Science of the Total Environment 670 (2019) 110–121

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Science of the Total Environment

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

Review

A review on Fenton process for organic wastewater treatment based on

optimization perspective
Meng-hui Zhang a, Hui Dong a,⁎, Liang Zhao a, De-xi Wang b, Di Meng a
a
SEP Key Laboratory of Eco-industry, School of Metallurgy, Northeastern University, Shenyang, Liaoning 110819, China
b
School of Chemical Equipment, Shenyang University of Technology, Shenyang, Liaoning 110819, China

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

• Review of single Fenton optimization

processes for organic wastewater
treatment.
• Review of coupled Fenton optimization
processes for organic wastewater
treatment.
• Key operational parameters are
discussed.
• Insights into future research directions
for optimized Fenton processes.

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

Article history: Water pollution caused by organic wastewater has become a serious concern worldwide. Fenton oxidation pro-
Received 3 January 2019 cess is one of the most effective and suitable methods for the abatement of organic pollutants. However, the pro-
Received in revised form 12 March 2019 cess has three obvious shortcomings: the narrow working pH range, the high costs and risks associated with
Accepted 13 March 2019
handling, transportation and storage of reagents (H2O2 and catalyst), the significant iron sludge related second
Available online 15 March 2019
pollution. In order to overcome these shortcomings, various optimized Fenton processes have been widely stud-
Editor: Jay Gan ied. Therefore, a summary of the study status of Fenton optimization processes is necessary to develop a novel
and high efficiency organic wastewater treatment method. Based on the optimization perspective, taking short-
Keywords: comings of Fenton process as a breakthrough, the fundamentals, advantages and disadvantages of single Fenton
Fenton process optimization processes (heterogeneous Fenton, photo-Fenton and electro-Fenton) for organic wastewater treat-
Advantages and disadvantages ment were reviewed and the corresponding reaction mechanism diagrams were drawn in this paper. Then, the
Optimization feasibility and application of the coupled Fenton optimization processes (photoelectro-Fenton, heterogeneous
Operation parameters electro-Fenton, heterogeneous photoelectro-Fenton, three-dimensional electro-Fenton) for organic wastewater
Organic wastewater treatment
treatment were discussed in depth. Additionally, the effect of some important operation parameters (pH and cat-
alyst, H2O2, organic pollutants concentration) on the degradation efficiency of organic pollutants was studied to
provide guidance for the optimization of operation parameters. Finally, the possible future research directions for
optimized Fenton processes were given. The review aims to assist researchers and engineers to gain fundamental

⁎ Corresponding author.
E-mail address: dongh@mail.neu.edu.cn (H. Dong).

https://doi.org/10.1016/j.scitotenv.2019.03.180
0048-9697/© 2019 Elsevier B.V. All rights reserved.
 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121 111

understandings and critical view of Fenton process and its optimization processes, and hopefully with the knowl-
edge it could bring new opportunities for the optimization and future development of Fenton process.
© 2019 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2. Single Fenton optimization processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.1. Heterogeneous Fenton process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.2. Photo-Fenton process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.3. Electro-Fenton process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3. Coupled Fenton optimization processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3.1. Photoelectro-Fenton process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3.2. Heterogeneous electro-Fenton process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.3. Heterogeneous photo-electro-Fenton process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.4. Three-dimensional electro-Fenton process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4. Operation parameters optimization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.1. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.2. Catalyst concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.3. H2O2 concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.4. Organic pollutants concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

1. Introduction
The treatment of organic wastewater is becoming an increasingly
critical issue in sustainable development, as it contains a large number
of refractory and toxic organic pollutants. The conventional separation
and transformation technologies are inefficient in the treatment of re-
fractory and toxic organic pollutants, which prompts people to seek
more effective new technologies. Advanced oxidation processes
(AOPs), such as photochemical oxidation, catalytic wet oxidation,
sonochemical oxidation, O3 oxidation, electrochemical oxidation, and
Fenton oxidation, have been widely applied and developed for direct
mineralization of organic pollutants or improvement of the biodegrad-
ability of organic pollutants through oxidation (Bokare and Choi,
2014; Sharma et al., 2018). Compared with other AOPs, Fenton process
is the most popular because of its some exciting advantages such as
wide application range, strong anti-interference ability, simple opera-
tion and rapid degradation and mineralization (Chen et al., 2011;
Wang et al., 2016).
Fenton oxidation was first discovered by H.J.H. Fenton in 1894
(Fenton, 1894), and its main development process is shown in
Supporting Information (SI) Fig. S1 (Haber and Weiss, 1932; Haber
and Weiss, 1934; Eisenhauer, 1964; Eisenhauer, 1965; Brillas et al.,
2009). The oxidation mechanism for Fenton process has been studied
for nearly 90 years. Researches show that Fenton process includes
more than 20 chemical reactions (Duesterberg et al., 2008; Pliego
et al., 2015), and its generally accepted core reaction is shown in
Eq. (1). The highly oxidative hydroxyl radical (•OH) formed from the re-
action of H2O2 with Fe2+ under strong acid can quickly and
nonselectively degrade most stubborn organic pollutants to carbon di-
oxide and water (Santos et al., 2011). The oxidation mechanism for
the Fenton process is shown in Fig. 1. Based on this principle, Fenton
process has been widely used in various kinds of organic wastewater
treatment.
Fe2þ þ H2 O2 þ Hþ →Fe3þ þ H 2 O þ OH ð1Þ
The degradation efficiency of organic pollutants in the Fenton pro-
cess depends on operation parameters such as wastewater pH, concen-
tration of Fenton reagent, and initial organic pollutants concentration, of
which wastewater pH is a highly important parameter. Owing to iron

Fig. 1. Reaction mechanism for the Fenton process.

112 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121
species catalyst deactivation, organic pollutants in wastewater cannot
be treated effectively at both low and high pH. The results show that
the pH range of 2–4 can achieve the best treatment efficiency (Barb
et al., 1951; Utset et al., 2000; Rodrigguez et al., 2003; Pignatello et al.,
2006). However, most pH values of organic wastewater are not within
this range. In order to achieve the optimal pH range in the Fenton pro-
cess, high amounts of chemicals are spent for adjusting organic waste-
water at pH 2–4 before decontamination, which increases costs of
organic wastewater treatment.
The classical Fenton reagents consist of H2O2 and homogeneous so-
lution of iron ions. Both of them are unstable in chemical properties and
easy to lose activity, resulting in waste of reagents (Luo et al., 2018). In
addition, concentrated H2O2 which is explosive and toxic is harmful to
humans (K. Zhao et al., 2018). Therefore, the storage and transportation
of concentrated H2O2 and homogeneous solution of iron ions not only
increase costs of organic wastewater treatment but also endanger the
relevant operators' health (D.L. Huang et al., 2017).
Fenton catalytic reactions basically consist of the oxidation of Fe2+ to
Fe3+ along with the •OH generation (Eq. (1)) and the reduction of Fe3+
to Fe2+ (Eq. (2)). However, the reaction rate of the former is about 6000
times that of the latter (Song et al., 2006; Martínez-Huitle et al., 2016),
which blisteringly interrupts the efficient cycling of Fe3+ and Fe2+ and
leads to accumulation of Fe3+ in the solution. The Fe3+ begins to precip-
itate above pH 3 in the form of oxyhydroxide which is so-called iron
sludge (Flynn, 1984; Gallard et al., 1999; Xue et al., 2018a, 2018b). It is
difficult to separate and recover iron sludge, which not only causes seri-
ous loss of iron species and reduction of catalytic activity, but also causes
secondary pollution to the environment (Nie et al., 2008; Pang et al.,
2010).
Fe3þ þ H2 O2 →Fe2þ þ HO2  þHþ ð2Þ
In summary, Fenton process has three obvious shortcomings: the
narrow working pH range, the high costs and risks associated with han-
dling, transportation and storage of reagents (H2O2 and homogeneous
solution of iron ions), the significant iron sludge related second pollu-
tion. In order to overcome three shortcomings, Fenton process is opti-
mized and improved unceasingly to form various optimized Fenton
processes. A summary of the study status of Fenton optimization pro-
cesses is necessary to develop a novel and high efficiency organic waste-
water treatment method. Therefore, based on the optimization
perspective, taking shortcomings of Fenton process as a breakthrough,
the fundamental principles and applications of various optimized
Fenton processes for organic wastewater treatment were reviewed.
Some important operation parameters including wastewater pH and
catalyst, H2O2, organic pollutants concentration in various optimized
Fenton processes were discussed in depth. The possible future research
directions for optimized Fenton processes were given.
2. Single Fenton optimization processes
The conventional Fenton process is optimized by heterogeneous sys-
tem, electrochemical theory and photocatalytic principle to form three
types of single Fenton optimization processes: heterogeneous Fenton
process, photo-Fenton process and electro-Fenton process.
2.1. Heterogeneous Fenton process
In order to overcome the disadvantages of conventional Fenton pro-
cess which is limited to the narrow working pH range and produces a
large amount of iron sludge, heterogeneous Fenton process has been
widely studied. Catalyst Fe2+ in the homogeneous Fenton system is re-
placed by solid catalyst containing catalytic active components in the
heterogeneous Fenton system, so that Fenton catalytic reactions occur
at the active site on the surface of solid catalyst, preventing the iron
ions leaching, extending the working pH range, and reducing the iron
sludge production (Xia et al., 2011; Qian et al., 2014; Zhang et al.,
2014; Liu et al., 2017). The results show that the iron ions leaching in
the heterogeneous Fenton system are extremely low and its concentra-
tions are much lower than the legal limit of 2 mg/L imposed by the di-
rectives of the European Union (Y. Wang et al., 2015; Yao et al., 2017).
The main reasons are as follows: (1) iron species with catalytic activity
are immobilized on some supports such as zeolite (Karthikeyan et al.,
2016), clay (Hadjltaief et al., 2014), graphene (Guo et al., 2013) and ac-
tivated carbon (Gu et al., 2013) by the hydrothermal method and other
preparation methods. The protective effects of the supports prevent iron
species from immersing in the solution, which reduces the loss of iron
species (Jin et al., 2017; Qian et al., 2017). (2) The structure and compo-
sition of the heterogeneous Fenton catalyst itself facilitate the electron
transfer from the electron donor to Fe3+, accelerating the reduction of
Fe3+ to Fe2+, achieving the efficient cycling of Fe3+ and Fe2+ on the het-
erogeneous Fenton catalyst (Sohn et al., 1971; Zhong et al., 2013; Lyu
et al., 2016). The reaction mechanism for the heterogeneous Fenton
process is shown in Fig. 2.
The key to the heterogeneous Fenton reaction is developing the
long-term stable heterogeneous Fenton catalysts with high catalytic ac-
tivity that can be used at a wide pH range and easy separated without
the aid of extra energy input (Dükkancı et al., 2010; Karthikeyan et al.,
2011; Xue et al., 2018a, 2018b). At present, the heterogeneous Fenton
catalysts mainly include supported catalysts (Hu et al., 2011; S.Z.
Zhang et al., 2015) and non-supported catalysts (Ortiz de la Plata
et al., 2010; Minella et al., 2014). The supported catalysts immobilize
iron species on various supports to overcome the challenge of iron
leaching. Zhou et al. (2014) prepared an efficient heterogeneous Fenton
catalyst by loading Fe2+ on high-specific-surface-area magnetic porous
carbon microspheres. The efficient heterogeneous Fenton catalyst pre-
pared was used in the heterogeneous Fenton process to remove methy-
lene blue (MB) from wastewater. The results indicated that the
degradation rate of MB exceeded 90% within 40 min at pH 6.18, which
indicated that the catalyst exhibited high catalytic activity for the or-
ganics degradation under neutral pH. Ma et al. (2018) prepared a
novel Fe-N-graphene wrapped Al2O3/pentlandite composite from
microalgae. The composite exhibited high Fenton catalytic ability,
which originated from the synergistic effects of Fe, Al and Ni. In addition,
the catalyst reused 12 times almost remained in the corresponding cat-
alytic activity, which showed that the catalyst had an excellent long-
term stability. The non-supported catalysts are mainly natural iron-
containing minerals, which can directly form heterogeneous Fenton
system with H2O2 to degrade refractory organic pollutants. Z.X. Liu
et al. (2018) proposed a template method strategy for synthesizing ul-
trasmall α-FeOOH nanorods (SFNs) and investigated their use for cata-
lyzing the degradation of an azo dye, methyl orange (MO). The high MO
degradation rate (98%) could be explained by the higher specific surface
area and more catalytic sites of SFNs. In addition, the MO degradation
rate was affected little by the pH under a pH range from 3 to 9, which
showed that the narrow working pH range in conventional Fenton pro-
cess could be solved by heterogeneous Fenton process.
In summary, compared with conventional Fenton process, heteroge-
neous Fenton process has many advantages such as the low iron ions
leaching, the efficient cycling of Fe3+ and Fe2+, the low iron sludge pro-
duction, the wide working pH range and the reusability and long-term
stability of catalysts. However, most studies on heterogeneous Fenton
process are conducted in lab scale, and its industrialization promotion
is limited by many disadvantages such as relatively harsh synthetic con-
ditions, complicated synthesis routes and high synthesis costs of hetero-
geneous Fenton catalysts, and design of heterogeneous Fenton reactor
(Li et al., 2014; Ganiyu et al., 2018).
2.2. Photo-Fenton process
Photo-Fenton process has drawn much attention to the abatement
of refractory organic pollutants due to the low iron sludge production.
 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121
Support
Fe(III)
Electron donor
e- Catalyst
Fe(II)
Fig. 2. Reaction mechanism for the heterogeneous Fenton process.
The combination of ultraviolet or visible light with conventional Fenton
process can enhance the catalytic capacity of catalysts and increase the
degradation efficiency of organic pollutants and reduce the iron sludge
production. The essence of photo-Fenton process is to accelerate the re-
duction of Fe3+ to Fe2+ by using the energy provided by light (Sun et al.,
2011; Babuponnusami and Muthukumar, 2014; Kalal et al., 2014; Lee
et al., 2014). Fe2+ rapidly reacts with H2O2 to generate Fe3+ which
mainly exists in the form of [Fe(OH)]2+ at pH 2.8–3.5 (Ahmed et al.,
2011; Simunovic et al., 2011; Sirés and Brillas, 2012). Under light irradi-
ation, [Fe(OH)]2+ undergoes metal charge transfer excitation,
regenerating Fe2+ that catalyzes the decomposition of H2O2 and pro-
ducing additional •OH that degrades organic pollutants (Eq. (3))
(Faust and Hoigné, 1990; Avetta et al., 2015). In addition, direct photol-
ysis of H2O2 also produces •OH which can be used for the degradation of
organic pollutants (Eq. (4)) (Li et al., 2013; Wang et al., 2018). There-
fore, synergistic catalytic effects of Fe2+ and light can produce more
•OH, which can enhance oxidation efficiency in the photo-Fenton pro-
cess. The reaction mechanism for the photo-Fenton process is shown
in Fig. 3.
½FeðOHÞ2þ þ hv→Fe2þ þ OH ð3Þ
H 2 O2 þ hv→2  OH ð4Þ
A light irradiation device is the core component in the photo-Fenton
process, which has a significant influence on the destruction rate of
Fe3+
·OH Fe2+
Fig. 3. Reaction mechanism for the photo-Fenton process.
113
·OH
H2 O 2
organic pollutants (Babuponnusami and Muthukumar, 2014; Rahim-
Pouran et al., 2015; R.L. Liu et al., 2018). The studies reported in the lit-
erature show that common light sources in the photo-Fenton process
mainly include ultraviolet light and sunlight. In the study carried out
by Poulopoulos et al. (2008), Fe3+ was added to the UV/H2O2 system
to form an efficient UV-Fenton system which could completely degrade
2-chlorophenol within a few minutes and remove 95% of total organic
carbon (TOC) within 150 min, indicating the powerful oxidation capac-
ity of UV-Fenton process. The application of ultraviolet irradiation de-
vices in the UV-Fenton process faces many challenges such as short
working life span, high energy consumption, high environmental pollu-
tion risks and high economic costs (Jo and Tayade, 2014). In order to
overcome these disadvantages, the alternative use of sunlight as a free
and renewable energy source has gained increasingly attention in the
photo-Fenton process (Kuo and Wu, 2010; Liu et al., 2013). Pliego
et al. (2014) compared the performance of conventional Fenton and
solar photo-Fenton processes for the treatment of the persistent anti-
depressant sertraline in aqueous solution. Compared with conventional
Fenton process, the removal rate of TOC by solar photo-Fenton process
increased by 2.46 times to 90%, indicating the powerful oxidation capac-
ity of solar photo-Fenton process. In addition, organic and inorganic li-
gands (citrate, pH = 5 (Katsumata et al., 2006); catechin, pH = 6 (Z.P.
Wang et al., 2015); polyoxotungstate, pH = 2.2–7.2 (Hu and Xu,
2014.)) were added to photo-Fenton system to prevent the precipita-
tion of iron ions and extend the working pH range for degradation of or-
ganic pollutants.
·OH
H 2O 2
114 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121
In summary, photo-Fenton system uses the energy provided by ul-
traviolet or visible light to accelerate the reduction of Fe3+ to Fe2+,
which can reduce the iron sludge production and the initial Fe2+ con-
centration input, and enhance the oxidation ability of photo-Fenton sys-
tem and the degradation efficiency of organic pollutants. However,
photo-Fenton process also has some disadvantages such as low utiliza-
tion rate of light energy, high operation costs and design of
photoreactor, which limits the development of photo-Fenton process
on a large scale (Pérez et al., 2013; Pliego et al., 2015; Wang et al., 2016).
2.3. Electro-Fenton process
Electro-Fenton process has been developed to overcome the limita-
tions of classical Fenton process: the accumulation of iron sludge and
the high costs and risks associated with handling, transportation and
storage of reagents. Conventional Fenton process can be notably im-
proved by electrochemistry because of its advantages such as versatility,
high energy efficiency, amenability of automation, and its environmen-
tal compatibility. Therefore, the combination of conventional Fenton
process with electrochemistry gives rise to the so-called electro-
Fenton process. Its essence is that H2O2 is in situ generated via the elec-
trochemical reduction of O2 on the cathode, which can avoid the costs
and risks associated with handling, transportation and storage of H2O2
(Martínez-Huitle and Brillas, 2009; Gao et al., 2015; Jiang et al., 2018).
And Fe3+ generated by Fenton reaction is reduced to Fe2+ on the cath-
ode, which can achieve the regeneration of Fe2+ and reduce the iron
sludge production (Zhou et al., 2012; Trellu et al., 2018). Electro-
Fenton process is classified into four categories depending on Fenton re-
agents addition or formation: cathode electro-Fenton process (EF-
H2O2), sacrificial anode electro-Fenton process (EF-Feox), Fe2+ cycling
electro-Fenton process (EF-Fere), cathode and Fe2+ cycling electro-
Fenton process (EF-H2O2-Fere) (Badellino et al., 2006; Diagne et al.,
2007; Zhang et al., 2007; Ting et al., 2008; Babuponnusami and
Muthukumar, 2014).
In the EF-H2O2 process, Fe2+ is externally added while H2O2 is in situ
generated via the electrochemical reduction of O2 on the cathode
(Eq. (5)) (Oturan et al., 2010), which can avoid the costs and risks asso-
ciated with handling, transportation and storage of H2O2. In the EF-Feox
process, H2O2 is externally added while Fe2+ is electro-generated using
a sacrificial anode (Eq. (6)) (Kurt et al., 2007), which can avoid the ad-
dition of Fe2+. However, EF-Feox process has some disadvantages
such as serious consumption of anode and a large amount of iron sludge
production. In the EF-Fere process, H2O2 and Fe2+ are both externally
added, but Fe3+ generated by Fenton reaction is reduced to Fe2+ on
the cathode (Eq. (7)) (Isarain-Chávez et al., 2011; Rahim-Pouran et al.,
2015), which can reduce the iron sludge production and the initial Fe2
+
concentration input. EF-H2O2-Fere process is the combination of EF-
H2O2 process with EF-Fere process. In the EF-H2O2-Fere process, H2O2
is in situ generated via cathodic reduction of O2 and Fe2+ is regenerated
through the reduction of Fe3+ on the cathode, which can avoid the ad-
dition of H2O2 and reduce the iron sludge production and the initial Fe2
+
concentration input. The reaction mechanisms for four kinds of
electro-Fenton processes are shown in Fig. 4.
O2 þ 2Hþ þ 2e− →H 2 O2 ð5Þ
Fe→Fe2þ þ 2e− ð6Þ
Fe3þ þ e− →Fe2þ ð7Þ
A key concern in the electro-Fenton process is the cathode which has
a significant influence on the performance for the treatment of refrac-
tory organic pollutants (Yu et al., 2014; L. Wang et al., 2015; Qiu et al.,
2018). From the basic principle of electro-Fenton process, the continu-
ous in-situ electro-generation of H2O2 plays a crucial role in the
electro-Fenton process and is affected by the types and properties of
cathode. Many reports have confirmed that the performance of H2O2
electro-generation can be greatly improved by gas diffusion electrode
owing to its porous structure by which oxygen or air can quickly reach
the electrode surface (Isarain-Chávez et al., 2010; El-Ghenymy et al.,
2012). In the study carried out by Yu et al. (2015), a novel H2O2 gener-
ation reactor using dual gas diffusion electrodes as cathodes was put
forward to degrade high initial concentration tartrazine (1000 mg/L).
The results showed that this reactor was cost-effective in H2O2 genera-
tion rate (11–12 mg/h/cm2), O2 utilization efficiency (1.93–8.84%) and
energy consumption (15.9–17.9 kWh/kg). And the TOC removal effi-
ciency could reach 66.1% within 120 min with a mineralization current
efficiency of 65.1%, indicating reactor's potential for the treatment of
high-concentrated wastewater. Activated carbon fiber is also a com-
monly used cathode because of its advantages such as no toxicity,
low-cost, good stability, conductivity, low catalytic activity for H2O2 de-
composition (Li et al., 2009; Zhao et al., 2016). In the study carried out
by Gong et al. (2016), levofloxacin (LEVO) was degraded by electro-
Fenton process using an activated carbon fiber felt cathode from the
point view of not only LEVO disappearance and mineralization, but
also biodegradability enhancement. The results showed that the chem-
ical oxygen demand (COD) and TOC removal rates were 79.6% and 61%
within the experimental time, respectively. And the biodegradability
(BOD5/COD) increased from 0 initially to 0.24 after 360 min treatment.
In addition, various materials have been widely tested as cathodes, in-
cluding carbon felt (C. Zhang et al., 2015), carbon nanotube (Zarei
et al., 2010), graphite (Le et al., 2017), graphite felt (H. Zhao et al.,
2018) and so on, to improve the performance of electro-Fenton process
for the treatment of refractory organic pollutants.
In summary, electro-Fenton process is a second generation Fenton
process, in which the continuous electro-generation of H2O2 from ca-
thodic reduction of O2 combined with the supply of Fe2+ continuously
regenerated on the cathode can allow for the formation of •OH. The ad-
vantages of electro-Fenton process compared with conventional Fenton
process are as follows: (1) the on-site production of H2O2, which can
avoid the risks related to its transport, storage, and handling; (2) the
continuous regeneration of Fe2+ on the cathode, which can minimize
the iron sludge production and improve the degradation efficiency of
organic pollutants. However, electro-Fenton process should be
improved by overcoming its disadvantages such as low H2O2
yield, low unit cell body throughput, low current density and low con-
ductivity (Martínez-Huitle and Brillas, 2009; Yuan et al., 2011; Sirés
et al., 2014).
Based on the fundamentals of single Fenton optimization pro-
cesses, their merits and demerits are summarized in Table 1. As
shown in Table 1, single Fenton optimization processes can over-
come the disadvantages of conventional Fenton process so these
processes can be regarded as the promising organic wastewater
treatment methods.
3. Coupled Fenton optimization processes
In order to further strengthen the advantages of single Fenton
optimization processes and improve the degradation efficiency of
organic pollutants, a coupling strategy amid single Fenton optimization
processes has gained increasingly attention. In this part, four types of
coupled Fenton optimization processes are discussed in depth:
photoelectro-Fenton process, heterogeneous electro-Fenton process,
heterogeneous photoelectro-Fenton process, three-dimensional
electro-Fenton process.
3.1. Photoelectro-Fenton process
The combination of electro-Fenton process with irradiation with ul-
traviolet or visible light gives rise to the so-called photoelectro-Fenton
process, and its schematic diagram is shown in SI Fig. S2. The effective-
ness of photoelectro-Fenton process has been demonstrated by treating
 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121 115

ˇ ˉ ˇ ˉ

Fe
Fe2+ -2e-
·OH
H 2O 2 Fe2+ H2 O 2

+2e- ·OH
O2

a. EF-H2O2 b. EF-Feox

ˇ ˉ ˇ ˉ

Fe3+
Fe3+
+e-
+e-
Fe2+
2+
H 2O 2 Fe ·OH
H2 O 2
·OH
+2e-
O2

c. EF-Fere d. EF-H2O2-Fere

Fig. 4. Reaction mechanisms for four kinds of electro-Fenton processes.

Table 1
Merits and demerits of single Fenton optimization processes.
Merits
Heterogeneous The low iron ions leaching; the
Fenton low iron sludge production;
process the wide working pH range;
the reusability and long-term
stability of catalysts.
Photo-Fenton The efficient cycling of Fe3+
process and Fe2+; the low initial Fe2+
concentration input; the low
iron sludge production; the
high hydroxyl radical
production.
Electro-Fenton The on-site production of
process H2O2; no risks associated with
handling, transportation and
storage of H2O2; the
continuous regeneration of Fe2
+
on the cathode; the low iron
sludge production.
Demerits
The harsh synthetic conditions
of catalysts; the complicated
synthesis routes of catalysts;
the high synthesis costs of
catalysts.
The low utilization rate of light
energy; the excessive
economical costs arising from
the use of light; the design of
photoreactor.
The low H2O2 yield; the low
unit cell body throughput; the
low current density; the low
conductivity.
model organic pollutants such as antibiotic nafcillin (Vidal et al., 2018)
and dyes (Thiam et al., 2015), as well as real landfill leachate (Moreira
et al., 2016). This process allows on one hand a faster regeneration of
Fe2+ by photolysis of Fe3+ species according to the Eq. (3) and on the
other hand a more •OH production by synergistic catalytic effects of
Fe2+ and light according to the Eqs. (1) and (4), which can enhance
the degradation or mineralization efficiency of organic pollutants. For
example, Gozzi et al. (2017) compared the performance of anodic oxi-
dation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF)
and solar photoelectro-Fenton (SPEF) for the treatment of tebuthiuron
and ametryn in aqueous solution. The results showed that partial min-
eralization was achieved for all the treatments, with the relative oxida-
tion ability growing in the sequence: AO-H2O2 b EF b SPEF. The powerful
oxidation capacity of SPEF could be explained by a faster regeneration of
Fe2+ by photolysis of Fe3+ species and a more •OH production by syner-
gistic catalytic effects of Fe2+ and light. Similarly, the powerful oxidation
capacity of SPEF was demonstrated by Santos et al. (2018). The TOC re-
moval rate of SPEF was 99%, which was 1.8 times that of EF and 18.3
times that of AO-H2O2, respectively.
116 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121
3.2. Heterogeneous electro-Fenton process
The combination of electro-Fenton process with heterogeneous
Fenton catalysts gives rise to the so-called heterogeneous electro-
Fenton process. The feasibility of heterogeneous electro-Fenton process
has been demonstrated by treating various kinds of model organic pol-
lutants containing tyrosol (Ammar et al., 2015), amaranth (Zhang et al.,
2012), pesticides (Zhao et al., 2012) and so on. This process is classified
into two categories depending on the function of heterogeneous Fenton
catalyst, and their schematic diagrams are shown in SI Fig. S3. In type 1,
heterogeneous Fenton catalyst performs function of catalyzing H2O2 de-
composition. In type 2, heterogeneous Fenton catalyst performs dual
function as catalyst as well as cathode in heterogeneous electro-
Fenton system.
Heterogeneous electro-Fenton process has some significant advan-
tages over classical electro-Fenton process such as powerful oxidation
capacity, large working pH range, excellent stability and reusability of
catalysts. In type 1, Barhoumi et al. (2017) studied the performance of
heterogeneous electro-Fenton process using chalcopyrite as heteroge-
neous Fenton catalyst for the degradation of solutions of the antibiotic
tetracycline (TC). The results showed that heterogeneous electro-
Fenton process showed to be more efficient than conventional electro-
Fenton process, achieving almost total mineralization of the TC solu-
tions (98% of TOC removal) after 360 min under optimum operating
conditions. In addition, Ouiriemmi et al. (2017) found that the degrada-
tion kinetics of vanillic acid oxidation in the heterogeneous electro-
Fenton process looked quite similar at each initial pH values (pH =
3,5,7), which indicated that this process exhibited powerful oxidation
capacity for organic pollutants over a wide pH range. Similarly, the pow-
erful oxidation capacity of heterogeneous electro-Fenton process (type
2) for organic pollutants over a wide range of pH was demonstrated
by Ganiyu et al. (2017). The TOC removal rates of acid orange II solutions
were more than 66% at pH 2–7.1. Besides, the prepared CoFe-LDH/CF
serving as a cathode as well as a catalyst source exhibited excellent sta-
bility and reusability as the TOC removal rate was still above 60% after
7 cycles of degradation. Similarly, excellent stability and reusability of
catalyst (or cathode) in the heterogeneous electro-Fenton process
(type 2) were demonstrated by Liang et al. (2017). They carried out het-
erogeneous electro-Fenton experiments with the GF-Co serving as a
cathode as well as a catalyst source. After ten-time runs, the MO degra-
dation efficiency of the GF-Co was still 89.5%, which was promising for
long-term practical application.
3.3. Heterogeneous photo-electro-Fenton process
The combination of electro-Fenton process, photo-Fenton pro-
cess and heterogeneous Fenton catalysts gives rise to the so-called
heterogeneous photo-electro-Fenton process. This process is also
classified into two categories depending on the function of heteroge-
neous Fenton catalyst, and their schematic diagrams are shown in SI
Fig. S4. The feasibility of heterogeneous photo-electro-Fenton
process has been demonstrated by treating various kinds of model
organic pollutants containing phenol (Babuponnusami and
Muthukumar, 2012), orange II (Ramírez et al., 2010), malachite
green (MG) (García-Rodríguez et al., 2016) and so on. This process
not only possesses the advantages of each single process, but also of-
fers more excellent degradation efficiency for organic pollutants
owing to synergistic effects of each single process. The work of
Babuponnusami and Muthukumar (2012) presented the removal of
phenol by heterogeneous photo-electro-Fenton process using
nano-zero valent iron (NZVI). The results showed that the process
could completely degrade phenol under a pH range from 2 to 6.2.
And the combination process was more effective than the corre-
sponding single process for the degradation of phenol. In addition,
in the study carried out by García-Rodríguez et al. (2016), a novel
carbon felt coated with iron oxides was used as air-diffusion cathode
in a stirred tank reactor with a boron-doped diamond anode to de-
grade MG solutions at pH 3 by heterogeneous electro-Fenton and
photo-electro-Fenton processes. The results showed that MG could
be completely degraded by both processes. However, the degrada-
tion and mineralization of dye solutions were faster for heteroge-
neous photo-electro-Fenton process due to synergistic effects
between processes.
3.4. Three-dimensional electro-Fenton process
Recently, three-dimensional electrodes (particle electrodes) are
attracting more and more attention because of its super-large specific
surface area, ultra-high space utilization and super-strong mass transfer
effect. The three-dimensional electrochemical system is a novel electro-
chemical reaction system formed by packing some particles between
two-dimensional electrodes in the conventional two-dimensional elec-
trochemical system, and its schematic diagram is shown in SI Fig. S5.
During electrochemical reaction, these particles can be easily polarized
by the external electric field to form charged microelectrodes on
which electrochemical redox reactions are carried out. It is obvious
that particle electrodes play an important role in improving the electro-
lytic efficiency. The main reasons are as follows: (1) the three-
dimensional electrodes have super-large specific surface area, which
improves the electrochemical reaction rate; (2) the distance between
reactants and electrodes is shortened, which improves the mass transfer
efficiency; (3) the reactor with three-dimensional electrodes possesses
lager area-volume ratio and high space utilization efficiency, which im-
proves the current efficiency.
Therefore, the combination of electro-Fenton process with three-
dimensional electrodes gives rise to the so-called three-dimensional
electro-Fenton process. The feasibility of three-dimensional electro-
Fenton process has been demonstrated by treating various kinds of
model organic pollutants containing MO (Liu et al., 2011), phenol
(Xiong et al., 2003), acid orange 7 (Zhao et al., 2010) and so on. In the
study carried out by Liu et al. (2012), solutions of rhodamine B (RhB)
were degraded at neutral pH by a novel three-dimensional electro-
Fenton process with foam nickel as the particle electrodes. The results
showed that three-dimensional electro-Fenton process was energy-
saving and high efficiency for wastewater treatment compared with
the counterpart electro-Fenton process. The RhB degradation rate in
the three-dimensional electro-Fenton process was 5.2 times that in
the electro-Fenton process, while the energy consumption per unit
COD mass of the former was only 18.6% of that of the latter. In addition,
in the study carried out by He et al. (2014), a kaolin-based iron molyb-
date Fe2(MoO4)3-kaolin-450 was successfully prepared to serve as both
particle electrodes and heterogeneous Fenton catalysts in the three-
dimensional electro-Fenton system for MO degradation. The degrada-
tion rate of MO was 92% within 10 min, which confirmed that the parti-
cle electrodes in this system could improve the electrolytic efficiency.
In summary, an overview of work done in the area of coupled Fenton
optimization processes in recent years is summarized in SI Table S1 (Ai
et al., 2007; Ramírez et al., 2010; Babuponnusami and Muthukumar,
2012; Liu et al., 2012; He et al., 2014; Chu et al., 2016; García-
Rodríguez et al., 2016; Barhoumi et al., 2017; Ganiyu et al., 2017;
Gozzi et al., 2017; B.B. Huang et al., 2017; Liang et al., 2017;
Ouiriemmi et al., 2017; Santos et al., 2018; Steter et al., 2018). As
shown in SI Table S1, coupled Fenton optimization processes allow
obtaining high mineralization degree with large working pH range so
these processes appear to be promising alternatives for treating refrac-
tory pollutants.
4. Operation parameters optimization
Operation parameters such as wastewater pH, catalyst concentra-
tion, H2O2 concentration and organic pollutants concentration have
been studied widely because of their significant effect on the
 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121
performance of processes (Fenton process and its optimization pro-
cesses) for the treatment of refractory organic pollutants. Therefore,
these parameters need to be optimized for achieving the best removal
efficiency and the lowest economic costs. In this part, some optimiza-
tion rules for these parameters are systematically outlined based on
the exhaustive analysis of the existing literature.
4.1. pH
The degradation of organic pollutants by conventional Fenton pro-
cess is very sensitive to the wastewater pH. At low pH values, the scav-
enging effect of •OH by H+ becomes stronger (Eq. (8)), resulting in
decrease in oxidation capacity of Fenton process (Nieto et al., 2011;
Hodaifa et al., 2013). At high pH values, the hydrolysis and precipitation
of Fe3+ in the solution become stronger, resulting in decrease in cata-
lytic capacity of Fe3+ (Ifelebuegu and Ezenwa, 2011; Fan et al., 2013).
Therefore, organic pollutants in wastewater cannot be treated effec-
tively by conventional Fenton process at both low and high pH. In
other words, there is always an optimum pH range for the degradation
of organic pollutants. The results show that the optimum pH range for
organic pollutants degradation by conventional Fenton process is
found to be 2–4. The effect of wastewater pH on organic pollutants deg-
radation in various Fenton optimization processes is similar to that in
conventional Fenton process. There is an optimum pH range beyond
which the degradation efficiency of organic pollutants decreases. How-
ever, different types of Fenton optimization processes have different op-
timum pH ranges for organic pollutants degradation. Wang et al.
(2014b) studied the effect of wastewater pH on the degradation of MB
by heterogeneous Fenton system. And the optimum pH range was
2–5, beyond which the degradation rate of MB decreased sharply. Zhai
et al. (2018) determined that the optimum pH range for the degradation
of natural gas extraction wastewater by photo-Fenton process was 3–6.
In the study carried out by L. Wang et al. (2015), the optimum pH range
for the degradation of atrazine by electro-Fenton process was broad-
ened to 4–10 due to Na6TPP as the electrolyte. However, it is worth not-
ing that the same type of Fenton optimization processes also have
different optimum pH ranges for organic pollutants degradation due
to the different experimental conditions such as composition and struc-
ture of catalysts, type and concentration of organic pollutants. For exam-
ple, Z.X. Liu et al. (2018) determined the optimum pH range for the
degradation of azo dyes by heterogeneous Fenton process was 3–9,
which was different from the optimum pH range (2–5) determined by
Wang et al. (2014b).
H þ þ OH þ e− →H2 O
4.2. Catalyst concentration
The different Fenton optimization processes are found to follow sim-
ilar oxidation mechanism: Fe2+ catalyzes the decomposition of H2O2 to
produce the highly oxidative •OH which can degrade most stubborn or-
ganic pollutants. Therefore, Fe2+ as catalyst is a highly important pa-
rameter affecting the degradation efficiency of organic pollutants.
Usually the degradation efficiency of organic pollutants increases with
the increasing of Fe2+ concentration (Wang et al., 2014a; Li et al.,
2018). However, Fe2+ cannot be added without any limitation. The ex-
cessive Fe2+ not only increases the operational costs and iron sludge
production, but also enhances the scavenging effect of •OH by Fe2+
(Eq. (9)) (Hsueh et al., 2005; Panizza and Cerisola, 2009), which has a
negative effect on the degradation of organic pollutants. In order to ob-
tain the maximum removal of organic pollutants, the study on the opti-
mum Fe2+ concentration can be a complicated but significant issue,
which can be determined experimentally. For example, the work of
Karci et al. (2012) showed the optimal TOC removal of 2,4-dichlorophe-
nol solutions could be obtained at 0.2 mM of Fe2+ concentration in the
117
photo-Fenton process, while further increasing of Fe2+ concentration to
0.8 mM decreased TOC removal efficiency.
Fe2þ þ OH→Fe3þ þ OH − ð9Þ
4.3. H2O2 concentration
According to the reaction of Fe2+ and H2O2 for •OH generation, the
effect of H2O2 concentration on the degradation of organic pollutants
by various Fenton optimization processes is similar to that of Fe2+ con-
centration. Therefore, H2O2 is also a highly important parameter affect-
ing the degradation efficiency of organic pollutants. Usually the
degradation efficiency of organic pollutants increases with the increas-
ing of H2O2 concentration (Rivas et al., 2001; Li et al., 2018). However,
H2O2 cannot be added without any limitation. The excessive H2O2 not
only increases the operational costs, but also enhances the scavenging
effect of •OH by H2O2 (Eq. (10)) (Borràs et al., 2010; Hu et al., 2018),
which has a negative effect on the degradation of organic pollutants.
In order to obtain the maximum removal of organic pollutants, the op-
timal H2O2 concentration should be examined. For example, the work of
Ramirez et al. (2007) showed the optimal degradation efficiency of or-
ange II could be obtained at 6 mM of H2O2 in the heterogeneous Fenton
process, while further increasing of the H2O2 concentration to 48 mM
does not obtain an increase but decrease in degradation efficiency.
In addition, it is worth noting that in electro-Fenton and its optimi-
zation processes, H2O2 can be generated via the electrochemical reduc-
tion of O2 supplied by pumps. Therefore, the air flow rate affects the
H2O2 production, which indirectly affects the degradation of organic
pollutants. Researches show that high air flow rate can be beneficial to
the degradation of organic pollutants. However, extremely high air
flow rate can cause decrease in H2O2 accumulation and disturb mass
transfer between electrodes and increase energy consumption of
pumps, which has a negative effect on the degradation of organic pollut-
ants. Thus, it is important for the degradation of organic pollutants to set
an optimal air flow rate.
H 2 O2 þ OH→H2 O þ HO2  ð10Þ
4.4. Organic pollutants concentration
ð8Þ
The stubborn organic pollutants can be degraded by highly oxidative
•OH formed from the reaction of H2O2 with Fe2+. Researches show that
a significant difference in degradation of wastewater with different or-
ganic loads is observed. Therefore, the concentration of organic pollut-
ants is an important parameter affecting the degradation efficiency of
organic pollutants. Most of Fenton optimization processes can obtain
high degradation efficiency with low concentration organic pollutants.
Besides, the increase in initial organic pollutants concentration always
leads to lower degradation efficiency and prolongs the degradation
time. For example, in the study carried out by García-Rodríguez et al.
(2016), the effect of initial MG concentration on the oxidative power
of heterogeneous electro-Fenton and photoelectro-Fenton processes
was studied. The time required for total decolorization increased with
the increasing of initial MG concentration. In addition, similar conclu-
sion could be drawn from the work of Poulopoulos et al. (2008). For
an initial concentration of 150 mg/L, 2-chlorophenol was totally
decomposed within 15 min by photo-Fenton process. However, for an
initial concentration of 3000 mg/L, the degradation rate was only 90%
within 150 min. The reason for this phenomenon could be the decrease
in H2O2 and Fe2+ with reaction, which was insufficient to degrade high
concentration organic pollutants.
118 M. Zhang et al. / Science of the Total Environment 670 (2019) 110–121
5. Outlook
Fenton optimization processes have been rapidly developed and
widely applied in organic wastewater treatment because of its signifi-
cant advantages over conventional Fenton process. In order to further
improve the effect of organic wastewater treatment, reduce operational
costs and environmental risks, the following issues should be given pri-
ority for significant developments:
(1) Degradation mechanism of organic pollutants by Fenton optimi-
zation processes. The research on degradation mechanism of or-
ganic pollutants is the theoretical basis for the development of
novel Fenton optimization processes. Further and more detailed
studies of Fenton optimization processes should be focused on
the degradation kinetics of organic pollutants, development of
rate expressions based on established degradation mechanism
and identification of reaction intermediates, and so on.
(2) Development of heterogeneous catalysts. Heterogeneous cata-
lysts play an important role in improving the efficiency of organic
wastewater treatment and reducing the costs of organic waste-
water treatment. The iron-containing catalysts with low leaching
rate, high stability, high catalytic activity and low preparation
costs are the main directions for the development of heteroge-
neous catalysts. In addition, the exploration of catalysts contain-
ing other metals has gradually become a trend in the
development of heterogeneous catalysts.
(3) Development of electrode materials. One of the key factors that
limit the development of electro-Fenton and its optimization
processes on a large scale is the costs and efficiency of electrode
materials. High efficiency electrode materials should possess
the following characteristics: high catalytic activity, high corro-
sion resistance, long working life span and low preparation
costs. The potential electrodes can be three-dimensional elec-
trodes and iron-graphite or iron‑carbon composite electrodes,
and so on.
(4) Analysis of economic costs. Economic costs are the restrictive fac-
tors for the large-scale development of Fenton optimization pro-
cesses. Comprehensive economic costs assessment can provide a
powerful costs support for the industrialization of these optimi-
zation processes. The detailed information of economic costs
such as chemicals costs, reactor investment costs, energy con-
sumption costs and so on should be accurately provided in future
work.
(5) Analysis of environmental impact. Considering the rapid growth
in the research of Fenton optimization systems together with
wide range of applications, it is only a matter of time before
these systems are scaled up. To avoid unintended consequences
caused by the development of large-scale Fenton optimization
systems, it is necessary to estimate their environmental perfor-
mance.
(6) Coupling between processes. The combination of Fenton optimi-
zation processes with other processes will be a trend in organic
wastewater treatment. The new coupling processes exhibit effi-
cient wastewater treatment performance due to synergistic ef-
fects between processes. For example, Fenton optimization
processes can be used as pretreatment of biological treatment
process to achieve better treatment effect.
6. Conclusions
Based on the optimization perspective, taking shortcomings of
Fenton process as a breakthrough, the feasibility of Fenton optimization
processes to degrade various types of organic pollutants was proved by
the achievement of high degradation rate and effective removal; the
fundamentals, advantages and disadvantages of Fenton optimization
processes for organic wastewater treatment were reviewed in detail;
the effect of operation parameters on the degradation of organic pollut-
ants was evaluated; the possible future research directions for opti-
mized Fenton processes were given. The following conclusions can be
drawn from the present work:
(1) Heterogeneous Fenton process can overcome the disadvantages
of conventional Fenton process which is limited to the narrow
working pH range and produces a large amount of iron sludge.
The key to the heterogeneous Fenton process is the development
of heterogeneous catalysts.
(2) Photo-Fenton process can overcome the disadvantage of conven-
tional Fenton process which produces a large amount of iron
sludge. The key to the photo-Fenton process is the reduction of
metal catalysts by photochemical process.
(3) Electro-Fenton process can overcome the disadvantages of con-
ventional Fenton process which contains the high costs and
risks associated with handling, transportation and storage of re-
agents and produces a large amount of iron sludge. The key to
the electro-Fenton process is the development of electrode mate-
rials.
(4) The maximum removal of organic pollutants by Fenton optimiza-
tion processes can be achieved at the optimum pH range, the op-
timal catalyst and H2O2 concentration. And most of Fenton
optimization processes can obtain high degradation efficiency
with low concentration organic pollutants.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2019.03.180.
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