Chemical Engineering Journal 433 (2022) 133574

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Chemical Engineering Journal

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

Levofloxacin degradation performance and mechanism in the novel

electro-Fenton system constructed with vanadium oxide electrodes under
neutral pH
Jiaxiang Liang a, Yanping Hou b, *, Hongxiang Zhu a, Jianhua Xiong b, Wenyu Huang b,
Zebin Yu b, Shuangfei Wang a, *
a
College of Light Industry and Food Engineering, Guangxi University, Nanning 530004, PR China
b
School of Resources, Environment and Materials, Guangxi University, Nanning 530004, PR China

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

Keywords: Heterogenous ferrum-based materials usually suffer from large overpotential between the redox of Fe3+/Fe2+
Antibiotics degradation and two-electron oxygen reduction reaction (2e− ORR), leading to less desired performance in electro-Fenton
Electro-Fenton (EF) process. Herein, heterogeneous vanadium oxide EF system (VO-EF) was proposed by electrodepositing
Vanadium oxides
VO on carbon paper cathode (VOx@CP) and anode (V3O7@CP) for levofloxacin degradation. The VOx@CP
Energy consumption
cathode showed the optimal potential of 2e− ORR at − 0.90 V (vs. SCE) with H2O2 generation rate of 1.44 × 10− 4
Degradation mechanism
mmol⋅L− 1⋅cm− 2⋅s− 1. Though overpotential disparity of 0.35 V was exhibited between the redox of VOx and 2e−
ORR, rapid H2O2 consumption rate was still achieved and facilitated ⋅OH generation. The oxygen vacancies
existed in V3O7@CP anode reduced oxygen evolution reaction potential, leading to the cell voltage decrease of
0.36 V. Levofloxacin (30 mg⋅L− 1) degradation efficiency of 97.67% was achieved in the VO-EF system within
120 min, and 19.19 mg⋅L− 1 TOC was mineralized with energy consumption of 12.3 J⋅mg⋅L− 1 TOC under neutral
pH condition. Complete mineralization and low H2O2 residue allowed good bioavailability in the effluent.
Levofloxacin degradation pathways and mechanism were proposed based on identified intermediates and
theoretical calculation. This study provides inspiration for developing novel EF systems for efficient pollutants
degradation.

1. Introduction
Antibiotics have shown great significance in the treatment of human
and animal disease; however, antibiotics, as emerging pollutants, also
exhibited potential threats towards ecosystems through inducing anti­
biotic resistance genes when being discharged to the environment [1,2].
Unfortunately, traditional wastewater bio-treatment plant shows
limited antibiotics removals, and the effluents cause the spread of an­
tibiotics in aquatic environment. Levofloxacin, as a class of fluo­
roquinolones, is commonly appeared in hospital and pharmaceutical
effluent. Due to its strong covalent bond of C-F, some toxic recalcitrant
degradation intermediates like fluorine-containing organic matters were
usually remained during levofloxacin decomposition [3]. What’s worse,
the strong antibacterial activity and low metabolic property of levo­
floxacin would lead to pollutants accumulation even in treated waste­
water [4,5].
Numerous efforts have been made for developing technologies for
efficient antibiotics degradation to prevent unexpected threats to eco­
systems, environments and human health. Intensive studies have shown
that photocatalysis, electrocatalysis, Fenton catalysis, electro-Fenton
process, etc., could be adopted for efficient degradation of antibiotics
[6]. For photocatalysis and electrocatalysis processes, more efforts were
devoted to developing efficient and stable photocatalysts (like 2D/2D
CoAl-LDHs/Ti3C2Tx [7], hollow tubular g-C3N4 isotype heterojunction
[8]) or desired electrocatalysts, as well as revealing contaminants
degradation mechanisms. For Fenton catalysis, recent reports mainly
focused on the study of heterogeneous interface mechanism, including
the iron cycling efficiency [9], surface-initiated reactions [10] and novel
materials developing [11]. Electro-Fenton (EF) process has been
considered as one of the most promising advanced oxidation technolo­
gies for efficient removal of refractory organic pollutants. The in-situ
generation of hydrogen peroxide (H2O2) through two-electron oxygen

* Corresponding authors.
E-mail addresses: houyp@gxu.edu.cn (Y. Hou), wangsf@gxu.edu.cn (S. Wang).

https://doi.org/10.1016/j.cej.2021.133574
Received 13 September 2021; Received in revised form 4 November 2021; Accepted 6 November 2021
Available online 12 November 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
J. Liang et al.
Scheme 1. Schematic illustration of the anode and cathode VO electrodeposition process.
reduction reaction (2e− ORR) occurring on cathode could avoid H2O2
transportation and storage (Eq. (1)), making a significant progress
compared with traditional Fenton technology. Though, the soluble
ferrous salts, as Fenton reagents, exhibit high efficiency in catalyzing
H2O2 to generate hydroxyl radicals (⋅OH) (Eq. (2)), they would precip­
itate when pH is higher than 4 (Eq. (3)). The ferric in the form of pre­
cipitate or ligand can hardly be reduced back to ferrous (FRR, Eq. (40),
which limits the application of EF in aquatic treatment under neutral or
alkaline pH conditions [12,13]. Besides, pH values of the hospital and
pharmaceutical effluents generally vary in a wide range [14]. In this
regard, series of heterogeneous EF cathode materials have been devel­
oped for widening the working pH range. Ferrum oxide, as the substitute
of soluble salts, can avoid the precipitation process during wastewater
treatment. And H2O2 generation and consumption are occurred on the
heterogeneous cathode, showing good degradation performance under
neutral pH. For example, the γ-FeOOH GPCA cathode was used in EF
system for sulfamethoxazole degradation within the pH range from 6.5
to 7.5 [15], showing a mineralization efficiency of 96% in 300 min. The
Fe3O4 nanoparticle compositing with carbon nanofiber exhibited effi­
cient decomposition of carbamazepine (100% in 180 min) under pH 7
[16]. And Fe@Fe2O3FCA showed excellent metalaxyl degradation per­
formance (removal of 98% in 240 min) under pH 6 [17]. Besides, other
ferrum-based EF materials (Fe0 [18], Fe3O4 [19], Fe(OH)2 [20] and FeS2
[21,22]) have also been well discussed. However, in traditional heter­
ogenous EF system, both the 2e− ORR and ferric reduction reaction
(FRR) occur on the surface of the cathode, but the 2e− ORR shows a
much higher optimal overpotential than FRR. Thus, applying the
optimal 2e− ORR potential for EF degradation can ensure an ideal H2O2
electro-generation but restrict the cycle of FRR [23], leading to limited
degradation efficiency and large amount of H2O2 residual, both of which
are undesired. Therefore, cathode materials that are able to balance 2e−
ORR and cathodic catalyst reduction so as to ensure great performance,
should be more desired. Besides, utilization of anode for improvement of
EF is another idea.
O2 + 2H+ + 2e− → H2O2, 2e− ORR
Fe 2+ +
+ H2O2 + H → Fe 3+
+ H2O + ⋅OH
Fe3+ + 3OH– → Fe(OH)3↓
Fe 3+ − 2+
+ e → Fe , FRR
−
2H2O – 4e → O2↑ + 4H +
Vanadium oxides are abundant on the earth, and they have been
used in the fields of supercapacitor [24], lithium ion battery [25] and
zinc ion battery [26], because the high valence states of VO (V2O5 and
V3O7) materials can offer higher theoretical capacity compared with
common transition metal oxides (Fe2O3, MnO2, Co3O4, etc.). Due to the
multi-valence feature, V-based materials have also been applied in cat­
alytic processes for environment remediation. The lower valence states
of vanadium oxide (VO) could be utilized to react with H2O2 [27] or
persulfate [28] to generate ⋅OH or SO4⋅− , which can be applied in
organic contaminants decomposition. Compared with the single redox
of Fe3+/Fe2+ in traditional EF, multi-redox of vanadium oxides shows a
broader optimal potential range for the reduction of individual high
Chemical Engineering Journal 433 (2022) 133574
valence state. VO can also achieve reversible conversion of multiple
valence states on the electrode surface without shedding, passivation,
thus maintaining great stability [29]. Besides, VO also owns rich oxygen
vacancies, which have been demonstrated to be favorable to enhancing
the efficiency of electrocatalysts, such as promoting oxygen evolution
reaction (OER, Eq. (5)) activity [30]. Therefore, it is believed that uti­
lization of VO for heterogeneous EF catalysis should exhibit desired
degradation performance.
In this work, VO-based cathode and anode were prepared by elec­
trodepositing different vanadium oxides onto carbon papers (CP), and
both of which were simultaneously used in an ensemble system (VO-EF)
for levofloxacin degradation under neutral pH condition. More specif­
ically, chemical structure composition information of both VOx@CP
cathode and V3O7@CP anode were characterized; radicals production
mechanism of VOx@CP cathode was investigated; the auxiliary contri­
bution to EF by V3O7@CP anode was discussed; and the overall per­
formance of levofloxacin degradation by VO-EF in terms of total organic
carbon (TOC) removal, energy consumption under neutral pH condition,
electrodes stability, and various typical antibiotics degradation were
evaluated. More importantly, levofloxacin degradation mechanism was
revealed based on both identified degradation intermediates and
Gaussian computation. Besides, microorganism inhibition by treated
water samples were also analyzed.
2. Materials and methods
2.1. Reagents
Sodium metavanadate, sodium sulfate, concentrated sulfuric acid,
sodium hydrate and hydrogen peroxide solution were bought from
Sinopharm Chemical Reagent Co., and ethanol absolute was bought
from Guangdong Guanghua Sci-Tech Co., Ltd. Acetonitrile, trifluoro­
acetic acid and antibiotics were from Macklin reagent. Titanium po­
tassium oxalate was from Sigma-Aldrich. Ultrapure water was used
throughout the whole experiment.
(1)
(2) 2.2. Electrodes synthesis
(3) The electrodeposition process was conducted according to previous
studies [29,31], and the VO anode and cathode preparation was shown
(4)
in Scheme 1. The commercial carbon paper (CP) was cut to be rectan­
(5) gular specification of 2.0 cm × 1.0 cm, then ultrasonic cleaned and
washed in ethanol and water for 20 min before electrodeposition. To
prepare electrodeposition solution, 0.60 g of NaVO3 was first added into
20 mL of water, then stirred and rose the temperature to 80 ℃ until the
powder was dissolved. Then, H2SO4 solution (1.0 mol⋅L− 1) was dropped
in the above solution to adjust the pH to 1.00. The pretreated CPs were
used as the anode and cathode, respectively, with only half of the
electrode (1.0 cm × 1.0 cm) being immersed in the electrodeposition
solution. Afterwards, − 2.0 V (vs. SCE) was applied to cathode for a
period of time (0, 5, 10 and 20 min), and the temperature was still kept
at 80 ℃. During the electrodeposition process, the color of the electro­
lyte was changed from saffron yellow to mazarine yellow, implying the
VO3− was reduced to VO2+ on the cathode (Eq. (6)). On the anode side,
the V3O7 was deposited on CP according to Eq. (7). On the cathode side,
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J. Liang et al. Chemical Engineering Journal 433 (2022) 133574

Fig. 1. SEM images of CP (a, b); VOx@CP cathode (c, d); and V3O7@CP anode (e, f); The section views of VOx@CP cathode (g, h) and V3O7@CP anode (i, j).

lower valence states of V2O3, VO2 and V6O13 were deposited on CP (Eqs. of the deposits on electrodes were investigated by X-ray diffractometer
(8)–(10)). After the electrodeposition process, the cathode (gray color) (XRD, Rigaku D/MAX 2500 V). The X-ray photoelectron spectrograph
and anode (kermesinus color) with VO deposited on them were (XPS, Thermo Scientific K-Alpha) was performed to ascertain the
obtained. chemical composition and valence states of vanadium oxides and CP.
Anodic deposition The oxygen vacancies in vanadium oxides were studied by XPS and
electronic paramagnetic resonance spectrometer (EPR, Bruker
VO3− + 4H+ + e− → VO2+ + 2H2O (6) EMXPLUS).
3VO2+ + 4H2O – 2e− → V3O7↓ + 8H+ (7)
2.4. Electrochemical tests
Cathodic deposition
Cyclic voltammetry (CV), linear sweep voltammetry (LSV), electro­
2VO3− + 6H+ + 4e− →V2O3↓ + 3H2O (8)
chemical impedance spectroscopy (EIS), H2O2 generation and EF
VO3− + 2H+ + e− → VO2↓ + H2O (9) degradation tests were conducted using the electrochemical workstation
(CHI-650D). The electrolyte was Na2SO4 solution (0.1 mol⋅L− 1), and in
6VO3− + 10H+ + 4e− → V6O13↓ + 5H2O (10) some cases, the pH was adjusted to acidity by using H2SO4 (1.0 mol⋅L− 1).
The saturated calomel electrode (SCE) was adopted as the reference
electrode. The specific test conditions were illustrated in corresponding
figure captions.
2.3. Characterization of electrodes

The morphologies of deposits on electrodes were observed by scan­

ning electron microscope (SEM, Zeiss Sigma300). The crystal structures

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J. Liang et al. Chemical Engineering Journal 433 (2022) 133574

Fig. 2. XPS spectra of CP, VOx@CP cathode and V3O7@CP anode (a); High-resolution spectra of V 2p and O 1s by VOx@CP cathode (b); V3O7@CP anode (c); The
XRD patterns of VOx@CP cathode (d); Crystal phase changes before and after reacting with 2.0 mmol⋅L− 1 of H2O2 with different times (e); and XRD pattern of
V3O7@CP anode (f).

2.5. Antibacterial properties test of the treated antibotic-containing water c

H2 O2 generation rate = mmol⋅L− 1 ⋅cm− 2 ⋅s− 1
(11)
t × S
The suppress efficiency of microorganisms was determined by inhi­
bition zone test [32,33]. The widely existed Escherichia coli and Staph­ where c is the detected H2O2 concentration (mmol⋅L− 1), S is the cathode
ylococcus aureus were chosen for the test. After the activation and working area (1.0 cm × 1.0 cm), t is the operation time (s).
purification process, Escherichia coli and Staphylococcus aureus were Antibiotics concentration measurement and levofloxacin degrada­
cultured in liquid medium for 24 h. The concentration of each suspen­ tion intermediates identification. The concentrations of levofloxacin,
sion was adjusted to 5 × 106 colony forming units per mL, then a 100 μL ciprofloxacin, chlortetracycline, tetracycline and chloramphenicol were
of microculture mixture was homogeneous coated on a solid nutrient measured by UV spectrophotometer at the λmax = 293 nm [34], 276 nm
agar plate. Lastly, 3 tablets were dipped into the treated water sample [35], 368 nm [36], 357 nm [37] and 278 nm [38], respectively. The
and placed on the microorganism coated agar plate in equidistance for antibiotics degradation efficiency was calculated by using the equation
microbial growth observation after 24 h. as following:
c
Degradation rate = × 100% (12)
2.6. Analytical methods c0

where c is the detected residual concentration (mg⋅L− 1), and c0 is the

Measurement of H2O2⋅H2O2 generation yield was detected using the
initial concentration of antibiotics (mg⋅L− 1). The levofloxacin concen­
potassium titanium (IV) oxalate method [23]. Typically, 0.5 mL of re­
tration was also measured by high performance liquid chromatography
action sample was mixed with 0.5 mL of titanium reagent and 1.5 mL of
(HPLC, LC-20AD), with the mobile phase of formic acid/acetonitrile
deionized water. The absorbance of the solution was measured using a
(80/20) (0.1 wt%), the flow rate of 0.6 mL⋅min− 1, and the detection
UV-5100 spectrophotometer (Shanghai Precision Instruments Co., Ltd.)
wavelength of 293 nm [39]. The degradation intermediates of levo­
at 400 nm. Since the H2O2 generation concentration by each applied
floxacin were identified by liquid chromatograph mass spectrometer
potential were proportional to the reaction time, the corresponding
(LC-MS, ORBITRAP ELITE). The theoretical calculation was conducted
generation rate was calculated by the following equation:

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J. Liang et al.
Fig. 3. The Nyquist plots and the Randles circuit of CP and VOx@CP cathode prepared under 5, 10 and 20 min of electrodeposition times (a); The H2O2 generation
rates by CP and VOx@CP under series of applied potentials (b).
using the Gaussian 09 program [40]. Geometry optimization and fre­
quency calculations were performed at M06-2X/6-31G(d,p)/SMD(H2O)
level [41–46]. The transition states were verified by their imaginary
frequencies. Single point energies were calculated with the 6-311 + G
(d,p) basis set [47] in combination with the M06-2X functional and SMD
solvation model. The Gibbs free energies were obtained by summing the
single points with thermal corrections from frequency calculations.
Quantification of hydroxyl radicals. The ⋅OH was quantified by
benzoic acid (BA) oxidation method [48]. Specifically, when BA (1
mmol⋅L− 1) was added into the electrolyte, p-hydroxybenzoic acid (p-
HBA) would be generated by ⋅OH oxidation. The cumulative ⋅OH con­
centration was determined by measuring the concentration of p-HBA as
follows:
The cumuluative [⋅OH] = [p − HBA] × 5.87 μmol⋅L− 1
(13)
The concentration of p-HBA was determined using the HPLC (LC-
20AD, Shimadzu) equipped with a UV detector and C18 column (5 μm ×
4.6 mm × 250 mm, SyncronisTM). The mobile phase was the mixture of
35% acetonitrile and 65% trifluoroacetic acid (0.1 wt%), and the flow
rate was 1.0 mL⋅min− 1.
Measurement of total organic carbon (TOC) removal and calculation
of energy consumption. The TOC removal was measured by the total
organic carbon analyzer (TOC, TOC-VSH). The corresponding energy
consumption was calculated as following [17,49]:
U × I × t
EC = J⋅mg⋅L− 1 TOC (14)
(TOC0 − TOCt )
where U is the cell voltage (V), I is the average reaction current (A), t is
the operation time (s), TOC0 and TOCt are the values of the original TOC
(mg⋅L− 1) and that at time t.
3. Results and discussion
3.1. Surface morphology and chemical compositions of the cathode and
anode
The SEM images of the VOx@CP cathode and V3O7@CP anode were
shown in Fig. 1. The CP showed relatively flat with slight wrinkle surface
(Fig. 1a, b), which was distinct from electrodeposited cathode and
anode. Smooth and uniform deposits covered on the surface were
observed on VOx@CP cathode (Fig. 1c, d), while the electrodeposited
anode displayed loose and porous structure (Fig. 1e, f). From the section
views, the VO showed a layer structure covering on the surface of the CP
cathode (Fig. 1g, h), while tight contact on anode was observed (Fig. 1i,
j).
XPS results of various materials were displayed in Fig. 2(a-c) and
Table S1. The survey scan spectrum of CP showed a strong signal peak at
284.6 eV, and the atomic percentages of C and O were 97.0 at. % and 3.0
at. %. As shown in Fig. 2b, in the VOx@CP cathode, the V 2p was divided
5
Chemical Engineering Journal 433 (2022) 133574
into V3+ (13.6 at. %) and V4+ (14.3 at. %), locating at the binding en­
ergies of 516.5 eV and 516.8 eV. Since element O was almost from VO,
two species of metal binding oxygen V-O (31.8 at. % of OI, 530.2 eV) and
hydroxyl or surface adsorb oxygen (10.7 at. % of OII, 531.5 eV) in O 1s
were observed. In V3O7@CP anode (Fig. 2c), the peak of V 2p was
slimmer and located at higher binding energy, exhibiting V4+ species of
only 23.8 at. % due to the unique existence crystal of V3O7. It was
apparent that the shape of O 1s was also different from the one in
VOx@CP cathode. The extra 7.1 at. % of OIII was found at 530.7 eV,
which represented the defective oxygen species [50–53].
As shown from XRD patterns (Fig. 2d), three types of VOs were found
on electrodeposited cathode, namely V2O3, VO2 and V6O13 (unified as
VOx in this study), referring to PDF#71-0342, PDF#76-0677 and
PDF#89-0100. In Fig. 2e, the lowest-valence state was first oxidized as
all the diffraction peaks of V2O3 disappeared but VO2 and V6O13 still
existed after 10 min of reaction with H2O2 (Eq. (18)). When the reaction
reached balance after 60 min, the diffraction spectrum of V3O7
(PDF#71-0454) was observed, indicating the complete oxidation of VOx
to V3O7 after reacting with excess H2O2 (Eqs. (19), (20)). The anode
showed only one crystalline phase of V3O7 (Fig. 2f), which was engen­
dered according to Eq. (7). The vanadium deposited amounts at different
operating times were shown in Fig. S1. On the surface of cathode, the
yield of V increased from 0.79 mg⋅cm− 2 to 3.3 mg⋅cm− 2 as the electro­
deposition time prolonged from 2 min to 20 min. While, the yield of
anode was from 0.61 mg⋅cm− 2 to 2.7 mg⋅cm− 2, lower than that of the
cathode, probably due to the current occupation of OER side reaction
(Eq. (5)) and multi-deposition steps (Eqs. (6), (7)).
V2O3 + 3H2O2 → 2VO2 + 4⋅OH + H2O (18)
3VO2 + 3H2O2 → V3O7 + 4⋅OH + H2O (19)
V6O13 + 3H2O2 → 2V3O7 + 4⋅OH + H2O (20)
3.2. Electrochemical performance and catalytic activity of VOx@CP
cathode
Fig. 3a presents the Nyquist plots of the VOx@CP cathode, with the
equivalent circuits in the insets. The VOx exhibited insufficient intrinsic
electrical conductivity, since larger charge transfer resistance (Rct)
values were observed as the deposition time extending (Rct 0 min = 7.48
Ω, Rct 5 min = 16.42 Ω, Rct 10 min = 16.19 Ω and Rct 20 min = 41.16 Ω).
Also, the layer microstructure (Fig. 1c, d) brought a longer electron
transfer path, causing the presentation of second semicircle arcs repre­
sented as layer resistance (Rl, Rl 0 min = 0 Ω, Rl 5 min = 7.42 Ω, Rl 10 min =
22.24 Ω and Rl 20 min = 23.45 Ω, Table S2). These results suggested that
antibiotics degradation performance was likely to decrease as the
resistance increased with excessive VOx layer growth.
H2O2 generation were tested under a series of potentials (Fig. 3b,
J. Liang et al. Chemical Engineering Journal 433 (2022) 133574

Fig. 4. The H2O2 consumption yield under different H2O2 initial concentration with or without power supply (a); LSV curves obtained under different reaction times
with initial 2.0 mmol⋅L− 1 of H2O2 (b); The H2O2 consumption rate by VOx@CP cathode with initial 2.0 mmol⋅L− 1 of H2O2 (c).

Fig. 5. Quenching experiments on levofloxacin degradation by VO-EF system (addition amount: c[t-butanol] = 200 mmol∙L− 1, c[methanol] = 200 mmol∙L− 1 and c
[L-histidine] = 20 mmol∙L− 1) (a); Kinetic fitting results (b); EPR spectrum of the DMPO-OH signal operating for 20 min (c); and the cumulative yield of ⋅OH by VO-EF
system under different potentials (d).

Fig. S2a and b). In the CP, the optimal potential for H2O2 electro-
generation was − 0.90 V, with a production rate of 2.93 × 10− 4 ± 6.4
× 10− 6 mmol⋅L− 1⋅cm− 2⋅s− 1. Further increasing the applied potential to
− 1.1 V only resulted in slight improvement of H2O2 generation rate
(3.09 × 10− 4 ± 9.1 × 10− 6 mmol⋅L− 1⋅cm− 2⋅s− 1). However, the VOx@CP
cathode showed a much lower rate (1.44 × 10− 4 ± 8.5 × 10− 6
mmol⋅L− 1⋅cm− 2⋅s− 1) at − 0.90 V, which was likely due to that some of
H2O2 was consumed by low-valence state of VO (Fig. 2e).
Different initial concentrations of H2O2 were added to the system to
learn the performance of VOx@CP cathode with or without power
supply, and results were shown in Fig. 4a. Under applied voltage of
− 0.45 V, H2O2 consumption rate increased from 0.060 min− 1 to 0.082
min− 1 with initial H2O2 concentration of 0.5 mmol⋅L− 1, and increased
from 0.034 min− 1 to 0.046 min− 1 with H2O2 concentration of 1.0
mmol⋅L− 1 respectively (Fig. S3a). While, for the case with initial H2O2
concentration of 2.0 mmol⋅L− 1 and without the power supply, the con­
sumption reached balance (1.45 ± 0.22 mmol⋅L− 1, and consumption
rate of 0.013 min− 1) in 120 min, indicating relatively complete trans­
form of VOx to V3O7. As − 0.45 V was applied to the VOx@CP cathode,
the consumption value and consumption rate were enhanced to 1.87 ±
0.009 mmol⋅L− 1 and 0.020 min− 1 in 120 min, respectively, and no
balance was observed, indicating that V3O7 could be reduced back to
VOx for continual participation in catalytic reaction of H2O2 under
− 0.45 V.
LSV curves in Fig. 4b showed the cathode electrochemical reaction
intensity in the range from open circuit to HER potential. Two reduction
peaks were found at the potentials of 0 V and − 0.45 V (vs. SCE), iden­
tifying as the redox of V3O7/V6O13, VO2 and V6O13, VO2/V2O3 accord­
ing to XRD patterns in Fig. 2d, respectively. After adding 2.0 mmol⋅L− 1
H2O2 into the electrolyte, peak signal appeared at − 0.45 V became
stronger over reaction time (− 0.46 mA⋅cm− 2 for 0 min vs. − 1.22
mA⋅cm− 2 for 2 min vs. − 2.86 mA⋅cm− 2 for 10 min), owning to the
oxidized state increasing, suggesting that − 0.45 V was the optimal
reduction potential of V3O7. According to LSV results, three represen­
tative potentials (− 0.20 V, − 0.45 V and − 0.90 V) were selected for H2O2
consumption tests, and results were shown in Fig. 4c. VO played an
important role in H2O2 consumption (value of 95.56 ± 4.43% and rate of
0.019 min− 1 by VOx@CP at − 0.45 V vs. 10.33 ± 2.40%, 0.002 min− 1 by
CP for 120 min, Fig. S3b). Lower H2O2 consumption was shown at the
potential of − 0.20 V (85.56 ± 6.92%, 0.014 min− 1 by VOx@CP) due to

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J. Liang et al.
Fig. 6. Nyquist plots of the V3O7@CP anodes prepared under 0, 5, 10 and 20 min of electrodeposition times (a); LSV curves of V3O7@CP anodes (b); The EPR spectra
of V3O7@CP anode, VOx@CP cathode and CP (c). The comparison of LSV curves between the system of VOx@CP cathode/V3O7@CP anode and VOx@CP cathode/CP
anode (d).
the low energy supply. Surprisingly, the H2O2 consumption rate (89.37
± 4.72%, 0.017 min− 1) at − 0.90 V was still similar to that at − 0.45 V,
implying that − 0.90 V was the optimal potential for pollutants degra­
dation in the VO-EF system, since both rapid H2O2 generation rate and
high H2O2 consumption rate could be obtained from VOx@CP (Fig. 3b).
And the redox of V6O13, VO2/V2O3 played primary role in H2O2 con­
sumption because corresponding overpotential was closer compared
with the redox of V3O7/V6O13, VO2 (0.35 V vs. 0.90 V, Fig. 4b).
The reactive oxygen species (ROS) in VO-EF was identified by
quenching tests [7,34,54,55], and methanol, t-butanol and L-histidine
were employed as scavengers for SO4⋅− and ⋅OH, ⋅OH and 1O2, respec­
tively. As shown in Fig. 5 (a, b), after using methanol and t-butanol to
trap SO4⋅− and ⋅OH, obvious inhibitions towards levofloxacin degrada­
tion were observed, and the kobs in these cases were also similar (0.008
min− 1 by methanol and 0.006 min− 1 by t-butanol), confirming that ⋅OH
was generated by VOx@CP cathode as active species for levofloxacin
degradation. Nevertheless, when capturing 1O2 using L-histidine, only
slight reduction of levofloxacin degradation was appeared, indicating
that the contribution of 1O2 to degradation was very limited. The radi­
cals generated by H2O2 consumption was further identified by EPR test,
as shown in Fig. 5c. Four peaks with the intensity ratio of 1:2:2:1 were
observed when the H2O2 was catalyzed by VOx@CP cathode. The hy­
perfine splitting constants of aN = aH = 14.9 G, which was attributed to
DMPO-OH, illustrating the generation of ⋅OH. The cumulative yield of
⋅OH under various of potentials were measured by benzoic acid oxida­
tion (Fig. 5d). The highest ⋅OH concentration of 307 μmol⋅L− 1 within
180 min was achieved by VOx@CP under − 0.90 V. Thus, − 0.90 V was
selected as the applied potential in VO-EF system for other degradation
experiments. The ⋅OH yield decreased to 180 μmol⋅L− 1 under − 1.1 V,
suggesting that both 2e− ORR and redox of VOx were inhibited in this
case. Only 76 μmol⋅L− 1 of ⋅OH was detected under − 0.45 V due to the
lack of H2O2. It was worth mentioning that no ⋅OH yield was found in CP
cathode/V3O7@CP anode system, demonstrating that the ⋅OH genera­
tion was attributed to VOx@CP cathode.
7
Chemical Engineering Journal 433 (2022) 133574
3.3. The function of V3O7@CP anode
According to the Nyquist plot of V3O7@CP anodes in Fig. 6a, the Rct
also increased as the VO deposited (Rct 0 min = 6.86 Ω, Rct 5 min = 8.36 Ω,
Rct 10 min = 11.93 Ω and Rct 20 min = 17.99 Ω, Table S2). The OER po­
larization curves of V3O7@CP anodes obtained from electrodepositing
times were shown in Fig. 6b. CP showed an onset potential of 0.70 V and
a potential of 1.96 V to reach an anodic current density of 10 mA⋅cm− 2.
To achieve the same current level, 1.63 V was required by V3O7@CP (the
onset potential was 0.96 V), showing enhanced electrocatalyst perfor­
mance. As the anode deposition time was extended to 20 min, the po­
tential increased to 1.73 V.
The oxygen vacancies were further investigated by EPR, and results
were shown in Fig. 6c. Obvious double peaks at g = 2.00 could be seen
from the V3O7@CP anode, while neither the VOx@CP cathode nor CP
showed any signals, which was consistent with XPS results (Fig. 2b and
c). It could be deduced that the improvement of electrocatalytic per­
formance of the anode was attributed to the existence of oxygen va­
cancies in V3O7 [30,56]. Nevertheless, the defect sites on the V3O7
showed negligible catalytic activity to neither O2 nor H2O2, because no
⋅OH was detected (Fig. 5d), implying that the V3O7@CP anode played an
auxiliary role in VO-EF system by reducing the OER potential rather
than producing ROS to degrade pollutants. The VO-EF was set as dual-
electrode system (VOx@CP cathode as the working electrode and
V3O7@CP anode as the counter electrode) and executed LSV test. In
Fig. 6d, the auxiliary effect brought by V3O7@CP anode can be observed,
with 0.36 V positive shift of the VO reduction peak (cell voltage of 2.39
V decreased to 2.04 V) and enhancement of current density from 2.7
mA⋅cm− 2 to 3.4 mA⋅cm− 2. Therefore, the employ of V3O7@CP anode
was proven to be beneficial for the VO-EF system under a lower cell
voltage with a higher reaction current.
3.4. Degradation performance of VO-EF system
To evaluate the performance of VO-EF system, a series of levo­
floxacin degradation experiments by different EF systems were carried
J. Liang et al. Chemical Engineering Journal 433 (2022) 133574

Fig. 7. Levofloxacin degradation efficiencies in different EF systems (a); CV curves obtained by VOx@CP cathode under neutral pH (b); The recycle and vanadium
leaching (operating for 120 min per experiment) (c); TOC mineralization results and energy consumptions (d); The H2O2 generation rates at series applied potentials
under pH 7.30 (e); Degradation efficiencies of various antibiotics in the VO-EF system (f).

out, and results were shown in Fig. 7a and Fig. S4a. The highest
degradation efficiency of 97.67 ± 0.98% with the rate of 0.020 min− 1
was achieved in the VOx@CP cathode/V3O7@CP anode system, fol­
lowed by the case using VOx@CP cathode/CP system (removal of 83.45
± 1.28%). By contrast, very low levofloxacin removals were obtained
from the systems using CP cathode/V3O7@CP anode (35.13 ± 1.39%)
and CP cathode/CP anode (25.42 ± 0.26%), which was likely due to no
radicals generation in these systems. Without oxygen supplement, only
30.28 ± 5.00% of degradation efficiency by VOx@CP cathode/CP anode
was obtained, suggesting that H2O2 was the essential reaction reagent,
and levofloxacin degradation did not occur by valence change in VO.
The levofloxacin degradation processes over time were also shown in
Fig. S5 (a, b).
To explore the stability of the VO-EF system, the CV tests of VOx@CP
and CP were carried out. As shown in Fig. 7b, several obvious redox
peaks of VO could be seen in VOx@CP, while no peak was found from
CP, indicating the peaks were attributed to the redox of VO. Two
reduction peaks of − 0.45 V and 0 V were also observed in LSV. Besides,
the oxidation peaks located at 0.24 V and 0.66 V were found, indicating
the VO showed a reversible valence transition as heterogeneous
material.
The degradation experiments and V leaching detection were per­
formed within 120 min for 20 times, and results were displayed in
Fig. 7c. Desired degradation efficiencies (ranging from 89.9% to 81.2%)
were maintained, while V leaching were kept within 0.3–0.7 mg⋅L− 1,
showing excellent reusability of the VO-EF system. In addition, no sig­
nificant changes were observed from XRD patterns and SEM images after
cycle tests (Fig. S6a, b and c).
To further identify the degradation status and performance, TOC
mineralization was conducted. In Fig. 7d, after 600 min of treatment,
19.19 mg⋅L− 1 TOC was removed by VO-EF system with an energy con­
sumption of 12.3 J⋅mg⋅L− 1 TOC under pH 7.30. TOC removal of 15.10
mg⋅L− 1 with lower energy consumption was obtained from the VOx@CP
cathode/CP anode EF system because the average reaction current was
smaller (Fig. 6d).
Fig. 7e shows that the optimal H2O2 generation rate decreased to
7.60 × 10− 5 ± 6.7 × 10− 6 mmol⋅L− 1⋅cm− 2⋅s− 1 by CP compared with the
one in acidic condition due to the lack of hydrogen ion in the electrolyte.
Interestingly, merely 1.77 × 10− 5 ± 6.3 × 10− 6 mmol⋅L− 1⋅cm− 2⋅s− 1 was
detected at − 0.90 V, which demonstrated the efficient H2O2 consump­
tion ability of VOx@CP cathode even under neutral pH. Besides the
levofloxacin, series of antibiotics degradation tests were carried out
(Fig. 7f), and degradation trends were well-fitted by pseudo first-order
kinetic model (Fig. S4b). The tetracycline and chlortetracycline
showed similar removal results (95.97 ± 2.10%, 0.032 min− 1 and 96.33
± 0.81%, 0.040 min− 1), while ciprofloxacin exhibited similar results

8
J. Liang et al. Chemical Engineering Journal 433 (2022) 133574

Fig. 8. The levofloxacin degradation by VOx@CP cathode prepared by different electrodeposition times (a). The effects of different levofloxacin initial concentrations
(b), pH values (c) and electrolytes (d) on degradation performance.

Fig. 9. Digital graphs of the inhibition zones of degradation water samples at different treatment times against: E. coli (a-d) and S. aureus (e-h). The tablets were
dipped in water samples treated by VO-EF in 0 min (initial), 200 min, 400 min and 600 min. The initial concentration of levofloxacin was 30 mg⋅L− 1, the pH was
7.30. The operating condition of VO-EF was the same in Fig. 8d.

(92.00 ± 1.49%, 0.022 min− 1) with levofloxacin. Yet, only 60.32 ±
4.27% of chloramphenicol was removed and the kobs was 0.011 min− 1.
These results showed that the VO-EF system generally exhibited good
performance for various antibiotics degradation.
Fig. 8a and Fig. S7a presented levofloxacin degradation performance
using VOx@CP cathodes obtained from various electrodeposition times.
The highest levofloxacin removal of 83.45 ± 1.27% and the kinetic
constant of 0.012 min− 1 were achieved within 120 min using the
VOx@CP cathode obtained from electrodeposition time of 10 min,
which was almost the same with that from the cathode with electrode­
position time of 20 min (81.80 ± 3.96%, 0.013 min− 1). This result
demonstrated that 10 min was the optimal condition for electrodepo­
sition. In Fig. 8b, the efficiency by VO-EF decreased from 93.86 ± 1.58%
to 41.84 ± 3.08% as the initial concentrations of levofloxacin increased
from 5 mg⋅L− 1 to 30 mg⋅L− 1. The trend was consistent with previous
studies [7,57]. Fig. 8c showed the effect of pH on pollutants degrada­
tion. The optimal efficiency of 80.30 ± 1.62% (with a kinetic constant of
0.157 min− 1) was achieved within 15 min under pH 3.0 (Fig. S7c). As
the pH increased, the degradation rate decreased, especially in the first
60 min, which was mainly due to lower H2O2 generation rate as pH
increasing. However, when the reaction time was prolonged to 120 min,
similar degradation efficiencies were still achieved under various pH
conditions, indicating that desired performance could be obtained even
in neutral condition. Fig. 8d exhibited the degradation performance in
different electrolytes. With the same electrolyte concentration of 0.1
mol⋅L− 1, the degradation efficiencies in 120 min were similar (97.67 ±
0.98%, 0.02 min− 1 in Na2SO4, and 91.03 ± 2.67%, 0.019 min− 1 in NaCl,
Fig. S7d), except that with NaNO3 (83.69 ± 5.43%, 0.018 min− 1) and
NaHCO3 ((52.79 ± 3.53%, 0.008 min− 1). The presence of HCO3–
brought a dramatical decrease of removal, which could be due to that

9
J. Liang et al. Chemical Engineering Journal 433 (2022) 133574

Fig. 10. Possible degradation pathways of levofloxacin by VO-EF system (a). Possible reaction pathways in the initial reaction of levofloxacin with ⋅OH (b).
Schematic diagram of Gibbs free energy for the ⋅OH-initiated reactions via hydrogen atom transfer (HAT) and radical adduct formation (RAF) pathways (c).

water should be responsible for the declined degradation because they

Fig. 11. Possible mechanism of the VO-EF system for levofloxacin degradation.
the HCO3– could act as the radical scavenger [34,58]. The levofloxacin
degradation by the VO-EF system was also tested in tap water (Fig. S8a).
Removal efficiency of 81.02 ± 2.39% and kinetics of 0.013 min− 1
(Fig. S8b) were obtained in this case, lower than that using distilled
water (kinetics of 0.020 min− 1). Some inorganic anions presented in tap
could consume radicals.
To estimate the bioavailability of the treated effluent, two classic
microorganisms, Escherichia coli (E. coli) and Staphylococcus aureus
(S. aureus), were applied against the antibiotic degradation products
obtained from different degradation times (Fig. 9). The diameters of
each inhibition zone were listed in Table S3. The initial sample showed
an obvious inhibition zone (26.5 ± 1.5 mm, Fig. 9a) due to severe
antibacterial properties of levofloxacin. As the degradation occurring,
lower concentration of levofloxacin resulted in less inhibition towards
microorganisms, leading to the inhibition zone decreased to 18.5 ± 0.5
mm (200 min, Fig. 9b), 11.0 ± 1.0 mm (400 min, Fig. 9c) and totally
disappeared in 600 min (Fig. 9d). Compared with E. coli, the levo­
floxacin showed less severe depressing effect on S. aureus as the initial
inhibition zone was 19.5 ± 1.5 mm (Fig. 9e). After 200 min of treatment,
the diameter of the zone decreased to 12.0 ± 1.0 mm (Fig. 9f), and no
ring was observed as the time extended to 400 min (Fig. 9g), though the
TOC of 6.7 mg⋅L− 1 was still remained (Fig. 7d), revealing that the low
concentration of levofloxacin and the intermediates exhibited negligible
effect to the growth of S. aureus. It was worth noting that, high con­
centration of H2O2 also suppressed microbial growth. When extra 2.0
mmol⋅L− 1 of H2O2 was added into electrolyte without EF disposal or

Table 1
The comparison of heterogeneous EF efficiency between previous ferrum oxide EF and the current VO-EF.
Electrodes Cathode; Anode; Pollutant (initial pH H2O2 residual Mineralization efficiency /disposal Energy Reference
concentration) mmol⋅L− 1 time consumption

γ-FeOOH GPCA; carbon felt; Sulfamethoxazle (10 mg⋅L− 1) 6.5–7.5 untested 96%/300 min / [15]
Fe3O4-NP@CNF; Pt wire; Carbamazepine (1 mg⋅L− 1) 7 ~40 (cumulated) 100%/180 min 37.3 J⋅mg⋅L− 1
TOC [16]
FeOx/NHPC750; Pt piece; Phenol (50 mg⋅L− 1) 6 ~1.0 83%/420 min / [64]
Fe@Fe2O3FCA; boron-doped Metalaxyl (500 mg⋅L− 1) 6 ~0.21 98%/240 min 23.0 J⋅mg⋅L− 1
TOC [17]
diamond;
FeCuC aerogel; boron-doped Methylene blue (50 mg⋅L− 1) 5 untested 82%/60 min 6.3 J⋅mg⋅L− 1
TOC [18]
diamond;
VOx@CP; V3O7@CP; Levofloxacin (30 mg⋅L− 1) 7.3 0.15 80%/600 min 12.3 J⋅mg⋅L− 1
TOC This work

10
J. Liang et al.
levofloxacin addition, inhibition zone of 25.0 ± 1.0 mm for E. coli
(Fig. S9a) and 19.5 ± 0.5 mm for S. aureus (Fig. S9b) were still observed.
Large amount of residual H2O2 was commonly existed in tradition EF
systems, which hindered the growth of microorganisms. In the VO-EF
system, the efficient catalysis of H2O2 by VO to produce ⋅OH for
degradation ensured a low residual concentration under neutral pH
condition (Fig. 7e). Therefore, the effluent showed negligible influence
on microbial growth (Fig. 9d, h).
3.5. Degradation intermediates identification and possible degradation
pathways
The LC-MS was carried out to further study levofloxacin degradation
process in the VO-EF system, and the result was shown in Fig. 10a (The
LC-MS spectra of the degradation intermediates was shown in Fig. S10
and specific information of the intermediates were listed in Table S4).
Four main possible degradation pathways were summarized according
to identified intermediates (P0 to P12). The pathway 1 was started from
the breakage of -C14 = C15- on heterocyclic ring (P0 to P1) according to
the previous natural bond orbital theory study [59]. After the F atom
was replaced by hydroxyl group and also losing a carboxyl group, the P2
was formed. The -C5-C6- was the possible site being attack by ⋅OH,
leading to ring opening reaction of piperazine [60]. The P5 (m/z = 211)
was finally detected. In pathway 2, demethylation, defluorination and
decarboxylation occurred in sequence on the piperazine ring to produce
P6 and P7. The P8 was formed by removing piperazine group and
remaining the amino group on the benzene ring. The P9 with the
smallest m/z = 194 was detected, and the oxygen in ketone group O17
and tertiary amine N16 that may act as hydrogen bond acceptors,
forming hydroxy and secondary amine group [61]. The depiperazine
reaction took precedence in pathway 3, producing P10; while the
carbonyl (O23), methyl group (C25 and C26) and F24 were replaced by
hydroxyl groups in pathway 4, producing P12. Both pathways shared
the same terminal product of P9. Compared with iron-based EF system,
the degradation process could be similar since the ROS was ⋅OH in both
systems. In particular, the process of depiperazine was also occurred
[62], and the breakage of -C14 = C15- on heterocyclic ring and
defluorination process were found in the study of Fe3O4/GF electrode
applied in EF system [63].
The quantum chemistry calculation was carried out to get deeper
insight into the levofloxacin degradation pathways. According to the
structure of the first intermediates in each pathway (P1, P6 P10 and P12,
Fig. 10a), ⋅OH-initiated oxidation reaction of levofloxacin was discussed
in two different mechanisms of hydrogen atom transfer (HAT) and
radical adduct formation (RAF). The OH-addition pathways were
assumed at C8 (RAF1) and C15 (RAF2) for the formation of P12 and P1,
while the H-abstraction reaction in C1 (HAT1) and C26 (HAT2) were the
key to forming the P10 and P6 (Fig. 10b). The Gibbs free energy barriers
were shown in Fig. 10c, and the optimized geometries of structures were
shown in Fig. S11. All the pathways were exothermic since reaction
energies were negative (from − 3.6 to − 26.8 kcal⋅mol− 1). HAT2 showed
the lowest energy of 6.1 kcal⋅mol− 1, indicating the H-abstraction in C26
was the most favorable reaction. HAT1 exhibited a similar value of 6.4
kcal⋅mol− 1, but larger value of 9.9 kcal⋅mol− 1 and 13.0 kcal⋅mol− 1 were
shown in RAF1 and RAF2, suggesting that the HAT was more likely to
occur than the RAF pathways in aquatic environments for the ⋅OH
attacking. The P6 and P10 were inclined to be formed compared with P1
and P12 during the ⋅OH attacking, which was consistent with previous
frontier electron density theory study [60]. It can be concluded that the
cracking of the piperazine moiety and demethylation were preferred
while higher energy was required in defluorination and benzene ring-
opening. Thus, pathway 2 and 3 were priority in levofloxacin
degradation.
The degradation mechanism of levofloxacin by the VO-EF system
was shown in Fig. 11 based on the discussion and analysis above.
11
Chemical Engineering Journal 433 (2022) 133574
3.6. The comparison of VO-EF with previous reported ferrum-based-EF
The performance of VO-EF system was compared with previously
reported ferrum-based-EF systems in the aspects of operation conditions,
mineralization efficiency and energy consumption, as shown in Table 1.
Series of ferrum-based materials showed remarkable treatment perfor­
mance. In comparison, the advantages of the VO-EF system were
demonstrated as the low H2O2 residual and low energy consumption
under neutral condition accompanied with a long treatment time due to
the high concentrate of levofloxacin, illustrating the great practical
potential for VO-EF system in the hospital and pharmaceutical effluent
treatment.
4. Conclusions
In this work, a novel VO-EF system, consisting of a VOx@CP cathode
and a V3O7@CP anode, was developed for efficient degradation of lev­
ofloxacin under neutral pH condition. In this system, the redox of VO2,
V6O13/V2O3 occurred on the VOx@CP cathode made significant
contribution to levofloxacin degradation by catalyzing the H2O2 to
generate ⋅OH. Under the optimal potential of − 0.90 V for 2e− ORR, the
VOx@CP cathode still achieved rapid H2O2 decomposition rate of 0.017
min− 1. Both electrochemical reactions showed good coordination,
ensuring efficient and continuous degradation of antibiotics. On the
other side, the oxygen vacancies in the V3O7 anode could reduce the
OER potential, allowing the system operating in a lower cell voltage. The
VO-EF system was able to remove 19.19 mg⋅L− 1 TOC with lower EC of
12.3 J⋅mg⋅L− 1 TOC under pH 7.30 in 600 min. What‘s more, compared
with the previous ferrum-based EF systems, the VO-EF system showed
lower energy consumption. Also, the effluent exhibited negligible inhi­
bition to microbial growth because of the lower H2O2 residual. Four
degradation pathways were proposed according to LC-MS results, and
pathway 3 was identified as the primary mechanism due to the lowest
energy required for the cracking of the piperazine moiety on the basis of
Gaussian calculation results. This work provides inspiration for devel­
opment of ferrum substitutional materials for heterogeneous EF systems
for efficient environmental remediation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (Nos. 21707021, 51668006), Natural Science Foundation of
Guangxi (No. 2020GXNSFAA297034), Guangxi Science and Technology
Research Program (No. AA18118013), and Research Project of Bosch
Branch of Guangxi University Graduate School (GXU-BFY-2020-036).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.133574.
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