS
activation process by ZnFe2O4 for antibiotic degradation.

1. Introduction
With the rapid development of the pharmaceutical industry and the
increasing drug consumption, pharmaceutical and personal care prod­
ucts are inevitably discharged into the water environment. The toxicity,
carcinogenicity, teratogenicity and mutagenicity of ibuprofen, diclofe­
nac, sulfadiazine, ampicillin and norfloxacin seriously threaten the
ecosystem and human beings [1]. What’s more, fluoroquinnlones (FQs)
are a large class of antibiotics, what are widely used in human and
veterinary medical practices. In recent years, FQs have become a new
type of widely concerned organic pollutants due to their large use and
high detection frequency [2]. The high electronegativity and small size
of fluorine make the C-F bond one of the strongest covalent bonds in
nature [3], which is difficult to be broken, so it always exists in the form
of fluorine-containing organic matter in the environment. It has been
reported that perfluorooctane sulfonyl compounds, as a fluorine-
containing organic compound, can cause bladder cancer and regenera­
tive lesions [4]. The FQs, as one kind of fluorinated organics, can cause
cell damage [5] and various diseases once the exhaust FQs are inevitably
discharged into the aqueous environment [6]. Therefore, it is an urgent
need to eliminate FQs from wastewater to degrade the FQs into small
molecule organics and break the C-F bond of organics, so that fluorine
existed as inorganic matter in water.
Unfortunately, the FQs are not easily eliminated by the traditional
biological process due to its refractory property, causing bio­
accumulation in long-term and toxicity in the environment. For the time
being, the research on defluorination is mainly focused on PFAS. Ion-
exchange can be combined with electrochemical, plasma, sonolysis, or
hydrothermal processes have been applied to the treatment of fluorine-
containing organic compounds [3]. It has been proposed that sulfurized
nanoscale zero-valent iron can defluorinated from florfenicol under
environmental conditions, but its defluorination efficiency is limited due
to its dependence on chlorine in the molecule [7]. In recent years,
advanced oxidation processes (AOPs) have shown favorable ability to
degrade refractory organic pollutants in wastewater due to their high
oxidation potential [8–11]. Hydroxyl radical (⋅OH) and sulfate radical

* Corresponding author.
E-mail address: kongljun@gzhu.edu.cn (L. Kong).

https://doi.org/10.1016/j.cej.2021.129225
Received 7 January 2021; Received in revised form 24 February 2021; Accepted 27 February 2021
Available online 4 March 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
Y. Zhong et al.
(SO-4⋅) with high oxidation potential are widely concerned, which can be
generated from chemical oxidants (O3, H2O2, KMnO4, persulfate salts,
etc) in AOPs. Especially, SO-4⋅ has a long life, a wide pH range, high
oxidation potential (E0 = 2.5–3.1 V) [12] and high selectivity to degrade
organic pollutants. The SO-4⋅ could be generated through activation of
peroxydisulfate (PDS) and peroxymonosulfate (PMS) by heat, photo,
alkali, ultrasonic and suitable transition metal ions (Fe2+, Co2+, Ni2+).
Compared with monometallic catalysts, bimetallic catalysts show better
performance in catalytic reactions of the environment, and have good
application prospects, which has aroused great interest in recent years.
In addition, active metals can not only provide new active sites, but also
promote the catalysis by the interaction between the two metal com­
ponents [13]. Among them, transition metal activation has attracted a
great quantity of attention due to that the transition metals have a
valence electron layer structure of (n-1) d1-10ns1-2. Their centers have
both d orbits and empty d orbits, which are both electrophilic and
nucleophilic. Spinel-structured catalysts such as spinel-type ferrite
MFe2O4 have excellent physical, chemical stability. The spinel-type
ferrites MFe2O4 (M = Ni, Co, Zn) have been widely investigated on
persulfate activation and photocatalysis to degrade organic pollutants in
water.
Photocatalysis is also a common advanced oxidation technique for
degradation of FQs by generating ⋅OH. Many oxide semiconductors,
such as TiO2, BiOCl、Bi2O3 and ZnO [14–17], have been proven as
effective photocatalysts due to their excellent photonasty, high photo­
catalytic activity, strong chemical stability, low cost and non-toxicity.
Among them, the spinel-type ferrites MFe2O4 (M = Ni, Co, Zn) have a
band gap of less than 2.0 eV, which has excellent visible light response,
stable chemical properties, favorable recyclability and corrosion resis­
tance. Specifically, the spinel ferrite of ZnFe2O4 (ZFO), a p-type photo­
catalyst with a narrow band gap of 1.9 eV provides additional catalytic
activity by virtue of its lattice structure and band gap. Thereby it can
improve the photodegradation efficiency significantly, in which the ul­
traviolet and Xe lights were used, resulting in the main consumption of
energy in the photocatalytic oxidation process [18].
To the best of our knowledge, photo-generated electron and hole
played important role in the photocatalytic process [19]. The recombi­
nation of photo-generated electrons with holes determined the photo-
catalytic activity. It is reported that photocatalytic degradation of lev­
ofloxacin (LEV) by ZnFe2O4 is only 11.82% due to the photo charge
carrier recombination [20]. Combination of CoFe2O4 and ZnO
(CoFe2O4/ZnO) nano-photocatalyst in the presence of PMS was reported
to enhance mineralization efficiency of Direct Blue 71 dye [21]. Acti­
vation of PMS by nitrogen-doped graphene/TiO2 or a hollow sphere of
CuWO4 under Visible light for organic pollutants were reported [22,23].
The photo-generated electron contributed to PMS activation, in which
the PMS was served as the electron-acceptor. It is not hard to be spec­
ulated that the PMS as electron-acceptor could suppress the recombi­
nation of photo-generated electrons and holes. These results inspired us
investigating the ZFO photocatalytic activation of PMS. LED irradiation
was reported for ofloxacin and ciprofloxacin photocatalytic degradation
[24], in which the LED was known as the energy-saving light source
[25], using LED lamp instead of UV lamp or xenon lamp can effectively
reduce energy consumption. Thus, it will be environment friendly and
promising to investigate the ZFO induced LED photocatalytic generation
of electron and hole for PMS activation in organic pollutants
degradation.
In this study, a novel integrated LED-assisted PMS activation system
was constructed for LEV degradation in the presence of both LED light
and PMS, in which the LEV is one of the FQs being discharged a large
amount in Pharmaceuticals in China [26]. Little attention was paid on
the degradation and defluorination of LEV by the photocatalytic PMS
activation system. It is hypothesized that the photo-generated electrons
favored the PMS activation and the PMS as electron-acceptor suppress
the recombination of photo-generated electrons and holes. This work
aims to investigate the coupling effect of photo-generated electrons
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Chemical Engineering Journal 417 (2021) 129225
assisted PMS activation by ZFO and PMS inhibited recombination of
electron and hole for LEV degradation. The LEV degradation and
defluorination efficiencies in the integrated LED-assisted PMS activation
system was investigated to understand the degradation pathway of
Levofloxacin, which is important for further understanding and evalu­
ating the toxicity of the byproducts due to the high toxicity of the
halogen containing organics in small molecule.
2. Materials and methods
2.1. Materials
Zinc acetate dihydrate (Zn (CH3COO)2⋅2H2O, >99.0% purity,
FuChen chemical), Iron nitrate nonahydrate (Fe (NO3)3⋅9H2O, 98.5%
purity, Macklin chemical), Citric acid monohydrate (C6H8O7⋅H2O, ≥
99.6% purity, Sigma-Aldrich), Levofloxacin (LEV, > 98.0% purity,
Aladdin chemical), Potassium monopersulfate triple salt (≥47% KHSO5,
Sigma-Aldrich). All the chemicals and solvents were used as received
without any further purification. Notably, deionized water was used
throughout the whole test.
2.2. Synthesis of ZFO
The catalysts were synthesized using a sol–gel method. The precursor
solution was prepared by adding Zn (CH3COO)2⋅2H2O, Fe (NO3)3⋅9H2O
and C6H8O7⋅H2O to 120 mL of deionized water at a molar ratio of 1:2:3.
The pH of the solution was adjusted to 7 with ammonia water and mixed
under magnetic stirring at 80 ℃ for 4 h to obtain a sol–gel solution. The
gel was then placed in a drying cabinet and dried at 125 ℃ for 12 h. The
dry gel was put into a muffle furnace and heated to 200 ℃ for 2 h. After
grinding, it was calcined at 500 ℃ for 2 h at a rate of 5 ℃/min. Then
obtained material was named ZFO-500. The other samples were pre­
pared according to the above method with different calcination tem­
perature are 300 ℃, 400 ℃, 600 ℃, 700 ℃, named ZFO-300, ZFO-400,
ZFO-600, ZFO-700 respectively. The preparation method is shown in the
Fig. S1.
2.3. Characterization and analytical process
The X-ray powder diffraction (XRD) pattern of the catalysts was
recorded on PW3040/60 diffractometer (PANalytical, Holland) with 2θ
ranging from 5 to 80◦ and scanning speed of 27.54 s per step by using Cu
Kα radiation (λ = 1.5406 Å, accelerating voltage = 40 kV, current = 40
mA). A field emission scanning electron microscope (FESEM, Gem­
inisem500, Germany) was used to determine the surface morphology
and the particle size on the surface. The optical properties were char­
acterized by UV–Vis diffuse reflectance spectra (Lambda 750 S, Perki­
nElmer, America) ranged from 200 to 800 nm, where BaSO4 was used as
the reflectance standard. The chemical species of Zn and Fe at the sur­
face of fresh and used catalysts were detected using an X-ray photo­
electron spectroscopy (XPS, Thermo fisher Scientific K-Alpha, America).
The particle size distribution has been detected by the particle size
analyzer (Brookhaven NanoBrook 90Plus PALS, America). Electron
Paramagnetic Resonance (EPR) spectra was determined using an EPR
spectrometer (Bruker A300, Germany).
2.4. LEV degradation experiments
Batch photocatalytic experiments were performed by Multi-channel
photochemical reaction system (PCX-50B, Beijing Perfectlight, China)
using a 5 W LED lamp (white light, wavelength range from 320 nm to
780 nm) at room temperature. Firstly, 0.0500 g of catalyst was dispersed
into 50 mL of LEV solution in a concentration of 10 mg⋅L-1 under dark
condition, furthering being stirred for 30 min to achieve adsorp­
tion–desorption equilibrium. After that, 1.0 mM of PMS was added to
the reactor to initiate the reaction under LED illumination. 3 mL of
Y. Zhong et al. Chemical Engineering Journal 417 (2021) 129225

supernatant was quickly extracted from the reactor at each determined
time interval, being filtrated through a 0.45 μm membrane. The residual
concentration of LEV in the filtrate was determined immediately using a
UV–Vis spectrophotometer (UV-2550, Shimadzu, Japan) at 287 nm, and
using an Ion Specific (A214-9609BNWP, Thermo Scientific, America) to
detect the concentration of fluoride ions. In addition, the effects of other
parameters on LEV degradation were also investigated following the
above process. Free-radical scavenging reagents were added in the LEV
degradation experiments to identify the free-radical species and the
degradation mechanism of LEV. Four continuous cycles were carried out
to determine the stability and reusability of catalyst. After each cycle,
the catalyst was thoroughly washed and dried with water, and then
immersed again in the same volume (50 mL) of fresh LEV solution (10
mg/L). The degradation intermediates of LEV were determined by a
triple quadrupole LC-MS instrument (Agilent 1260–6460, America) to
investigate the LEV degradation path way. A flame atomic absorption
spectrometer (FAAS, iCE3500 AA System, Thermo Scientific, America)
was used to determine the dissolved concentration of metal ions during
the degradation process. All degradation tests were repeated three
times.
3. Results and discussion
3.1. Characterization
calcination temperature. However, it can be seen that the XRD patterns
of ZFO calcined at 400–700 ℃ exhibit six clear distinctive peaks at 2θ
values of 29.9◦ , 35.2◦ , 42.8◦ , 53.2◦ , 56.6◦ and 62.2◦ corresponding to
(2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), (4 4 0) planes of ZFO (JCPDS
#22–1012), respectively, which confirmed the formation of a complete
cubic crystal structure. According to the XRD patterns, the crystallinity
of the material at each calcination temperature was calculated as shown
in the Table.1. It can be seen that the higher the temperature is, the
higher the crystallinity is. The size of crystallite catalyst recorded in
Table.1 was calculated by the Scherrer’s Eq. (1).
Kλ
D= (1)
BCOSθ
Where D is the crystallite size, λ is the X-ray wavelength, B is the full
width at half the maximum (FWHM) and θ is in accordance with peak
position, K = 0.9 (Scherrer constant).
The optical properties of the as-synthesized photocatalysts were
examined by UV-Vis DRS as shown in the inset of Fig. 1b and Fig. S2.
Table 1
Effective diameter of particle, crystallite size and crystallinity of materials
calcined at different temperatures.
Catalysts Effective Diameter (nm) Crystallite size D (nm) Crystallinity

ZFO-400 227.48 12.05 23.8%

X-ray diffraction pattern of the synthesized samples are shown in ZFO-500 421.64 17.60 24.52%
Fig. 1a. It can be seen that the material calcined at 300 ℃ has no obvious ZFO-600 746.20 22.91 29.7%
characteristic peak, which proves that ZFO can’t be formed at this ZFO-700 903.41 31.47 35.21%

Fig. 1. (a) X-ray diffraction patterns of the resulted catalysts; (b) UV–Vis diffuse reflectance spectrum (inset) and calculated band gap of the prepared ZFO-500; (c)
and (d) Scanning electron microscopy image of ZFO-500.

3
Y. Zhong et al.
ZFO-500 exhibits a broad absorption from UV to visible light [27]. It can
be observed that the absorption edge of ZFO-500 located at the visible
region of about 649 nm. Fig. 1b. illustrates Tauc plot for ZFO-500
catalyst. The band gap energy of ZFO-500 being calculated from equa­
tion Eq. (2) [28] is estimated to be 1.91 eV. In addition, the band gap
energies of ZFO-400, ZFO-600 and ZFO-700 are 1.83 eV, 1.88 eV and
1.93 eV, respectively, indicating that the ZFO could be activated by
visible light. Fig. 1c and Fig. 1d show the morphologies of the ZFO-500.
The bare ZFO-500 was presented as spherical particles. It could be
clearly seen that the average size of these sphere-like nanoparticles was
approximate to be 10–50 nm, which is similar to the calculated crys­
tallite size from XRD analysis.
( )
(αhv)1/n = A hv − Eg (2)
Where α is the absorbance index, h is the Planck constant, ν is the fre­
quency, n = 1/2 [29] , A is the constant and Eg is the Semiconductor
band gap.
X-ray photoelectron spectroscopy (XPS) was used to detect the
change of element chemical state of ZFO-500 before and after reaction,
as shown in Fig. 2 and Fig. S3. The presence of Zn, Fe, O can be clearly
observed, and C 1 s located at 284.8 eV was used for calibration. As
shown in Fig. 2b, the peaks of 1021.31 eV and 1044.32 eV are mainly
due to the binding energy of Zn 2p, indicating the high spin Zn2+ state
[30]. According to the literatures [31,32], four peaks at binding energies
of 710.6 eV (Fe 2p3/2), 712.43 eV (Fe 2p3/2), 719.44 eV (satellite peak)
and 725.02 eV (Fe 2p1/2) in the Fe 2p spectrum of fresh ZFO-500
catalyst (Fig. 2c) confirmed the presence of Fe (III), which contributed
to activate PMS as shown in Eq. (16). Fig. 2d is the energy spectrum of O
1 s measured by XPS. The peak of O 1 s at 529.98 eV and 531.44 eV
corresponds to the lattice oxygen (O*) and the surface adsorbed hy­
droxyl groups, respectively [33].
Fig. 2. XPS spectra for survey (a), Zn 2p (b), Fe 2p (c), and O 1 s (d) of fresh ZFO-500.
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Chemical Engineering Journal 417 (2021) 129225
3.2. LEV degradation in different system
The catalytic performance of the photo-assisted PMS activation sys­
tem was investigated by LEV degradation efficiencies in aqueous solu­
tion as shown in Fig. 3a, in which degradation of LEV by PMS activated
by ZFO coupled LED calcined at different temperatures was compared.
With the increment of calcination temperature, the degradation effi­
ciency decreased, which may be due to the increased particle size,
average crystallite size and crystallinity, as shown in Table 1 and
Fig. S4., resulting in the dwindle of catalytic activity. Crystallinity is
used to represent the proportion of crystalline regions in a polymer.
From Fig. 3b, the degradation efficiencies of LEV in ZFO-500/PMS, ZFO-
500/LED, ZFO-500/LED/PMS, LED/PMS systems were comparatively
presented. For LED/PMS system in the absence of catalyst, LEV was
hardly degraded since that PMS was difficult to be activated by LED light
alone [34,35]. Considering the ZFO-500/LED system, LEV degradation
efficiency of 19.26% was observed. Although the ZFO-500 was reported
for photocatalytic degradation of Methyl orange (MO) in the presence of
Xe light, the generation of hydroxyl radical contributed to MO degra­
dation [36]. The LED light is not powerful enough (5 W) to generate
efficient free radical such as ∙OH, leading to unfavorable ability to
degradation of LEV. Interestingly, LEV degradation efficiency of 45.26%
was observed in the ZFO-500/PMS system, indicating that PMS could be
activated by ZFO-500 to generate sulfate radical for LEV degradation
[37]. However, the LEV degradation efficiency in this system is unfa­
vorable. LEV degradation efficiency of 88.52% was observed in the ZFO-
500/LED/PMS, which is higher than the LEV degradation efficiencies in
the ZFO-500/PMS and ZFO-500/LED systems. Importantly, it is also
higher than the sum efficiencies of the ZFO-500/PMS and ZFO-500/LED
systems, indicating that coupling LED with ZFO-500 had a synergetic
effect on PMS activation for LEV degradation. LEV degradation kinetics
in all systems were evaluated by pseudo-first-order, the calculated
Y. Zhong et al.
Fig. 3. Effect of calcination temperature on the degradation of LEV (a) and kinetic rate constants(c); LEV degradation efficiencies (b) and kinetic rate constants (d)
under various systems (LED power: 5 W; ILED = 1.0 A; C0 (LEV): 10 mg/L; CPMS: 1 mM; dosage: 1 g/L).
kinetic rate constants were shown in Fig. 3b. Obviously, the kinetic rate
constant in ZFO-500/LED/PMS system was the highest of 0.024 min− 1
among the test systems, further confirming the synergetic effect of ZFO-
500 and LED on PMS activation. It was reported that SO-4⋅ and ⋅OH were
observed in the PMS activation system, while the ⋅OH was observed in
the photocatalytic system [38]. Then SO-4⋅ and ⋅OH may be generated in
the ZFO-500/LED/PMS system contributing to LEV degradation.
3.3. Optimization of catalytic performance
To further confirm the generation of free radical in the ZFO-500/
LED/PMS for LEV degradation, effect of catalyst dosage on LEV degra­
dation was showed in Fig. S5a. The degradation efficiencies of LEV in a
dosage of 0.1, 0.5, 1.0 and 1.5 g/L were 74.8%, 82.8%, 88.3% and
92.8%, respectively. Simultaneously, the calculated degradation kinetic
rate was augmented as the increase in the catalyst dosage as shown in
Fig. S6a. This result can be explained by the amplification of the number
of active sites as the increase in the dosage from 0.1 g/L to 1.5 g/L which
enhanced the photocatalytic activity for PMS activation.
Generally, pH value significantly affects the activities of photo­
catalytic and PMS activation. The alkaline solution is conducive to the
photocatalytic generation of OH as shown in Eq. (3) [39]. Effect of pH
value on LEV degradation efficiency was investigated in Fig. S5b and
Fig. S6b. Intriguingly, LEV degradation efficiencies under a wide pH
value range were similar, the difference among the LEV degradation
kinetic rate constants were not significant, suggesting that ZFO-500/
LED/PMS system had a wide pH range of PMS activation for LEV
degradation. The results indicated the advantage of ZFO-500/LED/PMS
that can be suitable in a wide pH range.
OH − + h+ →∙OH
Effect of PMS dosage on LEV degradation efficiency and rate constant
was evaluated in Fig. S5c and Fig. S6c. The results demonstrated that the
degradation efficiencies and rates accrued with the augment of PMS
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Chemical Engineering Journal 417 (2021) 129225
dose from 0.1 mM to 1 mM, and then tend to saturation, even to decrease
as the further increase in the PMS concentration to 1.5 mM. The optimal
dose of PMS concentration is 1.0 mM in this work. The added degra­
dation efficiency of LEV resulted from producing quantities of free
radicals such as SO-4∙ and ∙OH to accelerate the oxidation of pollutants.
Considering the further increases in the PMS dosage, the LEV degrada­
tion efficiency and kinetic rate constant were dwindled [40]. It is widely
reported that side reactions might occur for surfeit of PMS as shown in
Eqs. (4–6). SO-4∙/∙OH consumption was reported due to overdose PMS,
which is not favorable for LEV degradation. Thus, excessive PMS dosage
led to the oxidant species consumption. The LEV degradation kinetic
constant was consistent with the change of the LEV degradation effi­
ciency. Obviously, the consumption of SO-4∙/∙OH in the system was
significant once the PMS is 1.5 mM. The PMS dosage of 1.0 mM was used
in the following work.
SO−4 ∙ + SO−4 ∙→S2 O8 2− (4)
SO−4 ∙ + S2 O8 2− →S2 O8 − ∙ + SO2−4 (5)
SO−4 ∙/∙OH + HSO−5 →SO−5 ∙ + SO2−4 + H + + OH − (6)
LED photocurrent plays an important role in the light intensity, effect
of LED photocurrent on LEV degradation efficiency and degradation
kinetic rate constant was investigated in Fig. S5d and Fig. S6d. It can be
seen that the enlarge in LED photocurrent causes a significant rise in the
efficiency and rate of LEV degradation. LEV degradation efficiency and
rate constant raised from 83.8% to 88.4% and 0.012 min− 1 to 0.023
min− 1, respectively as the LED photocurrent ascended from 0.3 A to 1.0
A. According to Eq. (7), the increment of degradation efficiency and rate
constant may be attributed to the rise of photocurrent and power, which
enhances the generation of photo generated carriers, and the generation
of photo generated electron hole pairs is more conducive to the degra­
dation of levofloxacin. The photocurrent of 1.0 A is selected as the
optimal LED photocurrent in the subsequent experiments.
Y. Zhong et al. Chemical Engineering Journal 417 (2021) 129225

αP0
G(y) = exp(− αy)
Ahν
Where, y is the thickness of the semiconductor, G(y) is the generation
rate of photogenerated electron-hole pairs, α is the light absorption
coefficient, P0 is the intensity of incident light at the surface (y = 0) of
the semiconductor, A is the cross-sectional area of incident light, and hν
is the photon energy.
Fluorination ion is one of the halogen elements, the fluorination
containing intermediate product may be toxic after LEV degradation. It
is significant to investigate defluorination during the LEV degradation
process. Fig. S7 presented the defluorination efficiency at ZFO-500/
LED/PMS system under various catalyst dosages, photocurrent, pH
medium and PMS concentration. Obviously, defluorination efficiencies
increased as the increment of the catalyst dosage and photocurrent. It
may be due to the augment of oxidation capacity in ZFO-500/LED/PMS
system. Thus, the C-F bond could be attacked by the generated SO-4∙ and
∙OH radicals. It is consistent with the aforementioned LEV degradation
efficiency and rate constant. While defluorination under various pH
value is also similar to the degradation efficiency, suggesting that
degradation LEV and defluorination in the ZFO-500/LED/PMS system
are both ascribed to the radical-based degradation.
degradation. Besides, the LEV degradation rate was inhibited in the
(7)
presence of CO2− -
3 and H2PO4 while the degradation rates were similar in
the presence of CH3COO and Cl− . The results confirm the inhibition
−
effect of CO2− -
3 and H2PO4 on LEV degradation in the ZFO-500/LED/PMS
system. Although the CO–3∙ could be generated during PMS activation,
its oxidation potential is lower than that of SO-4∙, leading to the fact that
oxidation of LEV by CO–3∙ is almost negligible. The consumption of PMS
by CO–3∙ resulted in low LEV degradation efficiency. The similar results
were also observed in the presence of H2PO-4, resulting in a decreased
LEV degradation efficiency. It is well known that effects of inorganic
ions on the photocatalytic reactions may occur by (1) changing the ionic
strength of reaction medium and (2) inhibiting the catalytic activity of
the photocatalyst [41]. In this study, the inhibition of LEV degradation
in the presence of H2PO-4 and CO2− 3 can be ascribed to the completed
consumption of sulfate free radicals. It can be explained by Eqs. (8–14),
confirming that SO-4∙ played an important role in LEV degradation.
SO−4 ∙ + Cl− →SO2−4 + Cl∙ (8)
Cl∙ + Cl− →Cl−2 ∙ (9)
Cl−2 ∙ + Cl−2 ∙→Cl2 + 2Cl− (10)

SO−4 ∙ + CH 3 COO− →SO2−4 + CH 3 COO∙ (11)

3.4. Identification of dominant reactive species
SO−4 ∙ + CO2−3 →SO2−4 + CO−3 ∙ (12)
The effect of anions such as Cl-, CO2– -
3 , CH3COO and H2PO4 on LEV
–

degradation efficiency in ZFO-500/LED/PMS system was presented in SO−4 ∙ + H2 PO−4 →SO2−4 + H2 PO4 ∙ (13)
Fig. 4 since these salts are usually founded in real wastewater. These
anions may react with sulfate, further affecting the generation of radi­ H2 PO4 ∙→2H + + PO2−4 ∙ (14)
cals to degrade pollutants. As shown in Fig. 4a, the LEV degradation
efficiency follows the order of Blank ≈ CH3COO– ≈ Cl- > CO2−
3 > H2PO4,
-

suggesting that the presence of CH3COO− and Cl− could not inhibit the
LEV degradation while CO2− -
3 and H2PO4 significantly inhibited the LEV

Fig. 4. Inhibiting effect of anions on LEV degradation (a) efficiencies and (b) kinetic rate constants; (c) Inhibiting effect of scavengers on LEV degradation in the ZFO-
500/LED/PMS system. (d) A comparison of LEV degradation efficiencies in different systems.

6
Y. Zhong et al.
3.5. Reaction mechanism
In order to understand the reaction mechanism in-depth, a series of
radical capture experiments was conducted for identifying and con­
firming the dominant active species (Fig. 4(c-d)). Five commonly used
scavengers, ethanol (EtOH), Fe3+, Sodium oxalate (SO), iso-Propyl
alcohol (IPA), L-carnosine ((L-car), and L-Histidine (L-His)[42], were
used in this study as the scavengers of SO-4∙, e-, h+, ∙OH, ∙O–2 and 1O2,
respectively. Obviously, the scavengers greatly affected the LEV degra­
dation. EtOH can significantly react with SO-4∙ and ∙OH [43], while IPA
is an effective scavenger for ∙OH [44]. Both SO-4∙ and ∙OH played sig­
nificant role in LEV degradation due to the decrease in the LEV degra­
dation efficiency in the presence of EtOH and IPA as shown in Fig. 4c.
After the introduction of L-car, the conversion of O2 to ∙O–2 was limited,
as shown in Eq. (26), which reduces the degradation efficiency of LEV.
However, since ∙O–2 can produce 1O2 by reacting with H2O or ∙OH as
shown in Eqs. (27, 30), the effects of ∙O–2 and 1O2 on LEV degradation
were greatly limited. Besides, SO as a h+ scavenger greatly influenced
the LEV degradation efficiency because the h+ could active the HSO-5 for
generation of SO-5∙. The SO-5∙ could be converted into SO-4∙ and 1O2,
which greatly contributed to LEV degradation. It was reported that the
1
O2 could be generated by the presence of e-(CB) [45] and lattice oxygen
of CuFe2O4 as shown in Eq. (15) [46]. After observing the XPS of the
ZFO-500 before and after the reaction, as shown in Fig. 2 and Fig. S3.,
the lattice oxygen peak area at 530 eV decreased from 71.77 to 68.11%.
CuBi2O4 played photocatalytic activity in separation of e-(CB) [45] and
h+, resulting in the generation of ∙OH, SO-4∙ and 1O2. As shown in Fig. 1
(b), ZFO-500 exhibits an obvious absorption from UV to visible light.
The band gap is 1.91 eV. LED irradiation at a power of 5 W in the
presence of ZFO-500 could generate e-(CB) [45] and h+, which favors
PMS activation for generating ∙OH, SO-4∙ and 1O2 as shown in Eqs.
(19–21,29). Explicitly, 1O2 may mainly contributed to LEV degradation
in ZFO-500/LED/PMS system since the LEV degradation efficiency was
greatly decreased due to the presence of L-Histidine. Interestingly, LEV
degradation efficiency and kinetic rate were increased in the presence of
Fe3+, it may be due to that Fe3+ could capture e- to be converted into
Fig. 5. EPR spectra obtained from different systems in the presence of DMPO and TEMP.
7
Chemical Engineering Journal 417 (2021) 129225
Fe2+. The results were confirmed by the photo-Fenton reaction
comparing the LEV degradation efficiencies in ZFO-500/LED/H2O2 and
ZFO-500/Fe3+/LED/H2O2 systems as shown in Fig. 4d. Besides, capture
of e-(CB) [45] reduces the recombination of e- and h+. Thus, LED irra­
diation could assist the ZFO-500 for PMS activation to generate 1O2,
contributing to LEV degradation. Besides, the ∙OH and SO-4∙ species
played a secondary role in removing LEV.
To confirm the generation of ∙OH, SO-4∙, 1O2 and ∙O–2, EPR tests were
further carried out and shown in Fig. 5. Importantly, a strong charac­
teristic triplet signal [47] of TEMP-1O2 was observed (Fig. 5a), which
further confirmed the presence of 1O2 in the ZFO-500/LED/PMS system.
In addition, the EPR test confirmed the existence of h+ and ∙O–2 (Fig. 5b-
c). The EPR spectra of the 1:2:2:1 peak signal was obtained as shown in
Fig. 5d, which is the typical signal for DMPO-∙OH. Meanwhile, some
weak signals surrounding these four peaks could be assigned to DMPO-
SO-4∙[45]. The above results were consistent with the species quenching
experiments, suggesting that ZFO-500 can effectively activate PMS to
generate 1O2, ∙O–2, ∙OH and SO-4∙ under LED irradiation. Thus, LEV was
degraded into secondary products such as CO2 and H2O by the syner­
gistic multiple active species of ∙O–2, SO-4∙, ∙OH and 1O2. The mecha­
nism of LED-assisted PMS activation on ZFO-500 for defluorination and
degradation of Levofloxacin is summarized as follows Eqs. (15–31):
O* + HSO−5 →HSO−4 +1 O2 (15)
≡ Fe(III) + HSO−5 → ≡ Fe(II) + SO−5 ∙ + OH − (16)
≡ Fe(II) + HSO−5 → ≡ Fe(III) + SO−4 ∙ + OH − (17)
ZnFe2 O4 + hv→ZnFe2 O4 (e−CB + h+ (18)
VB )
HSO−5 + e−CB →SO−4 ⋅ + OH − (19)
HSO−5 + h+ − +
(20)
VB →SO5 ⋅ + H
HSO−5 + SO−5 ⋅ + e−CB →HSO−4 + SO2−4 +1 O2 (21)
Y. Zhong et al. Chemical Engineering Journal 417 (2021) 129225

2SO−5 ⋅→2SO−4 ⋅ + O2 (22) [50], (F) carboxylation/de-carboxylation. P1 [51] was formed through
hydroxylation of the single bond CH3 on the piperazine bond. P2-P3[52]
SO−5 ⋅ + H2 O→1.51 O2 + HSO−4 (23) were obtained by breaking piperazine bond, decarboxylation and
defluorination from P1. Under the attack of the active substance pro­
SO−4 ⋅ + OH − →SO2−4 + HSO−5 + ⋅OH (24) duced [53], piperazine cleavage side chain can be oxidized to generate
P4. The pathway III was started by the decarboxylation step, resulting in
SO−4 ⋅ + H2 O→SO2−4 + ⋅OH + H + (25) the production of P5[53]. Subsequently, the product P6-P10[52,54–56]
were obtained by demethylation, breaking the piperazine bond and
O2 + e− →⋅O−2 (26) replacement of F by ∙OH groups due to the attack of hydroxyl radical.
The LEV matrix is hydroxylated and carboxylated through the attack of
2H2 O + ⋅O−2 →1 O2 + 2OH − + H2 O2 (27) non-selective hydroxyl and superoxide radicals to obtain P11-P12. P13-
P15[55,56] were formed by the parent LEV through defluorination,
H2 O + h+ +
VB →H + ⋅OH (28) piperazine bond cleavage and demethylation on the morpholine ring.
Finally, all the generated intermediates would be degraded to smaller
HSO−5 + e−CB →⋅OH + SO2−4 (29) molecule compounds: such as H2O, CO2, inorganic ions and other in­
termediates of incomplete degradation [54].
⋅OH + ⋅O−2 →1 O2 + OH − (30)
/ / 3.7. Reusability and stability of catalyst
SO−4 ⋅ ⋅OH ⋅O−2 /1 O2 + LEV→intermediates→CO2 + H2 O (31)
Considering that stability and reusability are important character­
istic of catalyst for PMS activation, the ZFO-500 were repeated four
3.6. Degradation pathway of LEV times to evaluate its stability. As can be seen from Fig. 7, the degradation
efficiency of LEV was 75% within 180 min after four sequential cycles.
As we all known, AOPs often yield various kinds of intermediates due The degradation efficiency decreased only 12.4% in comparison with
to the highly-active and non-selective characteristics between the the initial cycle, suggesting good reusability and stability of the ZFO-
oxidative radical species and target contaminants, which might cause 500. However, the defluorination efficiency was decreased, probably
the creaturely toxicity and recalcitrance of parent compounds [48]. because the active sites on the catalyst surface were gradually occupied.
Thus, LC-MS measurement was employed to identify the intermediate Further, the phase structure and morphology of ZFO-500 used for four
structure and to further analyze the possible degradation pathway of times were evaluated in Fig. 7c–7d and Fig. S3 the characteristic peaks
LEV. The possible intermediates were summarized in Table S1 based on and morphologies assigned to ZFO-500 was not significant change after
the fragmentation patterns and molecular ions peaks. Besides, the evo­ the reaction [57], suggesting that the active sites was stable in the ZFO-
lution of corresponding products was proposed in Fig. 6. The main 500/LED/PMS system. In addition, according to the FAAS results listed
pathways include (A) hydroxylation, (B) de-piperazinylation, (C) de- in Table 2, the ferric ions in the solution after each cycle of the experi­
methylation [49], (D) defluorination, (E) oxidation of quinolone rings ment was not detected, and only about 0.230% of the zinc ions were

Fig. 6. Proposed pathway for degradation of LEV.

8
Y. Zhong et al.
Fig. 7. The stability of ZFO-500 in ZFO/LED/PMS system in cycling runs: (a) LEV degradation efficiency, (b) defluorination rate, (c) XRD patterns, and (d) Scanning
electron microscopy image of used ZFO-500.
Table 2
Dissolution rate of Zn2+ and Fe3+ in ZFO-500/LED/PMS system.
Cycle times Zn2+ Fe3+
1 0.231% 0%
2 0.234% 0%
3 0.234% 0%
4 0.237% 0%
dissolved. It can be concluded that spinel ferrite has good stability that
can be reused in environmental remediation [58].
4. Conclusion
Combination of PMS and heterogeneous photocatalysis using ZFO-
500 as catalyst under energy-saving LED light was presented as an
effective process for degrading LEV. LEV degradation could be rapidly
achieved due to the formation of reactive radicals like ∙O–2, SO-4∙, ∙OH
and 1O2 from PMS activation by LED assisted generation of e- and h+.
1
O2 was confirmed as the primary active species contributing to LEV
degradation. A possible degradation pathway of LEV was proposed
based on the intermediates determined by LC-MS. The ZFO-500 particles
displayed well activity and stability with neglectable leaching of Zn and
Fe. Therefore, the LED assisted ZFO-500/PMS process is believed to be a
promising strategy for the treatment of recalcitrant wastewater con­
taining antibiotic wastewater.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
9
Chemical Engineering Journal 417 (2021) 129225
the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China(21976042), the Project of Guangdong Provincial Key Labora­
tory of radioactive contamination control and resources
(2017B030314182), Guangdong Key Laboratory of Environmental
Catalysis and Health Risk Control (2018B030322014), the Natural Sci­
ence Foundation of Guangdong Province (2019A1515011543), Guang­
dong Province Universities and Colleges Pearl River Scholar Funded
Scheme (2018), University scientific research project of Guangzhou
Education Bureau (201831803), The research project of Guangzhou
University (YK2020012).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.129225.
References
[1] X. Liu, H. Pang, X. Liu, Q. Li, N. Zhang, L. Mao, M. Qiu, B. Hu, H. Yang, X. Wang,
Orderly porous covalent organic frameworks-based materials: Superior adsorbents
for pollutants removal from aqueous solutions, Innovat. 2 (2021), https://doi.org/
10.1016/j.xinn.2021.100076.
[2] L.J. Zhou, W.X. Wang, Y.J. Lv, Z.G. Mao, C.E. Chen, Q.L.L. Wu, Tissue
concentrations, trophic transfer and human risks of antibiotics in freshwater food
web in Lake Taihu, China, Ecotox Environ Safe 197 (2020), https://doi.org/
10.1016/j.ecoenv.2020.110626.
[3] J.N. Meegoda, J.A. Kewalramani, B. Li, R.W. Marsh, A review of the applications,
environmental release, and remediation technologies of per- and polyfluoroalkyl
substances, Int J Environ Res Public Health 17 (2020), https://doi.org/10.3390/
ijerph17218117.
Y. Zhong et al.
[4] L. Yang, L. He, J. Xue, Y. Ma, Z. Xie, L. Wu, M. Huang, Z. Zhang, Persulfate-based
degradation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate
(PFOS) in aqueous solution: Review on influences, mechanisms and prospective,
J Hazard Mater 393 (2020), 122405, https://doi.org/10.1016/j.
jhazmat.2020.122405.
[5] D.L. Wang, Q. Ning, J.Y. Dong, B.W. Brooks, J. You, Predicting mixture toxicity and
antibiotic resistance of fluoroquinolones and their photodegradation products in
Escherichia coli, Environ Pollut 262 (2020), https://doi.org/10.1016/j.
envpol.2020.114275.
[6] Y.F. Leng, H.L. Xiao, Z. Li, J. Wang, Tetracyclines, sulfonamides and quinolones
and their corresponding resistance genes in coastal areas of Beibu Gulf, China, Sci
Total Environ 714 (2020), https://doi.org/10.1016/j.scitotenv.2020.136899.
[7] Z. Cao, H. Li, G.V. Lowry, X. Shi, X. Pan, X. Xu, G. Henkelman, J. Xu, Unveiling the
role of sulfur in rapid defluorination of florfenicol by sulfidized nanoscale zero-
valent iron in water under ambient conditions, Environ Sci Technol (2021),
https://doi.org/10.1021/acs.est.0c07319.
[8] D. He, Y.C. Li, C. Lyu, L. Song, W. Feng, S.Y. Zhang, New insights into MnOOH/
peroxymonosulfate system for catalytic oxidation of 2,4-dichlorophenol:
Morphology dependence and mechanisms, Chemosphere 255 (2020), https://doi.
org/10.1016/j.chemosphere.2020.126961.
[9] W. Li, Y.L. Zhang, P.J. Zhao, P. Zhou, Y. Liu, X. Cheng, J.Q. Wang, B. Yang, H.
G. Guo, Enhanced kinetic performance of peroxymonosulfate/ZVI system with the
addition of copper ions: Reactivity, mechanism, and degradation pathways,
J Hazard Mater 393 (2020), https://doi.org/10.1016/j.jhazmat.2020.122399.
[10] H. Zhang, J. He, C. Zhai, M. Zhu, 2D Bi2WO6/MoS2 as a new photo-activated
carrier for boosting electrocatalytic methanol oxidation with visible light
illumination, Chin. Chem. Lett. 30 (2019) 2338–2342, https://doi.org/10.1016/j.
cclet.2019.07.021.
[11] Y. Chen, S. Lan, M. Zhu, Construction of piezoelectric BaTiO3/MoS2 heterojunction
for boosting piezo-activation of peroxymonosulfate, Chin. Chem. Lett. (2020),
https://doi.org/10.1016/j.cclet.2020.11.016.
[12] S. Xiao, M. Cheng, H. Zhong, Z.F. Liu, Y. Liu, X. Yang, Q.H. Liang, Iron-mediated
activation of persulfate and peroxymonosulfate in both homogeneous and
heterogeneous ways: A review, Chem Eng J 384 (2020), https://doi.org/10.1016/j.
cej.2019.123265.
[13] M. Hao, M. Qiu, H. Yang, B. Hu, X. Wang, Recent advances on preparation and
environmental applications of MOF-derived carbons in catalysis, Sci Total Environ
760 (2021), 143333, https://doi.org/10.1016/j.scitotenv.2020.143333.
[14] S. Moradi, S.A. Sobhgol, F. Hayati, A.A. Isari, B. Kakavandi, P. Bashardoust,
B. Anvaripour, Performance and reaction mechanism of MgO/ZnO/Graphene
ternary nanocomposite in coupling with LED and ultrasound waves for the
degradation of sulfamethoxazole and pharmaceutical wastewater, Sep Purif
Technol 251 (2020), https://doi.org/10.1016/j.seppur.2020.117373.
[15] Y.N. Chen, X.Y. Zhang, L.L. Wang, X.Y. Cheng, Q.K. Shang, Rapid removal of
phenol/antibiotics in water by Fe-(8-hydroxyquinoline-7-carboxylic)/TiO2 flower
composite: Adsorption combined with photocatalysis, Chem Eng J 402 (2020),
https://doi.org/10.1016/j.cej.2020.126260.
[16] X.F. Qu, Z.Q. Gao, X.H. Zhao, L. Shi, F.L. Du, H.B. Song, Construction of p-n type
Bi2O3/Bi4NbO8Cl 0D/2D heterojunction with enhanced photodegradation
performance for organic pollutants, Appl Surf Sci 529 (2020), https://doi.org/
10.1016/j.apsusc.2020.147248.
[17] L. Yao, H. Yang, Z. Chen, M. Qiu, B. Hu, X. Wang, Bismuth oxychloride-based
materials for the removal of organic pollutants in wastewater, Chemosphere
(2020), https://doi.org/10.1016/j.chemosphere.2020.128576.
[18] D.O. Adenuga, S.M. Tichapondwa, E.M.N. Chirwa, Facile synthesis of a Ag/AgCl/
BiOCl composite photocatalyst for visible - light - driven pollutant removal,
J Photoch Photobio A 401 (2020), https://doi.org/10.1016/j.
jphotochem.2020.112747.
[19] R.B. Xu, M.H. Su, Y.H. Liu, Z.B. Chen, C. Ji, M.L. Yang, X.Y. Chang, D.Y. Chen,
Comparative study on the removal of different-type organic pollutants on
hierarchical tetragonal bismutite microspheres: Adsorption, degradation and
mechanism, J Clean Prod 242 (2020), https://doi.org/10.1016/j.
jclepro.2019.118366.
[20] L. Li, C.-G. Niu, H. Guo, J. Wang, M. Ruan, L. Zhang, C. Liang, H.-Y. Liu, Y.-Y. Yang,
Efficient degradation of Levofloxacin with magnetically separable ZnFe2O4/NCDs/
Ag2CO3 Z-scheme heterojunction photocatalyst: Vis-NIR light response ability and
mechanism insight, Chem Eng J 383 (2020), https://doi.org/10.1016/j.
cej.2019.123192.
[21] P. Sathishkumar, N. Pugazhenthiran, R.V. Mangalaraja, A.M. Asiri, S. Anandan,
ZnO supported CoFe2O4 nanophotocatalysts for the mineralization of Direct Blue
71 in aqueous environments, J Hazard Mater 252 (2013) 171–179, https://doi.
org/10.1016/j.jhazmat.2013.02.030.
[22] Y. Zhao, G.L. Wang, L.J. Li, X.L. Dong, X.F. Zhang, Enhanced activation of
peroxymonosulfate by nitrogen-doped graphene/TiO2 under photo-assistance for
organic pollutants degradation: Insight into N doping mechanism, Chemosphere
244 (2020), https://doi.org/10.1016/j.chemosphere.2019.125526.
[23] M. Zhang, J. He, Y. Chen, P.-Y. Liao, Z.-Q. Liu, M. Zhu, Visible light-assisted
peroxydisulfate activation via hollow copper tungstate spheres for removal of
antibiotic sulfamethoxazole, Chin. Chem. Lett. 31 (2020) 2721–2724, https://doi.
org/10.1016/j.cclet.2020.05.001.
[24] Z. Wang, X. Cai, X. Xie, S. Li, X. Zhang, Z. Wang, Visible-LED-light-driven
photocatalytic degradation of ofloxacin and ciprofloxacin by magnetic biochar
modified flower-like Bi2WO6: The synergistic effects, mechanism insights and
degradation pathways, Sci Total Environ (2020), 142879, https://doi.org/
10.1016/j.scitotenv.2020.142879.
10
Chemical Engineering Journal 417 (2021) 129225
[25] M. Sarafraz, M.M. Amini, M. Adiban, A. Eslami, Facile synthesis of mesoporous
black N-TiO2 photocatalyst for efficient charge separation and the visible-driven
photocatalytic mechanism of ibuprofen degradation, Mater. Sci. Semicond.
Process. 120 (2020), https://doi.org/10.1016/j.mssp.2020.105258.
[26] P. Yang, Y. Chen, S. Jiang, P. Shen, X. Lu, Y. Xiao, Association between the rate of
fluoroquinolones-resistant gram-negative bacteria and antibiotic consumption
from China based on 145 tertiary hospitals data in 2014, BMC Infect Dis 20 (2020)
269, https://doi.org/10.1186/s12879-020-04981-0.
[27] Y. Huang, Y. Liang, Y. Rao, D. Zhu, J.J. Cao, Z. Shen, W. Ho, S.C. Lee, Environment-
friendly carbon quantum dots/ZnFe2O4 photocatalysts: Characterization,
Biocompatibility Mech. NO Removal Environ Sci Technol 51 (2017) 2924–2933,
https://doi.org/10.1021/acs.est.6b04460.
[28] F. Siadatnasab, S. Farhadi, A. Khataee, Sonocatalytic performance of magnetically
separable CuS/CoFe2O4 nanohybrid for efficient degradation of organic dyes,
Ultrason Sonochem 44 (2018) 359–367, https://doi.org/10.1016/j.
ultsonch.2018.02.051.
[29] N. Ahmadpour, M.H. Sayadi, S. Sobhani, M. Hajiani, A potential natural solar light
active photocatalyst using magnetic ZnFe2O4@TiO2/Cu nanocomposite as a high
performance and recyclable platform for degradation of naproxen from aqueous
solution, J Clean Prod 268 (2020).
[30] J. Wang, X.F. Lei, C. Huang, L. Xue, W. Cheng, Q. Wu, Fabrication of a novel
MoO3/Zn-Al LDHs composite photocatalyst for efficient degradation of tetracycline
under visible light irradiation, J Phys Chem Solids 148 (2021), https://doi.org/
10.1016/j.jpcs.2020.109698.
[31] J. Li, Y. Ren, F.Z. Ji, B. Lai, Heterogeneous catalytic oxidation for the degradation
of p-nitrophenol in aqueous solution by persulfate activated with CuFe2O4
magnetic nano-particles, Chem Eng J 324 (2017) 63–73, https://doi.org/10.1016/
j.cej.2017.04.104.
[32] R.N. Guo, Q. Meng, H.X. Zhang, X.Y. Zhang, B. Li, Q.F. Cheng, X.W. Cheng,
Construction of Fe2O3/Co3O4/exfoliated graphite composite and its high efficient
treatment of landfill leachate by activation of potassium persulfate, Chem Eng J
355 (2019) 952–962, https://doi.org/10.1016/j.cej.2018.08.168.
[33] W. Hong, L.Z. Li, R.N. Xue, X.Y. Xu, H. Wang, J.K. Zhou, H.L. Zhao, Y.H. Song,
Y. Liu, J.P. Gao, One-pot hydrothermal synthesis of Zinc ferrite/reduced graphene
oxide as an efficient electrocatalyst for oxygen reduction reaction, J Colloid Interf
Sci 485 (2017) 175–182, https://doi.org/10.1016/j.jcis.2016.04.035.
[34] S. Tang, Enhanced photocatalytic performance of BiVO4 for degradation of
methylene blue under LED visible light irradiation assisted by peroxymonosulfate,
Int. J. Electrochem. Sci. (2020) 2470–2480, https://doi.org/10.20964/
2020.03.09.
[35] X. Wang, W. Lu, Z. Zhao, H. Zhong, Z. Zhu, W. Chen, In situ stable growth of
β-FeOOH on g-C3N4 for deep oxidation of emerging contaminants by photocatalytic
activation of peroxymonosulfate under solar irradiation, Chem Eng J 400 (2020),
https://doi.org/10.1016/j.cej.2020.125872.
[36] S. Renukadevi, A. Pricilla Jeyakumari, Rational design of ZnFe2O4/g-C3N4
heterostructures composites for high efficient visible-light photocatalysis for
degradation of aqueous organic pollutants, Inorg. Chem. Commun. 118 (2020).
[37] B. Zhu, H. Cheng, J. Ma, Y. Kong, S. Komarneni, Efficient degradation of
rhodamine B by magnetically separable ZnS-ZnFe2O4 composite with the
synergistic effect from persulfate, Chemosphere 237 (2019), 124547, https://doi.
org/10.1016/j.chemosphere.2019.124547.
[38] X. Zhong, Y. Cai, H. Bai, W. Huang, B. Zhou, Visible Light driven spherical CuBi2O4
with surface oxygen vacancy enhanced photocatalytic activity: Catalyst
fabrication, performance, and reaction mechanism, Catalysts 10 (2020), https://
doi.org/10.3390/catal.10080945.
[39] C. Cai, Z. Zhang, J. Liu, N. Shan, H. Zhang, D.D. Dionysiou, Visible light-assisted
heterogeneous Fenton with ZnFe2O4 for the degradation of Orange II in water,
Appl. Catal. B 182 (2016) 456–468, https://doi.org/10.1016/j.
apcatb.2015.09.056.
[40] K. Zhu, J. Wang, Y. Wang, C. Jin, A.S. Ganeshraja, Visible-light-induced
photocatalysis and peroxymonosulfate activation over ZnFe2O4 fine nanoparticles
for degradation of Orange II, Catal. Sci. Technol. 6 (2016) 2296–2304, https://doi.
org/10.1039/c5cy01735a.
[41] M.A. Behnajady, M. Hajiahmadi, N. Modirshahla, Enhancement of removal rate of
an organic pollutant in the presence of immobilized TiO2 nanoparticles with
inorganic anions combination: optimization using taguchi approach, Ind. Eng.
Chem. Res. 51 (2012) 15324–15330, https://doi.org/10.1021/ie301521z.
[42] L. Yang, Y. Chen, D. Ouyang, J.C. Yan, L.B. Qian, L. Han, M.F. Chen, J. Li, M.Y. Gu,
Mechanistic insights into adsorptive and oxidative removal of monochlorobenzene
in biochar-supported nanoscale zero-valent iron/persulfate system, Chem Eng J
400 (2020), https://doi.org/10.1016/j.cej.2020.125811.
[43] P. Zhou, J. Zhang, Y. Zhang, G. Zhang, W. Li, C. Wei, J. Liang, Y. Liu, S. Shu,
Degradation of 2,4-dichlorophenol by activating persulfate and peroxomonosulfate
using micron or nanoscale zero-valent copper, J Hazard Mater 344 (2018)
1209–1219, https://doi.org/10.1016/j.jhazmat.2017.11.023.
[44] Y. Cao, W. Qiu, Y. Zhao, J. Li, J. Jiang, Y. Yang, S.-Y. Pang, G. Liu, The degradation
of chloramphenicol by O3/PMS and the impact of O3-based AOPs pre-oxidation on
dichloroacetamide generation in post-chlorination, Chem Eng J 401 (2020),
https://doi.org/10.1016/j.cej.2020.126146.
[45] J. Zhang, C. Zhai, W. Zhao, Y. Chen, R. Yin, L. Zeng, M. Zhu, Insight into combining
visible-light photocatalysis with transformation of dual metal ions for enhancing
peroxymonosulfate activation over dibismuth copper oxide, Chem Eng J 397
(2020), https://doi.org/10.1016/j.cej.2020.125310.
[46] J. Lyu, M. Ge, Z. Hu, C. Guo, One-pot synthesis of magnetic CuO/Fe2O3/CuFe2O4
nanocomposite to activate persulfate for levofloxacin removal: Investigation of
Y. Zhong et al.
efficiency, mechanism and degradation route, Chem Eng J 389 (2020), https://doi.
org/10.1016/j.cej.2020.124456.
[47] X. Wu, X. Gu, S. Lu, Z. Qiu, Q. Sui, X. Zang, Z. Miao, M. Xu, Strong enhancement of
trichloroethylene degradation in ferrous ion activated persulfate system by
promoting ferric and ferrous ion cycles with hydroxylamine, Sep Purif Technol 147
(2015) 186–193, https://doi.org/10.1016/j.seppur.2015.04.031.
[48] J. Zou, J. Ma, L. Chen, X. Li, Y. Guan, P. Xie, C. Pan, Rapid acceleration of ferrous
iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe
(II) cycle with hydroxylamine, Environ Sci Technol 47 (2013) 11685–11691,
https://doi.org/10.1021/es4019145.
[49] X. Wang, A. Wang, J. Ma, Visible-light-driven photocatalytic removal of antibiotics
by newly designed C3N4@MnFe2O4-graphene nanocomposites, J Hazard Mater 336
(2017) 81–92, https://doi.org/10.1016/j.jhazmat.2017.04.012.
[50] S.G. Fard, M. Haghighi, M. Shabani, Facile one-pot ultrasound-assisted
solvothermal fabrication of ball-flowerlike nanostructured (BiOBr)x(Bi7O9I3)1–x
solid-solution for high active photodegradation of antibiotic levofloxacin under
sun-light, Appl. Catal. B 248 (2019) 320–331, https://doi.org/10.1016/j.
apcatb.2019.02.021.
[51] K. Xu, W.W. Ben, W.C. Ling, Y. Zhang, J.H. QuZ.M., Qiang, Impact of humic acid
on the degradation of levofloxacin by aqueous permanganate: Kinetics and
mechanism, Water Res 123 (2017) 67–74, https://doi.org/10.1016/j.
watres.2017.06.037.
[52] Q.L. Ma, H.X. Zhang, X.Y. Zhang, B. Li, R.N. Guo, Q.F. Cheng, X.W. Cheng,
Synthesis of magnetic CuO/MnFe2O4 nanocompisite and its high activity for
degradation of levofloxacin by activation of persulfate, Chem Eng J 360 (2019)
848–860, https://doi.org/10.1016/j.cej.2018.12.036.
11
Chemical Engineering Journal 417 (2021) 129225
[53] A. Wang, Z. Chen, Z. Zheng, H. Xu, H. Wang, K. Hu, K. Yan, Remarkably enhanced
sulfate radical-based photo-Fenton-like degradation of levofloxacin using the
reduced mesoporous MnO@MnOx microspheres, Chem Eng J 379 (2020), https://
doi.org/10.1016/j.cej.2019.122340.
[54] H. Sun, P. Qin, Z. Wu, C. Liao, J. Guo, S. Luo, Y. Chai, Visible light-driven
photocatalytic degradation of organic pollutants by a novel Ag3VO4/Ag2CO3 p–n
heterojunction photocatalyst: Mechanistic insight and degradation pathways,
J. Alloy. Compd. 834 (2020), https://doi.org/10.1016/j.jallcom.2020.155211.
[55] Y. Gao, D.L. Zou, Efficient degradation of levofloxacin by a microwave-3D
ZnCo2O4/activated persulfate process: Effects, degradation intermediates, and
acute toxicity, Chem Eng J 393 (2020), https://doi.org/10.1016/j.
cej.2020.124795.
[56] Y.Q. He, H.X. Lv, Y.C. Daili, Q. Yang, L. Binnah, D.J. Liu, H.Y. Liu, Z.Y. Ma,
Construction of a new cascade photogenerated charge transfer system for the
efficient removal of bio-toxic levofloxacin and rhodamine B from aqueous solution:
Mechanism, degradation pathways and intermediates study, Environ Res 187
(2020), https://doi.org/10.1016/j.envres.2020.109647.
[57] K. Zhu, Q. Bin, Y. Shen, J. Huang, D. He, W. Chen, In-situ formed N-doped bamboo-
like carbon nanotubes encapsulated with Fe nanoparticles supported by biochar as
highly efficient catalyst for activation of persulfate (PS) toward degradation of
organic pollutants, Chem Eng J 402 (2020), https://doi.org/10.1016/j.
cej.2020.126090.
[58] A.A.P. Khan, P. Singh, P. Raizada, A.M. Asiri, Synthesis of magnetically separable
Bi2O2CO3/carbon nanotube/ZnFe2O4 as Z-scheme heterojunction with enhanced
photocatalytic activity for water purification, J. Sol-Gel Sci. Technol. 95 (2020)
408–422, https://doi.org/10.1007/s10971-020-05336-6.