Environmental Pollution 263 (2020) 114436

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Electrochemical oxidation of ceftazidime with graphite/CNT-Ce/

PbO2eCe anode: Parameter optimization, toxicity analysis and
degradation pathway*
Pingzhou Duan, Shiheng Gao, Jiawei Lei, Xiang Li, Xiang Hu*
Research Group of Water Pollution Control and Water Reclamation, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing,
100029, China

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the electrochemical degradation of antibiotic ceftazidime has been studied using a novel
Received 7 August 2019 rare earth metal Ce and carbon nanotubes codoped PbO2 electrode. A competitively high oxygen evo-
Received in revised form lution potential (2.4 V) and enhanced catalytic surface area were obtained, evidence by LSV and CV
11 February 2020
electrochemical characterization. The G/CNT-Ce/PbO2eCe electrode possessed a more compact structure
Accepted 21 March 2020
Available online 30 March 2020
and a smaller grain size than the other PbO2 and CeePbO2 electrodes, exhibiting a prolonged service
lifetime, evidence by accelerated lifespan test and recycling degradation experiment. As electrolysis time
reached 120 min, the removal efficiency of ceftazidime and TOC arrived at 100.0% and 54.2% respectively
Keywords:
Electrochemical degradation
in 0.05 M Na2SO4 solution containing 50 mg,L
1 ceftazidime. The effect of applied current density, pH
Ceftazidime value, initial ceftazidime concentration and chloride contents on the degradation performance were
G/CNT-Ce/PbO2eCe systematically evaluated. The results demonstrated that electrochemical oxidation of ceftazidime over
Degradation pathway the G/CNT-Ce/PbO2eCe electrode was highly effective, and the mineralization rate was greatly improved,
Ecotoxicity compared with pristine PbO2 electrode. Considering the toxicity was increased after 30 min electrolysis,
the intermediates were quantitatively investigated through HPLC-MS, GC-MS and IC technology. Ac-
cording to the identified products, a reaction mechanism has been proposed and pyridine and amino-
thiazole were detected with concentration from approximately 1 to 3 mg,L
1, which were regarded as
toxic byproducts during electrooxidation. Further electrocatalyzing by ring cleavage reaction and com-
plete mineralization to CO2, NO
þ
3 and NH4 was proposed, which demonstrated the G/CNT-Ce/PbO2eCe
electrode exhibited high efficiency for ceftazidime removal in mild conditions.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction environmental compatibility (Brillas and Martínez-Huitle, 2015).

In the past decades, electrochemical advanced oxidation pro-
cesses (EAOPs) have received widespread attentions for purifica-
tion wastewater or drinking water sources, as one of the most
powerful advanced oxidation processes (AOPs) that can even
degrade highly recalcitrant compounds (Feng et al., 2013).
Compared with other AOPs such as UVC radiation (H2O2/UVC,
Chlorine/UVC), ozone based processes (O3/UVC, O3/H2O2) and
Fenton based reactions (Fe2þ/H2O2 and photo-Fenton), EAOPs have
advanced oxidizing ability, mild working conditions and
*
This paper has been recommended for acceptance by Baoshan Xing.
* Corresponding author. College of Chemical Engineering, Beijing University of
Chemical Technology, No. 15 Beisanhuan East Road, Beijing 100029, PR China.
E-mail address: huxiang@mail.buct.edu.cn (X. Hu).
EAOPs have the advantages of minimizing organic pollutants
through indirect oxidation by highly reactive hydroxyl radicals
($OH) or by the produced electrons (e
), which can directly oxidize
organic compounds on the anode surface (Radjenovic and Sedlak,
2015; Sillanpa €a
€ et al., 2018). So far, it is broadly recognized that
the performance of EAOPs is greatly affected by the activity and
stability of anode (Vargas et al., 2016). Among which, SnO2eSb, lead
oxide (PbO2) and boron doped diamond (BDD) are the most
powerful non-active anodes, which have higher anodic potential
and weaker attachment with the produced $OH, thus they
demonstrate great potentials for eliminating organic pollutants
with high electrical efficiencies (Moreira et al., 2014; Wu et al.,
2014; Flores et al., 2017). However, BDD anode has a very high
cost and extreme difficulties to find an appropriate substrate for
deposition of the diamond layer limit its large-scale application.

https://doi.org/10.1016/j.envpol.2020.114436
0269-7491/© 2020 Elsevier Ltd. All rights reserved.
2 P. Duan et al. / Environmental Pollution 263 (2020) 114436
SnO2eSb anode has a very short lifetime especially when Cl
exists,
which can react with SnO2 to form SnCl4. Therefore, PbO2 ignited
people’s interest as a low-cost anode with high electrical conduc-
tivity (comparable to metals), high oxygen evolution potential and
reliable stability in controlled conditions (Li et al., 2011; Xie et al.,
2017).
On the other hand, carbon nanotubes (CNT) have great potential
application in electrocatalysis as supports due to their high specific
area, advanced mechanical and chemical properties as a novel 2-
dimensional material (Wang et al., 2019). Thus, it is expected to
improve electrocatalytic activity and stability of PbO2 electrode
through introducing a carbon nanotube interlayer. It was achieved
an OEP of 2.1e2.2 V on LAS-CNT-PbO2 electrode (Duan et al., 2012).
With close OEP values to BDD anode and superior surface areas, a
carbon nanotube modified PbO2 anode is regarded to have a
promising development for resilient wastewater treatment.
Furthermore, the doping of rare earth metals into PbO2 had pre-
sented high electrocatalytic activity and stability towards the
degradation of recalcitrant organic compounds (Dai et al., 2016a).
Cerium oxide (CeO2) was proved to be able to enhance the OEP
value and stability of both carbon nanotubes and non-active anodes
(Hu et al., 2016; Lin et al., 2013; Nazari et al., 2019), suggesting CeO2
is a reasonable choice as a dopant for PbO2 anode.
Recently, cephalosporin antibiotics including ceftazidime, cef-
triaxone, cephalexin etc., as one category of mostly prescribed an-
tibiotics and produced in large amounts, have been ubiquitously
measured in a broad density spectrum in aquatic environment and
produced wastewaters (Gurung et al., 2018; Haller et al., 2018;
Ribeiro et al., 2018). According to the accomplished works, cepha-
losporins are one of the pollutants most frequently detected.
Cephalexin (523.3e977.7 ng,L
1) and cefixime

1
(278.65e422.1 ng,L ) were reported in the inlet and outflow of
wastewater treatment facility located in Tehran, Iran (Mirzaei et al.,
2018). An investigation on the distribution and persistence of
cephalosporins demonstrated that the mean concentrations of the
seven cephalosporins were 12.85e141.55 mg,L
1 and

1
0.05e24.38 mg,L in cephalosporin producing wastewater
influent and effluent, respectively, and that up to 1.9 kg of cepha-
losporins was discharged per day from the pharmaceutical indus-
trial park in Shijiazhuang city, China (Yu et al., 2016). The
continuous discharge from WWTPs and/or hospitals were respon-
sible for the high level of antibiotics (Xu et al., 2016b). Ceftazidime
is the third generation of cephalosporins family and is often used to
treat respiratory, intestinal and abdominal infections, however, its
residual in ecosystem and bioaccumulation may generate chromic
toxic to living organisms and promote resistance genes (Wang and
Lin, 2012). Therefore, it is urgent to analyze the degradation
pathway and evaluate the toxicity of intermediates. Nevertheless,
the complete electrochemical degradation pathway of ceftazidime
is not thoroughly investigated and the mechanism of intermediate
toxicity fluctuation remains unclear. Deeper research into the
degradation pathway of the ceftazidime degradation process can
provide more comprehensive understandings of the intermediates
and benefit the implementation of wastewater treatment con-
taining ceftazidime.
In this study, a novel Graphite/a-PbO2/CNT-Ce/b-PbO2-Ce (G/
CNT-Ce/PbO2eCe) doped with CeO2 was fabricated by spraying a
CNT layer and electrodeposition a b-PbO2 active layer. Comparative
electrodes Graphite/a-PbO2/b-PbO2 (G/PbO2), Graphite/a-PbO2/
CNT/b-PbO2 (G/CNT/PbO2) and Graphite/a-PbO2/CNT-Ce/b-PbO2
(G/CNT-Ce/PbO2) were synthesized in same approaches, followed
by morphology, crystalline structure, chemical state and electro-
chemical performances characterizations. The electrochemical
degradation of ceftazidime and removal of total organic carbon
(TOC) were evaluated under different operation conditions.
Furthermore, all the intermediates detected by GC-MS and HPLC-
MS was completely analyzed with a deeper understanding by the
toxicity analysis with Microtox method using bioluminescent Vibrio
fischeri bacteria.
2. Material and methods
2.1. Preparing the graphite/CNT/PbO2 electrode
Firstly, the multi-walled carbon nanotubes purchased from J&K
Chemical Ltd. (Beijing, China) were refluxed in 50% HNO3 solution
at 105  C and washed with deionized water until pH ¼ 7, followed
by drying in a 100  C oven overnight, forming a CeOH group
introduced CNT powder. The fabrication of cerium doped CNT
(CNT-Ce) was synthesized by mixing CNT and Ce(NO3)4 in glycol
and calcined in nitrogen gas at 500  C. Secondly, graphite plates
underwent 10 min of ultrasonic cleaning in 10% NaOH, 10 min in
10% HNO3, 10 min in acetone successively, and rinsing with
deionized water. An intermediate layer of a-PbO2 was electro-
deposited in alkaline solution (0.1 M PbO, 3.5 M NaOH) at 40  C
under a current density of 3.5 mA,cm
2 for 1 h. Then CNT or CNT-
Ce sol was made by mixing 10 mg CNT, 10 mL Isopropanol and
0.05 mL Nafion®, dipped onto the graphite plate with 60 mL micro-
sampler to form the CNT interlayer. Finally, active b-PbO2 film was
electrodeposited in acid solution (0.5 M Pb(NO3)2, 0.05 M NaF, 1 M
HNO3) under a current density of 15 mA,cm
2 for 1 h. Graphite/
CNT-Ce/PbO2 plate was fabricated in the same way except for
changing the solvent to CNT-Ce composite. b-PbO2-Ce outerlayer
was electrodeposited in solution of 0.5 M Pb(NO3)2, 0.01 M
Ce(NO3)3, 0.05 M NaF, 1 M HNO3.
2.2. Characterization of graphite/CNT/PbO2 electrode
The linear sweep voltammetry (LSV), cyclic voltammetry curves
(CV), Nyquist plots (EIS) and accelerated lifetime test were con-
ducted in a CHI-660D electrochemical workstation (Shanghai
Chenhua Instrument Co. Ltd., China). Scanning electron microscopy
(SEM), X-ray diffraction (XRD) and X-ray photoelectron spectros-
copy (XPS) were adopted to investigate surface structure, elemental
composition and state of modified electrodes. The Hydroxyl radical
production levels of anodes were determined with terephthalic
acid (TA) as the capture reagent and fluorescence spectrophotom-
eter (F-7000 FL Spectrophotometer). Detailed information about
characterization process was enclosed in Supplementary Material.
2.3. Electrochemical oxidation of ceftazidime
The electrochemical degradation experiment was set up in a
150 mL beaker and a titanium plate (3 cm  3 cm) was used as
cathode. Analytical grade ceftazidime (C22H22N6O7S2, 99.8%) was
purchased from Alfa esar. Specific physico-chemical properties and
chemical structure of ceftazidime were depicted in Fig. S-1 and
Tables Se1. The degradation experiment process and parameter
optimization were described in Supplementary Material.
2.4. Analytical methods
The concentration of ceftazidime was determined by High-
performance liquid chromatography (HPLC, LC-10AT, Shimadzu,
Japan) equipped with a WondasilTM C-18 column
(4.6 mm  150 mm, 5 mm) as our previous study (Hu et al., 2016).
The intermediates were detected by UPLC-MS and gas
chromatograph-mass spectrometer (GC-MS, 6890GC/5973MSD,
Agilent, USA). Total organic carbon (TOC) was determined with
Shimadzu VCSN TOC analyzer for the calculation of current
 P. Duan et al. / Environmental Pollution 263 (2020) 114436 3

efficiency values. Inorganic ions and toxicity of the treated cefta-

zidime solution was evaluated. Detailed testing procedures were
depicted in Supplementary Material.

3. Results and discussion

3.1. Characterization of graphite/CNT/PbO2 electrode

The SEM morphology of differently fabricated G/CNT/PbO2

electrodes are shown in Fig. 1(a) ~ (d), respectively. It is demon-
strated that pyramid crystal shaped b-PbO2 particles have much
smaller grain size and more compact structure than pristine PbO2
electrode (Duan et al., 2012). Moreover, the formed b-PbO2 on CNT
interlayer is uneven and stratified which increase the specific sur-
face area of this electrode. The TEM of CeO2 modified and un-
modified CNTs were shown in Fig. S-2, indicating CeO2
nanoparticles were attached onto fibers. No exposed CNT can be
noticed in Fig. 1(c) and (d), indicating PbO2 layer can be finely Fig. 2. XRD pattern of G/CNT/PbO2, G/CNT-Ce/PbO2 and G/CNT-Ce/PbO2eCe electrodes.
growed on CNT interlayer with reliable stability (Duan et al., 2016;
Xu et al., 2017). Moreover, both G/CNT/PbO2 and G/CNT-Ce/PbO2
exhibited more porous structure, indicating a larger surface area. X-Ray Photoelectron Spectroscopy (XPS) was adopted to quan-
Specifically, the G/CNT-Ce/PbO2eCe electrode had smaller particles tify the surface elemental composition and the results are shown in
and more compact, stable morphology, indicating incorporation of Fig. 3. Fig. 3(a) present the general XPS survey spectrum of the G/
Ce into film could improve the structure effectively. In order to CNT-Ce/PbO2eCe electrode. The surface elements contain C, O, Pb,
further explain the changes of surface structures, the physico- Ce and F with atomic ratio of 22.95%, 34.81, 35.81%, 3.27% and 3.17%
chemical properties of different electrodes were presented in respectively. As shown in Fig. 3(b), five peaks at 883.6, 890.6, 899.1,
Tables Se2, indicating an increasing of catalyzing sites after CNT 901.7 and 918.1 eV were found for the G/CNT-Ce/PbO2eCe samples
and CeO2 added. and were assigned to Ce3d5/2 and Ce3d3/2. All these verified that
Fig. 2 presents XRD patterns of G/CNT/PbO2, G/CNT-Ce/PbO2 and cerium existed as Ce4þ (Xu et al., 2018). As shown in Fig. 3(c), the Pb
G/CNT-Ce/PbO2eCe electrodes. The crystal structure of PbO2 is pure 4f spectra, exhibits two well defined and symmetric peaks centered
b-PbO2 and the main crystal plane of b-PbO2 is (110) plane in all the at 142.7 eV and 137.9 eV, which corresponding to Pb 4f 5/2 and Pb
electrodes, which is in good agreement with standard data of the 4f 7/2, respectively (Xie et al., 2017). The binding energy of O1s was
JCPDS card (number: 760564). The diffraction peaks observed at indicated in Fig. 3(d). Beside the major peak at 529.2 eV, the sub-
2q ¼ 25.3 , 31.9 ,36.1, 49.0 , 58.8 , 62.4 and 66.7 are assigned to peak at the higher binding energy at 530.7 eV was observed, sug-
the (110), (101), (200), (211), (310), (301) and (202) planes of b- gesting the existence of weak bound oxygen species, such as the
PbO2. No diffraction peak of CeO2 was found because there was too adsorbed $OH or water.
little CeO2 in the PbO2 film to be detected by XRD analysis (Wang
et al., 2017b; Xu et al., 2018; Yao et al., 2018).

Fig. 1. SEM of (a) G/PbO2, (b) G/CNT/PbO2, (c) G/CNT-Ce/PbO2 and (d) G/CNT-Ce/PbO2eCe electrodes.
4 P. Duan et al. / Environmental Pollution 263 (2020) 114436
Fig. 3. XPS spectrum of G/CNT-Ce/PbO2eCe electrode: (a) total spectrum, (b) Pb 4f spectrum, (c) Ce 3d spectrum, (d) O 1s spectrum.
3.2. Electrochemical measurements
An enhancement of OEP is desired in the improvement of
electrode material for ceftazidime degradation. Fig. 4(a) shows the
LSV of differently modified G/PbO2 electrodes. As seen from the
polarization curve, the bare PbO2 electrode had an OEP value of
1.55 V (vs. SCE) which was similar to previous studies (Xu et al.,
2017). On the other hand, approximately 1.9 V OEP was observed
on G/CNT/PbO2 and G/CNT-Ce/PbO2 electrodes, which were higher
than those in previous studies (Dai et al., 2016b). The doping of Ce
onto CNTs have a slight promotion for the OEP value of PbO2
electrode. The enhancement of OEP values may attributed to the
smaller particle size of PbO2 crystal lattice (Xu et al., 2018). The
introduction of CNT interlayer makes great contribution to the
porosity of PbO2 outer layer which could inhibit water diffusing
into the interior, resulting in a weakened oxygen evolution reac-
tion. The increased OEP could limit the oxygen evolution reaction
and increase the production of $OH. Moreover, it would accelerate
the degradation efficiency of pollutant and benefit the current ef-
ficiency. The highest OEP value of 2.4 V (vs. SCE) was measured on
G/CNT-Ce/PbO2eCe, which may be attributed to the unique outer
electronic structure of rare metal elements (Wang et al., 2017b; Xu
et al., 2018). This is very competitive towards expensive BDD
electrodes as a cost-effective and high efficiency material (He et al.,
2015).
The CV of the modified PbO2 electrodes in 0.1 M Na2SO4 solution
containing 50 mg,L
1 ceftazidime at a scan rate of 10 mV,s
1 at
room temperature were shown in Fig. 4(b). It can be seen on G/CNT-
Ce/PbO2 and G/CNT-Ce/PbO2eCe electrode that there were slight
oxidation peaks at 1.05 V and 1.42 V vs. SCE prior to the oxygen
evolution potential. While the reverse potential scan showed one
cathodic peak at 0.76 V which corresponded to the reduction-
oxidation of Pb(II) and Pb(IV) in the film (El-Sherbini and Abd El
Rehim, 2004). It is indicated that compared with pristine PbO2
electrode, the introduction of CeO2 can improve oxidation peak
currents at lower potentials, demonstrating a higher direct oxida-
tion capacity and suggested that the novel electrode was more
applicable for the degradation of ceftazidime (Xu et al., 2016a). The
CV curves also demonstrated that CNT and CeO2 doping performed
an important role in increasing the specific surface area of PbO2
film, which could provide more catalytic sits for ceftazidime
decomposition. It has been reported that researchers normally
employ CV analysis to evaluate electrochemical surface area (Zhou
et al., 2017), because the voltammetric charge (q*) of an electrode
was calculated by a graphical integrator from the cyclic voltam-
metry curves. As seen from Fig. 4(b), G/CNT-Ce/PbO2eCe electrode
possessed a higher double layer capacitance compared with pris-
tine PbO2 electrode, proving it had the maximal electrochemical
surface area (Yang et al., 2016b).
The stability of novel G/CNT-Ce/PbO2eCe was examined by
accelerated lifetime test, as shown in Fig. 4(c). For comparison, G/
PbO2 and G/CNT-Ce/PbO2 were also tested under the same condi-
tion to illustrate the performance of CNT-Ce interlayer and CeO2
dopant. The electrode is regarded as invalided when the voltage
reaches beyond 15 V. It can be demonstrated that CNT-Ce interlayer
greatly promoted the accelerated lifetime from 12 h to 21 h. Further
CeO2 dopant increased it to 25 h. The enhancement of service life
can be attributed to the compact structure and the introduction Ce
into PbO2 film. Fig. 4(d) illustrate the consecutive degradation ef-
ficiency with traditional G/PbO2 electrode and novel G/CNT-Ce/
 P. Duan et al. / Environmental Pollution 263 (2020) 114436 5

Fig. 4. (a) LSV curves and (b) CV curves of G/PbO2, G/CNT/PbO2, G/CNT-Ce/PbO2 and G/CNT-Ce/PbO2eCe electrodes in 0.1 M Na2SO4 solution containing 50 mg,L
1 ceftazidime; (c)
accelerated lifetime test of G/PbO2, G/CNT-Ce/PbO2 and G/CNT-Ce/PbO2eCe electrodes in 1 M H2SO4 solution; (d) consecutive degradation test with G/PbO2 and G/CNT-Ce/PbO2eCe
electrodes under current of 80 mA in 0.05 M Na2SO4 solution containing 50 mg,L
1 ceftazidime; (e) Nyquist plots of bare G/PbO2, G/CNT/PbO2, G/CNT-Ce/PbO2 and G/CNT-Ce/
PbO2eCe electrodes; (f) fluorescent accumulation of $OH amount on different electrodes after 30 min electrolysis, inset figure is the linear fit of $OH accumulation strength with
electrolysis time.

PbO2eCe. Very prominent stability and electrocatalyzing
enhancement can be distinguished. Furthermore, Fig. S-3 shows
the surface morphology after 10 h usage under current of 80 mA.
Graphite/PbO2 was damaged with more fractures and collapses. On
the contrary, electrodes with a CNT-Ce interlayer had no significant
variation in morphology. Thus, introduction of CNT-Ce interlayer is
contributed to the enhancement of electrode stability and catalytic
activity at the same time.
Nyquist plots of were conducted to further investigate the
electrochemical impedance of the modified electrodes with
equivalent circuit model of Rs[CPEdl(RctCPE0)]. Rct represents the
charge transfer resistance of surface-electrolyte interface, Rs in-
dicates uncompensated ohmic resistance between working elec-
trode and reference electrode, CPEdl means constant phase element
of double layer and CPE0 equals constant phase element between
the electrode surface and substrate. As shown in Fig. 4(e),
6 P. Duan et al. / Environmental Pollution 263 (2020) 114436
semicircle patterns were gradually reduced which correspond to
the charge transfer reaction, demonstrating the addition of CNT
interlayer and CeO2 nanoparticles have decreased electrochemical
impedance. Lowest Rct of 5.12 U,cm
2 was obtained on G/CNT-Ce/
PbO2eCe indicating the fastest electron transfer rate.
The $OH generation capability was compared in Fig. 4(f). Fluo-
rescence intensity after 30 min electrolysis follow the sequence of
G/PbO2 < G/CNT/PbO2 < G/CNT-Ce/PbO2 < G/CNT-Ce/PbO2eCe.
Inset figure illustrates the intensity at 425 nm followed a linear
increase, proving the $OH radicals were continuously produced on
the anodes and G/CNT-Ce/PbO2eCe was fabricated with a highest
electro-catalytic ability.
3.3. Degradation performance and toxicity evaluation
Based on the above characterization results, the G/CNT-Ce/
PbO2eCe electrode should exhibit higher catalytic activity than
traditional PbO2 electrode. Therefore, electrochemical degradation
experiments were carried out in a 150 mL batch reactor under
current of 40 mA. Fig. 5(a) shows the concentration evolution of
ceftazidime as a function of electrolysis time. Clearly, the intro-
duction of CNT interlayer and CeO2 significantly enhance ceftazi-
dime removal efficiency, with an improvement from 80.8% to 100%
with 120 min electrolysis time. Moreover, as illustrated in Fig. 5(a),
the bioluminescence inhibition ratio exhibited great fluctuations
during the ceftazidime electrochemical oxidation. The biolumi-
nescence inhibition ratio rises up seriously after 30 min degrada-
tion and drops significantly afterwards. This phenomenon indicates
the production of some intermediates with even higher toxicity
than ceftazidime and a further decomposition lead to the abating of
toxicity. Similar results were reported in previous study, including
electrochemical oxidation of enrofloxacin (Wang et al., 2017a), the
antibiotic sulfachloropyridazine (Haidar et al., 2013), and ultra-
sound electrochemical degradation of cephalosporin pharmaceu-
tical wastewater (Yang et al., 2016a), etc. Thus, it is indicated that
the electrochemical degradation of antibiotics always import
higher toxic intermediates and the removal processes need to be
conducted thoroughly with enough electrolysis time and power.
The degradation process was also evaluated by current effi-
ciency (MCE) and total organic compounds (TOC) removal rate. As
seen in Fig. 5(b), the TOC removal rate was increased as a function
of treatment time and approximated 54.2% of TOC was eliminated
after 120 min electrolysis with our novel electrode. Compared with
the ceftazidime removal efficiency, TOC removal was much lower,
Fig. 5. (a) Ceftazidime removal efficiency and toxicity evaluation with bioluminescence Vibrio fischeri at 20  C. (b) TOC removal and current efficiency against time. The exper-
imental condition was 40 mA current, 20 mm electrode spacing, 50 mg L
1 ceftazidime initial concentration and 0.05 M Na2SO4 as supporting electrolyte.
indicating the ceftazidime was transformed into small molecules.
On the other hand, the current efficiency was calculated. As
observed, it decreased significantly with the electrolysis time in-
creases. Because it is commonly accepted that the electrochemical
oxidation of an organic pollutant follows a pseudo-first order ki-
netics as it mainly takes place in the nearness of the anode surface,
either by direct or by mediated oxidation (Liang et al., 2018; Lin
et al., 2013). Thus, the current efficiency drops seriously with the
removal of organic compounds in this system because the lower
concentration weakened the transport of pollutant to the anode
surface and consequently, the rate of electrons oxidizing organics.
The removal rate and current efficiency was kept stable and even
raised up may because the ceftazidime molecules are broken to
smaller organic compounds which are much easier to degrade.
3.4. Factors influencing ceftazidime electrochemical degradation
3.4.1. Effect of pH
The effect of pH was shown Fig. 6(a). No significant difference in
degradation efficiency were observed with an increase of pH from 2
to 10. This implies that there was a slight effect of pH on ceftazidime
degradation and the G/CNT-Ce/PbO2eCe electrode can be applied
in a wide pH range. Similar results were achieved on Ti/SnO2eSb/
CeePbO2 anode degrading sulfamethoxazole (Lin et al., 2013).
Specifically, the degradation rates of ceftazidime at higher pH were
slightly higher than that at lower pH values. At pH ¼ 10, a
maximum degradation efficiency (85.9%) was achieved and lower
removal efficiency was observed at acid conditions (72.7%). The
main mechanism for this phenomenon was that the rate of hy-
drolysis of ceftazidime was readily accelerated when pH deviates to
alkalinity (Kümmerer, 2009). Even though the degree of hydrolysis
and their degradation kinetics are differed according to pH values,
the TOC removal rates are favored at acidic conditions, as shown in
Fig. 6(b). This means that the hydrolysis process can only change
the structure of ceftazidime, however, TOC removal are resistant to
hydrolysis. Under the acidic conditions, Hþ would inhibit the
decomposition of $OH and the reaction of oxygen evolution. That’s
the reason why higher OEP values can be obtained in H2SO4 solu-
tion for LSV characterization. Moreover, a slight drop of pH value
can be obtained after electrolysis, which was probably resulted
from the formation of organic acids (Dai et al., 2016a).
3.4.2. Effect of current density
Fig. 6(c) and (d) depicts that the removals efficacy of ceftazidime
 P. Duan et al. / Environmental Pollution 263 (2020) 114436 7

Fig. 6. Effect of solution pH value on (a) degradation efficiency of ceftazidime and (b) TOC removal efficiency on G/CNT-Ce/PbO2eCe electrode. Effect of current density on (c)
degradation efficiency of ceftazidime and (d) TOC removal efficiency on G/CNT-Ce/PbO2eCe electrode. Effect of initial concentration on (e) degradation efficiency of ceftazidime and
(f) TOC removal efficiency on G/CNT-Ce/PbO2eCe electrode.
8 P. Duan et al. / Environmental Pollution 263 (2020) 114436
and TOC values significantly increased with the strengthening of
current density. Complete ceftazidime removal (100%) was ob-
tained at highest 80 mA after 90 min electrolysis, and the removal
of TOC has increased from 36.5% (20 mA) to 50.2% (80 mA). The
mechanism for this phenomenon is very straightforward that
enhanced amount of $OH were produced when current density
rises. Electron transfer rate controls direct oxidation at electrode
surface as well as indirect oxidation by $OH. Thus, the electro-
chemical degradation rate was accelerated.
3.4.3. Effect of initial concentration
The initial concentration of ceftazidime in the range of
5e100 mg,L
1 was selected to study its influence towards removal
and mineralization efficiency. Fig. 6(e) presents that the ceftazi-
dime removal rate increased from 93.7% to 96.7% after 120 min
electrolysis with initial dosage increased from 5 mg,L
1 to
100 mg,L
1. Oppositely, the TOC elimination decreased from 61.8%
to 33.4%. This contradictory phenomenon can be explained in terms
of diffusion control of $OH and organic molecules. Higher concen-
tration of ceftazidime resulted in higher probability of contact be-
tween ceftazidime and $OH. When the initial concentration
increased, more intermediates were produced as the reaction
proceeded under higher TOC concentrations. The limited produc-
tion of $OH would lead to a competition for the oxidizing reaction
of organic compounds with $OH and thus affect the removal rate
(Chen et al., 2016).
3.4.4. Effect of chloride ions
Simultaneous direct and indirect oxidation of organics can
improve the oxidative efficiency in presence of chlorides because
the generation of active chlorine species (Lan et al., 2017), while at
the same time toxic perchlorate and halogenated organic com-
pounds can be formed with non-active anodes. According to pre-
vious studies, halogenated organic compounds are hazardous to
living organisms and resistant to further oxidation (Feng et al.,
2013; Sillanp, 2018). For the generation of active chlorine, chlo-
ride ions are firstly oxidized to chlorine according to reaction (1).
Then the chlorine can be hydrolyzed to form hypochlorous acid as
reaction (2). Although the E0 value of Cl2 and HClO are 1.36 V and
1.49 V vs. SHE which is much lower than that of $OH, they are more
selectively target the unsaturated CeC bounds and have more
persistent existing time.
2Cl
/ Cl2 ðaqÞ þ 2e

Cl2 ðaqÞ þ H2 O 4 HClO þ Cl
þ H þ
As observed in Fig. 7(a), chloride ions significantly enhanced the
removal rate of ceftazidime with initial concentration of 50 mg,L
1.
The increase of chloride concentration greatly accelerated the
degradation rate. When chloride concentration reaches 0.05 M,
almost complete removal can be achieved within 15 min. This
result was in agreement with previous results when degrading
25 mg,L
1 Ciprofloxacin (CIP), in which complete removal was
achieved after 50 min with 2.25 mM KCl compared with 250 min
without chloride ions (Lan et al., 2017). Meanwhile, as observed in
Fig. 7(c), TOC removal rate was also increased with higher con-
centration of NaCl, indicating the formed active chlorine performed
positive effects on oxidizing total organic compounds. However,
compared with significant improvement of ceftazidime removal,
TOC elimination was only increased by around 10% with 0.05 M
chloride ions, indicating the limited capability of active chlorines. In
addition, a higher current efficiency was achieved which means
higher mineralization rate. It was commonly accepted that higher
mineralization rate indicates a more limited formation of undesired
reaction intermediates. However, toxicity evaluation was con-
ducted during electrochemical degradation process with presence
of chloride ions in Fig. 7(b), which demonstrated a significant in-
crease of toxicity with electrolysis time. Compared with Fig. 5(a),
the consistent growth of toxicity was probably resulted from the
formation of halogenated organic compounds, which was hardly be
further oxidized and continuously accumulated. Moreover, the
toxicity increased more rapidly with more abundant chloride spe-
cies. In summary, the degradation efficiency of organic pollutants is
favored by anodic oxidation when NaCl replaces Na2SO4 as elec-
trolyte due to the production of active chlorine species. The
mechanism has been discussed in previous literatures (Thiam et al.,
2018; Tran et al., 2009; Yang et al., 2016a), as expressed by Equa-
tions (3) and (4). However, although faster degradation rate is ob-
tained with NaCl solutions, the potential threatening of hazardous
chlorinated by-products is still worth mentioning (Panizza and
Cerisola, 2009; Radjenovic and Sedlak, 2015).
3.5. Intermediates and pathway of ceftazidime electrochemical
degradation
Quantitative analysis of the intermediates is helpful to get a
better understanding of the ceftazidime degradation mechanism
and pathways. To identify the intermediate products of ceftazidime
as a result of electrochemical decomposition, IC method was
applied to low molecule acid and ions analysis; GCeMS method
was employed to detect the macromolecular intermediate prod-
ucts; HPLC-MS method was adopted to examine the primary
products with relatively larger molecular structures. As shown in
Tables Se3, the identified intermediates by HPLC-MS and GC-MS
methods were given. The HPLC-MS figures are indicated in Fig. S-
4. The GC-MS figures are presented in Fig. S-5. Based on the
observed results and previous studies (Coledam et al., 2017; Guo
et al., 2016; Li et al., 2018), a possible degradation mechanism
including carboxylation, decarboxylation, radical reaction, ring
open and mineralization was proposed in Fig. 8 (Cai et al., 2017; He
et al., 2014). Through the CeN cleavage under the attack of $OH, the
pyridine was firstly separated resulting in the formation of M1 and
M12. Afterwards, the unstable -N-O- bond was disconnected with
the detection of M13 by GC-MS and M2 by HPLC-MS. The formation
of M3 and M4 was probably resulted from the dissociation of
amino-thiazole (M10) groups, including M7 and M8. b-lactam ring
was opened at carbon nitrogen bond because the O]CeN group
(1) has a strongly polarized structure, which was evidenced by the
formation of M5 and M6. The formed smaller compounds were
further attacked by $OH, resulting in the formation of small mo-
(2)
lecular organic acids (M9, M10 and M13). Following the cleavage of
pyridine ring, thizole ring and 4, 6-thiazine ring, maleic acid and
fumaric acid came into being and they would turn into smaller
molecule acid such as oxalic acid and formic acid. Previous study
showed the electrochemical degradation of pyridine is dominated
by $OH attacking the meta-position of pyridine and forming 3-
hydroxypyridine, according to the Gibbs free energy of the transi-
tion states. The pyridine ring undergoes cleavage with the forma-
tion of malonic, maleic, formic acids, and NO
3 . The last step was the
mineralization of the different small molecule compounds, which
ultimately converted to NHþ

4 , NO3 , CO2 and H2O.
The ECOSAR program was developed by US Environmental
Protection Agency and adopted to predict the toxicity of chemical
substances (Chen et al., 2018; Pan et al., 2017). In this paper, the
toxicity of intermediate byproducts was evaluated using the ECO-
SAR program, as shown in Tables Se3. As can be seen, the elec-
trochemical degradation process produced chemical substances
with less toxicity. However, some chemical intermediates have
similar toxicity or even higher toxicity such as M7, M11 and M12.
 P. Duan et al. / Environmental Pollution 263 (2020) 114436
Fig. 7. (a) Effect of NaCl concentration on removal rate of ceftazidime on G/CNT-Ce/PbO2eCe electrode; (b) Effect of NaCl concentration on toxicity of solution against electrolysis
time; (c) Effect of NaCl concentration on TOC removal and current efficiency. The experimental condition was: 40 mA current, 20 mm electrode spacing, 50 mg,L
1 ceftazidime
initial concentration and 0.1 M Na2SO4 as supporting electrolyte.
The mineralization of ceftazidime was evaluated by measuring
the concentration of NHþ

4 and NO3 with electrolysis time. As indi-
cated in Fig. 9(a), a continuous increasing concentration can be
observed throughout the electrochemical degradation process and
the increase of NHþ

4 was much faster than that of NO3 , suggesting
the eNH2 was firstly removed from organic molecules through
deamination and further electrooxidized to NO
3 . The results
demonstrated that the novel G/CNT-Ce/PbO2eCe anode performed
remarkable ability to mineralize ceftazidime in our study. The for-
mation maleic acid increased to the peak at 120 min, while oxalic
acid increased continuously in the process until 300 min. It could be
deduced that the tendency of ceftazidime decomposition went
toward short carbon chain under electrolysis. In addition, it was
observed that fumaric acid also decreased with increasing elec-
trolysis time, indicating that low molecule acid eventually con-
verted to CO2. The concentrations of other low molecule acids are
depicted in the inset of Fig. 9(b). It was confirmed that amount of
NO
þ
3 and NH4 was much less than the theoretical calculation from
the breakage of amino group and pyridine. This conclusion might
be attributed to the incomplete degradation of ceftazidime con-
taining amino group. Thus, a quantitative study towards pyridine
and amino-thiazole was conducted as demonstrated in Fig. 9(c).
The possible intermediates methanetricarboxylic acid (M9),
9
amino-thiazole (M10) and pyridine (M11) were quantitatively
investigated through HPLC, because of their availability on the
market. The samples were concentrated 30 times through solid
phase extraction. Detailed analysis methods and HPLC figures are
enclosed in Supplementary Material as Fig. S-6 and Fig. S-7. As can
be seen in Fig. 9(c), the concentration of pyridine was raised up
quickly at the beginning 180 min, indicating it is fragile to be
separated from ceftazidime molecules. The accumulated pyridine
was removed after 300 min treatment, which proves that the
electrolysis process was capable to damage the pyridine ring
structure. In addition, amino-thiazole was produced, however, its
amount was much lower than pyridine. The reason might be there
were methyl groups and amino groups attached which makes it
difficult to be degraded. The decline of amino-thiazole quantity also
demonstrated the successful mineralization. Lastly, as a stable
organic acid, methanetricarboxylic acid was originated from the
oxidation of many intermediates which leading to its continuous
accumulation, also in quite low concentrations.
4. Conclusion
In this study, typical rare earth metal Ce and CNT doped PbO2
electrodes prepared by thermal decomposition and
10 P. Duan et al. / Environmental Pollution 263 (2020) 114436

Fig. 8. Proposed degradation pathway of ceftazidime.

Fig. 9. Production of (a) NHþ

4 , NO3 ; (b) maleic acid, fumaric acid and oxalic acid; (c) pyridine, aminothiazole and methanetricarboxylic acid during the ceftazidime electrochemical
oxidation on the G/CNT-Ce/PbO2eCe anode. The experimental condition was 80 mA current, 20 mm anode-cathode distance, and 50 mg,L
1 initial ceftazidime concentration.

electrodeposition technology were used for electrochemical oxidation of ceftazidime on G/CNT-Ce/PbO2eCe electrode was su-
degradation of ceftazidime in aqueous solution. Electrocatalytic perior to other electrodes, suggesting the addition of CeO2 and CNT
 P. Duan et al. / Environmental Pollution 263 (2020) 114436
interlayer could enhance the mineralization capability. The
improved degradation performance was attributed to stronger $OH
generation ability and larger electrochemical active surface area,
indicated by LSV and voltammetric charge quantity in CV. Accel-
erated lifetime test and recycling usage of PbO2 electrodes illustrate
G/CNT-Ce/PbO2eCe had prolonged service lifespan and catalytic
ability, compared to traditional PbO2 electrodes. This can be
explained by the more compact structure and regular grain size of
G/CNT-Ce/PbO2eCe than the other PbO2 electrodes. The main
influencing factors on electrochemical decomposition of ceftazi-
dime over G/CNT-Ce/PbO2eCe electrode were evaluated as a
function of pH values, initial ceftazidime concentration, current
density and contribution of chloride ions. During electrochemical
degradation of ceftazidime, intermediate products were identified
by HPLC-MS, GCeMS and IC methods. Methanetricarboxylic acid,
amino-thiazole and pyridine were quantitively measured, indi-
cating the electrolysis of ceftazidime starts with the cleavage of
groups on side chains and separation of amino and carboxyl groups.
Following ring cleavage reactions of b-lactam were also investi-
gated, resulted in the accumulation of 4,6-thiazine ring chemicals.
IC test illustrated the eNH2 groups were transformed into NHþ 4 ions
in aqueous and reduced into NO
3 on the cathode. Altogether, the
as-synthesized G/CNT-Ce/PbO2eCe anode has reliable practical
performance for degrade ceftazidime pollutants, according to the
remarkable TOC reduction and toxicity elimination.
Declaration of competing interest
We declared that we have no conflicts of interest to this work
submitted.
Acknowledgements
We thank the National Natural Science Foundation of China
(Project No. 51278022 and Project No. 51178022) for financial
support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2020.114436.
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