Chemical Engineering Journal 452 (2023) 139592

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Chemical Engineering Journal

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MOF-derived N-Co/Fe-PC composite as heterogeneous electro-Fenton

catalysis combined with electrocoagulation process for enhanced
degradation of Cu-CIP complexes from wastewater
Chengye Sun a, Jun Wang a, Cheng Gu b, Chao Wang b, Shuai Sun a, Peipei Song a, *
a
College of Resources and Environment, Key Laboratory of Agricultural Environment, National Engineering Research Center for Efficient Utilization of Soil and Fertilizer
Resources, Shandong Agricultural University, Tai’an 271018, China
b
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China

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

Keywords: Recently, heavy metal-antibiotic complexes have been frequently detected in wastewater, posing a serious threat
Metal-organic frameworks to the human health. In this study, a novel combination of heterogeneous electro-Fenton (hetero-EF) and elec­
N-Co/Fe-PC trocoagulation process was developed for efficient removal of Cu-ciprofloxacin complexes (Cu-CIP). As hetero-EF
Cu-ciprofloxacin
cathode catalyst, N doped porous carbon loaded with Co/Fe sites (N-Co/Fe-PC) was innovatively synthesized,
Heterogeneous electro-Fenton
Electrocoagulation
and Fe/Co–N–C structure was formed. The homogeneous mixing of Fe3C and Co3Fe7 resulted in the electron
Removal mechanism transfer and accumulation on Fe3C, which optimized the active substance and facilitated the oxygen reduction
reaction. The effects of current, electrolyte type, pH, and concentration were comprehensively investigated, and
the optimum removal efficiency of Cu, CIP, and TOC were 99.69 %, 96.40 %, and 83.62 %, respectively. Besides,
it revealed that ⋅O–2 was the dominant contributor to the Cu-CIP degradation. As a result, Cu-CIP complexes were
degraded into small molecules and released Cu2+ with the ring-opening demethylation of the piperazine ring,
cleavage and demethylation of carboxyl group, hydroxylation of the piperazine ring, and β-cleavage reactions of
cyclopropyl group. Meanwhile, they were also adsorbed by aluminum hydroxide/hydroxyl oxides especially
γ-AlOOH generated from the anode and finally coprecipitated. This study will provide a novel technology and
theoretical basis for enhanced degradation of heavy metal-antibiotic complexes from wastewater.

1. Introduction complexes accelerates the spreading of antibiotic resistance genes

through co-selection on microbial communities [10,11]. For instance,
With the acceleration of industrial production and urbanization, the ciprofloxacin (CIP) can be complexed with Cu2+ to form Cu-CIP, which
types of contaminates in wastewater have become increasingly complex has been proved to be highly toxic and affect CIP migration and trans­
[1]. Various antibiotics and their derivatives enter the aquatic system formation in vivo [12,13]. Compared with CIP, Cu-CIP can reduce the
through wastewater discharge or surface runoff, leading to the spread of epithelial permeability and absorption rate of CIP in the lungs of ani­
antibiotic resistance [2–4]. Meanwhile, heavy metal contaminated mals. In addition, Cu-CIP also reduces the nitrification of activated
wastewater was another urgent concern [5]. In fact, antibiotics and sludge and affects the generation of antibiotic resistance genes [14].
heavy metals have been often simultaneously detected in wastewater Therefore, Cu-CIP can cause more complex ecotoxicological effects. In
[6]. For example, Cu2+ and sulfamethoxazole were 0.02 ± 0.01 and conclusion, it is necessary to develop an efficient method for Cu-CIP
0.033 ± 0.043 mg/L in pharmaceutical wastewater [7]. Since many removal.
antibiotics contain dimethyl amino (C2H6N-), carbonyl (–C– – O–), and At present, there are few studies on the treatment of Cu-CIP complex
hydroxyl (–OH), which can act as electron donors to coordinate with wastewater, and the adsorption method has been mainly used [15,16].
heavy metals to form antibiotic-heavy metal complexes, and thus the However, the treatment efficiency is low and the complex cannot be
structure of pollutants is more complicated and the treatment difficulty degraded. In fact, electrochemical technology has been widely applied
is increased [8,9]. Besides, the formation of antibiotic-heavy metal for wastewater treatment in recent years due to its high efficiency, easy

* Corresponding author.
E-mail address: songpeipei@sdau.edu.cn (P. Song).

https://doi.org/10.1016/j.cej.2022.139592

Available online 6 October 2022

1385-8947/© 2022 Elsevier B.V. All rights reserved.
C. Sun et al. Chemical Engineering Journal 452 (2023) 139592

operation, and so on. It can be divided into many derivative methods (e. 2. Experimental section
g. anodic oxidation, electrocoagulation and electro-Fenton methods)
[17]. The electrochemical methods are highly integrated and capable of 2.1. Material and chemicals
treatment of various contaminations. For example, electro-Fenton and
anodic oxidation are capable of degradation of refractory pollutants, and Ciprofloxacin was of USP grade. P-phthalic acid was of 98 % purity.
the electrocoagulation can flocculate and precipitate inorganic or The concentration of polytetrafluoroethylene (PTFE) dispersion was 60
organic contaminated [18]. Studies showed that the combination of wt%. Other reagents were of analytical reagent (AR) degrade. The specs
electro-Fenton or anodic oxidation and electrocoagulation significantly of carbon black (CB) and carbon paper was Cabot Vulcan xc-72 and TGP-
improved the removal efficiency [19–21]. However, there are some H-060, respectively. The wastewater was prepared by dissolving
disadvantages, such as the need for the acidic condition, additional CuSO4⋅5H2O and CIP in Na2SO4 solution at equal molar ratio, and the
hydrogen peroxide or transition metal ions, and the high cost stable concentration of Cu-CIP was expressed by the mass concentration of CIP
anodes. Heterogeneous electro-Fenton (hetero-EF) is one of the [36–38].
emerging electrochemical methods that can overcome the above back­
wards [22]. In hetero-EF, H2O2 is in-situ generated during the oxygen 2.2. Synthesis of the cathode
reduction reaction (ORR) that occurred on the cathode surface, and then
is decomposed into radical ⋅OH by cathode catalyst for the degradation Firstly, Co/Fe-MIL-101 was synthesized following a typical proced­
of pollutants [23]. Since hetero-EF mainly relies on Fe, Co, Mn and other ure: 5 mmol FeCl3 and Co(NO3)2 at different molar ratio was dissolved
transition metal elements loaded on the cathode surface to catalyze with 5 mmol p-phthalic acid (PTA) in 30 mL N,N-Dimethylformamide
Fenton-reaction, it can broaden the pH range and avoid the formation of (DMF), then the mixture was stirred for 2 h before transferred into an
iron sludge [24]. Recently, due to its high specific surface area, abun­ 100 mL autoclave and kept at 110 ◦ C for 24 h. The obtained Co/Fe-MIL-
dant pore structure, adjustable morphology and versatility [25], metal 101 was washed by DMF and EtOH before being kept in vacuum drying
organic frames (MOFs) has been widely applied as the precursor of oven at 60 ◦ C for 12 h, and then 0.4 g Co/Fe-MIL-101 was mixed with
hetero-EF catalysts. To improve the conductivity, surface area and the 0.2 g melamine in 20 mL EtOH under ultrasound. The mixture was
metal nodes number, MOFs are usually calcinated at a high temperature calcinated in tube furnace under nitrogen atmosphere with the heating
and doped with heteroatom (e.g. N, S and B) [26–28]. The co-doping of rate of 5 ◦ C/min. The obtained material was washed by continuously
transition metal atoms and heteroatoms N on carbon matrix can form a stirring for 12 h in 1 M hydrochloric acid solution and kept in vacuum
highly heterogeneous electronic coordination structure (M–N–C drying oven at 60 ◦ C for 12 h.
structure), which along with the metal center are beneficial to the The cathode was built by the following procedures: firstly, the
fracture of O– – O bond and the reduction of O2 [29]. Among different catalyst and carbon black were mixed with 0.1 mL 60 wt% polytetra­
M N C structure, cobalt-nitrogen co-doped carbon (Co–N–C) has
– – fluoroethylene (PTFE) and 1 mL isopropanol. After ultrasonic dispersion
been proved of high catalytic activity, excellent stability and high for 1 h, the mixtures were continuously stirred at 80 ◦ C until it turned
electrocatalytic selectivity for ORR [30–32]. Combined with the H2O2 into a paste shape. The paste was coated on one side of a carbon paper (2
decompsation transition metal Fe, a N doped Co/Fe bimetallic carbon cm × 2 cm × 0.2 mm). After compacted and dried, it was calcined in a
material derived from MOFs is a potential efficient hetero-EF catalyst. chamber electric furnace at 350 ◦ C for 20 min. The other side was coated
Studies indicate that MIL-101 is a kind of MOFs with large pore size and with 20 mg carbon black. The prepared electrode was called N-Co/Fe-PC
specific surface area, which is easy to be synthesized and regulated with cathode.
different metal ions [33], and hence Co/Fe-MIL-101 would be an ideal
catalyst not yet synthesized. Mere hetero-EF is capable of degraded 2.3. Characterizations
antibiotic and heavy metal complex, while it may not be able to deal
with heavy metal ions released after decomplexation. However, elec­ The morphologies and elemental mapping were examined by scan­
trocoagulation (EC), an electrochemical process that only uses sacrificial ning electron microscope (SEM) (Quanta FEG 250, Thermo Fisher Sci­
anode to treat pollutants without adding coagulants, can just make up entific. Co) equipped with an energy dispersive X-ray spectroscope
for this [34]. It can effectively remove heavy metal ions from wastewater (EDS). The X-ray diffraction patterns (XRD) (Smartlab SE, Rigaku) of
[35], and is easy to integrate with other electrochemical methods. Co/Fe-MIL-101, N-Co/Fe-PC and the electrode surfaces were measured
As a result, in this study, an antibiotic-heavy metal complexes Cu-CIP to find out the elemental components and their chemical states, the X-
was treated. A bimetallic MOF (Co/Fe-MIL-101) was synthesized as the ray photoelectron spectroscopy (XPS) (Thermo ESCALAB 250XI,
precursor of hetero-EF catalysts. By co-calcination of Co/Fe-MIL-101 Thermo) of N-Co/Fe-PC was carried out to confirm its elemental com­
with melamine, N doped porous carbon (N-Co/Fe-PC) was synthesized posite and valence state. The cyclic voltammetry (CV) of N-Co/Fe-PC
for the cathode. The composition, morphology, and structural infor­ were implemented using a CHI 760E (CH Instruments, Inc.) in 6 mM
mation of the materials were investigated. Based on the N-Co/Fe-PC K3Fe(CN)6 solution, adopting three-electrode system (glassy carbon
cathode, hetero-EF and coupled hetero-EF with electrocoagulation were electrode for working electrode, a saturated calomel electrode for
built. The effects of cathode preparation conditions and operating fac­ reference electrode, and a platinum wire electrode for counter elec­
tors on Cu-CIP degradation were evaluated. The Box-Behnken design trode). To build the working electrode, 5 mg Co/Fe-PC was dissolved
(BBD) method was applied to investigate the interaction among various into 2 mL DMF and ultrasonically dispersed for one hour, and then 5 μL
influencing factors and the optimum conditions. To find out the oxida­ of the mixture was coated on the surface of a glassy carbon electrode
tive free radical species in coupled hetero-EF and electrocoagulation, until being dried.
ESR, fluorescence spectrum method and free radical quenching experi­
ments were carried out. Besides, to reveal the removal mechanism, the 2.4. Experimental procedures
degradation pathway was deeply explored by HPLC-MS and character­
ization of flocs. Based on this study, a novel and efficient electro­ The hetero-EF reactor was constructed with a N-Co/Fe-PC cathode
chemical technology was constructed, which is of great significance for and a graphite anode in a space of 2 cm in a 200 mL beaker powered by a
the treatment of heavy metal–organic complexes. DC power supply with aeration of 1 L/min flow rate. The pH was
adjusted by 0.5 mol⋅L-1 HNO3 and NaOH. The hetero-EF/EC reactor was
built with the same procedure, while the anode was replaced with an
aluminum electrode (2 cm × 2 cm × 0.2 mm). 5 mL samples were
collected in certain interval for further analysis. The concentration of

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Fig. 1. SEM images of (a, b) Co/Fe-MIL-101 and (c, d) N-Co/Fe-PC, (e) EDS mapping of N-Co/Fe-PC, and (f) XRD patterns of N-Co/Fe-PC, catalyst side and carbon
black side of the cathode.

CIP was measured with a UV–vis spectrophotometer. Cu was detected by which could optimize the adsorption/desorption energy of active spe­
the atomic absorption spectrophotometer. The removal efficiency was cies and further promote the occurrence of ORR [43], and thus facili­
envaulted by C/C0, in which C0 was the initial concentration and C was tated the generation of H2O2 and the degradation of Cu-CIP. Compared
the sampling concentration⋅H2O2 accumulation was measured by the with the carbon black side without N-Co/Fe-PC, the characteristic peaks
potassium titanium oxalate method [39]. To confirm the reactive free of the N-Co/Fe-PC appeared on the N-Co/Fe-PC side of the cathode,
radicals, free radical quenching experiments were carried out. The ⋅OH indicating that the N-Co/Fe-PC was successfully loaded on the N-Co/Fe-
was quenched with tertiary-butyl alcohol (TBA) and the O–2⋅ was PC side of the cathode.
quenched with benzoquinone (BQ). To analyze the elemental composition and valence distribution of the
catalyst, XPS analysis of N-Co/Fe-PC was carried out as shown in Fig. 2
3. Results and discussion (a–f). The corresponding contents of C, N, O, Fe and Co in N-Co/Fe-PC
synthesized were 80.49 %, 9.4 %, 7.20 %, 1.88 % and 1.02 %, respec­
3.1. Characterizations tively. The results showed that the content ratio of Co and Fe was
approximately 1:2 and abundant nitrogen element was doped on the
The morphology characteristics of Co/Fe-MIL-101, N-Co/Fe-PC were catalyst. Four Fe 2P1/2 peaks were found at 710.3 eV, 711.5 eV, 714.5 eV
analyzed. As described from Fig. 1(a, b), the particles were octahedral and 718.4 eV (13.4 eV from Fe 2P3/2), which were attributed to the
with a size of 200 nm approximately, which was consistent with the metallic Fe in Co3Fe7, Fe2+, Fe3+and the satellite peak, respectively
description of the morphology of MIL-101 in previous studies [40], (Fig. 2(b)) [27,42,44]. For Co 2p, the peak at 778.9 eV corresponded to
indicating that MIL-101 was successfully synthesized. As shown in Fig. 1 the 2 p1/2 peak of metallic Co, and the peak at 794.2 eV corresponded to
(c, d), with ultrasonic mixing with melamine and calcination at 700 ◦ C in the 2 p3/2 peak of metallic Co. The peak at 781.2.0 eV was attributed to
N2 atmosphere, part of the N-Co/Fe-PC particles maintained octahedral the 2 p1/2 peak of Co2+, and the peak at 797.0 eV was consistent with the
structure, while some of that split into smaller irregular particles. The N- 2 p3/2 peak of Co2+ [45]. The peak at 786.9 eV corresponded to the 2 p1/
Co/Fe-PC particles with irregular spherical protrusions appeared on the 2 peak of the Co satellite peak, and the peak at 803.9 eV was attributed to
crystal surface, and its crystal size remained at 200 nm approximately. the 2 p3/2 peak of the Co satellite peak (Fig. 2(c)) [46]. In addition, the
To investigate the elemental distribution in the catalyst N-Co/Fe-PC, 284.8 eV in C 1s corresponded to the 1s peak of C in C–C state, while the
EDS analysis were carried out. As illustrated from Fig. 1(e), C, N, O, Fe 285.5 eV, 286.8 eV and 289.1 eV corresponded to the 1s peak of carbon
and Co elements were uniformly distributed, there was no obvious loss atoms in C– – N, O-C–– O and C–N/C–O, respectively, which indicated
of Fe and Co elements in Co/Fe-MIL-101 during calcination, and N was that N and O were doped in the carbon layer [32,47]. And the peak at
successfully doped by co-calcination with melamine. 292.1 eV corresponded with π-π* carbon (Fig. 2(d)) [48]. The four peaks
XRD was carried out to further investigate the crystal structure of N- at 398.1 eV, 398.8 eV, 399.8 eV, 401.1 eV and 404.0 eV were attributed
Co/Fe-PC catalyst, the N-Co/Fe-PC side and the carbon black side of the to the N 1s peak of pyridinic nitrogen, Co/Fe-N, graphite nitrogen,
cathode. As shown in Fig. 1(f), a wide peak at 22–28◦ was the diffraction pyrrolic nitrogen and N–O (Fig. 2(e)) [32,41,49,50], respectively.
peaks of graphitized carbon, which a was attributed to the carbon black Finally, the five peaks at 529.8 eV, 530.6 eV, 531.4 eV, 532.1 eV and
and the calcination of MIL-101 [41]. In addition, the characteristic peaks 532.7 eV corresponded to the O 1s peak of Co3O4, Fe2O3, Fe–O–C,
composed of Fe, Co, C, N were also detected in the N-Co/Fe-PC powder C–– O and C–O, respectively (Fig. 2(f)) [32,51,52]. The active sites of
and the N-Co/Fe-PC side of the cathode. The diffraction peak at 37.7◦ Fe-C, Fe-N, and Co-N in XPS and XRD analysis proved that M–N–C
corresponded to the (2 1 0) crystal plane with the parameter of Fe3C structure was formed. The formed Fe–N–C and Co–N–C structures
crystal plane [42], and its peak also corresponded to the PDF card not only exhibited high catalytic activity, excellent stability and high
(JCPDS No. 35-0772). The diffraction peaks at 43.7◦ , 50.9◦ and 75.0◦ electrocatalytic selectivity for ORR, but also was able to activate H2O2 to
were attribute to (1 1 1) and (2 0 0) crystal planes of Co5.47N (JCPDS No. generate free radicals.
41-0943) [41]. The diffraction peaks at 44.7◦ and 65.1◦ were consistent The specific surface area of Co/Fe-MIL-101 and N-Co/Fe-PC were
with the (1 1 0) and (2 0 0) planes of Co3Fe7 (JCPDS No. 48-1817). The calculated as 240.793 m3/g and 272.995 m3/g, respectively, and the
homogeneous mixing of Fe3C and Co3Fe7 caused the electron transfer average pore size of Co/Fe-MIL-101 and N-Co/Fe-PC were calculated as
from Co3Fe7 to Fe3C, leading to the electron accumulation on Fe3C, 3.064 nm and 3.397 nm, respectively, which meant the specific surface

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Fig. 2. (a–f) XPS spectra of N-Co/Fe-PC, (g) N2 adsorption/desorption curves, and (h) pore size distribution.

area of Co/Fe-MIL-101 increased and pore characteristic was changed 3.2. Cu-CIP removal performance of hetero-EF
by co-calcination with melamine. BET results (Fig. 2(g)) showed that the
N2 adsorption/desorption isotherm of Co/Fe-MIL-101 were type I To analyze the effects of cathode preparation parameters on the
isotherm, while the N2 adsorption/desorption isotherm of N-Co/Fe-PC degradation of Cu-CIP in hetero-EF system, the calcination temperature,
were type IV isotherms with a H4 hysteresis loop, which confirmed that Co/Fe ratio, and the catalyst/carbon black ratio were investigated. As
N-Co/Fe-PC was porous carbon with mixed slit-like micropores and displayed in Fig. 3(a), after 120 min, Cu-CIP degradation efficiency
mesopores. This structure not only increased the specific surface area of reached 50.4 %, 53.4 %, and 57.7 % using cathode loaded with N-Co/Fe-
the catalyst, but also provided more attachment points for Fe, Co clus­ PC calcinated under 500, 600 and 700 ◦ C, respectively. The results
ters. The pore size distribution revealed that Co/Fe-MIL-101 was mainly revealed that with the increase of calcination temperature, the degra­
distributed in the microporous structure, while N-Co/Fe-PC presented a dation efficiency of Cu-CIP increased, and when the calcination tem­
microporous-mesoporous hierarchical porous structure. perature was 700 ◦ C, the degradation efficiency of Cu-CIP was the
highest. According to the thermogravimetric analysis (TGA) of Co/Fe-

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Fig. 3. Effects of (a) calcination temperature (500, 600, and 700 ◦ C), (b) Co/Fe ratio (0:1, 1:3, 1:2, 1:1, 2:1, and 3:1), (c) catalyst/carbon black ratio (1:0, 1:2, 2:1,
and 0:1), (d) current (75, 100, 125, 150, and 200 mA), (e) initial concentration (5, 10, 20, and 40 mg/L), and (f) pH (3, 5, and 7) on Cu-CIP degradation.

MIL-101 as shown in Fig. S1, based on the previous studies [28,46], it Cu-CIP, because the carbon black was capable of catalyzing ORR to
was concluded that when the calcination temperature was increased to accelerate the generation of H2O2 and the catalyst can activate the H2O2
about 660 ◦ C, Fe3O4 in the catalyst was converted into Fe0, and Fe0 and to promote the production of ⋅OH. The highest Cu-CIP degradation ef­
the carbon species generated at high temperature could promote Fe3+/ ficiency was obtained when the catalyst/carbon black ratio was 2:1.
Fe2+ redox cycle, thereby accelerating the oxidative degradation of Cu- To analyze the effects of different operating parameters on the
CIP [28,46]. In addition, more complete carbonization, larger specific degradation of Cu-CIP in hetero-EF system, the current, pH, and initial
surface area and porosity and higher mass transfer efficiency were ob­ concentration were also evalutaed. As shown in Fig. 3(d), the degrada­
tained at higher temperature, which improved the catalytic perfor­ tion efficiency of Cu-CIP increased with the increase of current. When
mance. Therefore, 700 ◦ C was selected for calcination temperature in the current increased to 200 mA, the degradation efficiency of Cu-CIP
the subsequent experiments. As illustrated from Fig. 3(b), among was the highest, which might be due to the increased yield of H2O2
different Co/Fe ratios, N-Co/Fe-PC with Co/Fe molar ratio of 1:2 ach­ and the redox cycle of Co2+/3+ and Fe2+/3+, facilitating the continuous
ieved the highest Cu-CIP removal efficiency. Cyclic voltammetry (CV) production of ⋅OH, and thus increased the degradation efficiency of Cu-
tests of N-Co/Fe-PCs synthetized at different Co/Fe molar ratio also CIP, which was consistent with the study of Zhou et al. [26], and also
verified this phenomenon (Fig. S2). As shown in Fig. 3(c), when Co/Fe supported by the ESR tests under different currents as shown in Fig. S3.
molar ratio was 1:2, the peak current reached the maximum value, As displayed in Fig. 3(e), the degradation efficiencies of Cu-CIP with four
indicating the best catalytic performance. Therefore, N-Co/Fe-PC with initial concentration levels yielded at 56.0 %, 62.0 %, 65.9 % and 36.2
Co/Fe molar ratio of 2:1 was used in the subsequent experiments. A %, respectively. Lower initial concentration hindered the diffusion of
proper catalyst/carbon black ratio was essential for the degradation of Cu-CIP, and thus weakened the binding with reactive oxidative free

Fig. 4. (a) The cyclic stability of the N-Co/Fe-PC cathode, and (b) the XRD patterns of the N-Co/Fe-PC cathode before and after reaction.

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Fig. 5. Effects of (a, b) current (50, 100, and 150 mA), (c, d) electrolyte type (NaCl, NaNO3, and Na2SO4), (e, f) NaCl concentration (5, 10, and 15 mM), (g, h) pH (3,
5, and 7), and (i, j) initial concentration (10, 20, 40 and 80 mg/L) on Cu and CIP removal efficiency.

radicals, so the degradation efficiency was limited. With higher con­ were also determined. From Fig. 5(a, b), Cu and CIP were effectively
centration, Cu-CIP along with its degradation intermediates might removed under the three current levels. When the current was 150 mA,
occupy the active sites of the cathode and consume the reactive oxida­ the removal efficiency of CIP reached 79 %, while that of Cu was only
tion free radicals, and thus reduced the degradation efficiency. There­ 37.7 % at 10 min. After 60 min, when the current was 100 mA, the
fore, the subsequent experiments were carried out with the initial removal efficiencies of Cu and CIP was higher than that when the cur­
concentration of 20 mg/L. As shown in Fig. 3(f), the degradation effi­ rent was 50 mA and 150 mA, so 100 mA was applied in the subsequent
ciencies of Cu-CIP with three pH levels yielded at 47.5 %, 45.9 % and experiments. The effects of electrolyte type (10 mM NaCl, NaNO3 and
61.7 %, respectively. In the range of pH 3–7, the degradation efficiency Na2SO4) was shown in Fig. 5(c, d). At 60 min, with NaNO3 and NaCl, the
of Cu-CIP increased with the increase of pH. This phenomenon could be removal efficiency of Cu yielded at 97.6 % and 97.1 %, respectively,
explained by combining the experimental results in the subsequent which were higher than 83.3 % when Na2SO4 was used as electrolyte.
chapter 3.4 and (Eqs. (9) and (10)) [53–55], since O−2 ⋅/HO2⋅ played the For CIP removal, the removal efficiency using NaCl as electrolyte
major role in the oxidative degradation of Cu-CIP in the Hetero-EF reached 92.1 %, higher than 81.0 % and 76.2 % by NaNO3 and Na2SO4.
system, and when pH increased, it was favorable for the formation of So NaCl was favored for the removal of Cu-CIP, which mainly because
O−2 ⋅/HO2⋅, leading to higher degradation efficiency of Cu-CIP, which with NaCl, Cl− might destroy the oxide layer of aluminum anode, and
was proved by the ESR tests as demonstrated in Fig. S4. In addition, the catalyze the anodic dissolution by pitting corrosion to accelerate the
comparisons between prepared N-Co/Fe-PC and those reported mate­ formation of coagulants, thereby facilitated the removal of Cu and CIP
rials were displayed in Table S1. It can be seen that N-Co/Fe-PC com­ [56]. Besides, anodic oxidation based on chlorine electrolysis occurred,
posite exhibited larger specific surface area and superior treatment Cl− lost electrons on the anode surface and was oxidized to produce
efficiency. oxidic species such as Cl2, HOCl and OCl− (Eq. (1)~(3)), which were
To investigate the cyclic stability of the N-Co/Fe-PC cathode, six also determined and confirmed by the titrimetric method, and thus
cycles of experiments were carried out under the same reaction condi­ promoted the oxidation and the mineralization of Cu-CIP [18,57].
tions. As demonstrated from Fig. 4(a), the degradation efficiency
2Cl− + 2e− = Cl2 (1)
declined by 2.17 % averagely in each cycle, indicating that the cathode
based on N-Co/Fe-PC had good cyclic stability. Besides, the XRD pat­
Cl2 + H2 O = HClO + H + + Cl− (2)
terns of the cathode before and after 6 times of cyclic experiments were
investigated as shown in Fig. 4(b), there was no obvious difference, Cl2 + 2OH − = ClO− + H2 O + Cl− (3)
indicating that the cathode had superior stability.
The effects of NaCl concentration on the removal of Cu and CIP were
described in Fig. 5(e, f), the removal efficiencies of Cu and CIP were
3.3. Cu-CIP removal performance of hetero-EF combined higher with 10 mM and 15 mM NaCl than that with 5 mM NaCl. At 30
electrocoagulation min, Cu and CIP were effectively removed at all levels. As illustrated
from Fig. 5(g, h), when pH was 3–7, the removal efficiencies of Cu and
The effects of current, electrolyte type, electrolyte concentration, CIP increased with the increase of pH. Lower pH blindered the removal
initial concentration, and pH on the removal of Cu-CIP by combined efficiency of Cu-CIP, which was due to that, under the acidic condition,
heterogeneous electro-Fenton electrocoagulation system (hetero-EF-EC) Al3+ was the main specie of Al, it could not generate enough flocs to
were comprehensively evaluated and the optimal operating conditions

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Fig. 6. 3D surface plots for (a, b) Cu and (c–f) CIP removal efficiency. (Current: 50–150 mA, pH: 3–7, Time: 5–35 min, Initial concentration: 10–80 mg/L).

remove Cu-CIP. The effects of initial concentration on the removal ef­ removal efficiency were illustrated in Tables S3 and S4. Since the P value
ficiencies of Cu and CIP was shown in Fig. 5(i, j), at 50 min, the removal of the models was < 0.0001, the relevance between Y1/Y2 and the fitting
efficiencies of Cu were 87.4 %, 93.9 %, 94.4 %, and 87.4 % with the equation was significant. R2 for Cu and CIP removal were 0.9681 and
initial concentrations of 80, 40, 20 and 10 mg/L, respectively, and the 0.9703, which represented a good correlation. The Adj R-Squared and
removal efficiencies of CIP were 95.1 %, 93.4 %, 88.1 %, and 96.7 %, Pred R-Squared values were 0.9361 and 0.8161, as well as 0.9405 and
respectively. 0.8287, respectively, and the difference was 0.12 (<0.2) and 0.1118
To investigate the interaction between different factors and obtain an (<0.2), indicating the reliability of the models was high. For Cu
optimal optimum parameter for Cu-CIP removal, response surface removal, X1, X2, X3, X4, X1X4 and X2X3 were significant influence factors.
methodology (RSM) was applied, and Box-Behnken Design (BBD) was For CIP removal, X1, X2, X3, X4, X1X3, X1X4, X2X4, and X3X4 were also
adopted. The current, initial concentration of Cu-CIP, pH and time were prominent. Fig. 6(a–f) displayed the combined effects of four variables
selected as variables, and were labeled as X1, X2, X3, and X4, respec­ on Cu and CIP removal efficiency. As can be seen from Fig. 6(a) and (d),
tively. The removal efficiencies of Cu and CIP were labeled as Y1 and Y2. with the increase of current and reaction time, the removal efficiency of
The BBD design was shown in Table S2. ANOVA results for Cu and CIP Cu and CIP gradually increased, and when the current or reaction time

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C. Sun et al. Chemical Engineering Journal 452 (2023) 139592

Fig. 7. (a) H2O2 concentration, (b) fluorescence spectra of hydroxyterephthalic acid, (c) DMPO spin-trapping EPR spectra, and (d) Cu-CIP degradation with
different scavengers.

was the maximum value, the increase was the most obvious, and there the products was carried out. The concentration of Co, Fe, and Cu were
was a positive correlation between them. From Fig. 6(b) and (e), the 0.002, 0.002 and 0.015 mg/L, respectively, which were far below the
removal efficiency of Cu and CIP gradually increased with the increase standard limit. Compared with other studies, hetero-EF-EC process with
of pH and the decrease of initial concentration, and they were negatively N-Co/Fe-PC catalysis exhibited great potential for efficient degradation
correlated. From Fig. 6(c), with the increase of current and pH, CIP of Cu-CIP complexes as shown in Table S5.
removal efficiency rose, and they were positively correlated. As can be
seen from Fig. 6(f), with the decrease of reaction time and the increase of
concentration, CIP removal efficiency decreased. According to experi­ 3.4. Mechanisms
mental data, the final regression model was expressed by the second-
order polynomial equation as follows (Eqs. (4) and (5)). Adsorption of Cu-CIP by the cathode and the oxidation of Cu-CIP by
electro-Fenton reaction were the two possible processes that contributed
Y1 = 157.840 − 1.290X1 − 1.786X2 + 5.018X3 − 4.049X4 − 0.0001X1 to the removal of Cu-CIP in hetero-EF system. As shown in Fig. S5, the
× X2 + 0.075X1 × X3 + 0.017X1 × X4 − 0.138X2 × X3 − 0.005X2 adsorption of Cu-CIP on the cathode reached the adsorption equilibrium
× X4 + 0.276X3 × X4 + 0.004X12 + 0.017X22 − 0.538X23 + 0.038X42 (4) at 80 min, and the removal efficiency was only 7.6 % at 120 min. While
with electro-Fenton reaction, the removal efficiency of Cu-CIP reached
Y2 = 68.500 − 1.070X1 + 0.146X2 − 17.248X3 + 3.463X4 + 0.001X1 65.9 % at 120 min. Therefore, the oxidation of Cu-CIP by electro-Fenton
reaction was the dominant process of Cu-CIP removal in heterogeneous
× X2 + 0.125X1 × X3 + 0.014X1 × X4 − 0.137X2 × X3 − 0.032X2
electro-Fenton system.
× X4 − 0.087X3 × X4 + 0.0019X12 + 0.005X22 + 1.810X32 − 0.041X42 (5) The oxidative species contributed to the oxidation of Cu-CIP in
hetero-EF system was explored. Fig. 7(a) displayed that the accumula­
Besides, the optimal conditions were predicted and verified. It
tion of hydrogen peroxide was increasing as time went by, and the
showed that with the conditions of current 140 mA, time 40 min, pH 6.6
accumulation of hydrogen peroxide reached 160.5 mg/L at 120 min.
and concentration 20 mg/L, the optimum removal efficiency of Cu, CIP,
However, after 60 min, the accumulation rate of H2O2 decreased, which
and TOC were 99.69 %, 96.40 %, and 83.62 %, respectively. Meanwhile,
was due to the loss of hydrogen peroxide caused by the activation of
the concentration of Co and Fe were also detected, which were only
H2O2 by Fe2+/Co2+ to form ⋅OH or Fe3+/Co3+ to form ⋅O−2 [55].
0.003 and 0.004 mg/L. In addition, the leaching toxicity experiment of
DMPO was adopted to capture the oxidative free radicals generated

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C. Sun et al. Chemical Engineering Journal 452 (2023) 139592

Fig. 8. Proposed degradation pathway involved in the combination of hetero-EF and electrocoagulation process.

in the reaction system at 30 min and the ESR tests of DMPO-radical decreased from 72.2 % to 64.6 % and 66.9 %, respectively. The degra­
adducts were carried out. The characteristic peaks of DMPO-⋅OH and dation efficiencies of Cu-CIP in hetero-EF with 1 mM and 5 mM p-BQ
DMPO-⋅O–2/⋅HO2 adducts appeared in ESR spectra (Fig. 7(c)), which decreased from 72.2 % to 55.3 % and 23.9 %, respectively. The results
proved that ⋅OH and ⋅O–2/⋅HO2 were generated in hetero-EF system. ⋅OH indicated that ⋅O–2/⋅HO2 played the dominant role in the degradation of
could react with terephthalic acid and form 2,4-Dihydroxybenzoic acid, Cu-CIP, and ⋅OH played a secondary role, which was consistent with the
which was a strongly fluorescent compound that could be detected by previous results [54,55].
the fluorescence spectrometry [58]. As shown in (Fig. 7(b)), the fluo­ Based on XRD, XPS, ESR, and free radical quenching experiments,
rescence signal of hydroxyterephthalic acid increased, indicating that the possible catalytic mechanism of CIP degradation catalyzed by N-Co/
the production of ⋅OH increased with time went on. Furthermore, to find Fe-PC cathode in the hetero-EF system was proposed. Firstly, O2 mole­
out which radical played the dominant role, TBA and p-BQ were adopted cules were adsorbed onto the surface of the N-Co/Fe-PC and carbon
as ⋅OH and ⋅O–2 scavengers. As demonstrated in Fig. 7(d), the degradation black on the cathode and was transformed to H2O2 during ORR (Eq. (6))
efficiencies of Cu-CIP in hetero-EF with 10 mM and 100 mM TBA [59], the Fe0 and Co0 was oxidized by H2O2 and generated Fe2+ and

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C. Sun et al. Chemical Engineering Journal 452 (2023) 139592

Fig. 9. (a) XRD, (b) FTIR, and (c, d) XPS analysis of reaction products.

Co2+ (Eq. (7)) [32]. Then the H2O2 was activated by Fe2+/Co2+ to was replaced by –OH with the attack of free radicals to form two hy­
generate ⋅OH and Fe2+/Co2+ was transformed into Fe3+/Co3+(Eq. (8)) droxylated products G and H [55]. In Path 3, the C atom at the carboxyl
[60]. The generated Fe3+/Co3+ was able to activate H2O2 thus generate position of CIP was attacked by free radicals to generate hydroxylated
⋅O–2/⋅HO2 (Eq. (9) and (10)) [54,55]. product I. Under the further attack of free radicals, the piperazine ring
was replaced by hydroxyl to generate intermediate product J. Mean­
O2 + 2H + + 2e− →H2 O2 (6)
while, the intermediate product J also lost the cyclopropyl group (-C3H5)
under the attack of free radicals to form the intermediate product K.
Fe0 /Co0 + H2 O2 + 2H + →Fe2+ /Co2+ + 2H2 O (7)
Under the action of free radicals, the intermediate product K underwent
β-fracture reaction and was further oxidized by free radicals to break the
Fe2+ /Co2+ + H2 O2 → ⋅OH + Fe3+ /Co3+ + OH − (8)
C–N and C–O single bonds to generate the intermediate L [61].
Meanwhile, in hetero-EF-EC system, the current passes through the
Fe3+ /Co3+ + H2 O2 →Fe2+ /Co2+ + O−2 ⋅ + 2H + (9)
sacrificial Al0 anode, and loses electrons to form Al3+, (Eq. (11)), and
electrolyzes water molecules to generate O2 (Eq. (12)). At the same time,
Fe3+ /Co3+ + H2 O2 →Fe2+ /Co2+ + HO2 ⋅ + H + (10)
a hydrogen evolution reaction also occurred to generate hydrogen and
The generated oxidative free radical was responsible for the degra­ OH– (Eq. (13)).
dation of Cu-CIP, however, when the degradation efficiency of Cu-CIP
reached 65.9 %, the removal efficiency of TOC was only 56.0 %, indi­ Al0 − 3e− →Al3+ (11)
cating that the degradation intermediates of Cu-CIP in the solution were
2H2 O − 4e− →O2 + 4H + (12)
not fully mineralized. Therefore, the intermediates at 120 min were
detected by HPLC-MS as shown in Fig. S6 and Table S6. Based on the
3H2 O + 3e− →2/3H2 + 3OH − (13)
results, the possible degradation pathway was proposed in Fig. 8. In
pathway 1, ⋅OH and ⋅O−2 attacked piperazine and product A was As shown in Fig. 9(a, c), the main component of floc was γ-AlOOH.
generated with H atom replaced by –OH, then the piperazine ring was The multi-nuclear aluminum γ-AlOOH played a role in bridging
opened and product B–D were produced with the continuous free radical adsorption and convolution net capture, and realized the capture of
attacking, and then demethylated to form intermediate products E and F pollutants. Fig. 9(d) showed that the floc contained Cu, which verified
[55]. In pathway 2, H atoms situated on C atoms on quinoline groups the removal of Cu2+ from wastewater. In Fig. 9(b), quinoline, –CH2,

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C. Sun et al. Chemical Engineering Journal 452 (2023) 139592

Fig. 10. Cu-CIP complexes removal mechanism involved in the combination of hetero-EF and electrocoagulation process.

–OH, –COOH and other organic groups were also detected, and the Acknowledgements
degradation products of Cu-CIP containing these groups were also
determined by HPLC-MS, indicating that the organic small molecule This work was supported by the National Natural Science Foundation
degradation products of CIP ligand were successfully removed. The of China (42177069, 41807125, and U1906225), the State Key Labo­
mechanism of hetero-EF-EC process for Cu-CIP removal was revealed as ratory of Pollution Control and Resource Reuse Foundation
shown in Fig. 10, the homogeneous mixing of Fe3C and Co3Fe7 caused (PCRRF20020), and the National Key Research Development Plans of
the electron transfer and accumulation on Fe3C, which optimized the Special Project for Site Soils (2018YFC1801001).
adsorption/desorption of active species and further promoted the per­
formance of ORR. With the continuous free radical attack, Cu-CIP was Appendix A. Supplementary data
degraded into small molecule organics and Cu2+ was released into
wastewater. At the same time, flocs were generated on the anode surface Supplementary data to this article can be found online at https://doi.
and diffused in the system, which completely coprecipitated with the org/10.1016/j.cej.2022.139592.
degradation products of Cu-CIP (Cu2+, small molecule organic matter,
and inorganic ions). References

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