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Chemical Engineering Journal 347 (2018) 379–397

Contents lists available at ScienceDirect

Chemical Engineering Journal


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

Review

Insight into electro-Fenton and photo-Fenton for the degradation of T


antibiotics: Mechanism study and research gaps

Xiaocheng Liua,c, Yaoyu Zhoua, , Jiachao Zhanga, Lin Luoa, Yuan Yanga, Hongli Huanga,

Hui Penga, Lin Tangb, Yang Muc,
a
College of Resources and Environment, Hunan Agricultural University, Changsha 410128, China
b
College of Environmental Science and Engineering, Hunan University, Changsha 410082, China
c
Department of Chemistry, University of Science & Technology of China, Hefei 230026, China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Fundamental and key parameters of


EF and PF process are systematically
reviewed.
• Recent advances in pH, catalyst, elec-
trode, light source, device are in-
vestigated.
• Decay pathway and toxicity evalua-
tion to eliminate antibiotics are dis-
cussed.
• The unfilled gaps and research needs
for the EF, PF, PEF and SPEF are pro-
posed.

A R T I C LE I N FO A B S T R A C T

Keywords: With the development of the degradation of persistent organic pollutants in the wastewater, antibiotics have
Electro-Fenton been considered as emerging pollutants. Their lasting effects on the entire ecosystems directly resulted in ir-
Photo-Fenton reversible damage all over the world. Electro-Fenton, photo-Fenton, photoelectro-Fenton and solar photoelectro-
Antibiotic Fenton processes have been adopted to the elimination of antibiotics for the considerable efficiency. The me-
Mechanism
chanism, advantage, disadvantage, and the impacts of key parameters for each method are discussed based on
Key parameters
the recent works, respectively. The cost aspects of electro-Fenton and photo-Fenton are analyzed for practical
Gaps
application. The degradation pathway as well as the toxicity evaluation of the antibiotics is reviewed. Finally,
research needs and unfilled gaps have been proposed, including blocks from unpredicted impurities, pilot-scale
study for the remediation of polluted water, pretreatment of antibiotic effluent, cognition of high-performance
electrode, and characterization of intermediates. All of them suggested that electro-Fenton and photo-Fenton
could be adopted as an ecological and efficiency ways for the elimination of antibiotics.

1. Introduction antibiotic against bacteria has been hailed as a four-edged sword, which
means resistance to bacterial infection, control of infectious diseases,
Antibiotics, different from other drugs, have not aroused sufficient enhancement of antibiotic resistance and damage of the beneficial
attention for the negligible direct toxicity. Exactly, the effect of bacteria [1]. There is no doubt that the complete reversion of antibiotic


Corresponding authors.
E-mail addresses: zhouyy@hunau.edu.cn (Y. Zhou), yangmu@ustc.edu.cn (Y. Mu).

https://doi.org/10.1016/j.cej.2018.04.142
Received 17 January 2018; Received in revised form 30 March 2018; Accepted 20 April 2018
Available online 22 April 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

tolerant variants is impossible, causing by the most notorious obstacle Hydroxyl radicals play a vital role in EF/PF/PEF process, oxidizing
of antibiotic resistance [2]. Meanwhile, forefront researchers also pay most organics into CO2, H2O and inorganic ions via dehydrogenating or
attention to antibiotic resistance genes (ARG), leading an unpredicted hydroxylating reaction for the high standard reduction potential (E0
future of environmental organisms [3]. The abuse of antibiotics even (%OH/H2O) = 2.80 V/standard hydrogen electrode (SHE)) [29]. Mean-
increases the concentration reaching a specific level that would while, the Fe2+ is the representative of Fenton process, whereas the
strengthen bacterial transcription [4]. Therefore, the worldwide oc- Fenton-like process could be carried out with diverse metal ions (e.g.,
currence of the antibiotics suggested the urgency to figure out several Cu2+) for the decomposition of H2O2 [18].
effective and economical methods.
Fe2+ + H2 O2 →Fe3+ + OH− + %
OH (1)
Fenton process is commonly used in water treatment processes
[5,6]. The photo-Fenton (PF), electro-Fenton (EF), photoelectro-Fenton The photolysis of H2O2 plays a vital role in the PF process to break
(PEF) and solar photoelectro-Fenton (SPEF) are highly superior to the the OeO bond for the production of %OH (Eq. (2)), leading the proce-
conventional treatments without altering the structure of antibiotics dure of propagation (Eqs. (3–5)), and termination (Eqs. (6–8)) [32].
[7–9]. Indeed, recent sound investigation on the electrode and light
source would accelerate the development of antibiotics degradation by H2 O2 + hv →2 OH (2)
EF and PF, respectively. In addition to the comprehensive study on the %
OH + H2 O2 →H2 O + HO2 %
(3)
wavelength of artificial light source for PF [10], the sunlight also uti-
% %
lized to the antibiotic decay by compound parabolic collector (CPC) HO2 + H2 O2 → OH + H2 O + O2 (4)
[11], and NETmix@ photoreactor [12]. Several strategies for mod- % − % −
OH + HO2 →HO2 + OH (5)
ification of the cathode have shown great superiority [13–15], whereas
Ti4O7 was proposed as a convincing alternative to the classic high 2HO2 %→H2 O2 + O2 (6)
performance electrode in the EF degradation [16,17]. %
OH + HO2 %→H2 O + O2 (7)
Actually, the forms of energy input are not the only difference, and
%
there is always a misunderstanding that the improve methods about the 2 OH →H2 O2 (8)
pH and catalyst are interchangeable between the EF and PF processes. 3+ %
The continuous Fe2+ in the PF process is mainly determined by the The presence of Fe blocks the continuous generation of OH in
photo activity of the Fe(OH)2+, and it could be improved by organic the classical Fenton process, leading a slow decomposition of H2O2 and
ligand for the generation of the [Fe3+(RCO2)]2+ [18]. Meanwhile, the unpleasant generation of hydroperoxyl radical (HO2%) (Eq. (9)).
introduction of organic matter would change the solubility of Fe [19], Therefore, the introduction of the photo current in PF process has
indicating a modified method for the neutral PF process [20]. Never- certainly improved by photo-reduction of Fe3+ according to the (Eqs.
theless, the methods for the wide range pH and natural pH are ac- (10) and (11)), whereas the limited rate for the regeneration of Fe2+
complished by the generation of the O2%– [21], and hydrolysis of cat- significantly hinder the Fenton process. Interestingly, the reduction of
alyst [22]. Besides, the participation of the carbon materials for the Fe3+ and production of %OH could accomplished at the same time in the
synthesis of the catalyst could improve the adsorption capacity, further PF process (Eq. (12)) [33]. Moreover, some Fe(III)–carboxylate com-
enhancing both of the EF [23], and PF catalytic efficiency [24]. plexes generated from the coordination of Fe3+ and organic inter-
Moreover, the pilot plant study for the antibiotic removal is regarded as mediates have a considerable adsorption in the UV–vis region for the
a key parameter in the section of PEF and SPEF. reduction of Fe3+ (Eq. (13)), named ligand-to-metal charge transfer
Furthermore, the degradation pathways in the PF, EF, PEF and SPEF (LMCT) [8]. The zero-valent iron (ZVI) could also be the source of Fe2+
process are suitable to provide an impressive cognition of the structure in the PF process for the photo-oxidation of Fe0 (Eq. (14)), accompanied
of antibiotics. Each detection instrument as well as the concise reaction with series reaction with H2O2 and O2 [34].
of the complete pathway for PF, EF, PEF and SPEF is reviewed, and the Fe3+ + H2 O2 →Fe2+ + HO2 %+ H+ (9)
characteristics of specific investigation are refined. The eco-toxicity
%
[25], luminescence assay [17,26], and antimicrobial activity (AA) Fe 2+
+ H2 O2 →Fe(OH) 2+
+ OH (10)
[27,28] for the treated antibiotic solution are discussed. Interestingly, 2+ 2+ %
Fe(OH) + hν→Fe + OH (11)
the intermediates of the antibiotics after the EF and PF process might
3+ 2+ + %
improve the original toxicity. Fe + H2 O + hν→Fe +H + OH (12)
To our knowledge, several excellent reviews have been published %
[Fe 3+
(RCO2 )] 2+
+ hv →Fe 2+
+ CO2 + R (13)
previously focusing on the EF process [29,30], PF process [18], and
antibiotic removal [31]. However, there is no paper summarized data Fe0 + hv → Fe2 + + 2e− ( < 400 nm) (14)
on the performance of EF and PF process for the degradation of anti-
biotics. In this paper, we present a critical review in this topic (Fig. 1), Additional H2O2 is easy to break down wastefully, increasing the
comparing the fundamental and key parameter of the recent research cost of the Fenton and PF processes. Nevertheless, the cathode of EF
on the antibiotic decay by EF, PF and PEF/SPEF process, respectively. process carried out the generation of in-situ H2O2 (Eq. (15)), considered
The essences of the degradation pathway and toxicity evaluation are as an important evaluation indicator for the current efficiency. Inter-
figured out, and the analysis of the cost aspects in related field and estingly, the accumulation of H2O2 in the EF system is limited for the
unfilled research gaps in this field are presented. reduction at the cathode surface (Eq. (16)) and the H2O2 disproportion
at the bulk solution (Eq. (17)) [9]. The competition of evolution of H2
2. The fundamental of EF and PF process (Eq. (18)) would enhance if the current density is excess. Compared to
the PF process, the reduction of Fe3+ is more direct and fast though Eq.
2.1. The mechanism of EF and PF process (19) on the cathode, causing no obvious obstruction to the EF process.
O2 + 2H+ + 2e− → H2 O2 (15)
EF and PF processes always compare with each other in wastewater
treatment based on the separation and degradation of organic and in- H2 O2 + 2H+ + 2e− → 2H2 O (16)
organic pollutants according to different mechanisms. The Fenton re-
action is the fundamental reaction for the generation of homogeneous 2H2 O2 → O2 + 2H2 O (17)
hydroxyl radicals (%OH) though Eq. (1), and the strategies for the im-
provement of efficiency are mainly in accordance with each parameter. 2H+ + 2e− → H2 (18)

380
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 1. Trends in the number of publications on the topic of “Fenton and antibiotic”, “electro Fenton and antibiotic” and “photo Fenton and antibiotic” (data obtained
from Web of Science on November 11, 2017).

% −
Fe3 + + e− → Fe2 + (19) OH + SO42 →OH− + SO4%− (30)
The hydrogen peroxide is not the only way to produce hydroxyl SO4%− +e −
→SO42 − (31)
radicals, for the EF process, electrode material (M) used to the oxidation
of water has a vital effect on the generation of heterogeneous hydroxyl
radical (M(%OH)) though Eq. (20). Generally, the higher current would
increase the amount of M(%OH), whereas the extra electricity would 2.2. The advantage and disadvantage of EF and PF process
lead unexpected evolution of O2 on the anode (Eqs. (21) and (22)). The
H2O2 would also be oxidized into HO2% considered as a weak oxidant As the representative of advanced oxidation processes (AOPs), the
(Eq. (23)), and finally convert into O2 on the anode (Eq. (24)) [35]. investigation on operational parameters of EF and PF processes have
Although, the Fe anode has been once adopted to the EF process due to been discussed in some excellent reviews, respectively [8,18,29,30].
the oxidation of Fe provides the Fe2+ via Eq. (25), which has been Nevertheless, the key parameters for the degradation of antibiotics in
abandoned for the severe anodic corrosion [36]. the recent researches have shown different trends for EF and PF pro-
cesses. For instance, the nanoscale zero-valent iron (nZVI) presents a
%
M + H2 O →M( OH) + H+ + e− (20) pH-responsive characteristic in the Fenton process as if it could be
2H2 O→ O2 + 4H+ + 4e− (21) simply used to PF and EF processes [38]. Actually, the nZVI is suitable
for the heterogeneous PF process according to the Eq. (14) while the
investigation on performance of nZVI in the EF process is valueless
%
2M( OH) →2M + O2 + 2H+ + 2e− (22) [39].
% − EF and PF processes seem to be the extension of Fenton process, but
H2 O2 →HO2 + H +
+e (23)
there is a huge difference between them in terms of the main me-
% −
HO2 →O2 + H +
+e (24) chanism and key parameters. The typical PF process would occur in the
simultaneous presence of Fe, hv and H2O2, showing a higher efficiency
Fe → Fe2 + + 2e− (25)
than Fenton process and lower energy consumption than EF process
In addition, the conductivity of solution for the EF process is ne- [18]. Most of the high performance catalysts for Fenton process are
cessary, and the Na2SO4 is the most common electrolyte due to the low available for PF process, and the excess salt conductivity is not neces-
activity of SO42−. However, the effect of electrolyte could not always sary for the reaction of photo current. Moreover, the semiconductor in
been ignored, and the presence of Cl− would introduce the Cl2 and the photocatalysis is usually adopted to produce active electron-hole
HClO to the EF process (Eqs. (26) and (27)) [37]. There are several pairs, accelerating the oxidation, reduction and radical reaction [40].
unexpected reactions between the %OH and Cl− (Eqs. (28) and (29)), Although the hv for the most of PF process usually need extra energy
whereas the high concentration of SO42− also contribute to the con- input, the energy loss in the treated solution is negligible as compared
sumption of hydroxyl radicals (Eqs. (30) and (31)) [30]. to EF process.
As a matter of fact, the capacity of PF process is still limited even if
2Cl− → 2e− + Cl2 (26)
the hv promotes photo-reduction of Fe2+ and direct photolysis of H2O2.
Cl2 + H2 O→ H+ + Cl−+HClO (27) The optimal dosage of H2O2 is significantly determined by the con-
centration of pollutant, and the total organic carbon (TOC) removal is
not satisfied for PF process without efficient semiconductor [12].
%
OH + Cl− →% OHCl− (28) Moreover, the instability of the H2O2 increases the difficulty to control
% − the H2O2/Fe2+ molar ratio, blocked by unexpected reaction in the ty-
OHCl +H +
→Cl +
H2 O (29)
pical Fenton process [8]. The alleged initial concentration of H2O2 in

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

previous study must take the actual parameters of wastewater into iron source of the PF process is FeSO4·7H2O particularly for the
consideration, hindering the practical degradation of antibiotics from homogenous catalysis, and it could certainly combine with semi-
unstable source. conductor catalyst for the environmental remediation [40].
The EF and PEF processes are both electrochemical advanced oxi- Bansal et al. fabricated the support materials for the TiO2 by mixing
dation processes (EAOPs), known for the considerable efficiency for the clay beads with foundry sand (FS)/fly-ash (FA), and the synergistic
almost all of the antibiotics. The TOC and dissolved organic carbon effect of the photocatalysis and PF process for the degradation of ce-
(DOC) are common indicators for the assessment of mineralization phalexin (CEX) was investigated over composite beads (FS/FA/TiO2)
degree for the EF and PEF process, which are more convincing in terms [49]. As seen in Fig. 2a, the iron leaching from support for the PF and
of the elimination of toxicity [26]. For instance, the problem caused by immobilized TiO2 on the support for the photocatalysis accomplished
initial concentration of antibiotics shows slightly influence to the mi- the dual process with synergistic effect. Lima et al. carried out the
neralization, and even the extremely higher concentration could be heterogeneous PF degradation of three types of antibiotics with the
easily settled by prolonging the treated time [41,42]. The concentration Fe2O3–TiO2 film which fabricated with sol–gel synthesized Fe2O3 as
of in-situ H2O2 in the EF process is much lower than the dosage in the PF well as commercial Fe2O3, TiO2 and Fe2O3–TiO2 composites [12]. The
process, continuously generating on the cathode to produce %OH. The TiO2 and Fe2O3 were adopted as the electron charge carrier conductor
regeneration of Fe2+ maintain a suitable ratio of Fe2+/Fe3+ by directly and hole charge carrier conductor for the heterogeneous PF, respec-
electron reduction of Fe3+ (Eq. (25)). In addition, the heterogeneous M tively, and the Fe leaching was observed in the solution contributed to
(%OH) on the anode is also a vital part of the anode oxidation during the the homogeneous process (Fig. 2b).
electrocatalysis, especially for the BDD and Pt anode [43]. Besides, the introduction of carbon materials for the synthesis of
Nevertheless, the large energy loss in the treated solution caused a heterogeneous catalyst also improves the homogeneous PF process for
serious waste, let alone negative impact of excess salt to the aquatic the adsorption of antibiotics. Kakavandi et al. adopted the co-pre-
organisms in freshwater. The electric current contributes to different cipitation method to prepare the Fe3O4@C, and the degradation of TC
key parameters of EF process, and the heterogeneous catalyst in Fenton was combined with the adsorption procedure improving the stability,
process and PF processes could not simply introduced without suitable activity and recyclability [24]. Meanwhile, multiwalled carbon nano-
characteristics. Although the carbon based heterogeneous catalysts are tubes (MWCNT) could decorate with the Fe3O4 for the degradation of
universally applicable to promote the contact of active substances with norfloxacin (NOR), and Shi et al. confirmed the enhancement of the
large surface for EF [23], and PF processes [24]. Moreover, the in- MWCNT by transmission electron microscope (TEM), X-ray diffraction
troduction of electric current caused an extremely serious corrosion for (XRD) and Fourier transform infrared (FT-IR) [50]. In summary, the
both of electrode and catalyst if the electrocatalytic system is vulner- recent investigation on iron catalyst for antibiotic decay by PF process
able [36]. Hence, there should be separated discussions on the key tends to improve the recyclability and activity using decoration and
parameters blocked the total degradation process of antibiotics, espe- immobilization methods, and the TiO2 and carbon based materials have
cially for the distinguish function of the catalysis in every aspects. shown convincing performance.

3. Treatment methods and key parameters

3.1. The degradation of antibiotic by PF process 3.1.3. Initial H2O2 concentration


The H2O2 is the main source of %OH in the PF process (Eqs. (1) and
3.1.1. pH (2)), but the instability of the H2O2 certainly disturbs the control of
The pH significantly affects the oxidation state and solubility of the accurate concentration. There is no obvious regular pattern for the in-
Fe in the PF process, and the coordination of natural organic matter itial H2O2 concentration to the various systems according to the
(NOM) could moderate the extreme condition [19]. The weakly ionized Table 1. Nevertheless, the investigation on H2O2/Fe2+ molar ratio is
H2O2 would bring about H+ causing decomposition of H2O2 into O2 interesting with the analysis of data and mechanism. The best molar
and H2O at basic condition [44]. ratio of H2O2/Fe2+ for the PF process is limited [51], mainly blocked by
The structure of oxacillin (OXA) seems to have vulnerable moiety the recombination of %OH (Eq. (8)), the scavenger of H2O2 (Eq. (3)),
due to the efficient degradation process at pH of 5.6 [45], and the effect direct oxidation of Fe2+ by %OH (Eq. (32)). Moreover, the combination
of additives is not obvious [46]. Meanwhile, the introduction of powder of activated sludge (AS) process and sequencing batch reactor (SBR)
activated carbon supported magnetite nanoparticles (Fe3O4@C) as the under 12 h the hydraulic retention times (HRTs) increase the optimal
heterogeneous catalyst for the degradation of tetracycline (TC) could H2O2/Fe2+ molar ratio of the PF process [52].
not change the optimum pH with the assessment of the response surface %
method (RSM) [24]. Iron citrate could slightly improve the pH of the PF OH + Fe2+ →Fe3+ + OH− (32)
treatment of ciprofloxacin (CIP) and fluoxetine (FLU) after the anae- Interestingly, the additional H2O2 is not necessary for the photo-
robic treatment to 4.5 for the influence of the ligands [47]. Interest- degradation of antibiotics, and some heterogeneous catalyst would
ingly, the ethylenediamine-N,N’-disuccinic acid (EDDS) has been suc- accomplish the Fenton like process attributed to the generation of O2%–
cessfully adopted to moderate the pH of PF process, reducing the cost of with in-situ generation of H2O2 (Eq. (33)). Huang et al. proposed an
previous acidification and secondary treatment [48]. Moreover, the interfacial reaction of the Fe3O4 and oxalate under UV irradiation for
oxalate has accomplished the modification of PF treatment of levo- the degradation of NOR [53]. As illustrated in Fig. 3a, the complex of
floxacin (LEV) at mild pH [20]. Obviously, most value of pH for the Fe3O4 and oxalate enhance the utilization of optical energy, generating
degradation of antibiotics is at acidic range achieving the best perfor- the O2%– for the in-situ generation of H2O2 without excess radical re-
mance in the PF process as illustrated in Table 1, the modification action. The C3N4@MnFe2O4-graphene nanocomposites have adopt to
methods with organic matter is seem to moderate the mild pH of PF the antibiotic degradation under visible light [54], and the capture of
process. photo-excited electrons on the semiconductor moiety by O2 is the
source of O2%– (Fig. 3b). Although the initial concentration of H2O2
3.1.2. Iron source and heterogeneous catalyst plays a vital role during the PF process, the development of novel
Many people would mistake PF process for conventional photo- catalyst for in-situ H2O2 seems to be more valuable to overcome the
catalysis with semiconductor, indeed, the function of light in the main negative impact of one-off adding mode.
PF process is to maintain the concentration of Fe2+ from the additional
iron source as Eqs. (11–13) [45]. The most common and convenient O2%− + 2H+ →H2 O2 (33)

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Table 1
The key parameters of the PF process for degradation of antibiotics.
Antibiotics pH Initial H2O2 concentration Iron source (catalyst) Light source Ref.

Amoxicillin 3.0 15–40 mM FeSO4·7H2O UV lamp (365 nm) [51]


Ampicillin
Cloxacillin
Amoxicillin Cloxacillin 3.0 17.97–53.9 mM FeSO4·7H2O UV lamp (365 nm) [52]
Oxacillin 5.6 1000 μM FeSO4·7H2O UV lamp (less than 387 nm) [45]
Tetracycline 3 ± 0.2 3 mM Fe3O4@C UV-C lamp (PHILIPS) [24]
Ciprofloxacin 4.5 100 μM Iron citrate Black-light lamp (365 and 410 nm) [47]
Fluoxetine
Oxacillin 5.6 1000 μM FeSO4·7H2O Philips lamp (TL-D Actinic BL) [46]
Ciprofloxacin 3.0 4.2 mM FeSO4·7H2O Philips lamp (365 nm) [28]
Cephalexin 3.5 4.41 mM FeSO4·7H2O/ TiO2 immobilized clay beads Philips UV tubes (365 nm) [49]
Sulfamethoxazole 2.8 0.59–2.94 mM FeSO4·7H2O Compound parabolic collector [11]
Erythromycin
Clarithromycin
Ciprofloxacin 2.8 2.5 mM FeSO4·7H2O/Fe2O3–TiO2 composites NETmix@ photoreactor [12]
Sulfamethoxazole
Trimethoprim
Norfloxacin 3.0 98 mM Fe3O4-multiwalled carbon nanotubes Solar simulator xenon lamp [50]
Penicillins 3.0 10 mM FeSO4·7H2O Philips black lamps (365 nm) [91]
Tinidazole 2.0/6.8 100–1500 μM FeSO4·7H2O UVC and Solar [92]
Levofloxacin 3.0–6.0 147–588 μM FeSO4·7H2O UV lamp (280–400 nm) [20]

3.1.4. Light source acidic condition is vital for the oxygen reduction reaction (ORR) on the
The light source of the irradiation procedure of antibiotic waste- cathode (Eq. (15)), and the major EF process shows the highest mi-
water for the PF process is usually carried out by UV lamp at the wa- neralization capacity at the pH value of 3.0 (Table. 2).
velength of 365–410 nm (Table. 1), which might be benefit to the Eqs.
O2 + e− →O2%− (34)
(11–13). The photo-current from the UV lamp requires external elec-
trical energy although the solar could not reach a satisfied miner- Nevertheless, several EF systems could function at natural pH, and
alization [55]. The solar PF process has a negligible cost for the input of some practical strategies have been proposed to widen the pH of the EF
energy, and the available UV light in the natural light is limited. The process. Li et al. combined the microbial fuel cell (MFC) and MBR
solar disinfection with in-situ PF process has been applied for the su- technology to degrade the TC by FeOOH/TiO2 granular activated
periority bacterial inactivation, whereas the investigation on the anti- carbon (FeOOH/TiO2/GAC) [57]. The electrical energy supply for the
biotic decomposition under visible light requires the assistance of continuous equipment is provided by the MFC system, and the deem-
equipment [56]. Romero et al. compared the simulated sunlight, pilot phasis on the pH value might be caused by both of the weak current
plant with sunlight, CPC, black blue lamps (λ = 365 nm) and UVC density for the ORR (Eq. (15)) and the introduction of heterogeneous
(λ = 254 nm) for the PF process, and the CPC pilot plant shows a lower FeOOH/TiO2/GAC (Fig. 5a). Meanwhile, Barhoumi et al. firstly in-
energy consumption and higher efficiency than the powerful artificial troduce the chalcopyrite (CuFeS2) to the heterogeneous EF process for
solarbox (SB) [10]. the degradation of TC [22], and the cooperation of the Fe2+ and Cu2+
Karaolia et al. employ the CPC and membrane bioreactor (MBR) to for the generation of %OH was also investigated (Fig. 5b). Fig. 5c shows
improve the solar PF degradation of erythromycin (ERY), sulfa- an interesting time-course of pH value for the different dosage of
methoxazole (SMX), and clarithromycin (CLA) [11]. In the latest re- chalcopyrite, and the decrease of the pH value accompanied with the
search, the light source for the degradation of antibiotics was generated increase of CuFeS2 could be explained by Eq. (35).
from novel static mixer photoreactor (called NETmix® photoreactors),
giving a comparison of CPC for the solar PF process [12]. Generally, the CuFeS2 + 16Fe3 + + 8H2 O→ Cu2 + + 17Fe2 + + 2SO24− + 16H+ (35)
PF process carried out a complete mineralization of antibiotic waste-
Thus, the pH adjustment for the EF process with chalcopyrite seems
water after the MBR pretreatment for the pilot-scale study (Fig. 4a).
to be unnecessary, which is still an important step for the pyrite EF
Meanwhile, the PF process largely improves the low ratio of BOD5/COD
process [26,41]. Furthermore, the synergistic effect of Fe and Cu is also
(biodegradability) as a convincing pretreatment, while the SBR is not
interested in the fabrication of the cathode to enhance the electron
effective for the antibiotic wastewater for the low biodegradability
transfer on the surface for a wider pH (Fig. S2). Zhao et al. prepared the
(Fig. 4b). Sincerely, the UV light provides direct available light with
iron–copper–carbon (FeCuC) aerogel by embedding the Fe-Cu nano-
continuous energy consumption for PF process, whereas the photo-
particles into 3D carbon matrix, proposing a surface-based reaction
reactor and CPC show a potential pilot-scale study for the mineraliza-
mechanism for the pH range from 3.0 to 9.0 [15]. Jiang et al. reported a
tion of antibiotic at μg L−1 and ng L−1 level.
Fe-Mn binary oxide (FMBO) modified electrode that could remain
considerable efficiency at the pH range from 3.0 to 10.0 [58]. In the
recent research, the main strategies to avoid the pre-acidification and
3.2. The degradation of antibiotic by EF process
secondary adjustment during the EF process can be concluded as the
introduction of one-electron oxygen reduction process, surface-based
3.2.1. pH
reaction mechanism, and the synergy of bimetallic catalyst.
The pH is also essential for the solubility and oxidation state of iron
ion as PF procedure [9], whereas the Fe(III)-carboxylate complexes are
not suitable for the EF process due to a natural photoactivity instead of 3.2.2. Iron source and catalyst
electrocatalytic activity (Eq. (13)). As a convincing alternative (Fig. S1), The FeSO4·7H2O is a cheap and convenient source for the homo-
the sodium tetrapolyphosphate (Na6TPP) has been adopted to improve geneous EF process, and the reduction of Fe3+ on the cathode guar-
the one-electron oxygen reduction processes in the EF process (Eq. (34)) antee the stability for a long time (Eq. (19)). The optimum pH at 3.0 for
[15], showing highly efficient at a pH range of 4.0–10.2. Moreover, the homogeneous EF will largely increase processing costs for the

383
X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 2. Schematic illustration of combination of photocatalysis and PF process for the degradation of antibiotics: (a) TiO2 immobilized clay beads, reprinted with
permission from ref [49]. Copyright 2017 Elsevier. (b) Fe2O3–TiO2 film, reprinted with permission from ref [12]. Copyright 2016 Elsevier.

neutralization of excess acid with a secondary processing, and the re- process would oxidize the H2 into H2O2, for example, the Fe3O4 and Pd
maining iron ion would cause an additional pollution to the effluent nanoparticles (Fe3O4-Pd) could be combined and use to catalyze the
[29]. Thus, the solidification for the recycle procedure and adaptability electrochemical-heterogeneous Fenton (EC-HF) process [59,60].
for a wide pH range are vital characteristics for the heterogeneous Moreover, the iron doped carbon fiber materials (e.g., FeCx/N-doped
catalyst. carbon fiber composites (FeCx/NCNFs) [23] and iron(II) phthalocya-
The pyrite (FeS2) is regarded as a sustainable iron source for the EF nine polyacrylonitrile (FePc/PAN) nanofibers [61]) seem to enhance
process, and it has been successfully applied to the LEV [41], and sul- the heterogeneous catalysis efficiency by extra adsorption of the pol-
famethazine (SMT) by Barhoumi et al. [26] In the latest research, lutant. Obviously, the highly efficient natural mineral could be devel-
Barhoumi et al. improved the pH of TC decay by CuFeS2, and clarify the oped as practical heterogeneous catalyst for the EF process, and nearly
Fenton’s-like reaction for Cu2+ alone with Fenton reaction in the EF no carbon based catalyst adopts to the antibiotic removal by EF.
degradation [22]. The natural pyrite and chalcopyrite should be sieved
with a filter of less than 80 μm after ground finely and then the pyrite 3.2.3. Cathode and generation efficiency of H2O2
power must accept the sonication in 95% ethanol for 5 min and rinse The efficiency of EF process is largely depended on the cathode
with deionized water and 95% ethanol after being washed by 1 M HNO3 which largely affected the production of hydrogen peroxide. The carbon
and finally dried at 30 °C. Moreover, both of the best doses of the pyrite felt (CF) and graphite felt (GF) are the most common and convenient
and chalcopyrite are figure out and efficiently improve the conven- cathode for the degradation of antibiotics (Table. 2). The electro-
tional EF process. chemically active surface area (ECSA) of CF/GF is considerable, and the
Besides, the noble metal (e.g., Pd and Pt) introduced in the EF reduction of the Fe3+ could be accomplished instantly (Eq. (19)). Thus,

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Fig. 3. Schematic illustration of the degradation of antibiotics under irradiation by Fenton like process: (A) Fe3O4 and oxalate, reprinted with permission from ref
[53]. Copyright 2017 Elsevier. (B) C3N4@MnFe2O4-graphene nanocomposites, reprinted with permission from ref [54]. Copyright 2017 Elsevier.

the generation efficiency of H2O2 is an important characteristic for the degradation of LEV during EF process [14]. The surface of GF was
cathode, bringing out numerous researches on the modification and corroded and etched during the heated process in the mixture of
activation method. Interestingly, the GF with high ECSA were used as C2H5OH and N2H4·H2O, generating vacancies and edge planes for the
anode for the degradation of SMT, found a great apparent rate constants improvement of the oxygen and nitrogen containing functional groups
at low current (50 mA) [43]. However, the GF might burn for a higher [63]. The hydrophilic property and the electro-catalytic activity were
current (> 100 mA) while common used anode could reach a more improved by the nanoparticles, nitrogen and oxygen containing func-
complete TOC removal with a higher current. tional groups attached to the surface of cathode (Fig. 6c). With regard
CF, graphite and reticulated vitreous carbon (RVC) were compared to the modification substance in EF process, Ling et al. compared the
for the reduction of Fe3+ and generation of the hydrogen peroxide in improvement of Fe loading by modification of acid potassium dichro-
the EF process by means of a Merck specific analytical test (Fig. 6a). mate, hydrogen peroxide, nitric acid, concentrated sulfuric acid and
Although the RVC shows the distinctive electrocatalytic activity, the sodium hypochlorite for the active carbon felt (ACF) [64].
cost of CF is well below the RVC cathode, indicating a practical value Besides, the anodized GF materials prepared by electrochemical
for the further study [62]. The modification of the GF cathode could be treatment [65], and KOH activation method [66], resembling to the
accomplished by hydrothermal synthesis with C2H5OH and N2H4·H2O function of modification method in the EF process. Meanwhile, the
(Fig. 6b), exhibiting an obvious improve of the TOC removal for the carbon fiber is suitable for the cathode membrane, and has been applied

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Fig. 4. (a) The deep mineralization of antibiotic effluent after MBR though solar PF process, reprinted with permission from ref [11]. Copyright 2016 Elsevier. (b)
The pretreatment of antibiotic wastewater for the SBR though PF process, reprinted with permission from ref [52]. Copyright 2011 Elsevier.

Table 2
The key parameters of the EF process for degradation of antibiotics.
Antibiotics pH Anode Cathode Iron source (catalyst) Applied current Ref.

Tetracycline 3.0 Ti/RuO2-IrO2 CF FeSO4·7H2O 200–500 mA [69]


Pt
BDD
Levofloxacin 3.0 RuO2/Ti ACF FeSO4·7H2O 2.22–9.26 mA cm−2 [94]
Levofloxacin 3.0 Pt CF FeSO4·7H2O 60–500 mA [93]
Levofloxacin 3.0 BDD CF Pyrite 100–400 mA [41]
Enoxacin 3.0 Pt CF FeSO4·7H2O 50–300 mA [95]
Norfloxacin 3.0 Pt CF BDD FeSO4·7H2O 30–500 mA [72]
BDD Pt
Sulfamethazine 3.0 BDD GF FeSO4·7H2O 100–1000 mA [43]
Pt
DSA
Sulfamethazine 3.0 BDD CF Pyrite 100–1000 mA [26]
Pt
−2
Tetracycline Natural Anode chamber (graphite particles) Cathode membrane FeOOH/TiO2/GAC 0–350 mA m [57]
Amoxicillin 3.0 Ti4O7 CF FeSO4·7H2O 10–120 mA [17]
Tetracycline Natural Pt CF Chalcopyrite 50–500 mA [22]
BDD
Ciprofloxacin 3.0 Pt CeO2/RGO composite FeSO4·7H2O 100–450 mA [13]
Ciprofloxacin 3.0 Pt CexA1−xO2 (A = Zr, Cu and Ni) modified CF FeSO4·7H2O 100–500 mA [68]
Ciprofloxacin 3.0 Cylindrical Pt mesh CF FeSO4·7H2O 60–500 mA [74]
Levofloxacin 3.0 Ti/RuO2-IrO2 N-doped GF FeSO4·7H2O 100–400 mA [14]

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Fig. 5. Schematic illustration of the natural pH system for the degradation of antibiotics by EF process: (a) Combination of microbial of fuel cell (MFC) technology by
FeOOH/TiO2 granular activated carbon (FeOOH/TiO2/GAC) for the tetracycline, reprinted with permission from ref [57]. Copyright 2017 Elsevier. (b) Chalcopyrite
degradation mechanism of the tetracycline and the time-course of pH, reprinted with permission from ref [22]. Copyright 2017 Elsevier.

Fig. 6. (a) Comparison of the graphite, carbon felt, reticulated vitreous carbon (RVC) cathode, reprinted with permission from ref [62]. Copyright 2016 Elsevier. (b)
Flow diagram of the degradation of antibiotic by modified cathode, reprinted with permission from ref [14]. Copyright 2017 Elsevier. (c) Schematic illustration of the
mechanism of modification of cathode, reprinted with permission from ref [63]. Copyright 2014 Elsevier. (d) Sandwiched structure of the membrane stack cathode,
reprinted with permission from ref [67]. Copyright 2015 American Chemical Society.

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

to the EF process for the sequential influent treatment [67]. As illu- efficiency of the CF/GF cathode with considerable ECSA.
strated in Fig. 6d, a sandwiched structure of membrane stack was The Pt anode is made up of expensive precious metal while the
consist of carbon nanotube (CNT) separated by polytetrafluoroethene synthesis of BDD anode requires the strict condition, and both of them
(PTFE) layer, and 3 pieces of CNT membrane seem to represent the hinder the realization of industrialization [73]. The Pt mesh anode
cathode, bulk solution and anode, respectively. Interestingly, the fab- possessing cylindrical shape seems to provide large ECSA with less
rication of cathode chamber could be achieved by cathode membrane, consumption of precious materials [74]. Nevertheless, the dimension-
and the modification of the poly (vinylidene fluoride) (PVDF) would ally stable anode (DSA) could hardly reach equivalent efficiency as Pt
strengthen the physical and chemical stability of the carbon fiber cloth or BDD anode for the less generation of DSA(%OH) and unexpected
[57]. firmer adsorption on the surface of anode in the EF process for de-
Moreover, the rare earth elements have been introduced to the gradation of SMT [43]. The coating technology and other strategies for
degradation of antibiotics in EF system, combined with the carbon- the preparation of conventional DSA (e.g., Ti/RuO2-IrO2, RuO2/Ti) are
based material as cathode. Li et al. fabricate a 3D cerium oxide/reduced sophisticated enough for the industrialization with a much lower ex-
graphene oxide (3D CeO2/RGO) cathode to degrade the CIP, and the pense [75].
generation of the hydroxyl radical and superoxide from the cycle of Aiming at a balance between the high efficiency of BDD and low
Ce4+/Ce3+ are investigated, respectively [13]. In the recent research, cost of DSA, the ceramic anode with deposition of Ti4O7 plasma pro-
the same team produce lattice defects in the CeO2 by doping transition duced Ti4O7(%OH) are fabricated for the degradation of amoxicillin
metal (Zr, Cu and Ni), improving the O2 diffusion on the CexA1-xO2 (AMX) by EF process (Fig. 7b). The TiO2 were put into a hydrogen
(A = transition metal ions) cathode [68]. Exactly, the transition metal plasma plume ionized by 38 kW electric arc generated from copper
replaces the Ce in the precursor, and the Ce0.75Zr0.25O2 has the best annular anode and tungsten cathode, and the argon was used as carrier
electrocatalytic activity and electrosorption feature for the degradation gas at rate of 30 g min−1 [16]. Melted TiO2 particles are quenched by
of CIP. The modification and activation of cathode are economical and the cold titanium plate, and the results of XRD show that the main
durable methods for a better antibiotic decay in EF system, and the CF/ phase of the plasma coating is Ti4O7 instead of Ti3O5, Ti5O9, Ti6O11.
GF has been considered as the ideal cathode for further improvement. The Ti4O7 anode has a similar performance to the commercial BDD
Actually, the non-metallic reagents could increase the nitrogen or anode mineralization of AMX in the EF process, and the source of the
oxygen functional groups to generate more H2O2, whereas the metallic Ti4O7 is highly abundant TiO2 and the production cost is relatively low
modified method would introduce the cooperation with other metal [17].
ions. Nevertheless, most of the mentioned system is integral for the EF
system, and the fabrication of dual-chamber could combined with MFC
[57], and bioelectrochemical system (BES) by porous clapboard and
3.2.4. Anode and applied current
cationic exchange membrane [64], respectively. The graphite particles
Compared to the cathode materials, the high performance of anodes
were added in the anode chamber while the FeOOH/TiO2/GAC,
are relatively expensive (e.g., boron-doped diamond (BDD), Pt) to
FeOOH/GAC or GAC was used to fill the cathode chamber, and the
produce more available heterogeneous hydroxyl radical (Eq. (20)).
energy for the MFC were supplied by 4 electron ORR on the GAC sur-
Oturan et al. firstly carried out a comprehensive comparison of the
face (Eq. (36)), generally considered as an unexpected reaction com-
anode materials for the degradation of TC by EF and electrochemical
peted with 2 electron transfer (Eq. (15)) in EF process on the cathode
oxidation (EO) process, including Ti/RuO2-IrO2, Pt and BDD anode, and
[57]. Meanwhile, the anode chamber of BES reactor is consist of gra-
BDD was the best anode in the EF and EO process [69]. The generation
phite fiber brushes and anaerobic sludge, and the wastewater was
of M(%OH) on the anode is mainly depending on the overvoltage for
treated mainly by cathode chamber [64].
oxygen evolution, and the overvoltage for the BDD is higher than Pt
indicating more M(%OH) generation under the same current density O2 + 4H+ + 4e− → 2H2 O (36)
(Fig. 7a). Moreover, the physisorbed BDD(%OH) is more reactive and
available for the degradation of the organics than the chemisorbed Pt Furthermore, there are some interesting findings in terms of the
(%OH) on the anode surface [70,71]. Interestingly, the BDD and Pt were relationship between the electrode materials and optimum applied
tried as cathode to the degradation of NOR with EF treatment, showing current or current density for the EF process, since the definition and
that Pt is more suitable for the cathode than BDD in terms of the gen- fundamental of the applied current or current density for the EAOPs
eration of H2O2 [72]. Indeed, the effective surface of the Pt is higher have been well detailed [9]. The range of applied current or current
than BDD for the ORR, giving a logical explanation for the highest density of the degradation of antibiotics by EF process was illustrated in

Fig. 7. Schematic diagram of anode materials: (a) Conventional anode for the removal of sulfamethazine, reprinted with permission from ref [26]. Copyright 2016
Elsevier. (b) Novel Ti4O7 anode for the degradation of amoxicillin, reprinted with permission from ref [16]. Copyright 2016 Elsevier.

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

Table. 2, and the common applied current seem to be range from 100 to the anodic oxidation (AO), EF and SPEF for the degradation of enro-
400 mA. Generally, the removal of antibiotics would be more complete floxacin (ENR), and the constant current density was selected as
with an increasing current. Nevertheless, it could not be indefinite for 50 mA cm−2 with the 20 cm2 BDD and Pt anode [78]. The TOC removal
the Eq. (22) as well as the adsorption characteristics of different het- of ENR in the SPEF could reach 80% after 2 h under the flow rate of
erogeneous %OH on the anode. The analysis of the applied current range 200 L h−1 in the recirculation flow plant. Meanwhile, Pérez et al. car-
from 100 to 1000 mA for the SMT decay shows that the optimum ap- ried out the degradation of metronidazole (MTZ) by SPEF process with
plied current for the Pt and DSA seem to be 500 mA with GF cathode, a 90.2 cm2 Pt anode area at the current density of 55.4 mA cm−2,
whereas the optimum current for BDD might be higher than 1000 mA achieving a 36% DOC removal after 5 h treatment of SPEF process
[43]. This excellent electric property of BDD highly attributed to the under 200 L h−1 [79]. Nevertheless, the applied current density in the
highest overvoltage and physisorption of heterogeneous %OH [76]. PEF process for the removal of TMP is 5 mA cm−2, and the nearly
Interestingly, the effective current for the degradation of OXA is complete removal is achieved after 2.5 h degradation with 10 cm2 BDD
relatively low (10–120 mA) for the vulnerable moiety, which is in at the flow rate of 40 L h−1 [77]. Moreira et al. accomplish a complete
agreement with the previous hypothesis in PF process under relatively degradation of TMP after 0.5 h SPEF treatment with the 10 cm2 BDD
neutral pH [17,45]. Besides, the optimum current would be affected by and Pt anode, and the flow rate was set as 40 L h−1 at the maximum
the 3D CeO2/RGO cathode, and the reduction of Ce4+ might compete current density of 150 mA cm−2 [80]. Moreover, Pérez et al. investigate
with the generation of H2O2 when the applied current is higher than the SPEF process using the FM01-LC flow reactor for the ERY decay,
400 mA [13]. Moreover, the electric current generated from the 4e− on and the electrodes were 64 cm2 platinized Ti plate anode and 517 cm2
the GAC is extremely low and unstable, and the modification of TiO2 cathode [81]. The optimum cathodic current density for the SPEF
and FeOOH certainly ensure the stability of TC effluent quality [57]. system was found at 0.16 mA cm−2, reaching a 69% DOC removal after
The high performance anode significantly improve the removal effi- 5 h treatment under flow rate of 180 L h−1. The PEF and SPEF system
ciency and stability of EF system, but the unacceptable expend of anode was usually carried out by pilot-scale equipment, and the control of
is not suitable for the large scale antibiotic degradation. The optimal volume and flow rate for the reactor must receive enough attention. It
applied current for the antibiotic degradation should meet the reg- seems to maintain the stable operation that the heterogeneous catalysts
ulatory limits and pursue the waste of energy as low as possible. The have not been applied to the PEF and SPEF so far.
MFC has been investigated for the EF process, indicating an alternative
to the DC power.
3.3.2. Electrode
Carbon-PTFE air-diffusion cathode is the most common electrode
3.3. The degradation of antibiotic by PEF and SPEF process for the PEF/SPEF process, and the general ACF/GF could also be
adopted as well (Table. 3). The carbon-PTFE air-diffusion cathode is
3.3.1. Basic parameters usually embedded in the equipment combined with a same size anode
The pH and iron source are usually limited to the 3.0 and (Fig. 9a). Interestingly, the 2-ethylanthraquinone (2-EAQ) in the PTFE
FeSO4·7H2O for the most investigations on the antibiotics decay by electrode could highly improve the generation of H2O2 ensuring the
PEF/SPEF process (Table. 3). Moreira et al. comprehensively in- enough ORR in the flow plant (Fig. 9b), and 2-EAQ has been success-
vestigated the degradation of trimethoprim (TMP) in the PEF process, fully adopted for the modification of the carbon cathode [82]. Mean-
figuring out the function of the pH and Fe3+ speciation coordinated while, the air-diffusion cathode is a special gas diffusion electrode for
with carboxylate complexes [77]. The theoretical Fe3+ speciation could the wastewater degradation, improving the ORR reaction with lower
avoid the formation of Fe(OH)3 precipitation in the PEF system, and the energy consumption [83]. Moreover, the multifunctional iron con-
optimum pH should be set lower than 5.5 despite the species of ligand taining MOFs would be modified on the carbon cathode for the SPEF
(e.g., citrate, oxalate, malate and tartrate) and molar ratio (Fig. 8). process to introduce the photo activity to the conventional EF process
Moreover, the solution of TMP and Fe3+ has an absorption peak at (Fig. 9c). Zhao et al. fabricate a MOF(2Fe/Co)/carbon aerogel (MOF
wavelength of 270 nm further enhanced by the introduction of ligands. (2Fe/Co)/CA) for the SPEF process, and the characteristic of the gen-
Indeed, both of the stability in the EF process and photo-activity in the eration of electron-hole pair on the semiconductor enhance the de-
PF process are required for the iron based catalyst of the PEF process, composition of in-situ H2O2 with the hole scavenger of CCl4 [84].
and the iron containing (metal organic frameworks) MOFs materials The main functionality of anode materials for the PEF/SPEF process
seem to be a good solution for the characteristics of multifunction [40]. is similar to the EF process to generate the M(%OH). Despite the un-
The current density would be associated with the flow rate and acceptable expense, the BDD and Pt are more suitable for continuous
electrode to achieve an equivalent efficiency. Guinea et al. compared flow plant than the DSA due to the highly stable and efficient feature.

Table 3
The key parameters of the PEF process for degradation of antibiotics.
Antibiotics pH Electrode Iron source Light source Device Ref.

Enrofloxacin 3.0 Anode: Pt and BDD FeSO4·7H2O Solar photoreactor 2.5 L flow plant [78]
Cathode: Carbon-PTFE air-diffusion Philips TL/6W/08 fluorescent black light
Trimethoprim 3.0 Anode: Pt and BDDn FeSO4·7H2O Compound parabolic collector 2.2 L flow plant [80]
Cathode: Carbon-PTFE air-diffusion Philips TL 6 W/08 fluorescent black light
Trimethoprim 3.5–5.5 Anode: BDD Fe(III)-carboxylate Compound parabolic collector 2.2 L flow plant [77]
Cathode: Carbon-PTFE air-diffusion complexes UVA lamp
Metronidazole 3.0 Anode: Pt FeSO4·7H2O Compound parabolic collector 10 L solar plant [79]
Cathode: Carbon-PTFE air-diffusion
Trimethoprim 2.8 Anode: BDD FeSO4·7H2O UVA and UVC lamp 2.2 L flow plant [85]
Cathode: Carbon-PTFE air-diffusion
and Pt
Trimethoprim 3.0 Anode: RuO2/Ti FeSO4·7H2O Sunlight Photo-voltaic [42]
Cathode: ACF cell
Erythromycin 3.0 Anode: Platinized Ti FeSO4·7H2O Filter-press FM01-LC flow reactor with compound 10 L solar plant [81]
Cathode: GF parabolic collector

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Fig. 8. The theoretical function of the solution pH and actual Fe3+ speciation: 35.8 μM Fe3+ with (a) 107 μM oxalate, (b) 35.8 μM citrate, (c) 35.8 μM tartrate and (d)
35.8 μM malate, reprinted with permission from ref [77]. Copyright 2015 Elsevier.

The coating technique is a sophisticated method for the dispersion of and UVB section for the photo reduction of Fe2+ (Eqs. (11–13)) due to
noble metal on the electrode, compensating the electrochemical prop- the excess energy input of UVC makes no difference for the PF [10].
erty by larger area. The platinized Ti plate anode with an area of 64 cm2 In addition to the combination of the solar heterogeneous photo-
was adopted for degradation of ERY with conventional 517 cm2 GF catalysis (SPC) for the SPEF [86], the utilization of sunlight could in-
cathode, and the cost of this pilot plant would be more practical [81]. In crease by the CPC in the SPEF due to the natural light irradiation is not
addition, the photovoltaic cell was introduced to the SPEF process for concentrated enough to make an obvious improvement [79,81]. The
the TMP decay with RuO2/Ti mesh anode and ACF cathode possessing a CPC usually equip with a recirculation of pilot device for the solar
size of 20 cm2 area [42]. It is noteworthy that the gas diffusion property photoreactor instead of the static treated solution [87], including the
makes the electrode adaptable to the flow plant, and the size of elec- pump, air pump, heat exchangers, power supply, electrochemical cell,
trode must act in concert with the entire pilot plant during the anti- reservoir and rotameter (Fig. 10b). In the recent research, Pérez et al.
biotic decay by PEF and SPEF process. adopted the FM01-LC flow plant equipped with CPC photoreactor for
the degradation of ERY, and the low applied current density
3.3.3. Light source and pilot-scale device (j = 0.16 mA/cm2) achieve 75% current efficiency with convenient Pt
The PEF/SPEF procedure is a suitable subject for the further in- coating anode and GF cathode [81].
vestigation on the pilot-scale device, promoting the utilization of en- Interestingly, there is a novel photovoltaic cell that could supply the
ergy input such as the sunlight, UV light, applied current, and the EF process under sunlight as solar assisted PEF process, and Zhang et al.
aeration. Moreira et al. comprehensively compared the AOPs and employed it to the degradation of TMP with a comparison of the AO,
EAOPs for the effluent after secondary treatment with additional 5 mg/ AO-H2O2, EF and SPEF processes [42]. As illustrated in Fig. 10c, 72
L TMP [85], including the UVC, H2O2/UVC, AO, AO-H2O2, AO-H2O2/ mono-crystalline silicon solar cells with an active surface area of
UVC, PEF-UVC, PEF-UVA in 2.2 L flow plant (Fig. 10a). Both of the PEF- 12 × 10 cm2 per cell connected in 6 columns and 12 rows were used to
UVC and PEF-UVA processes were investigated at the neutral pH or at construct the panel. Moreover, the solar cell is superior to the men-
the pH = 2.8, and the PEF-UVC in the acidic condition and the H2O2/ tioned MFC for the degradation of antibiotics without the electricity
UVC are superior to the other treatment. Interestingly, the excellent input due to the limited current density to the electrode [57]. As
performance of H2O2/UVC is attributed to the generation of %OH from compared to the EF and PF processes, the recent research on the PEF
extreme high cleavage of H2O2. The wavelength of the UVA, UVB and and SPEF processes for the antibiotic removal tend to introduce pilot-
UVC was 320–400 nm, 275–320 nm and 200–275 nm, respectively, scale device for the practical application, including the CPC photo-
whereas the light source of PF process is usually carried out under UVA reactor and photovoltaic cell.

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Fig. 9. Schematic illustration of highly efficient cathode: (a) Carbon-PTFE air diffusion cathode in the pilot device, reprinted with permission from ref [80].
Copyright 2016 Elsevier. (b) The function of 2-ethylanthraquinone (2-EAQ) in the PTFE cathode, reprinted with permission from ref [82]. Copyright 2014 Elsevier.
(c) The iron containing MOFs based cathode for the introduction of photo-activity, reprinted with permission from ref [84]. Copyright 2017 Elsevier.

4. The degradation pathway of antibiotics certainly required a volatile mobile phase (e.g., ammonium formate
buffer or ammonium acetate buffer) for the electrospray ionization
The degradation of antibiotics in aqueous matrices has been re- (ESI). Therefore, the common mobile phase for the HPLC (e.g., phos-
viewed by Homem et al., giving an overview of the conventional re- phate buffer) can’t reach a well-defined peak due to the poor volatility
moval process and a detailed classification and comprehensive en- that hindered the precise determination of the intermediates. Hence,
vironment analysis [31]. The common investigated structure of the solid-phase extraction (SPE) is usually introduced to the pretreat-
antibiotics in the EF/PF/PEF is summarized in Fig. 11, giving an in- ment of the sample to concentrate the antibiotic in solution avoiding
tuitive understanding of the degradation pathway. The studies on the the interference of non-volatile salt [88–90].
antibiotic degradation by EF and PF process are so limited for the
complex structure, i.e. the degradation mechanism must be measured
by LC-MS/MS, HPLC/ESI-MS or GC–MS. The introduction of MS

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Fig. 10. (a) Comparison of the pilot plant of UV, H2O2-UV, AO, AO-H2O2, and PEF, reprinted with permission from ref [85]. Copyright 2016 Elsevier. (b) Schematic
diagram of compound parabolic collector (CPC) in the SPEF, reprinted with permission from ref [87]. Copyright 2011 Elsevier. (c) Novel photovoltaic cell driven
SPEF process reprinted with permission from ref [42]. Copyright 2016 Elsevier.

4.1. PF degradation pathway 4.2. EF and PEF degradation pathway

The mentioned antibiotics in the investigation of the PF process The EF and PEF are more convincing for the discussion of complete
include AMX [51], ampicillin [51], cloxacillin (CLX) [51], OXA [45], degradation pathway, and final conversion of AMX (Eq. (37)) [17], LEV
TC [24], CIP [47], CEX [49], ERY [11], CLA [11], SMX [12], TMP [12], (Eq. (38)) [14], SMT (Eq. (39)) [26], NOR (Eq. (40)) [72], ERY (Eq.
NOR [50], LEV [20], penicillins [91] and tinidazole [92]. Since the PF (41)) [81], TMP (Eq. (42)) [80], CEX (Eq. (43)) [27], ENR (Eq. (44))
process cannot always achieve complete mineralization, the discussion [78], TC (Eq. (45)) [22] and CIP (Eq. (46)) [74] were figured out to
on the degradation pathway is limited to the OXA [45], CIP [28], CEX calculate of the mineralization current efficiency (MCE) during the EF
[49], and tinidazole [92]. Serna-Galvis et al. proposed six possible and PEF process by Eq. (47). Moreover, following reactions are con-
pathways for the degradation of OXA by PF process [45], (P1) hydro- cluded from the ion chromatography, ion exclusion chromatography
xylation of the aromaticring, (P2) opening of the β-lactam ring, (P3) and TOC analyser, and time course of these inorganic ions could be
oxidation of the thioether moiety, (P4) isomerization of OXA, (P5) considered as mineralization indicators.
breakdown of the central secondary amide and (P6) decarboxylation
C16 H19 N3O5 S+ 40H2 O→ 16CO2 + 3NO−3 + SO24− + 99H+ + 94e− (37)
(Fig. S3). Villegas-Guzman et al. compared the degradation of CIP by
H2O2/UV, Fe2+/H2O2/UV and TiO2/UV [28], and illustrated the de- C18 H20 FN3O4 + 41H2 O→ F− + 3NO−3 + 102H+ + 98e− (38)
gradation pathway based on attack of the %OH (P1–P3) and the oxida-
tion of photo-induced holes (P4-P6) (Fig. S4). The CEX decay in the C12 H14 N4 O2 S+ 26H2 O→ 12CO2 + 4NH+4 + SO24− + 50H+ + 52e−
combination of PF and photo catalysis was analyzed with the frag- (39)
mentation of 8 intermediates (Fig. S5). Velo-Gala et al. investigated the
degradation mechanism of tinidazole for the obtaining of selected by- C16 H18 FN3O3 + 29H2 O→ 16CO2 + 3NH+4 + F− + 64H+ + 66e− (40)
products, including C9H11N2O2, C11H14NO2S, C16H27N4O7S2 [92]. Sin- C37 H67 NO13 + 64H2 O→ 37CO2 + NO−3 + 195H+ + 194e− (41)
cerely, these antibiotic degradation pathways suggested that the PF
process just bring about the primary break of structure rather than C14 H18 N4 O3 + 31H2 O→ 14CO2 + 2NH+4 + 2NO−3 + 72H+ + 72e− (42)
complete mineralization.
C16 H17 N3O4 S+ 41H2 O→ 16CO2 + 99H+ + 3NO−3 + SO24− + 94e− (43)

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Fig. 11. The illustration of common investigated antibiotics in EF, PF and PEF/SPEF processes.

C19 H22 FN3O3 + 35H2 O→ 19CO2 + F− + 3NH+4 + 80H+ + 82e− (44) the tR and intermediates might be more convincing than the former for
the recognition of the degradation pathway. Although the hydrogen
C22 H24 N2 O8 + 36H2 O→ 22CO2 + 2NH+4 + 88H+ + 90e− (45) evolution reaction (HER) was discussed as a compete reaction for the
consumption of the proton and electron (Eq. (18)), the additional HER
with no slash on the ORR seem to be effective for the N atom directly
C17 H18 FN3 O3 HCl·H2 O·+ 30H2 O→17CO2 + F− + Cl− + 3NH4+ +
connected on the ben ring. In the recent research, Liu et al. firstly
69H+ + 70e− (46)
characterized the HER during the degradation of LEV, proposing the
nFVSΔ(TOC)exp interesting mechanism for the enhancement of the modified electrode
MCE(%) = × 100
4.32 × 107mlt (47) [14].
Moreover, the degradation pathways of SMT [26], TC [22], NOR
It is noteworthy that the degradation pathway of LEV in the EF [72], enoxacin (ENO) [95], CEX [27] and MTZ [96] during the EF
process has been discussed by three papers from different aspects, process were detailed in the recent investigation. Barhoumi et al. in-
whereas the decarboxylation, demethylation, and de-piperazinyl are vestigated the mechanism of SMT in the pyrite EF process based on the
regarded as the basic reaction (Fig. S6–8). Yahya et al. investigated the BDD(%OH) mineralization [26]. The results of GC–MS provide the tR
specific intermediate of LEV according to the different mass-to-charge with the specific molecular mass, and suggest that the cleavage of N-C
ration resulted from mass spectra (MS), and the possible intermediates bond, N-S bond and the desulfonation on the benzene ring led the main
were figured out based on the analysis of the structure and the results of pathway (Fig. S9). Recently, Barhoumi et al. proposed the degradation
MS [93]. In addition, Gong et al. give a more comprehensive by-product pathway of TC during the EF process based on the attack of homo-
analysis for the fragment of LEV intermediates, which might have the genous %OH with the catalyst of solid chalcopyrite [22]. HPLC-MS and
same retention time (tR) as the complete structure in the results of GC–MS are adopted to identify high molecular weight polar byproducts
UPLC-QTOF-MS chromatogram [94]. Moreover, the latter’s matching of

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and the lower molecular weight polar and non-polar byproducts, re- comprehensive comparison of EF and PF processes and those of other
spectively, and the multiple hydroxylation reactions, demethylation wastewater processes are valuable to choose the best strategy accord-
and decarboxylation are essential to the complete mineralization (Fig. ingly. Generally, the optimal pH for the EF and PF process is always
S10). acidic without any modification ensuring the oxidation state and so-
Besides, Özcan et al. concluded the main reaction pathway of the lubility of iron catalyst, and the pretreatment of acidification and sec-
NOR in the EF process from both of the LC-MS and GC–MS analysis ondary treatment for the neutralization might increase the budget
[72]. Substitution of fluoride as well as hydroxylation was two parallel [8,30]. Therefore, an economical alternative to promote the suitability
reactions in the beginning (Fig. S11), and the hydroxylation would be of catalyst in the mild or broad pH should be investigated for EF and PF
detailed in the LEV with the similar structure as illustrated in Fig. 11. processes, respectively. For example, the utilization of NOM in the
Annabi et al. illustrate the possible by-products of ENO in the EF pro- wastewater might improve the solubility of Fe2+/Fe3+ [19], whereas
cess with the data of UPLC-MS/MS [95], giving the comprehensive the introduction of O2%– for the production of H2O2 is more effective
analysis of the intermediates. The similar reaction for the generation of [21]. The photolysis and EO processes seem to be available in the mild
ENO I, II, III, IV can be found during the mineralization of LEV (Fig. pH, but the removal efficiency is not satisfied as compared to EF and PF
S12). Coledam et al. proposed the degradation mechanism of the CEX processes.
on the BDD anode according to the data of retention time, molecular Moreover, the raw materials for the synthesis of heterogeneous
ion and main fragment ions from LC-MS/MS [27]. The hydroxylation, catalyst certainly increase cost, especially for the less durable and
breakdown of the cephem group and oxidation of substituent methyl poorly recyclable catalyst. Some of noble metal loading catalysts show a
group are attributed to the total mineralization of CEX (Fig. S13). higher removal rate of EF process [59], whereas the natural mineral
Ammar et al. investigated the MTZ decay mechanism on the BDD anode catalysts are more practical for the improvement of efficiency [22,41].
[96], reaching the complete mineralization by denitration and hydro- The semiconductor improves the utilization of hv for the PF process,
xylation (Fig. S14). and the heterogeneous catalyst could be immobilized on the stable
Meanwhile, the degradation mechanism of TMP and MTZ were in- semiconductor to achieve a better recyclability. In addition, the mul-
vestigated in the SPEF process. Zhang et al. determine the tR and the by- tifunctional iron containing MOFs possess considerable efficiency both
products of TMP by UPLC-QTOF-MS/MS chromatograms [42], and the in the PF and EF processes, but the high cost for the preparation and
main reactions were concluded as carbonylation, hydroxylation and poor stability might hinder the practical application [40].
demethylation (Fig. S15). Pérez et al. combined the results of LC-MS The electric and photo current are essential for the EF and PF pro-
and previous study on the TMP [79], giving a good reference to the cesses, attributed to the cost of energy consumption. The DC power is
TMP decay by EAOPs (Fig. S16). Furthermore, the same group identi- enough to carry out EF process, and the budget is largely determined by
fied the intermediates of ERY by GC–MS during the SPEF process the electrode materials showing a distinctive MCE values [43,69].
without investigation on the degradation pathway [81]. The EF, PF and Nevertheless, most of the high performance anode certainly increases
SPEF could achieve complete mineralization of antibiotics in several the cost of device, let alone the corrosion on the traditional stainless
hours, and the investigations on the intermediates provide a clear re- steel anode [36]. Therefore, the investigations on the modification of
cognition of degradation mechanism and predict the potential toxicity. cathode with accessible regent are more convincing to improve the
cheap but inefficient DSA anode. Generally, the energy consumption of
4.3. The toxicity evaluation of antibiotics in PF and EF PF as well as other photocatalysis processes is lower than the EF and
related electrocatalysis processes, and the investigation on the service
The toxicity of antibiotics arouses an indirect threat to the medical life of device of light source for a continuous illumination is certainly
treatment, because the remaining toxicity of antibiotic containing ef- beneficial. The utilization of solar light requires investment on the pilot
fluents would increase the antibiotic resistance. The growth inhibition equipment to enhance the hv in sunlight, providing valid photo-activity
tests were firstly introduced to evaluate the sulfonamides (SNs) after for the PF process [11,79].
the electrochemical treatment by the duckweed of Lemna minor and Purification of antibiotic wastewater by adsorption process is also a
green algae of Scenedesmus vacualatus (Fig. S17), and the L. minor test common process, which seems to be cheaper as compared to the EF and
confirmed that the eco-toxicity of the sulfathiazole (STZ) and SMT was PF process [97]. The antibiotic concentrated on the adsorbent remains
obviously increased for the high growth inhabitation [25]. the complete structure, and untimely separation of exhausted adsorbent
Instead of the evaluation of the eco-toxicity, the assessment using would cause a secondary pollution. Moreover, the regeneration of ex-
the Microtox methods for several of bacterial are more frequent. The hausted adsorbent is necessary for the continuous removal of antibiotic
Vibrio Fischeri bacteria was adopted to comprehensively investigate the in wastewater. Apparently, the cost of complete treatment of adsorption
toxicity during the EF process (Fig. S18), and the highest toxicity was process shows no superiority to the EF and PF process, let alone the
observed as 90 min and 60 min for the SMT [26] and AMX, respectively unsatisfied time-consuming and final treatment of solution from the
[17]. Indeed, the luminescence inhibition has an unpredicted trend due regeneration process.
to the various of intermediates generated in the degradation process Biological treatment process might be the most practical and so-
lead a change of the toxicity. Besides, Escherichia coli cell was employed phisticated process if the wastewater is degradable and debugging
to assess the degradation product of CEX by growth inhibition assays process has been accomplished. The removal of different antibiotic in
[27], and the inhibition index indicates that the 3 h of electrolysis the AS process shows distinctive characteristic for adsorption and bio-
caused no damage to the cephem functional group (Fig. S19). In the degradation, and the low biodegradability of fluoroquinolones waste-
recent research, Escherichia coli and Staphylococcus aureus were chosen water increases the difficulty for the cultivation of microorganisms
to evaluate AA of CIP treated by TiO2/UV, H2O2/UV and PF process [98]. It might cause much higher expend for control of sludge return
(Fig. S20), and the PF process shows a strong removal of the AA after ratio, increasing the risk of destroying the balance of biological system.
5 min treatment [28]. In conclusion, the complete structure of anti- In most case, the treated time of independent SBR for the antibiotics
biotic is not the symbol of the highest toxicity, and there should be seems to be much longer than EF and PF processes, and the effluent
more comprehensive evaluation on the treatment residual to avoid an after the biological treatment is still not in agreement with regulatory
unnatural emergency of toxicity. limits [99].

5. The cost aspects of EF and PF and other processes 6. The gaps need to be filled

Cost aspects are vital for the practical application, since a Firstly, the contamination of natural water environment is often

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X. Liu et al. Chemical Engineering Journal 347 (2018) 379–397

complex, and the assessment often involved with numbers of indicators, confirmed the generation of HClO on the BDD anode [107]. The effect
leading pollution of surface water directly and groundwater mainly of the Cl− can be attractive for the real wastewater purification, and the
through leaching and infiltration. Hence, it is also significant to remove incomplete oxidation might even change the toxicity for the un-
these unpredictable substances. Antonin et al. compared the EO, EF, predicted intermediates. The formation of Fe3+-CIP chelate in the EF
PEF and SPEF for the degradation of CIP in synthetic urine matrix and process was evaluated by Chen et al., and the reduction of Fe3+ on the
sulfate medium [100], proposing a mechanism study of CIP by EAOPs cathode was promoted with the optimal chelate ratio (0.25 mM of Fe2+
in sulfate medium (Fig. S21). The final mineralization efficiency has an and 1.50 mM of Fe3+) [108]. Meanwhile, the carcinogenicity of N-
interesting improvement in the urine, indicating a well application of containing pollutants aroused the interesting research on the amines
EF, PF, PEF and SPEF to antibiotics in high urea content. Jojoa-Sierra and nitro-derivatives. The quantification of N-volatile species in the
et al. investigated the degradation of NOR in urine, municipal waste- degradation of the N-containing pollutants could be assessed by dif-
water and seawater [101], giving a comparison of the AA as well (Fig. ferential electrochemistry mass spectroscopy (DEMS) [109]. Interest-
S22). ingly, the special structure of N-containing pollutants has its own be-
Secondly, compared to the experiment for the degradation of or- havior, affected by the HER on the modified cathode. In the latest
ganic micropollutants performed in the laboratory, the pilot-scale stu- research, the degradation pathway of LEV was refined with the in-
dies are more realistic for the remediation of the polluted wastewater at troduction of HER, leading the conversion of the amino and nitro
a low antibiotic concentration [9]. Moreover, the pilot plant in the PEF groups on aromatic ring [14]. As a result, the additional HER reduced
and SPEF are more convincing for the degradation of antibiotics at huge the stability of LEV, showing in a 2.2 times higher value of initial MCE
flow rate (e.g., NETmix® photoreactors [12] and MBR in PF process and more complete mineralization.
[11]). Nevertheless, most of research on the antibiotic decay in EF
process is at laboratory-scale [102], whereas the “filter”-type EF device Acknowledgements
for the pilot-scale degradation has been proposed (Fig. S23). Facile
preparation method of the high performance carbon cathode seems to The study was financially supported by the National Natural Science
be a possible approach to the development of pilot device [103]. Fur- Foundation of China (51709103), the National Program for Support of
thermore, the detection of the SMX and TMP based on the electro- Top-Notch Young Professionals of China (2012), the Program for New
chemical sensor is also benefit for the monitor of end-point of industrial Century Excellent Talents in University from the Ministry of Education
level wastewater [104]. of China (NCET-11-0129), Project of Science and Technology of Hunan
Thirdly, the improvement of partial degradation of antibiotic ef- Province (2016WK2010).
fluent with a high concentration and low biodegradability could be
effective for lower energy consumption, followed by biological de- Appendix A. Supplementary data
gradation with a mixed culture of bacteria in the SBR or aerobic method
[99]. Olvera-Vargas et al. improved the ratio of BOD5/COD of the Supplementary data associated with this article can be found, in the
metoprolol from 0.012 to 0.44 after 1 h EF treatment, and the further online version, at http://dx.doi.org/10.1016/j.cej.2018.04.142.
aerobic treatment would achieve about 90% TOC removal [105]. Al-
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