Jurnal Proplit 2

Journal of Environmental Chemical Engineering 4 (2016) 762–787
Contents lists available at ScienceDirect
Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece
A review on Fenton-like processes for organic wastewater treatment

Nannan Wanga,b , Tong Zhengb , Guangshan Zhangb , Peng Wanga,b,*
a
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, PR China
b
School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, PR China
A R T I C L E I N F O A B S T R A C T
Article history: Fenton-like processes have been studied widely in recent years and are considered promising for organic
Received 11 August 2015 wastewater treatment. Due to the demand for high efficiency wastewater treatment, a summary of the
Received in revised form 5 December 2015 study status of Fenton-like processes is necessary to develop a novel and high efficiency organic
Accepted 10 December 2015
wastewater treatment method. In this review, some important effect parameters (pH, H2O2 dosage,
Available online 15 December 2015
catalyst dosage, temperature) in hetero-/homo-geneous Fenton-like processes are discussed, and then
the physical field/phenomenon-assisted hetero-/homo-geneous Fenton-like processes are presented.
Keywords:
After that, catalyst types and the evaluation of wastewater treatment costs for various Fenton-like
Fenton-like
Photo-Fenton-like
processes are summarized and discussed. Finally, possible future research directions and some guidelines
Electro-Fenton-like for Fenton-like processes are given.
Microwave-Fenton-like ã 2016 Published by Elsevier Ltd.
Cavitation-Fenton-like
Catalyst
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
2. Fenton-like processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
2.1. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
2.2. H2O2 dosage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 764
2.3. Catalyst dosage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
2.4. WW treatment temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
3. Physical field/phenomenon-assisted Fenton-like processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
3.1. Photo-Fenton-like processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
3.2. Electro-Fenton-like processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
3.3. Cavitation-Fenton-like processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
3.4. Microwave-(another physical field)-Fenton-like processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774
4. Catalyst types studied in hetero-/homo-geneous Fenton-like processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
4.1. Heterogeneous catalyst from natural minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
4.2. Heterogeneous catalyst from composite by artificial synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
4.3. Heterogeneous catalyst from nano materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
4.4. Heterogeneous catalyst from industrial waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 779
4.5. Homogeneous Fenton-like catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 779
4.6. Study status of the catalyst based on different metal elements and the corresponding WW treatment efficiency . . . . . . . . . . . . . . . 780
5. Cost evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 780
5.1. Effect of parameters associated with H2O2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 780
5.2. Effect of parameters associated with the catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 780
5.3. Effect of parameters associated with the WW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 781
5.4. Input energy and related issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 781
6. Proposed future research directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
* Corresponding author at: School of Municipal and Environmental Engineering, Harbin Institute of Technology, No. 73 Huanghe Road, Nangang District, Harbin 150090, PR
China. Fax: +86 451 86283109.
E-mail addresses: pwang73@hit.edu.cn, pwang73@vip.sina.com (P. Wang).
http://dx.doi.org/10.1016/j.jece.2015.12.016
2213-3437/ ã 2016 Published by Elsevier Ltd.
N. Wang et al. / Journal of Environmental Chemical Engineering 4 (2016) 762–787 763
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
1. Introduction surface of the catalyst. The position at which catalysis occurs in the
heterogeneous system determines that the diffusion and adsorp-
In recent years, advanced oxidation processes (AOPs) have been tion processes of H2O2 and other reactants to the surface of catalyst
studied as a promising kind of organic wastewater (WW) could be significant for the catalysis process [49,50].
treatment method based on the in situ generation of hydroxyl For the study of the Fenton-like processes mentioned above,
radicals (HO), which have a strong oxidation capacity (standard various organics were chosen as target contaminants such as dyes
potential = 2.80 V versus standard hydrogen electrode) [1,2]. Under [35,51], drugs [52–54], and pesticides [46]. Most of the above
treatment by AOPs complex organic molecules can be either organic compounds present in the WW are refractory to biological
oxidized by HO to smaller organics or completely mineralized to treatment and toxic to aquatic organisms, even to human beings.
carbon dioxide (CO2) and water (H2O) [3–6]. Many organic WW The concentration range studied was always from hundreds of
treatment methods that are based on OH generation can be called mg/L to hundreds of mg/L [38–56].
AOPs, such as Fe(II)/H2O2 [7], Fe(II)/H2O2/UV, ozonation (O3) [8], In recent years, some typical reviews [43–58] have been
O3/H2O2 [9], H2O2/UV [10], hetero-/homo-geneous Fenton-like published regarding different aspects of the introduction of
processes, TiO2/UV [11], ZnO/UV [12], and some other processes Fenton/Fenton-like processes. Pliego et al. [58], in their review,
involving the photo field, electric field, cavitation effect, micro- presented various methods that can enhance Fenton-like processes,
wave field, etc. [13]. such as radiation, electrochemistry, and heterogeneous catalysts;
One of the most frequently used AOPs is the Fenton process Bautista et al. [57] provided detailed information on the application
where Fe2+ is used as the catalyst and hydrogen peroxide (H2O2) as of the Fenton process for the treatment of industrial WW. Brillas et al.
the oxidant. The mechanism of the Fenton process has often been [43] gave a profound introduction to the electro-Fenton processes
described [14,15]. It has many advantages such as its high and the related electrochemical technologies. In our review, the
performance and simplicity (operated at room temperature and important effect parameters (pH, H2O2 dosage, catalyst dosage,
atmospheric pressure) for the oxidation of organics [16,17] and its temperature, etc.) are discussed in detail, and then the physical
non-toxicity [18] (H2O2 can break down into environmentally safe fields/phenomenon-assisted Fenton-like processes are presented.
species like H2O and oxygen (O2)). After that, a conclusion about the most suitable catalysts is made in
Based on the above advantages, the Fenton process has been the forth section and the costs of different Fenton-like processes are
applied to treat many kinds of WW such as olive-oil mill WW [19], compared in the fifth section. Finally, recommended research
textile WW [20], laboratory WW [21], pesticide WW [22], cosmetic directions for the future and some guidelines are given. The aim
WW [23], dye WW [24,25], fermentation brine from green olives of this review is to discuss Fenton-like processes from aspects that
[26], pharmaceutical WW [27], cork cooking WW [28], pulp mill are significant in the study of Fenton-like processes and were
effluents [29], and phenolic WW [30]. However, although the previously seldom considered but are valuable (such as the types of
Fenton process has been studied widely and has performed well in catalyst). We hope that this paper, based on the systematic
the above WW treatments, it still has some disadvantages such as introduction below, will provide valuable viewpoints and promote
high operating cost, limited optimum pH range (always works best the development of Fenton-like processes.
at around pH 3), large volume of iron sludge produced, and
difficulties in recycling of the homogeneous catalyst (Fe2+) [31]. 2. Fenton-like processes
Additionally, the required concentration range of the iron ion is
50–80 ppm for batch processes, which is clearly above the 2 ppm Fenton-like processes consist of heterogeneous and homoge-
limit imposed by the European Union (EU) directives for direct neous Fenton-like processes. Heterogeneous Fenton-like processes
discharge of wastewater into the environment [32]. can be established by replacing Fe2+ in the Fenton reagent with a
In order to overcome these disadvantages, enhancement of the solid catalyst, while homogeneous Fenton-like processes are due to
Fenton process has attracted much attention by researchers. Some a combination of other metal ion(s)/metal ion-organic ligand
other kinds of hetero-/homo-geneous catalyst (except for Fe2+) complexes and H2O2 [59]. In Fenton-like systems pH, H2O2 dosage,
were used to replace Fe2+, including Fe3+ [33], Cu2+/Cu+ [34], schorl catalyst dosage, and reaction temperature have been studied
[35], pyrite [36], and nano zero-valent iron [37]. These established widely because of their significant effect on the oxidation capacity
systems are called hetero-/homo-geneous Fenton-like processes. of the Fenton-like reagent. Thus, the systematic introduction and
Furthermore, physical field(s)/phenomenon can also be used in analysis of these parameters is necessary.
both the classic Fenton process and hetero-/homo-geneous
Fenton-like processes to enhance the WW treatment efficiency. 2.1. pH
The typical physical fields/phenomenon include the photo field,
electro field, cavitation effect, and microwave field, which In Fenton-like processes pH is a highly important parameter for
correspond to the photo-Fenton/Fenton-like processes [38–40], effective WW treatment. However, in the previous studies the
electro-Fenton-like processes [41–43], cavitation-Fenton-like pro- researchers always reached different conclusions about the pH. In
cesses [44–46], and microwave-Fenton-like processes [47,48], the heterogeneous Fenton-like processes some studies revealed
respectively, in both hetero- and homo-generous Fenton-like that 3 was still the best pH, while others showed that the neutral
processes. condition (even alkaline conditions) could achieve a better organic
The basic difference between the homogeneous and heteroge- WW treatment efficiency. Yang et al. [51] and Xu et al. [35], from
neous Fenton-like processes involves the different positions where different research groups, applied magnetic NdFeB-activated
the catalytic reactions occur. In the homogeneous system, the carbon (AC) and schorl, respectively, to treat dye WW. Both of
catalysis process can occur in the whole liquid phase, while in the them observed that the organics in WW could be treated
heterogeneous system the catalysis process always occurs on the effectively under acidic condition (pH 3 (Fig. 1a) and 2–4,
764 N. Wang et al. / Journal of Environmental Chemical Engineering 4 (2016) 762–787
Fig. 1. Effect of pH on the removal rate of organics in two different heterogeneous Fenton-like processes [51,60].
respectively), and the treatment efficiency decreased obviously pH range because at least some studies (especially in the
with an increase in pH (No. 1 and 8 in Table 1). However, Huang heterogeneous systems) have showed a satisfactory WW treat-
et al. [60] and Feng et al. [61], from different research groups, had ment efficiency under neutral/alkaline conditions.
different study results. Both of their studies showed that organic
WW could be treated effectively under close to neutral (pH 6.0) 2.2. H2O2 dosage
(even slightly alkaline (pH 9.0)) conditions when iron oxide/SiO2
composite (Fig. 1b) and pyrite were applied, respectively (No. 5 and In the Fenton-like processes, H2O2, as the dominant source of
6 in Table 1). HO under catalysis, plays a critical role in the treatment of organic
The different solubilities of a metal ion (such as the Fe ion) on WW. The optimum H2O2 dosage must be determined experimen-
the surface of a catalyst and the different activities of active sites on tally. Insufficient H2O2 dosage will result in a decrease in the
the catalyst surface could be the primary reason. Some kinds of organic WW treatment efficiency due to a deficiency of HO
catalyst could play a catalytic role mainly by means of the generated by H2O2 decomposition under catalysis. On the contrary,
dissolution of metal ions from the catalyst surface, while other excessive H2O2 dosage is not encouraged either. Firstly, when
kinds of catalyst may perform mainly through the active sites on Fenton-like processes are used for pre-treating high concentration
their surface. For the former case, the increase in pH could be able organic WW for the purpose of improving the ratio of BOD
to stop/slow the leaching of metal ions from the solid catalyst (Biochemical Oxygen Demand) to COD (Chemical Oxygen Demand)
surface and inactivate the metal ions in the aqueous phase due to (BOD/COD or B/C), a massive amount of H2O2 could have a negative
hydrolysis and precipitation. For the latter case, the catalysts could effect on the reactivity of the microorganisms that are used to treat
be more resistant to pH because they play the catalytic role the pretreated organic WW in the subsequent bio-treatment
through the active sites. process. Secondly, an excessive H2O2 dosage would increase the
Nevertheless, although the result is different, all of their treatment cost significantly when the volume of organic WW is
research results showed that the pH used in organic WW very high. In China the price range of industrial grade H2O2 (27.5%,
treatment could not be increased without any limitation; in other w/w) in recent years is approximately ¥1100–1300/ton. Hence the
words, there was always an optimum pH value/range for the WW H2O2 dosage must be in the optimal range. Thirdly, excessive H2O2
treatment. dosage could cause an increase in the COD of the effluent. Although
In the homogeneous Fenton-like processes, many researchers this kind of COD cannot pose any harm to the environment, it
[62–66] have reported pH 2.5–3.0 to be the optimum pH range for probably makes the quality of treated WW cannot satisfy the
the degradation of most organic compounds. These studies showed discharge standard because of the innocuous COD. The last, but
that with a decrease in pH (<2.5), the scavenging effect of the HO quite significant, point is that the scavenger effect of H2O2 on HO
radicals by H+ becomes stronger (reaction Eq. (1)). (see reaction equation (2)) would be greater when the H2O2 dosage
is excessive [68–72].
HO + H+ + e ! H2O (1)
H2 O2 þ HO ! H2 O þ HO2 ð2Þ
On the contrary, for pH > 3.0 the hydrolysis and precipitation of
Fe3+ in the solution can reduce the catalytic capacity of itself (No. In the previous studies the required theoretical H2O2 dosage
12–14 and 16–18 in Table 1). However, there are also different was calculated [73–75] as for the following example of the reaction
results from a small number of studies. You et al. [67] revealed that between CaHbNcOd and H2O2 given in reaction equation (3).
at pH 6 a better treatment result was obtained when they treated
1 5
molasses alcohol WW using Fe3+ as the homogeneous Fenton-like Ca Hb Nc Od þ 2a þ b þ c d H2 O2
2 2
catalyst (No. 15 in Table 1). This could be due to the coagulation of
! aCO2 þ ð2a þ b þ 2c dÞH2 O2 þ cHNO3 ð3Þ
ferric species [66], which can play an important role under neutral
conditions. According to reaction Eq. (3), theoretically one mole of CaHbNcOd
According to the statement above, the study of the optimum pH requires ð2a þ ð1=2Þb þ ð5=2Þc dÞ moles H2O2. So the H2O2
value/range could be a complicated but significant issue, which can dosage should be determined by the type of contaminant and
only be determined experimentally. Nevertheless, the previous the initial concentration of the contaminant. If the H2O2 dosage is
studies have presented a positive trend for the broadening of the lower than the theoretical value, then theoretically the removal
Table 1
Conclusion of typical studies of the Fenton-like process alone.
NO.a Pollutant Catalyst Dos.b Experiment conditions Treatment Additional information Ref.
efficiency
pH H2O2 Reaction Othersc
Dos. time (min)
(mM)
1 Argazol blue Schorl 7.0 g/L 3.7 31.7 17.8 [ABB] = 200 mg/L; 100% First-order kinetic model was more [35]
BFBR (ABB) WW vol. = 100 mL; (discoloration) favourable to describe the discoloration of
T = 55 C. AB than thesecond-order and Behnajady–
Modirshahla–Ghanbery models.
2d ABB Schorl 10.0 g/L 2 48.5 9/200 [ABB] = 200 mg/L; 100% The discoloration of BF-BR follows the [80]
FeO and WW vol. = 100 ml; (discoloration, first-order kinetics and the reaction rate
1
Fe2O3account for T = 55 C. 4 min) constant is 0.367 min ; The adsorption
24.35% (wt%) 72% (TOC, of AB on the Schorl, the heterogeneous
200 min) and homogeneous Fenton/Fenton-like
processes govern the fast discoloration of
AB.
3d Rhodamine B Schorl 3.3 g/L 2 48.5 30/200 [RhB] = 100 mg/L; 100% The catalyst can be used at least 10 times [82]
(RhB) WW vol. = 100 mL; (discoloration, with no obvious decrease of discoloration
T = 60 C. 30 min) rate.
65% (TOC,
200 min)
4 RhB Schorl 2.5 g/L 2 45 110 [RhB] = 50 mg/L; 98.90% From the ANOVA analysis, the calculated F [83]
WW vol. = 100 mL; (discoloration) value was 16.14, which is larger than the
T = 60 C. criticalvalue of 2.42 for F0.05(14, 15).
5e Textile WW Pyrite 10.0 g/L 9 9.7 60 WW COD = 1402 mg/L; 70% (COD) BOD5/COD is increased from 0.25 to 0.56. [61]
WW BOD5 = 345 mg/L; The H2O2/pyritereaction could be active at
WW vol. = 0.8 L. a wide pH range.
6 Aniline Iron oxide/SiO2 6 50 160 [Aniline] = 2 104 M; 73.30% The decomposition of H2O2decreased [60]
100.0 g/L T = 30 C. (Aniline) withincreasing concentrations of H2O2.
7f Chicago sky blue Fe2+/activated 3 2.3 20 [CSB] = 0.012 mM; 88% (CSB) The leaching iron concentration is [17]
(CSB) carbon (AC) WW flow rate = 2.5 mL/ 47% (TOC) 0.4 ppm, which is lower than European
Iron account for 7% min; limits.
(wt%) T = 50 C.
Wcat/Q = 4.1 g min/
mL (Wcatis the mass
of catalyst and Q the
total feed flow rate)
8 Methyl orange Fe2+/NdFeB- 3 0.6 60 [MO] = 20 mg/L; 97% (MO) The MO degradation ratio could reach [51]
(MO) AC10.0 g/L WW vol. = 200 mL; 97.1% after 5 cycles; the catalytic
Iron account for T = 20 C. degradation process follows the pseudo-
94.4% (wt%) first order kinetics model.
9 Acid orange II FeOOH-C 5 15 120 [AOII] = 100 mg/L; 98% (AOII) A membrane module was used in this [84]
(AOII) 1.0 g/L WW vol. = 100 mL; work to separate the solid catalyst and
T = 30 C. effluent.
10d p-Nitrophenol Coal fly ash 2 4.9 40 [p-NP] = 100 mg/L; 99% (p-NP) The homogenous catalysis of leached iron [75]
(pp-NP) 10.0 g/L WW vol. = 100 mL; for p-NP removalwas negligible. The
Fe2O3account for T = 25 C. lower reaction time and higher AFA load
5.73% (wt%) should be selected for catalytic stability
and reusability.
11 Sawmill WW Fe3+ 3 376.5 60 COD = 3000 mg/L; 80% (COD) Feeding the overall H2O2amount in three [81]
25.0 mg/L Ecotoxicity = 40 toxicity 70% (TOC) times throughoutthe reaction time leads
units; to higher efficiency since thismode of
BOD/COD = 5 103; H2O2addition avoids high concentrations
WW vol. = 200 mL; of OH and OOH radicals at the earlier
T = 120 C. oxidation stages allowing a better
availability of these species throughout
the whole reaction system.
12 Malachite green Fe3+ 3 50 15 [MAG] = 3.0 105 M; 95.50% (MAG) The degradation of Malachite Green dye [62]
(MAG) 56.0 mg/L Room temperature. 70% (TOC) in the Fenton-like oxidation process can
be described with a pseudo-second-order
kinetic model.
13 Olive-oil mill Fe3+ 3 2941 180 WW COD = 4100 mg/L; 92.60% (COD) The apparent activation energy is 8.7 kJ/ [65]
WW (OMW) 6588.4 mg/L [phenol]T = 44 mg/L; 99.80% (total mol; The results show that the Fenton-
T = 30 C. phenols) like process is a relative cheap solution for
OMW treatment and the treated WW can
be used for irrigation.
14 OMW Fe3+ 4 882.4 240 OMW COD = 4017 mg/L; 96.80% (COD) The optimum[FeCl3]/[H2O2] ratio was in [63]
400.0 mg/L Total phenol = 66.2 mg/L; 99.20% (total the range 0.026–0.058 (w/w).
Ambient temperature. phenols)
15 Molasses Fe3+ 6 6.7 7 WW CODCr = 1604.7 mg/L; 92.80% The solution was firstly stirred for 30 s at [67]
alcohol(MA) 207.0 mg/L WW vol. = 300 mL; (discoloration) 300 r/min, and then stirred for 90 s at
75.50% (CODCr) 150 r/min, finally stirred at 50 r/min for
5 min.
Table 1 (Continued)
efficiency
pH H2O2 Reaction Othersc
Dos. time (min)
(mM)
16 17b-Estradiol Fe3+ 3 10 60 WW COD = 386.5 mg/L; 95% (E2) The degradation of E2 and EE2 accord [64]
(E2); 58.6 mg/L WW BOD = 273.8 mg/L; 98% (EE2) with pseudo second order kinetics and
17a- WW DOC = 92.5 mg/L; the activation energies were 27.8 and
Ethinylestradiol WW Vol. = 150 mL; 22.5 kJ/mol. There was an increase of 82%
(EE2) T = 25 C. in the BOD/COD ratio after 2 h of
treatment.
17 Pulp WW Fe3+ 3 14.7– 60 WW COD = 964 mg/L; 98% Color is mainly removed by coagulation/ [66]
400.0 mg/L 29.4 (residence WW BOD = 400 mg/L; (discoloration) settling and the residual hydrogen
time in Flow rate of WW is 100 L/h; 75% (COD) peroxide is negligible after the treatment.
oxidation Room temperature; 95% (aromatic
reactor) The oxidation process by compound)
Fenton-like process was
followed by the
coagulation process at pH
5.0.
18 Nalidixic Acid Fe3+ 3 10 60 [NA] = 50 mg/L; 100% (NA) Sixteen degradation intermediates were [33]
(NA) 14.0 mg/L WW vol. = 50 mL; identified using LC–MS. NA was degraded
T = 35 C. with the electrophilic attack of hydroxyl
radical towards the C3 position.
19 Pretreated Fe3+ 4.2 200 40 COD = 8800–10500 mg/L 80% (COD,WW WW was treated by the Fenton-like [85]
cheese whey 50.4 mg/L (after pretreatment); pretreated system after being pre-processed through
WW BOD = 8–9 g/L (after using FeCl3); a coagulation-flocculation stage.
pretreatment); 100% (COD,
WW vol = 300–500 mL; WW
Temperature = 19.7 2.3 C pretreated
(after pretreatment using using Ca(OH)2)
FeCl3);
Or
T = 21.4 1.3 C (after
pretreatment using Ca
(OH)2).
20 Benzoic Acid Fe3+ 1.1 mg/L 3 2 25/180 [BA] = 20 mM; 100% (BA, Addition of Mn(II) to the Fe(III)/ [86]
(BA) Mn2+ 27.5 mg/L WW Vol. = 100 mL; 25 min) H2O2system significantly enhances the
I = 0.05 M; 47% (TOC, oxidation of BA and the mechanism still
T = 25 0.5 C. 180 min) accords with the HO oxidation.
21 Phenolic Cu2+ 500.0 mg/L 4.7 12000 65 WW COD = 74000 mg/L; 43% (30 C) Degradation of contaminant followed [87]
compounds Total polyphenol = 62% (50 C) first-order kinetics and the activation
from olivemill 20.56 g/L; (both for energy was 21 kJ/mol.
WW WW vol. = 100 mL; Phenolic
T = 30/50 C. compound
a
No. 1–10 are the heterogeneous Fenton-like process and No. 11–21 are the homogeneous Fenton-like process.
b
Dos. represents dosage.
c
Vol. represents volume; T is the abbreviation of temperature.
d
Both of the adsorption and the homogeneous contribution are responsible for the treatment of the WW.
e
The homogeneous contribution is responsible for the treatment of the WW.
f
The adsorption plays an important role in the treatment of the WW.
rate of CaHbNcOd can never reach 100%. So the actual concentration H2O2 was added in one step, more H2O2 could be wasted due to
of H2O2 added should be higher than the theoretical value and the decomposition.
required amount should be determined by experiment.
Some researchers found that stepwise addition of H2O2 is a good
way to improve the treatment efficiency of a WW. One of the typical 2.3. Catalyst dosage
studies is by Zhang et al. [76]. In their study, a Fenton-like process was
used to treat landfill leachate and stepwise addition of H2O2 was An increase in the catalyst dosage is sometimes beneficial to
applied. The study results showed that the stepwise addition of H2O2 improve the removal rate of the organics in the WW. However, the
could give a better WW treatment efficiency (15.6% higher than that catalyst cannot be added without any limitation. The excessive
for a single step). The more moderate distribution of H2O2 explains loading of catalyst in both hetero- and homo-geneous Fenton-like
the improved treatment of the WW [77]. Moreover, a delay in the processes may have a negative effect during the WW treatment,
decomposition of H2O2 is also recommended in our review as an i.e., the scavenger effect may occur (see Eq. (4)),
explanation for this phenomenon. Firstly, the step-wise addition of Fe2þ þ HO ! Fe3þ þ OH ð4Þ
H2O2 can ease off the dramatic increase in the H2O2 concentration,
thus avoiding the side reaction shown in reaction Eq. (2). Secondly, If the catalyst loading in the aqueous solution exceeded the
the step-wise addition of H2O2 can avoid the rapid decomposition of optimum range, the generated HO would be consumed by the
H2O2 (especially under alkaline conditions). It is well known that the excess catalyst.
pH has a significant effect on the stability of H2O2, i.e., acidic In addition to the above effect, the catalyst loading can present
conditions are beneficial for the stability of H2O2 while alkaline other effects. In heterogeneous Fenton-like processes, the produc-
conditions will accelerate the decomposition of H2O2. If all of the tion cost of the solid catalyst could be a limiting parameter in
physical field/phenomenon, the solid catalyst loading is in the

range 1–10 g L1 in most studies (87.5%), while 100 g L1 can
sometimes also be used; the homogeneous catalyst presents an
obvious difference: a catalyst concentration of 20–60 mg L1 is
used when treating the model WW, while a catalyst concentration
of 200–500 mg L1 is necessary for the industrial WW. For a
Fenton-like process that is enhanced by a physical field/phenome-
non, the solid catalyst loading is obviously decreased in most cases
(0.1–5 g L1, 69.2%), while a lower ( 0.05 g L1, 11.5%) or higher (10-
40 g L1, 19.2%) catalyst loading can also be used in some cases.
The homogeneous catalyst presents a similar trend to that of
the solid catalyst, i.e., the catalyst concentration is relatively low
compared to that of the unenhanced Fenton-like processes; a
concentration range of 1.7–28 mg/L is always used when treating
model WW, while a higher concentration (at least 120 mg/L) must
be used for industrial WW.
2.4. WW treatment temperature

Fig. 2. Typical stability study of catalyst used in heterogeneous Fenton-like process
[51].
WW treatment temperature has a significant effect on the
treatment efficiency of organic WW. Although the temperature
organic WW treatment. Higher catalyst loading would obviously used for Fenton-like processes is typically around 25–30 C [17],
increase the WW treatment cost; in the homogeneous Fenton-like the effect of higher temperature was still studied by some
processes the excessive concentration would result in the researchers due to the existence of some inevitable facts such as
generation of a large volume of sludge, which would increase (I) textile effluents are usually around 50 C [35,78], and (II) higher
the need for subsequent sludge treatment processes. Additionally, temperature could be beneficial to reduce the catalyst dosage [79].
it could cause the metal concentration in the effluent to exceed the When a lower temperature (20–40 C) was applied, the researchers
regional discharge standard for the WW, which would cause always have the same viewpoint, i.e., the treatment efficiency can
further problems due to the requirement for subsequent treatment be improved by increasing the temperature, because higher
of the effluent. temperatures can provide more energy to overcome the reaction
According to the statement above, optimization of the catalyst activation energy [35,62,80] and then accelerate the reaction by
loading in both hetero- and homo-geneous Fenton-like processes increasing the reaction rate constant according to the Arrhenius
should be conducted. In addition, for heterogeneous Fenton-like equation [64].
processes the use of catalyst recycling is also recommended However, when a higher temperature (>40 C) was applied,
depending on the results of a study of its stability. different conclusions were reached in the different studies. Munoz
In heterogeneous Fenton-like processes, the performance of et al. [81] showed that the TOC (total organic carbon) removal rate
recycled catalyst is affected by the leaching characteristics of the for sawmill WW increased obviously with an increase in
active metal element on the solid catalyst surface, which can result temperature (50–120 C) and the H2O2 utilization efficiency was
in the deactivation of the heterogeneous catalyst. Zhang et al. [75] also increased (15 and 83 mg TOC converted per g H2O2 at 50 and
used acid-activated fly ash to treat p-nitrophenol WW. The 120 C, respectively) (Fig. 3A); Mesquita et al. [17] and Zazo et al.
experimental results showed that the removal efficiency of p- [79] both showed that the conversion of TOC had no obvious
nitrophenol decreased with an increase in the run time, variation when the temperature was between 50 and 70 C (Fig. 3B)
meanwhile leaching of elemental Fe occurred in all of the and between 110 and 130 C, respectively; Hashemian [62] showed
experimental runs. A typical stability study result from another that the removal rate of Malachite Green can neither keep
paper is shown in Fig. 2 [51]. It showed that the removal rate of the increasing nor remain constant, but has a decreasing trend with
contaminant did not decrease obviously even when the catalyst the increase in temperature (30–70 C) (Fig. 3C).
was used five times, i.e., the catalyst can remain stable for five runs. These different conclusions could be associated with the
According to the first five tables in this paper, the catalyst competition between organic degradation by the attack of HO
loading has no absolute optimum range for a specific kind of and by the side reaction (2). With an increase in the temperature,
Fenton-like process, but still presents some obvious statistical more HO can be generated. The reaction rate of organics
rules, which could be valuable for the determination of catalyst degradation (g 1) and the side reaction (2) (g 2) can both be
loading. For Fenton-like processes that are not combined with any accelerated due to higher temperatures. However, the different
Fig. 3. Effect of higher WW treatment temperature [17,62,81].

reaction activation energies (E) between organics and HO will alkaline conditions. Some of the detailed conclusions regarding
result in the different results. According to Arrhenius equation, organic WW treatment in heterogeneous photo-Fenton-like
when E is relatively low, the reaction rate constant (k1) will have a systems are shown in No. 1–9 in Table 2.
relatively rapid increase (with the increase in temperature) In homogeneous photo-Fenton-like systems the photochemical
compared with that of the side Reaction (2). However, when E reduction of the metal catalyst is the main pathway during the
is relatively high, the experiment may show the opposite results. catalytic oxidation process. Taking photo-Fe3+–H2O2 system as an
According to the statement above, although increasing the example, except for the reactions in the Fe3+-H2O2 system, two
temperature is always beneficial for the treatment of WW, special extra reactions can occur due to the existence of photo irradiation.
attention should be paid when the WW temperature is higher than The first reaction involves Fe3+ ions (which exist in the form of Fe
40 C. A specific optimum temperature should be determined (OH)2+ under acidic condition) undergoing a photochemical
experimentally as different catalysts could present different reduction process to form Fe2+ ions under UV–vis radiation
performances for the reaction rate of organic degradation. (Eq. (5)) [92–95]; the second reaction involves H2O2 generating
HO via a photolysis process under shorter wavelength radiation
3. Physical field/phenomenon-assisted Fenton-like processes (Eq. (6)) [94–96].
3.1. Photo-Fenton-like processes FeðOHÞ2þ þ hv ! Fe2þ þ HO ðl < 580nmÞ ð5Þ
The role of photochemistry in a Fenton-like process is to

provide energy using ultraviolet and/or visible light to reduce the H2 O2 þ hv ! 2HO ðl < 310nmÞ ð6Þ
catalyst loading and/or to enhance the catalytic capacity of the Photo-generated ferrous ions (Eq. (5)) can enter the Fenton
catalyst in both heterogeneous and homogeneous Fenton-like system directly, produce more HO, and finally improve the
processes; the essence is related to the redox processes [88]. In the removal rate of the organic pollutants (see No. 10–13 in Table 2).
heterogeneous photocatalytic system, the photo-induced reduc- The photo-Fe3+–H2O2 system always performs well at pH 3.0,
tive dissolution of the solid catalyst has been accepted by where Fe(III) hydroxyl complexes are more soluble and Fe(OH)2+ is
researchers [89,90]. In this review, iron oxide is taken as an more photoactive [94,97–100]. When working at higher pH (>3), an
example to illustrate the proposed mechanism as Fe(III) oxide have inorganic/organic ligand is always needed (reaction Eq. (7)) to
been studied widely. The proposed model of photo-reductive complex the ferric ion [96,101]; this can prevent the precipitation
dissolution of g -FeOOH is shown in Fig. 4 [91]. of iron ion. The most effective ligands that are used frequently
We can see from Fig. 4 that a charge transfer process from include, but are not limited to: citrate, oxalate, EDTA (ethylene
organic ligand to metal happens after the formation of Fe(III)- diamine tetraacetic acid), humic acids, EDDS (ethylenediamine
organic ligand complexes on the solid phase; in other words, this disuccinic acid), and catechin.
model illustrates a photo-induced Fe(III)/Fe(II) redox cycle
between the solid and aqueous phases. In this model the FeIII L þ hv ! FeII þ Lþ ð7Þ
irradiation of ultraviolet and/or visible light promotes the
The high yield of Fe(II) in the presence of ligands increases the
formation and the release of Fe2+ into aqueous phase from the
amount of HO generated under near neutral conditions, thereby
solid surface; this process results in the occurrence of the Fenton
improving the removal efficiency of organic pollutants in the WW.
process in the presence of H2O2. Thus, photo-irradiation is the
Wang et al. [53] used catechin as a ligand to complex Fe3+ ions and
essence of photo-Fenton-like processes.
the Inderal removal rate can reach to 75% within 120 min at pH 6.0
In addition to the iron-based catalyst, other kinds of transition
(No. 14 in Table 2).
metal catalyst like the Cu-based catalyst also attracts much
In addition to the Fe3+-catalyzed homogeneous photo-Fenton-
attention in organic WW treatment. Kalal et al. [92] and Lam et al.
like processes, Cu2+ and Cu2+-complexes can also act as the catalyst
[93] developed copper pyrovanadate and Copper/MCM-41, respec-
(see reaction Eqs. (8) and (9)) in homogeneous Fenton-like
tively, to treat organic WW. In the study by Kalal et al. [92]
processes by photo irradiation under neutral conditions [102].
researchers found that copper pyrovanadate had better catalytic
Some study results are shown in Table 2 (No. 16 and 17).
capacity than that of CuO and V2O5; the shell of the copper
pyrovanadate could be the main reason as the copper pyrovana- CuII L þ hv ! CuI þ Lþ ð8Þ
date can increase the surface hydroxyl groups and enhance the
interfacial electron transfer. The study by Lam et al. [93] shows that
Copper/MCM-41 was a pH-insensitive catalyst that can overcome Cuþ þ H2 O2 ! Cu2þ þ HO þ OH ð9Þ
the low efficiency issues of the Fenton process under neutral/
Finally, the use of soluble bio-organic substances (SBO) as
potential photocatalysts has also attracted much attention by
researchers in recent years. One of the typical studies is from
Gomis’s research group [103], where SBO was applied to treat
crystal violet (CV). In this study, a mechanism involving the
photosensitizer-pollutant complexes (CV-SBO) theory was pro-
posed. According to the study result, 66.7% discoloration was
achieved after a 300 min treatment time at pH 7.0 (see No. 18 in
Table 2).
3.2. Electro-Fenton-like processes
Electrochemical processes can be combined with Fenton-like

processes (EF-like processes) during WW treatment to improve
Fig. 4. Model of photo-reductive dissolution of FeOOH in the heterogeneous system
the Fenton-like processes. A large number of study results have
[91]. been published in recent years. Sires et al. [110], in their review,
Table 2
Study conclusion of Fenton-like process combined with photochemistry.
efficiency
pH H2O2Dos. (mM) Reaction Othersc
time
(min)
1 Naproxen (NPX) Hydrated 6.5 0.5 13.0 1.3 120 Xenon arc lamp 50–60% (TOC) Zeolite was studied in this work, [104]
hematite (hyd- (2700 kJ/hm2, and in the presence of Zeolite,
Fe2O3); 300–800 nm); photolysis of NPX is accelerated.
Hematite (Fe2O3); Temperature = 25 C;
Magnetite [NPX = 10 mg/L;
(Fe3O4) 0.05 g/L NPX total vol. = 1 L;
Treated vol. = 200 mL.
2 Phenol Magnetite 0.2 g/L 5 5 (Na2S2O8) 4 UVA = 20 W 98% (phenol) Sulphate radical is a strong one- [101]
FeII/FeIII = 0.30– (295–400 nm; max electron oxidant; although
0.43 emission = 365 nm); magnetite naturally contains
[Phenol] = 9.4 mg/L; FeII, the air-exposed oxide
WW Vol. = 50 mL; surface is fully oxidized to
T = 30 C. FeIIIand irradiation is required to
produce FeII.
3d Reactive orange Lepidocrocite- 2 3.3 50 10 UV LED lamps on the 81% Photo Fenton-like process has [105]
29 (RO29) granular activated top of the WW solution (decolorization) higher capacity on treating WW
carbon nano with 4 cm distance than Fenton-like process,
composite from solution surface; photocatalytic, adsorption,
(g-FeOOH-GAC) WW COD = 420 mg/L; photolysis, and H2O2/UV
5.0 g/L WW pH 6.8; processes.
WW conductivity =
3.09 mS/cm;
WW Vol. = 400 mL;
Flow rate =
1.98 mL/min.
4 Acid orange 7 a-Fe2O3/S 6.9 1.9 14/60 High-pressure Hg lamp 95% (AO7, a-Fe2O3/S showed little Fenton [106]
(AO7) 0.1 g/L power = 300 W; 14 min, vis); reactivity in the dark, but had an
Phenol OR 100% (AO7, excellentheterogeneous Fenton
Halogen lamp 60 min, UV); activity under either UV or
power = 1000 W; 85% (phenol, visible irradiation. Other kinds
[AO7] = 35 mg/L; 60 min, UV or of a-Fe2O3had no activation.
[Phenol] = 40 mg/L; vis)
WW vol. = 100 mL.
5d Reactive red 195 Iron(III)- 6 3 100 Visible light (9.65 W/ 79% (TOC) The catalytic activity is affected [107]
(RR195) alginatefiber cm2, wavelength by Na2SO4or NaCl slightly and
complex = 400–1000 nm;) can keep at constant after four
5.0 g/L UV irradiation recycles of use.
Fe content is (365 nm; 2.51 W/cm2)
affected by the Fe [RR195] = 0.05 mM;
concentration T = 25 C.
during
preparation.
6 Rhodamine 6G Layered Fe- 6.5 0.5 (R6G) 15 Hg lamp 98% (R6G) Fe-titanates possess layered [108]
(R6G) titanate (R6G) 10.0 (MB) power = 500 W (305– 98.5% (MB) structures, and Fe3+ions located
Methyl Bule 0.3 g/L 5.6 (MB) 11.7 (MO) 387 nm); 97%(MO) in the interlayer. The leakage of
(MB) 6.7 R6G Con. = 5.99 mg/L; Fe is almost negligible under
Methyl Orange (MO) MB Con. = 23994 mg/L; optimal pH and can be used for
(MO) MO Con. = 19640 mg/L; at least 4 cycles with effective
vol. = 30 mL; remove of pollutants.
T = 25 C.
7 Petroleum Nanozero-valent 3 5 60 UV lamp power 95.8%(TPH) Degree of significance for TPH [38]
hydrocarbon iron = 125 kW; Con., nZVI dosage, H2O2dosage,
(TPH) 0.02 g/L UV pH and reaction time are 7.643,
wavelength = 247.3 nm; 9.33, 13.318, 15.185 and 6.588%,
[TPH] = 0.7 mg/L; respectively. Photo-Fenton like
T = 24–26 C. process using nZVI could be
used as a pretreatment.
8 Neutral Red Copper 8 (NR) 4.0 (NR) 120 Tungsten lamp power 75% (NR, COD) Degradation accord with [92]
(NR) Pyrovanadate 6 (AB) 5.0 (AB) = 200 W; 60% (AB, COD) pseudo-first-order reaction, rate
Azure-B (AB) 0.05 g/L (NR) T = 25 C; constant is 2.081 104 s1and
0.06 g/L (AB) [NR]=7 105 M; 3.876 104 s1for neutral red
[AB] = 1.2 105M; and azure-B. The catalyst
WW vol. = 1 L. activity decreases slightly, only
around 5% in the 5th run after
30 min reaction.
9 Orange II (O2) Cu/MCM-41 7 14.4 120 UV-C lamp power 70% (TOC) TOC removal rate keeps [93]
1.0 g/L = 8 W; constant after four cycles. The
[O2] = 0.3 mM; leaching of the developed
WW vol. = 200 L; catalyst is below 0.5 mg/L.
T = 35 C.
10 Fe3+ WW contain 2.5–5.5 3900 1080 Medium-pressure 93% (COD) In the experiment of the real [99]
high mercury-vaporized naval desusting WW, H2O2was
Table 2 (Continued)
efficiency
time
(min)
Citric acid and concentration Fe3 lamp power = 450 W; added multiple times, and the
COD in naval + ion and no need UV energy-40-48%, treatment efficiency is better
derusting WW to add it Visible energy-40–43%, using multiple points than that
externally. Infrared-the rest; in one point.
WW COD = 46700 mg/
L;
WW vol. = 800 mL;
T = 40 3 C.
11 K-acid Fe3+ 3 30 60 UV-C-2.5 W/m2; 99% (K-acid) The treatment efficiencies of K- [100]
28.0 mg/L (UV-A-8.1 W/m2; 95% (COD) acid WW are similar under UV-
Visible light-6.0 W/ 90.5%(TOC) C, UV-A or visible light
m2); respectively. The degradation
[K-acid] = 715 mg/L; route of K-acid would be
WW COD = 450 mg/L; multistep hydroxylation via HO
WW TOC = 130 mg/L. attack and desulphonation or
the addition of HO to the carbon
atom bearing the sulphonate
group.
12 Bromocresol Fe3+ 3 0.1 60 Three low pressure 100% (BCG) Results showed that color [97]
green (BCG) 5.6 mg/L mercury lamps total removal followed the increasing
power = 45 W; order: Fe(III)/H2O2 < Fe(II)/
[BCG] = 6 105 M; H2O2 < Fe(II)/H2O2/Solar < Fe
WW vol. = 100 mL. (II)/H2O2/UV254nm < Fe(III)/
H2O2/UV254nm.
13 Phenol red (PR) Fe3+ 3.5 0.12 mL 130 Tungsten lamp power 94% (PR) The ferric ions on exposure to [98]
1.7 mg/L 30% = 200 W; light generate a proton and OH
Light radicals and it isreduced to
intensity = 60 mW/cm; ferrous state. These ferrous ions
[PR] = 1.33 104 M. further react with
H2O2producing OH and
oxidized back to ferric ions.
14 Inderal Fe3+/catechin 6 H2O2was 120 Xenon short-arc lamp 75% (inderal) The degree and rate [53]
50.0 uM (Fe3+) generated by power = 150 W; ofInderaldegradation at near-
200.0 uM the wavelength > 300 nm; neutral pH were markedly
(catechin) photochemical [Inderal] = 10 mM; increased upon use of the Fe(III)-
process. WW vol. = 50 mL. catechin complex.
15 Antibiotic Fe3+/oxalic acid 7 4.4 60 UV power = 30 W; 96.70% Coagulation process was used [109]
fermentation Fe3+ comes from UV (decolorization) before the photo-Fenton-like
the coagulant wavelength = 254 nm; 93.50% (COD) process.
( [Oxalic acid] = 45 mg/L;
polyferricSulfate) T = 20 2 C.
after coagulation
process.
16 Diclofenac Cu2+ 7 10 240 Six 4-W Black Light 47% (DCF) The UV/Cu(II)/H2O2system is [95]
(DCF) 1.0 uM Blue lamps; 66%(CBZ) much more efficient than the Cu
Carbamazepine Max (II)/H2O2systemdue to the
(CBZ) wavelength = 365 nm; enhanced reduction of Cu(II) by
[DCF] = [CBZ] = 1 mM; HO2or O2
T = 22 2 C.
17 Methel orange [Cu(HL)Cl] (1) 6.5 for 24 2 UV power = 300 W; 97% (MO, for The photocatalytic property of [39]
(MO) OR (1); [MO] = 2 105 M; (1)) this type of complex has some
[Cu(HL)Br] (2) 6.7 for Ambient temperature. 88% (MO, for relationship with structure.
3.11 106 M 2 (2))
HL is the
multidentate
schiff base N-[(2-
oxy-acetate)-
benzyl]-2-
aminotha-nol
18 Crystal violet Soluble bio- 7 0.24 300 Medium- 66.7 Dissolved organic matter (DOM) [103]
(CV) organic pressuremercury arc (decolorization) has received much attention
substances (SBO) lamp power = 125 W; from researchers in recent years
25.0 mg/L wavelength > 300 nm; because of its photochemical
[CV] = 10 mg/L; properties. SBO was isolated
T = 25 C. from urban biorefuses.
a
b
c
Vol. represents volume; T represents temperature.
d
The adsorption plays an important role in the treatment of WW.
offered a global perspective on the experimental setup transportation. In addition, in the electro-Fenton-like processes
including laboratory scale and pilot scale equipment based this kind of H2O2 can also be consumed prior to being decomposed
on a general introduction of electro-Fenton-like processes. to H2O and O2. This property gives higher selectivity for the
Brillas [111] introduced electro-Fenton processes in detail and targeted reactions [115].
proposed that the oxidation capacity of electro-Fenton process- Secondly, besides the generation of H2O2 in situ, a homogeneous
es comes from the attack of (OH)-O-center dot on the anode metal catalyst Mn+ (such as Fe2+, Mn2+, Cu2+, and Co2+
surface and in the medium where Fenton reaction occurs. In [40,42,114,116]) can either be supplied by sacrificing the corre-
addition, the removal of industrial chemicals, the effect of sponding metal anode directly or regenerated on the surface of
experimental parameters, the decay kinetics of contaminants, cathode after external addition of metal ion. The reaction for
and the corresponding intermediates were discussed. Yu et al. regenerating active metal catalyst on the cathode surface is shown
[112], based on the application of Boron-doped diamond, in reaction Eq. (11).
presented the important parameters of the electro-Fenton
processes when treating three sorts of bio-refractory organics Mðnþ1Þþ þ e ! Mnþ ð11Þ
(pharmaceuticals, pesticides, and dyes). Nidheesh and Gandhi- Due to the advantages mentioned above, the EF-like processes
mathi [113] verified the effectiveness of electrochemical has been studied and used widely for the degradation of various
reactions in a bubble column reactor. organic pollutants, including dyes [117], pesticides [118], amines
For the electro-Fenton-like processes, the source of the oxidant [119], and phenolic compounds [120].
and catalyst is diverse. Firstly, in both hetero- and homo-geneous Actually, homogeneous EF-like processes can be classified into
Fenton-like processes, H2O2 can be generated in situ via a two- five categories by differentiating the sources of H2O2 and the
electron reduction of dissolved oxygen on the surface of the catalyst, while the heterogeneous EF-like processes is relatively
cathode in an acidic solution when electrochemical process is simple (providing the heterogeneous catalyst externally and
applied (reaction Eq. (10) [114]). generating H2O2 in situ on the surface of cathode by bubbling
oxygen/air). The five kinds of homogeneous EF-like processes are
O2 þ 2Hþ þ 2e ! H2 O2 ð10Þ
as follows [41,43,114,116,121–128]:
The production of H2O2 in situ via an electrochemical processes
is beneficial for an increase in the organics degradation efficiency, a (1) Peroxi-coagulation (PC) process (Fig. 5a) . In this process,
decrease in the cost, and a reduction in the risks associated with H2O2 is generated in situ on the cathode surface by bubbling
Fig. 5. Typical electro-Fenton-like systems [43].

Fig. 6. Degradation mechanism of dye in magnetite-catalysed Fenton-like process [131].
air/oxygen and the metal ion catalyst is provided by a sacrifice then the reaction could be terminated or become slower. In order
anode. to solve this problem, the development of a kind of composite
(2) EF-Fere process (Fig. 5b). H2O2 and the metal ion catalyst are electrode with catalytic capacity could be a good idea. Liu et al.
both added externally and the metal ion catalyst is regenerated [115] applied Co3O4–graphite composite as the electrode to treat
by reduction of the cathode. organic pollutants in WW (see No. 2 in Table 3). This study showed
(3) Electrochemical peroxidation (ECP) process (Fig. 5c)/Anodic that the degradation of organics presented pH-independence
Fenton treatment (AFT) process (Fig. 5d). In these two within a wide range of pH (2.0–10.0).
processes, H2O2 is added externally and the metal ion catalyst
is provided by a sacrifice anode. The difference between them 3.3. Cavitation-Fenton-like processes
simply arises from either using or not using a salt bridge, i.e.,
the use of undivided or divided cells. Two kinds of cavitation can be used in WW treatment, i.e.,
(4) H2O2 is generated in situ on the cathode surface by bubbling acoustic cavitation and hydrodynamic cavitation. Acoustic cavita-
air/oxygen and metal ion catalyst is added externally and tion is always generated by the passage of high frequency sound
regenerated by reduction of the cathode. waves, i.e., ultrasonic (US), whereas hydrodynamic cavitation can
(5) H2O2 is generated in situ on the cathode surface by bubbling occur when the pressure varies in the fluid due to a sudden change
air/oxygen and the homogeneous catalyst (including the metal in the linear flow rate of the fluid [133,134].
ion catalyst mentioned in the above four items and other
soluble catalyst such as PW11O39Fe(III)(H2O)4 [127]) is
provided externally.
EF-like processes has been studied by many researchers and

exhibit excellent capacity to treat organic WW. Babuponnusami
and Muthukumar [37] applied nano zero-valent iron (nZVI) to treat
phenol WW (see No. 3 in Table 3) due to the high reactivity of nZVI.
When the pH was 6.2, 100% of the phenol was removed within
30 min. Wang et al. [127] developed a Keggin-type iron-substituted
heteropolytungstate anion as the homogeneous Fenton-like
catalyst and treated dimethylphthalate WW successfully at pH
6.86 within 80 min (see No. 8 in Table 3). In addition, the use of
NaHCO3 was also reported because it can enhance the generation
of HO in the electro-Fenton processes where graphite was used as
electrode [129,130]. To achieve satisfactory WW treatment,
Nidheesh et al. [131] presented a typical mechanism for the
heterogeneous Fenton-like processes, which is catalysed by
magnetite (see Fig. 6). Some other typical studies are presented
in No. 1, 4–7 in Table 3.
Generally speaking, the EF-like system requires an acidic
situation. If the pH is close to neutral or an alkaline condition
exists, the metal catalyst will precipitate from the solution and
Fig. 7. Typical scheme of acoustic cavitation.
Table 3
Study conclusion of Fenton-like process combined with electrochemistry.
NO.a Pollutant Catalyst Dos. Experiment conditions Treatment Additional information Ref.
/Cathodeb efficiency
time (min)
1 Lissamine Green Acid mine 2 H2O2was 60 (LGB) Electrodes are graphite 99% (decolorat- The decoloration rate of LGB is [41]
B (LGB) drainage sludge/ generatedin situ. 180 sheets with 60 mm ion of LGB); 87% at pH 6 after 60 min; AMDS
Pirimicarb alginate gel (pirimicar- distance; 98% (degradati- can act as a catalyst at pH 6,
beads (AMDS/ b) Electrolyte is on of because metal will leach out at
AB) Na2SO4with 0.01 M; pirimicarb) pH 2; alginate gel beads was
20.0 g/L Fe Voltage = 5 V (DC); used to immobilize the metal on
concentration is [LGB] = 10 mg/L; AMDS in order to stop the
26350 ppm [Pirimicarb] leaching of metal when AMDS
= 100 mg/L; works at low pH.
WW vol. = 0.15 L.
Air flow rate = 1 L/min
(cathode surface,
started 10 min ahead
of time)
2 Sulforhodamine Co3O4-graph-ite 2.0– H2O2was 150 (SRB) Cathode is Co3O4- 100% (SRB) The removal rate of SRB did not [115]
B (SRB) cathode 10 generated by 240 (2,4- graphite; 98.60% (2,4- decrease obviously after catalyst
2,4- Co3O4-graphite DCP) Anode is Pt net DCP) was used for five times; The
Dichlorophenol cathode from pH (1.0 cm2); Co3O4- graphite composite
(2,4-DCP) 2–10. Electrolyte is electrode displays good
Na2SO4with 10 g/L; electrochemicalcharacteristics
Voltage = 6 V (DC); and can produces H2O2and OH
[SRB] from pH 2–10.
= 1.0 105 M;
[2,4-
DCP] = 1.0 103 M;
WW vol. = 50 mL;
T = 20 C.
3 Phenol Nano zero- 6.2 14.7 30 Electrodes are 100% (Phenol) The removal rate constant (kobs) [37]
valent iron stainless steel with was proportional to the NZVI
0.5 g/L 50 mm distance; and H2O2dosage and inversely
Surface area of proportional to the initial phenol
electrodes = 25 cm2; concentration and initial pH of
Current the solution; H2O2can be
density = 12 mA/cm2; generated also by electrolysis in
Electrolyte is the system.
Na2SO4with 1 g/L;
Low pressure mercury
lamp = 8 W (254 nm);
[Phenol] = 200 mg/L;
WW vol. = 1 L.
4 Methyl Orange Fe3+ 120.0 mg/L 3 H2O2is produced 90 Cathodeand anode are 100% Response surfacemethodology [132]
(MO) electrochemically bothgraphite; (decolorazation) was selected to optimize the
via oxygen Current = 2.1 A; 96.93% (COD) operating conditions. NaCl was
reduction onthe [MO] = 106 mg/L; used to supply the active
cathode. [Cl] = 16.36 mM; chlorine.
[Na2SO4] = 0.05 M;
WW vol. = 500 mL;
O2 flow rate = 1 L/min.
5 Metomyl Fe3+ 5.6 mg/L 3 H2O2was 200 Cathode is carbon belt; 100% (Metomyl) Fe(III) was the most efficient [124]
produced from Anode is Pt grid; 98.20% (COD) catalyst compared with cobalt,
reduction of Current = 200 mA; silver, and copper. metomyl
O2dissolved in the [Metomyl] = 200 g/L degradation obeyed apparent
solution Lannate Vol. = 150 mL; first-order reaction kinetics.
[Na2SO4] = 0.05 M;
Room temperature.
Air was bubbled for
10 min through the
solution at about
1 L/min.
6 Rhodamine B Fe0 15.0 mg/L 2.5 H2O2was 180 Cathode and anode are >90% (RhB) The rate of RhB removal at [121]
(RhB) Fe3+ 5.0 mg/L generatedin bothgraphite; optimum catalysts
situby adding Voltage = 8 V; concentrations follows the order
cathodic [RhB] = 10 mg/L; of Fe0 > Mn2+ > Fe3+ > Fe2+ > Cu2+;
potentialand Room temperature. ferric ions was the best catalyst
bubbling air. for the RhB removal with a less
concentration of 5 mg/L.
7 Glyphosate; Mn2+ 3 H2O2was 60/360 Cathode is carbon belt; 95% (Glyphosa- The high mineralization degree [42]
Aminome-thyl 5.5 mg/L generatedin situin Anode is Pt; te, 60 min) for glyphosate solutions
phosphonic Acid the treatment Current = 100 mA; 100% (AMPA, revealed thegreat performance
(AMPA) process. [Glyphosate] = 0.1 mM; 360 min) of the EF-like process with Mn2+,
WW vol. = 200 mL; which promotes the C–N
[Na2SO4] = 0.05 mM; cleavage by HO attack as the
T = 23 2 C.
Table 3 (Continued)
NO.a Pollutant Catalyst Dos. Experiment conditions Treatment Additional information Ref.
/Cathodeb efficiency
time (min)
first step and the C–P cleavage in
a further step.
8 Dimethyl- Keggin-type iron 6.9 H2O2was 80/120 Cathode is graphite; 100% (DMP, The reference electrode was Ag/ [127]
phthalate (DMP) substituted generatedin Anode is platinum 80 min) AgCl (3MKCl). The application of
heteropolytu- situby adding flake; 56% (TOC, a cathodic potential is necessary
ngstate anion cathodic Cathodic 120 min) for DMP removal because it
(PW11O39Fe(III) potential-nd potential = 0.5 V; reduces O2in solution to H2O2in
(H2O)4) 1.0 mM bubbling oxygen. [DMP] = 0.1 mM situat the graphite electrode and
[DMP] = 20 mL in poses reduction of Fe(III) to Fe
cathodic (II), which further catalyses
compartment. H2O2reduction to HO.
O2flow rate = 60 mL/
min.
a
b
c
Cavitation provides an effective alternative to degrade organics. with enormous force, resulting in the activation of the surface of
The formation of cavitation microbubbles is the direct trigger. The the catalyst. In the case of shockwave damage, the enhancement
microbubbles can grow continuously until they reach a critical size, effect involves the damage of shock waves generated by cavitation
which can cause a violent implosive collapse. The rapid implosion bubbles collapsing near the solid surface in the liquid phase.
of cavitation bubbles is followed by a localized extremely high In organic WW treatment, in order to combine the advantages
temperature and high pressure of about 5000 C and 500 atm, of cavitation and a Fenton-like process, they must be applied
respectively [135–137]. Under this kind of extreme conditions together. The enhancement effect of cavitation to Fenton-like
water can be transformed into different oxidizing species via processes in homogeneous and heterogeneous systems are
pyrolysis, such as H, HO, HO2, and H2O2 [44,138]. A typical different. In the homogeneous system the extremely high
scheme for acoustic cavitation and an ultrasonic-Fenton/Fenton- temperature and the presence of oxidizing species generated
like system are shown in Figs. 7 and 8, respectively. The by cavitation are the main reasons for this enhancement, while in
hydrodynamic cavitation can be generated by the orifice plate the heterogeneous system the activation effect of the cavitation
and/or slit venturi at the laboratory scale [133,134,137]. on the surface of solid catalyst could be the main mechanism.
In the liquid–solid system, however, the mechanism of Zhou et al. [141] showed that cavitation could play an acceleration
enhancing Fenton-like processes by the cavitation bubbles is role when combined with the UV/Fe3O4/oxalate system. Huang
different from that in the homogeneous system mentioned above. et al. [142] applied Fe3O4 nanoparticles as well as a heterogeneous
First of all, the energy needed to produce cavity nucleation is lower catalyst to treat bisphenol A (BPA). The study results showed that
due to the existence of the solid-liquid interface [140]. Secondly, Fe3O4 nanoparticles performed a better activity in the cavitation-
microjet impact and shockwave damage [136] near the solid Fe3O4–H2O2 system than that in the Fe3O4–H2O2 system; BPA can
surface can occur when the cavitation bubbles collapse. In the case be degraded in a wide pH range. In addition, Fe3O4 nanoparticles
of microjet impact, the asymmetry environment near the solid can be used as many as 5 times while still maintaining good
surface makes the cavitation bubbles collapse dissymmetrically, stability and activity. Some other studies associated with the
resulting in a fast-moving stream of liquid toward the solid surface cavitation-Fenton-like processes have been summarized in
with velocities >100 m/s. The microjets hit the surface of the solid Table 4.
3.4. Microwave-(another physical field)-Fenton-like processes
Microwave (MW) radiation is a wavelength band of the

electromagnetic spectrum with frequencies ranging from
300 MHz to 300 GHz [74,151]. Only frequencies of 2450 and
915 MHz are permitted for use in non-military applications. MW
has attracted much attention in organic WW treatment because of
its unique heating mode. MW irradiation can penetrate many lossy
media (such as water, transition metal oxides, and activated
carbon). When dipole molecules are subjected to a MW field,
rotation of the dipoles occurs immediately but cannot adequately
follow the direction variation rate of the MW field. This causes a
time delay and then causes a huge amount of energy to be
consumed, which is expressed by thermal effects [152,153]. Due to
the non-uniformity of MW irradiation, “hot spots” can be
generated on the surface of the MW absorbent; this is an
extremely important feature of MW radiation as chemical
reactions can be enhanced by the “hot spots” effect. Another
important feature, namely the non-thermal effect, cannot be
Fig. 8. Typical ultrasonic-Fenton/Fenton-like system [139].
Table 4
Study conclusion of Fenton-like process combined with cavitation.
NO.a Pollutant Catalyst Experiment conditions Treatment Additional information Ref.

Dos.b efficiency
pH H2O2Dos. Reaction Othersc
(mM) time
(min)
1d BPA Tourmaline 2 50 120 US power = 500 W; 98.40% (BPA) The experiment result was due to the [56]
5.0 g/L US synergism of homogeneousoxidation, a
frequency = 40 kHz; heterogeneous Fenton-like process and
[BPA] = 5 mg/L; cavitation effects of ultrasonic irradiation.
WW vol. = 150 mL.
2 C.I. Acid Orange 7 Goethite 5 7.8 30 US power = 80 W/L; 90% The decolorization reaction mainly takes place [143]
(CIAO7) 0.4 g/L US frequency (decolorization) on the surface of goethite; More aggressive
= 20 kHz; conditions are required to achieve higher TOC
T = 20 C; removalthan those employed to simply break
[CIAO7] = 79.5 mg/L; the chromophore group.
WW vol. = 250 mL.
3e Direct Orange 39 Goethite 3 294 90 US max 97% (DO39) The kinetics of decolorization accord with first- [144]
(DO39) 10.0 g/L power = 120 W; order reaction and the rate constant was
Fe account US 0.0189 min1.The variations of catalyst and
for 32.7% frequency = 35 kHz; H2O2dosage did not affect the iron dissolution.
(wt%) Temperature = 25 C; After four cycles of use, catalyst capacity did not
[DO39] = 0.01 g/L; decrease obviously.
WW vol. = 500 mL.
4 4-chloroph-enol Zero valent 7.2 H2O2was 60 US power = 385 W; 100% (4CP) 4CP and EDTA were found to follow pseudo [145]
(4CP) iron (ZVI) generated US frequency 83% (EDTA) first-order degradation kinetic in the US/Fenton
EDTA 25.0 g/L by ZVI/ = 20 kHz; 76% (TOC) like system at neutralpH; Ultrasound presented
EDTA T = 20 C; significant positive effect on the degradation of
ligand. [4CP] = 100 mg/L; 4CP andEDTA.
EDTA
Con. = 0.32 mM;
WW vol. = 400 mL.
Air/Argon flow
rate = 1.0 L/min.
5 Reactive Black 5 ZVI 25.0 g/L 6.8 Self- 180 US 100% (RB5) UV was used to improve the Fenton-like [146]
(RB5) produced frequency = 20 kHz; 96.5% (EDTA) system, but no improvement was observed.
EDTA in reaction [RB 5] = 200 mg/L; 68.60% (TOC)
system [EDTA] = 0.4 mM; 92.20% (COD)
WW vol. = 500 mL;
Purified was
supplied at the flow
rate of 1.0 L/min.
6 1-Alkyl-3- Nano ZVI 3 60 120 US power = 300 W; 92% ([C4mim] The degradation of [Cnmim]Br accords with the [147]
methylimidazolium 0.25 g/L US frequency Br) second order kinetics. This is the first report to
bromides = 45 kHz; illustrate the degradation pathway and kinetics
([Cnmim]Br, T = 30 C; of [C4mim]Br in US-nZVI/H2O2system.
n = 2,4,6,8,10) [[Cnmim]
Br] = 2.0 mM;
WW vol. = 25 mL.
7 Phenol ZVI 0.6 g/L 3 70.6 60 US power = 180 W; 100% (Phenol) H2O2can be generated in the US-Fenton-like [44]
Zero valent US frequency 37% (TOC) process, and the generation rate in acidic and
copper = 300 kHz; higher US frequency is higher than that in other
(ZVC) 5.0 g/ T = 20 5 C; circumstance. ZVC catalytic capacity is obvious
L [Phenol] = 2.5 mM; weaker than that of ZVI via the comparison
WW vol. = 100 mL. study in 20 kHz of US.
Air flow rate
= 1.5 L/min.
8 Bisphenol A (BPA) Nano-ferr- 7 160 480 US power = 100 W; 96% (BPA) Steel pickling waste liquor was employed to [142]
oferric US frequency 45% (TOC) obtain Fe3O4nanoparticles to utilize resources
(Fe3O4) = 40 kHz; comprehensively and reduce the cost of
0.6 g/L T = 35 1 C; preparation; catalyst showed good stability and
[BPA] = 20 mg/L; activity even after five recycles.
WW vol. = 200 mL.
9 Nitrobenzene (NB) Nano 7 10 15 (nano US power = 100 W; 100% (NB) a-Fe2O3is a poor catalyst in usual [45]
a-Fe2O3 a-Fe2O3) US frequency heterogeneous Fenton but shows a different
1 g/L 25 (CuO) = 20 kHz; activity when combined with ultrasonic.
T = 25 2 C
[NB] = 10 mg/L.
10 Acid orange 3 (AO3) Coal fly ash 3 5.4 160 US power = 250 W; 96% (AO3) The reaction accord to the Behnajady’s kinetic [148]
2.5 g/L US model; although some linkage of AO3 was
frequency = 25 kHz; broken, complete mineralization dose not been
Room temperature; achieved.
[AO3] = 100 mg/L;
WW vol. = 50 mL.
11 Phenol Coal fly ash 6 1.5 300 US power = 500 W; 88% (phenol) Coal ash can provide active sites for phenol [149]
1.0 g/L US frequency degradation; too high concentration of H2O2in
Fe account H2O2/coalash/ultrasonic system would reduce
= 40 kHz; the degradation rate.
Table 4 (Continued)
Dos.b efficiency
(mM) time
(min)
for 7.35% T = 25 C;
(wt%) [Phenol] = 10 mg/L;
WW vol. = 100 mL.
12e C.I. Direct Black 168 Coal fly ash 3 2.9 90 US power = 250 W; 99% (CIDB 168) Three kinds of solid catalysts, namelyfly ash, [135]
(CIDB 168) 2.0 g/L US kaolinite or diatomaceous were examined. The
Fe2O3 frequency = 40 kHz; degradation of dye was 99.0%, 92.2% and 88.3%,
account for T = 40 2 C respectively within 90 min.
5.38% [CIDB 168]
(wt%) = 100 mg/L;
WW vol. = 50 mL.
13 p-Chlorobe-nzoic FeOOH 3 20 60 US 66% (p-CBA) The higher apparent rates of US/FeOOH– [150]
(pp-CBA) 2000.0 mg/ frequency = 20 kHz; H2O2system versus FeOOH–H2O2alone was due
L Power to the continuous cleaning and chemical
density = 76 W/L; activation of the FeOOH surface by the chemical
[p-CBA] and physical effects of ultrasound.
= 3.19 103 M;
WW vol. = 150 mL;
T = 20 C.
14 Diazinon Co2+or Ag+ 3 2.94 60 US 40.10% The toxicity of the diazinon was obviously [46]
10.0 mg/L frequency = 20 kHz; (diazinon, for reduced by a sono-Fenton process. The most
US power = 100 W; Ag+) important mechanism of degradation was the
[diazinon] 9% (TOC, for substitution of sulfur by oxygen on the P=S
= 50 mg/L; Ag+) bond in diazinon through oxidation.
WW vol. = 1000 mL; 35% (diazinon
T = 25 C. Co2+)
7% (TOC for
Co2+)
a
b
c
d
Both of the adsorption and the homogeneous contribution are responsible as well for the treatment of WW.
e
The adsorption plays an important role in the treatment of WW.
ignored either. This refers to other effects besides the thermal The proposed reason is that after the absorption of MW radiation
effect, including the chemical effect, electrical effect, and magnetic each H2O2 molecule can be activated and then divided into two
effect [154–156]. HO more easily. In heterogeneous Fenton-like processes, it was
The combination of MW irradiation with the Fenton-like found that MW irradiation could obviously enhance the photo-
processes has shown obvious superiority compared with the catalytic activity of a catalyst with a high defect density by the
Fenton-like process alone. As shown in Table 5, within a relatively polarization effect, i.e., MW radiation can promote the transition of
short reaction time ( 7 min) when compared with the Fenton-like electrons excited by photons to the catalyst surface and then
process alone (see Table 1), many kinds of organic WW have been decrease the possibility of recombination of the electron-hole pair
treated effectively in both MW-assisted homo-/hetero-generous [157].
Fenton-like processes. In the MW-assisted heterogeneous Fenton- The combination of UV and MW irradiation can be realized
like processes (No. 1–3 in Table 5), we find that the catalyst can conveniently by the use of MW electrodeless ultraviolet (MWEUV)
always be reused several times (even at least 8 times, with the lamp, which has been used in organic photochemistry since 1999
leaching of a small amount of catalyst (No. 3 in Table 5)). [158]. A MWEUV lamp is a glass cavity that is filled with an
In addition to the combination of the Fenton-like process with excitable substance (usually a metal) and an inert/noble gas and
the single MW field mentioned above, the combination of the then sealed under a low-pressure condition (0.266–2.66 kPa).
Fenton-like process with two kinds of physical fields (including the Under MW irradiation, the inert gas in the glass cavity can be
MW field) was also studied. However, this kind of study has not ionized by the collision of accelerated electrons (separated from
attracted enough attention by researchers; only a minority of the environment by the ambient energy), and then more electrons
studies were conducted. First of all, MW irradiation has shown a will be released by the collision over a short period of time. After
positive effect on electro-Fenton-like processes by accelerating the that, the huge number of electrons released can excite the metal
reduction of Fe(III) to Fe(II). The possible reason was that “hot atoms inside the cavity to higher energy levels, and finally, UV/
spots” could be generated on the surface of the electrode under visible light is emitted when the excited metal atoms return to the
microwave irradiation. These high temperature shear forces can be ground state [159]. A typical MW-UV-Fenton-like process is shown
helpful to promote the transduction of electrons to the cathode in Fig. 9. In this process, the MWEUV lamp was immersed in the
surface, and then accelerate the Fe(III) reduction. Wang et al. [114] reaction system and then excited by the MW irradiation. The MW-
showed that under MW irradiation, more HO can be generated in UV-Fenton-like process started after the MWEUV lamp was
the MW-electron-Fenton-like processes, which was 2.3 times illuminated.
higher than that in the absence of MW irradiation. Some studies associated with the MW-photo-Fenton-like
Furthermore, another representative work is the combination processes were conducted by Liao and co-workers [161,162]. In
of microwave radiation with photochemistry to improve the WW these studies, researchers developed two photo-catalysts, i.e., ZrOx
treatment efficiency. In the homogeneous Fenton-like processes, and ZrOx/ZnO, to treat organic pollutants in the WW. When ZrOx or
the MW-UV system could generate more HO via reaction Eq. (6). ZrOx/ZnO was used as catalyst, the study results showed better
Table 5
Study conclusion of Fenton-like process combined with MW-chemistry.

Dos.b efficiency
(mM) time
(min)
1 Rhodamine B Fe3O4 4 50 5 MW power = 300 W; 99% (RhB) Six cycle uses for RhB removal revealed that the [55]
(RhB) 1.3 g/L [RhB] = 100 mg/L; magnetic catalyst was stable, recoverable, highly
WW Vol. = 40 mL; active, and easy to separate using an external magnet.
T = 80 C.
2 2-nitrophenol CuO/Al 4 6 5 MW power = 300 W; 97% (2-NP) The apparent activation energy of 2-NP conversion [47]
(2-NP) 5.0 g/L [2-NP] = 200 mg/L; 79% (TOC) was estimated to be
WW vol. = 10 mL; 73.1 kJ/mol. The catalyst exhibited limited stability,
T = 60 C. after 4 experimental runs in acidic medium, the
catalyst activities decreased by about 4%.
3 4-nitrophenol CuO/Al2O3 6 25 6 MW power = 100 W; 93% The catalyst can be reused at least 8 times and still [163]
(4-NP) 40.0 g/L [4-NP] = 50 mg/L; (4-NP) keep the high catalytic capacity (more than 90% of 4-
WW vol. = 100 mL; NP was removed). The total leaching amount of
T = 70 C. copper after 5 cycles was less than 1%.
4 Pharmaceutical Fe3+ 4.4 38.2 6 MW power = 300 W; 57.50% BOD5/COD was enhanced from 0.165 to 0.470; MW-Fe [54]
WW 1372.0 mg/ COD = 49913 mg/L; (COD) (III)–H2O2process reduced the yield of sludge and
L WW vol. = 50 mL; improved COD removal efficiency; the qualities of
T = 28 C. sludge (such as settling and biodegradation quality)
were improved.
5 Pharmaceutical Fe3+ 6.5– 250 6 MW power = 539 W; 62% MW irradiation makes the catalyst dosage and [164]
WW 420.0 mg/ 7.1 COD = 1590-2200 mg/ (TOC) oxidant dosages were both reduced, and reaction
L L; time was shortened too.
TOC = 150–210 mg/L;
WW vol. = 1000 mL;
Coloration = 50.
6 Olive mill WW Cu2+ 4.7 3941.2 7 MW power = 680 W; 90% MW/H2O2 system use less treatment time compared [165]
(OMW) 200.0 mg/ COD = 74500 mg/L; (decolorizat- with UV/H2O2system; The removal of pollutants was
L [Polyphenols] = 16500 ion) most likely due to MW radiation rather than the
mg/L; 81.8% substitution of iron by Cu(II).
WW vol. = 100 ml. (phenolic
compounds)
a
b
c
catalytic capacity when compared with that of P25 TiO2. Under the Generally speaking, there are four advantages when iron-
optimal conditions, the TOC removal rates of dimethyl phthalate bearing minerals are applied as the catalyst: (I) the catalyst can be
(DMP) in WW were at least 84% when ZrOx or ZrOx/ZnO was used, removed from the treated WW easily by sedimentation and/or
which is at least 11% higher than that of P25 TiO2. In addition, the filtration; (II) the catalyst life can be extended by recycling the
degradation half-time of DMP was also shortened obviously (45%). catalyst from the treated WW; (III) the initial pH of the WW could
The proposed mechanism for the high activity of ZrOx could be be extended into the neutral range (such as pH 5–9); (IV) the
attributed to the co-existence of three Zr oxides with different reaction system is not affected much by inorganic carbonate
valences. This would induce higher electron and hole mobility [175].
under MW irradiation. Tourmaline is a kind of complex borosilicate mineral and has
the trigonal space group R3 m [176]. The general formula of
4. Catalyst types studied in hetero-/homo-geneous Fenton-like tourmaline may be written as XY3Z6 [T6O18][BO3]V3W, where
processes X = Ca, Na, K or vacancy; Y = Li, Mg, Fe2+, Mn2+, Al, Cr3+, V3+, or Fe3+;
Z = Mg, Al, Fe3+,V3+, or Cr3+; T = Si or Al; B = B; V = OH or O; and
4.1. Heterogeneous catalyst from natural minerals
In heterogeneous Fenton-like processes natural mineral mate-

rials with special crystal structures or properties have been studied
as excellent alternative catalysts because of their high catalytic
activities and long-term stabilities [166]. Fenton-like processes
using mineral materials as the catalyst are called mineral-
catalyzed Fenton-like processes and most of the catalysts used
are natural iron-bearing mineral materials, such as schorl [35–83],
goethite (a-FeOOH) [167,168], pyrite (FeS2) [61], hematite
(a-Fe2O3) [169,170], magnetite (Fe3O4) [131–172], ferrihydrite
[173], and lepidocrocite [105]. Garrido-Ramirez et al. [174] have
given a detailed introduction on the application of iron-oxide
minerals in their review (while clays-based and nano catalysts are
also introduced), which is helpful to improve our understanding of
the catalysts associated with the natural mineral.
Fig. 9. Typical MW-UV-Fenton-like system [160].
W = OH, F, or O [177,178]. Members of the tourmaline group of The application of a composite makes it possible to reuse the active
minerals can be classified according to which metal element metal element because of the composite’s property of being easily
occupies the place of Y, such as schorl (Y = Fe2+), dravite (Y = Mg), separated from treated WW by means of the precipitation method.
tsilaisite (Y = Mn), olenite (Y = Al), and elbaite (Y = Li, Al) [179]. The This could reduce the cost of WW treatment as mentioned in
basic structural units are hexagonal rings of T6O18 that form the Section 2.3.
basal plane and are connected with Na, Li, and Al octahedra and Considering clay-based catalysts as an example, clay has been
distorted BO3 groups in planar coordination along [0 0 0 1] with a used widely as a catalyst support because it is relatively cheap
three-fold symmetry structure [180]. Tourmaline can generate an when compared with other catalyst supports. Many kinds of clay-
electrostatic charge when it is subjected to a tiny pressure and/or based catalyst were developed in recent years, such as Fe/laponite
temperature variation. The previous study, which uses the model [185], montmorillonite [186], Cu–Al/montmorillonite [187], and
predictions method, has shown that organic compound oxidation Fe/bentonite [188]. In these studies, the organic pollutants in WW
rates in mineral-catalyzed Fenton-like systems were improved were treated effectively (pollutant removal rate > 95% and TOC
when electrostatic effects were taken into account [171]. Hence, removal rate
45%) under the optimum operating conditions.
the electrostatic charge generated by tourmaline would have a In addition to clay-based catalysts, other kinds of catalyst can
reinforcement capacity for the Fenton-like reaction. exhibit excellent catalytic performances as well. As shown in
Schorl, one kind of well-known mineral of the tourmaline previous studies (No. 6–9 in Table 1, No. 3–6, 9 in Table 2, and No.
group, has been studied widely as a heterogeneous catalyst in 2 in Table 5), many bio-refractory contaminants (Chicago Sky Blue,
organic WW treatment. In addition to its natural property of Methyl Orange, Reactive Red, Rhodamine 6G, Reactive Organic 29,
bearing iron, the characteristics of pyroelectricity and piezoelec- aniline, and m-nitrophenol, etc.) have been eliminated effectively
tricity are also rather attractive [181], which can improve the (70–97% removal rate of pollutants, at least 70% TOC removal rate)
catalysis process in the Fenton-like processes. As shown in No. 1– at the optimum treatment time (3–160 min) by the composite-
4 in Table 1, two kinds of azo dye (Argazol Blue and Rhodamine B) catalysed Fenton-like processes.
WW were studied using schorl as the heterogeneous catalyst. We However, we should pay attention to the effect of the support
can see that the treatment time would be shorter when more on the catalytic activity. Supports with highly porous natures, high
schorl catalyst is used; a discoloration rate of more than 98% was stabilities, and large surface areas are preferable. The supports
achieved within 4 min when the catalyst dosage was at least 10 g/L. used frequently in recent years include, but are not limited to: clay,
In addition, the pH values shown in No. 1–4 in Table 1 are all the activated carbon, zeolite, silica, fibers, alumina, fly ash, and
optimum pH value in the cited papers. Although all of the studies magnetite. Navalon et al. [189] gave a specific and detailed
were conducted under acidic situations, organic pollutants can discussion of the effect of the clay’s structure in their review paper,
actually also be treated effectively under neutral conditions, which while Nidheesh [190] presented a clear introduction of heteroge-
are illustrated clearly in these studies. neous Fenton-like catalysts used in WW treatment in a wide range
Besides the tourmaline group, many other iron-bearing mineral of WW treatment processes.
materials are also used in WW treatment. Pyrite can always be Sometimes a composite material can also act as a catalyst in the
found in the vicinity of coal and metal ore mines [182]. As an iron form of an electrode. In recent years, cobalt oxide (Co3O4) has
sulphide mineral, pyrite has a high reactivity capacity due to its attracted much interest due to its unique physical and chemical
high specific surface area and porosity, which makes pyrite properties. Research has showed that the 3 d orbitals of the Co ions
susceptible to being oxidized by an oxidant (H2O2, Fe3+, and O2, displayed a significant catalytic effect in a Fenton-like system [115].
etc.) [36]. Goethite is the most common form of iron oxide mineral According to this property, Liu et al. [115] developed a novel
that can be found in the oxic soils of temperate regions. Its ubiquity composite electrode by pressing Co3O4 and graphite together. The
and high catalytic activity enable it to be a useful, naturally- Co3O4-graphite composite electrode displayed excellent electro-
occurring catalyst in Fenton-like systems for the treatment of chemical characteristics and can produce H2O2 and HO within a
contaminated soils and groundwater systems [170]. Hematite is a wide pH range (2–10). Meanwhile, the target pollutants (sulfo-
kind of accessory mineral that is distributed in many kinds of rock. rhodamine B and 2, 4-dichlorophenol) were both degraded
The iron content in hematite could be more than 70%, so it is an effectively (more than 98% of removal rate) under the optimum
important kind of iron ore. Magnetite is one of the most stable reaction conditions (see No. 2 in Table 3).
mixed-valence oxides (Fe2+–Fe3+) at ambient temperature, and it is
the most abundant in natural settings [101]. After modification, all 4.3. Heterogeneous catalyst from nano materials
of the ores mentioned above can be used as effective heteroge-
neous Fenton-like catalysts. According to the study results, more Nano materials have attracted the attention of many research-
than 50% mineralization, a 70% COD removal rate, and more than ers in WW treatment field due to their large surface areas, which is
90% discoloration/degradation were achieved (see No. 5 in Table 1, the important and special feature of nano materials. The large
No. 1, 2 in Table 2, and No. 2, 3 in Table 4) within 2 h. surface area makes nano materials exhibit many advantages in the
chemical catalysis field, such as low diffusion resistance, easy
4.2. Heterogeneous catalyst from composite by artificial synthesis accessibility to reactants, and a large number of active sites [45].
They can be synthesized by several common methods, such as
Many composites have been studied for use as heterogeneous chemical co-precipitation [45–192], the hydrothermal method
catalysts in Fenton-like processes, such as Fe2+/AC [17], a-Fe2O3/S [193], and different physical assistant methods (including the
[106], CuO/Al [47], Fe2+/Magnetic NdFeB-AC [51], layered Fe- Langmuir–Blodgett technique [194], g-ray radiation [195], and
titanate [108], FeOOH–C [84], Iron(III)-alginate fiber [107], Iron microwave irradiation [196]).
oxide/SiO2 [60], Cu/MCM-41 [93], iron-loaded mangosteen [183], In the WW treatment field, many kinds of organic pollutant
TiO2/glass sphere [184] and the magnetite-based catalysts [172]. have been degraded effectively in the nano material-catalyzed
They can be synthesized by the impregnation method Fenton-like processes. There are many kinds of nano material,
[17,47,84,105,107], the combination of impregnation and negative including, but not limited to: nano zero-valent iron (nZVI)
pressure [51], hydrothermal treatment [106], the combination of [37,38,147,197], nano a-Fe2O3, nano CuO [45], nano-ferroferric
hydrothermal treatment and ion exchange [108], and the MOCVD [142]. Nano zero-valent iron, as the typical catalyst used in organic
(metallorganic chemical vapour deposition) technique [93],etc. WW treatment, can remain in suspension and produce HO
effectively by corroding its surface in an aqueous solution because 4.5. Homogeneous Fenton-like catalyst
of its nano size and large specific surface area. We can see from No.
7 in Table 2, No. 3 in Table 3, and No. 6 in Table 4 that organic In the homogeneous Fenton-like processes, the catalysts used in
pollutants (such as petroleum hydrocarbon, phenol, and 1-alkyl-3- the Fenton-like processes include Fe3+, Cu2+, Mn2+, Co2+, and Ag+
methylimidazolium bromides) were all removed significantly [42,46,67,87]. Sometimes organic or inorganic ligands are also used
within 30-120 min (>90%). for complexing and stabilizing the metal ion (such as Fe3+) over awide
Besides nZVI, Huang et al. [142] applied ferroferric oxide pH range. The ligands studied include, but are not limited to: citrate,
nanoparticles to treat bisphenol A WW. In this study, 96% of the oxalate, EDTA, humic acids, and EDDS [199–204]. Under radiation of
bisphenol A and 45% of the TOC were removed within 480 min (see UVorvisible light,the stabilized metal ion(especially the Fe3+ ion)can
No. 8 in Table 4). Elshafei et al. [45] used nano a-Fe2O3 and nano be reduced easily, which is helpful to generate more HO.
CuO particles to treat nitrobenzene WW. The experimental results Taking Fe3+ as an example, a large number of studies about the
showed that nano a-Fe2O3 performed better than nano CuO 3+
Fe -catalyzed Fenton-like processes for the treatment of organic
particles. Nitrobenzene was removed completely after reaction WW have been reported (Tables 1–5). Many types of organic WW
times of 15 and 25 min when nano a-Fe2O3 and nano CuO particles (dyes, antibiotic, nitrobenzene, textile, sawmill WW, etc.) have
were applied, respectively (see No. 9 in Table 4). Hu et al. [191] been treated effectively. At least 90% pollutant removal rate, at
synthesized a Bi2Fe4O9 single-crystalline catalyst, which can be least 80% COD removal rate, and at least 50% TOC removal rate are
photoexcited by visible light. Under its catalysis 73% of the always achieved in the presence or absence of a physical field.
bisphenol A was removed in this study. These excellent perform- In addition to Fe3+, Cu2+ and Mn2+ also move to the forefront as
ances in organic WW treatment could allow nano materials to be homogeneous catalysts in the Fenton-like processes. The basic
extended to become a potential alternative type of heterogeneous mechanism of the Cu2+-catalyzed Fenton-like processes has been
Fenton-like catalyst. shown to be as follows [95]:
4.4. Heterogeneous catalyst from industrial waste Cu2þ þ H2 O2 ! Cuþ þ HO2 þ Hþ ð12Þ
Fly ash is a fine powder-like solid waste that is produced from

modern power stations and steel mills. It is usually discarded as an HO2 $O
2 þH
þ
ð13Þ
industrial waste and the annual production of coal fly ash is at least
200 million tonnes globally [75,149]. Coal fly ash consists totally of
the noncombustible matter in coal and a small amount of carbon Cu2þ þ O þ
2 $Cu þ O2 ð14Þ
remaining from incomplete combustion of the combustible matter.
According to the detection result of X-ray fluorescence spectros-
copy, we know that the detailed components of coal fly ash include Cu2þ þ HO2 $Cuþ þ O2 þ Hþ ð15Þ
SiO2, CaO, Al2O3, Fe2O3, MgO, K2O, P2O5, Na2O, SrO, ZrO2, and ZnO.
[75]. In the past several decades, due to the complex composition
of coal fly ash, it has been applied in the construction field only.
Cuþ þ H2 O2 ! Cu2þ þ HO þ OH ð16Þ
According to statistical results [198], most coal fly ash was used in
2+
the production of cement and concrete in many countries and a The main mechanism of the Mn -catalyzed Fenton-like
small part of the coal fly ash was used to produce aerated/ processes in terms of the electrochemistry is as follows [42]:
nonaerated block, brick, and structural fill, etc. Although the above
applications of coal fly ash are successful, there is still a huge Mn2þ þ H2 O2 þ Hþ ! Mn3þ þ H2 O þ HO ð17Þ
amount of fly ash (70–75%) that is unused and that causes serious
environmental problems when it is merely disposed in landfills
and/or storage lagoons [75,149]. Hence, exploring new application Mn3þ þ e ! Mn2þ ð18Þ
methods of coal fly ash appears to be rather urgent to enable the
2+
effective treatment of coal fly ash. Iboukhoulef et al. [87] applied the Cu -H2O2 Fenton-like
In recent years, due to the fact that it possesses a porous surface process to treat phenolic compounds in olive mill WW (see No.
and active metal elements (such as the iron element), fly ash has 21 in Table 1). A 43% and 62% phenolic compound removal rate was
been explored for use in the heterogeneous Fenton-like processes. achieved when the reaction temperatures were 30 and 50 C,
The study results (see No. 10 in Table 1 and No. 10–12 in Table 4) respectively. Lee et al. [95] also applied the Cu2+–H2O2 Fenton-like
show that organic contaminants have been removed effectively in process to degrade two pharmaceutical compounds in the
the coal fly ash-catalyzed heterogeneous Fenton-like processes. At presence of UV light (see No. 16 in Table 2). Under the optimum
least 85% of the pollutants are degraded under optimum reaction parameters a 47% diclofenac removal rate and a 66%
experimental conditions. carbamazepine removal rate were achieved within 240 min. Balci
In addition to coal fly ash, the use of acid mine drainage sludge et al. [42] treated glyphosate and aminomethylphosphonic acid
was also reported [41] as a heterogeneous catalyst in the (AMPA) using the electro-Fenton-like processes with Mn2+ as the
electrochemical processes after treatment by incineration and catalyst (see No. 7 in Table 3). The experimental results showed
grinding. Alginate gel beads were selected as supports to that 95% of the glyphosate and 100% of the AMPA were removed
immobilize AMDS (acid mine drainage sludge) and avoid leaching within 60 min and 360 min, respectively.
of the metal from the AMDS when operating under acidic In addition, for the Fe3+-catalyzed Fenton-like processes, some
conditions. Lissamine Green B and pirimicarb were both degraded improved methods were also studied. Firstly, researchers found
effectively within 60 min and 180 min, respectively, under opti- that Mn2+ can also act as the intensifying element in the Fe3+/H2O2
mum experimental conditions (see No. 1 in Table 3). These good process in addition to acting as the catalyst in the electrochemical
study results indicate that a potential application exists for processes. Zhao et al. [86] added the Mn2+ ion into the Fe3+/H2O2
industrial waste containing a high metal content in organic WW oxidation system to degrade benzoic acid and achieved satisfactory
treatment. This would be beneficial for both environmental treatment results. 100% of the benzoic acid and 47% of the TOC
protection and to reduce economic concerns. were removed within 25 min and 180 min, respectively (see No.
20 in Table 1). Zhao et al. [86] found that when Mn2+ was added, the Thus, we will discuss the experimental conditions individually in
reactions posed by the addition of Mn2+ could have an effect on the different sections.
chain propagation processes of the Fenton-like system; i.e.,
introduce manganese species with other valences and, corre- 5.1. Effect of parameters associated with H2O2
spondingly, additional reactions, which would finally improve the
WW treatment efficiency. The H2O2 dosage and/or the source of the H2O2 have a
Secondly, Wang et al. [127] used a Keggin-type iron-substituted significant effect on the WW treatment cost. As mentioned in
heteropolytungstate anion PW11O39Fe(III)(H2O)4 as the catalyst to Section 2.2, the investment on H2O2 must be considered because of
substitute for Fe3+ in the Electro-Fenton-like system for the its high price. In addition to the optimization of H2O2 dosage that is
treatment of dimethylphthalate WW. The study shown that the conducted in the studies, the feeding mode of H2O2 should also be
organic WW is treated successfully; 100% of the dimethylphthalate investigated because of its potential to reduce the H2O2 dosage
and 56% of the TOC were removed when reaction time was 80 min [76–207]. In the study by Zhang et al. [76] researchers found that,
and 120 min, respectively (see No. 8 in Table 3). These aforemen- at the same total H2O2 dosage, the removal rate of COD (in landfill
tioned improvement methods provide some interesting ideas for leachate) reached 62.9% when the continuous feeding mode was
the enhancement of the homogeneous Fenton-like processes. applied, while only a 47.3% COD removal rate was obtained when
H2O2 was added in one step. The higher COD removal rate for the
4.6. Study status of the catalyst based on different metal elements and continuous addition mode of H2O2 means that a higher H2O2
the corresponding WW treatment efficiency utilization rate occurs, which is beneficial for reduction of the H2O2
dosage.
According to Tables 1–5, some typical metal elements (Fe, Cu, In electro-Fenton-like processes, the effect of the H2O2 dosage
Mn, Ag, Co, etc.) have been applied as either the important on the WW treatment cost is more complicated because of the
component of the heterogeneous catalyst or the homogeneous possibility of generating H2O2 on the surface of the cathode (see
catalyst. However, not all the metal elements mentioned above can reaction Eq. (10)). Additionally, the activity and stability of the
attract enough attention from researchers. The catalysts based on cathode cannot be ignored because they can have an important
the Fe element have been studied widely, taking up the maximum effect on the rate of H2O2 generation and the reuse performance of
percentage (84.4%) of the studies in Tables 1–5, while the Cu the cathode (which can affect the WW treatment costs). Yu et al.
element has the second greatest percentage (10.9%) (which is far [208] developed a simple method using carbon black and
below the percentage for the Fe element). However, the catalytic polytetrafluoroethylene to modify graphite felt (which is used as
capacities of the Mn, Ag, and Co elements only attracted the the cathode). After the cathode modification more H2O2 was
attention of a minority of the researchers (No. 7 in Table 3 for the generated (a 10.7 times higher rate than before the modification) in
Mn element; No. 14 in Table 4 for the Ag element; No. 2 in Table 3; a wider pH range. Meanwhile, the modified cathode showed an
and No. 14 in Table 4 for the Co element). improved catalytic stability during the generation of H2O2 for
For the Fe-based catalytic system, the average treatment 10 reuse cycles.
efficiencies calculated from Tables 1–5 are 94.9% for initial
pollutants and 76.2% for COD (or TOC), while the maximum 5.2. Effect of parameters associated with the catalyst
removal rate is 100% for both initial pollutants and COD and the
minimum removal rate is 66% for the initial pollutants and 37% for The source, preparation method, modification method, activity,
TOC. A percentage removal rate of at least 90% accounts for 84.3% of and stability of the heterogeneous catalyst can affect the WW
the initial pollutants and 38.5% for the COD (or TOC). However, for treatment cost. As mentioned in Section 4, the heterogeneous
the Fenton-like system based on the catalyst containing other catalyst can be obtained from a wide range of sources (nature,
kinds of metal element, the data for WW treatment efficiency industrial waste, artificial synthesis). In order to obtain a
cannot have an obvious representation because the small amount heterogeneous catalyst with improved catalytic activity and
of data has no statistical significance (due to the small number of stability, the preparation/modification method (that can affect
studies mentioned above). Thus, in light of the above statistical the WW treatment cost) is a critical step.
analysis, we find that the catalysts based on other metal elements Taking fly ash as an example, this is a rather inexpensive source
(except for the Fe element) still need more attention. Some new of catalyst and is usually considered to be a solid waste. Before the
kinds of catalyst that have been explored can show excellent modification required to produce the catalyst, the rather low price
catalytic performances (such as No. 2 and 7 in Table 3), which are of fly ash ($15 ton1) mainly relates to the costs of transportation,
similar to those of the Fe element. In addition, exploring new chemicals, and electrical energy, etc. [209]. In addition to this
catalysts based on multiple kinds (
2) of metal elements could be a industrial waste, the use of natural minerals has some similar
new research direction as different metal elements could have aspects, i.e., the low price of the resource and the potential
synergistic effect during catalytic activity [205]. requirements for modification. The situation for artificial hetero-
geneous catalysts, however, is different situation because the
5. Cost evaluation preparation step has the most significant effect on the activity and
stability of the catalyst [105,108,172].
The wastewater treatment costs of Fenton-like processes can be The cost for both the modification of industrial waste/natural
affected by some significant factors that relate to H2O2 (source and minerals (for the catalysis purpose) and the preparation of a
dosage), the catalyst (source, modification/preparation, activity, heterogeneous catalyst has seldom been discussed until now
and stability), the wastewater (nature of organics, removal level, because the cost of the modification/preparation method differs
and concentration), the combination of the Fenton-like process between laboratories, as well as between the laboratory scale and
with other WW treatment technologies, and the input energy if the industrial scale due to issues relating to the amplification of the
physical file/phenomenon are/is used. Studies have been con- scale of production.
ducted to reduce the WW treatment costs relating to one or more The ability to produce a catalyst with the best catalytic activity
of the aspects mentioned above. Since these experimental and stability is the primary target of modification and preparation
conditions can be vastly different for each of the research groups, because the catalytic activity and stability can affect the WW
the direct comparison of WW treatment cost is really difficult. treatment cost by influencing the catalyst loading and the reuse
Table 6 Fig. 10 compares the treatment costs of Fenton oxidation and

Operation costs for an 85% COD removal rate for synthetic WWs and a 70% COD
CDEO for different treatment efficiencies (and also shows the cost
removal rate for actual olive oil WW [210].
of oxidation by ozonation). We can see that a much higher
Organics Operation cost (s/m3) investment is needed when a lower COD in the effluent is required.
Conductive-diamond electrochemical oxidation Fenton For CDEO, the cost is at least 10 s/m3 when nearly complete
Butyric acid 11 35
removal of COD is required. With regard to the effect of the
2-Propanol 9 71 concentration of organics on the treatment cost, we can see from
4-Chlorophenol 13 2 Fig. 11 that the total treatment cost for a mixture of five commercial
2-Naphthol 13 7 pesticides (using a combination of the photo-Fenton process with
Eriochrome Black T 35 46
MBR as the treatment method) varies significantly with the
Olive oil 11 5
decrease in dissolved organic carbon, i.e., the lower the pollution
load, the lower the cost. Moreover, Pérez et al. [211] also reported
that coupling the photo-Fenton process with MBR resulted in a 12%
capacity of the catalyst, respectively. These are the main reasons cost reduction when compared with that of coupling the photo-
for the optimization of the heterogeneous catalyst loading and the Fenton process with the traditional activated sludge process.
investigation into the stability of the catalyst that is found in many
studies [47,51,142]; in other words, a lower catalyst loading and an 5.4. Input energy and related issues
increased number of reuse cycles are highly recommended.
For the homogeneous catalyst, prevention of precipitation/ When a physical field/phenomenon is used to enhance Fenton-
flocculation of the catalyst is critical because this effect (usually like processes, additional attention must be paid to reducing the
caused by an increase in pH) will result in the deactivation of the input energy and WW treatment cost.
catalyst, which can adversely affect the reduction of the WW For the photo-Fenton-like processes, it is beneficial for
treatment cost. For photo-Fenton-like processes [46,102], more researchers to note that the transmittance of the WW and the
HO can be generated and the optimum pH range can be extended solid catalyst loading (in the heterogeneous photo-Fenton-like
to the neutral range after the addition of a ligand, i.e., a lower H2O2 system) should be considered because the two parameters could
dosage is required due to the generation of more HO, and the have a negative effect on the WW treatment. When treating WW
operation can be simplified due to the absence of the requirement with poor transmittance and/or an excessive amount of solid
for adding acid before treatment and adding alkali after the catalyst is added, the light intensity in the WW could decrease
oxidization process is complete. dramatically, giving rise to a serious reduction in the WW
treatment efficiency and a dramatic increase of investment on
5.3. Effect of parameters associated with the WW input energy. Hence, pre-treatment of the WW with low
transmittance [212] and the optimization of the solid catalyst
The nature and concentration of the WW and the required level loading would be necessary.
of removal of the contaminants have been proven to have a marked The value of the input photo-energy can be calculated using
influence on the WW treatment [210,211]. In the study by Eq. (19) [211]:
Cañizares et al. [210] researchers investigated the treatment costs
of synthetic wastewaters contaminated with different types of pA
W ¼t ð19Þ
organics and that of actual wastes. As shown in Table 6 (from Vt
Cañizares et al. [210]), we can see that the Fenton process has a where W in Eq. (19) is the photo-energy accumulated per unit
lower cost when treating actual wastewater (5 s/m3 for a 70% COD volume (J L1); t is the irradiation time (s); p is the average incident
removal rate), while the conductive-diamond electrochemical irradiation on the radiation area (w m2); A is the illuminated
oxidation (CDEO) process cost 11 s/m3. Conversely, the cost of collector area (m2); Vt is the total volume of the treated WW (L).
CDEO is competitive with that of Fenton oxidation when treating For the electrochemical processes, we should pay attention to
WW polluted by specific organics. the occurrence of passivation on the electrode surface in practical
Fig. 10. Variation of the treatment cost with COD removal in the treatment of olive oil mill wastewater. (1-conductive-diamond electrochemical oxidation; 2-Fenton
oxidation; 3-ozonation oxidation) [210].
Fig. 11. Cost of the combination process of photo-Fenton with MBR to treat 10 m3/day as a function of the concentration of organics (A: Dissolved organic carbon
(DOC) = 500 mg L1, mineralization = 57%; B: DOC = 500 mg L1, mineralization = 40%; C: DOC = 200 mg L1; mineralization = 33%; D: DOC = 50 mg L1; mineralization = 20%)
[211].
applications [213]. During WW treatment at the industrial scale, The calculation of the absorbed energy can be achieved using
high treatment efficiency always occurs in the early stages. With Eq. (22) [74]:
the passage of time the initial pollutants and intermediates could
W abs ¼ DT r C p ð22Þ
be adsorbed on the electrode surface, giving rise to complete or
partial blocking of the active sites on the electrode surface [114]; where Wabs is the energy absorbed by unit volume of the WW
hence the surface condition of electrodes should be checked often (J m3); DT is the temperature rise of the WW (K); r is the density
in practical applications. of the WW (kg m3); Cp is the heat capacity (J kg1K1).
The calculation of input electric energy is shown in Eq. (20) Before calculating the investment on energy consumption,
[210]:
consideration of the energy utilization rate W abs =W input 100%
W ¼Q V ð20Þ is recommended. Additionally, during WW treatment heat
recovery should be taken into consideration because it is helpful
where W in Eq. (20) is the input electric energy per unit volume to reduce the treatment costs for the WW (by means of saving
(kWh m3); Q is the specific electrical charge passed (kAh m3); V energy).
is the cell potential (V). The cost of cavitation has not always been calculated because it
When the MW enhanced Fenton-like processes are used, the is widely known that when cavitation is applied alone the WW
input energy and absorbed energy are always different [214]. Input treatment technology is cost intensive [139,215–218]. Thus,
energy can be obtained from Eq. (21): coupling between cavitation and other WW treatment technolo-
pt gies is encouraged to reduce the WW treatment cost. Weng et al.
W input ¼ ð21Þ
Vt [139] applied a zero-valent iron catalysed Fenton-like process that
is enhanced using US cavitation to treat dye WW. The treatment
where Winput here is the MW input energy per unit volume of
cost is shown in Table 7.
treated WW (J m3); p is the input power (W); t is the irradiation
It can be seen from Table 7 that the total cost was affected by
time (s); Vt is the total volume of the treated WW (m3).
power intensity, decolourization rate, and irradiation time, etc., and
Table 7
Cost analysis of a zero-valent iron catalysed Fenton-like process enhanced by US cavitation [139].
Power intensity (W L1) Decolourization rate (%) Irradiation time (min) Power consumption (kWh m3) Electricity cost (USD m3) Total cost (USD m3)
80 80 30 40.0 3.20 (92.8%)a 3.45
100 98 25 41.7 3.33 (93.0%) 3.58
120 98 15 30.0 2.40 (90.6%) 2.65
140 98 10 23.3 1.87 (88.2%) 2.12
a
The ratio of electricity to total cost.
was in the range 2.12–3.58 USD m3. Moreover, we can see that the amount of solid catalyst will result in a serious decrease of the
investment on input energy (electricity) accounts for at least 88.2%. light intensity in the WW medium.
In addition to the above study, Chakinala et al. [216] combined (3) The most attractive advantage of electrochemical processes is
hydrodynamic cavitation with a zero-valent iron catalysed Fenton- the generation of H2O2 in situ and the regeneration of the metal
like process to treat industrial WW. The study result showed that the catalyst, both via reduction on the cathode surface. The H2O2
corrosion effect (posed by hydrodynamic cavitation) on the surface generated in situ is used more efficiently than that added
of zero-valent iron resulted in the latent remediation of the WW, i.e., externally, while the regeneration of the catalyst is also
the organics in WW were degraded continuously without any beneficial to reduce the concentration of metal ion in the
treatment after the 15 min treatment by the hydrodynamic treated WW. However, in practical applications passivation of
cavitation-enhanced heterogeneous Fenton-like process took place. the electrode surface should be checked and managed. The
This is rather beneficial to reduce the WW treatment cost. initial pollutants and intermediates could be gradually
adsorbed on the electrode surface, causing complete/partial
6. Proposed future research directions blocking of the active sites on the electrode surface.
(4) The “hot spots” effect is the main mechanism for MW radiation
(1) Fenton-like processes have presented a broader prospect than to enhance the Fenton-like processes. However, the non-
the Fenton process due to the advantages of the Fenton-like thermal effect of MW radiation is still in controversy as
processes (the catalyst can be recycled, the WW treatment cost researchers have many different opinions (such as that the MW
is relatively low, the WW treatment efficiency can easily satisfy non-thermal effect plays an important role in the WW
the discharge standards, etc.). Further and more detailed treatment, or that no MW non-thermal effect was found in a
studies of the Fenton-like processes should be focused on the specific study). Nevertheless, many studies have shown that
degradation kinetics of the organics and the mechanisms of MW irradiation can enhance the WW treatment efficiency
each specific Fenton-like process for the degradation of the significantly and even relieve the passivation issue of the
organics; this could provide a powerful theoretical support for electrode in electrochemical processes by means of promoting
developing novel Fenton-like processes. the transduction of electrons to the electrode surface.
(2) The catalyst plays an important role in the performance of a (5) The Fenton-like processes can be enhanced significantly by the
Fenton-like processes. The catalytic capacity of catalyst could use of cavitation phenomenon via the generation of micro-
be mainly affected by the property of leaching and the validity bubbles. When cavitation microbubbles reach a critical size,
of active sites on the catalyst surface. Thus, the development of they will have a violent implosive collapse, followed by
a kind of catalyst with low leaching rate (high stability) and localized extremely high temperature (hot spots) and high
high reactivity is quite important for effective organic WW pressure. Some studies have shown the effectiveness of
treatment and reduction of WW treatment cost. In addition, cavitation when combined with the Fenton-like processes.
the exploration of catalysts based on other kinds of metal (6) A homogeneous catalyst can be used easily when compared
elements (other than the Fe element) could be helpful for the with a heterogeneous catalyst because the corresponding
development of a catalyst. inorganic compound can be used directly as the target catalyst
(3) Physical fields/phenomenon (including photo, electro, cavita- in a homogeneous system. Additionally, some special homo-
tion, and microwave) can have positive effects on the geneous catalysts were also studied (such as a Keggin-type
performance of Fenton-like processes during WW treatment. iron-substituted heteropolytungstate anion).
Although single physical field/phenomenon-assisted Fenton- (7) Many kinds of heterogeneous catalyst have been studied in
like processes have been studied widely, the combination of recent years, including, but not limited to: natural minerals,
different physical fields/phenomenon has not attracted enough composites by artificial synthesis, nano materials, and
attention (only a small number of studies were conducted). industrial wastes.
Hence, in future studies, various combinations of different (8) A comprehensive exploration of novel catalysts based on other
physical fields/phenomenon should be studied in more depth, kinds of metal element (such as Cu, Mn, Ag, and Co, but not Fe)
such as the photo-electro-Fenton-like processes, MW-cavita- still requires large numbers of studies to be completed in the
tion-Fenton processes, and MW-electro-Fenton-like processes. future, because only a minority of the studies conducted so far
have related to these metal elements.
(9) The cost evaluation of different Fenton-like processes has been
7. Conclusions conducted in some studies. However, more comprehensive
evaluation is needed because it can provide powerful cost
(1) For the Fenton-like processes, although some studies still support for the development of pilot/industrial scale of Fenton-
revealed that 3 is the optimum pH value, other studies have like processes.
illustrated that organics can be degraded effectively in the
neutral (even alkaline) range. The various conclusions show
the possibility of extending the optimum pH of Fenton-like Acknowledgements
processes to the neutral/alkaline range.
(2) In the photo-Fenton-like processes, photochemical process is The work was supported by State Key Laboratory of Urban
critical for the reduction of the metal catalyst in both the Water Resource and Environment (Harbin Institute of Technology)
hetero- and homo-geneous Fenton-like processes. In the (2015DX03) and National Science Foundation for Post-doctoral
heterogeneous Fenton-like processes, photo-induced reduc- Scientists of China (2014M561356).
tive dissolution of the solid catalyst is the primary mechanism
for enhancing the Fenton-like processes, while in the
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Journal of Environmental Chemical Engineering 4 (2016) 762–787

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

A review on Fenton-like processes for organic wastewater treatment

physical ﬁeld/phenomenon, the solid catalyst loading is in the

2.4. WW treatment temperature

Fig. 3. Effect of higher WW treatment temperature [17,62,81].

3.1. Photo-Fenton-like processes FeðOHÞ2þ þ hv ! Fe2þ þ HO ðl < 580nmÞ ð5Þ

The role of photochemistry in a Fenton-like process is to

3.2. Electro-Fenton-like processes

Electrochemical processes can be combined with Fenton-like

Fig. 5. Typical electro-Fenton-like systems [43].

Fig. 6. Degradation mechanism of dye in magnetite-catalysed Fenton-like process [131].

EF-like processes has been studied by many researchers and

3.4. Microwave-(another physical ﬁeld)-Fenton-like processes

Microwave (MW) radiation is a wavelength band of the

NO.a Pollutant Catalyst Experiment conditions Treatment Additional information Ref.

NO.a Pollutant Catalyst Experiment conditions Treatment Additional information Ref.

In heterogeneous Fenton-like processes natural mineral mate-

Fly ash is a ﬁne powder-like solid waste that is produced from

Table 6 Fig. 10 compares the treatment costs of Fenton oxidation and

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3.1. Photo-Fenton-like processes FeðOHÞ2þ þ hv ! Fe2þ þ HO ðl < 580nmÞ ð5Þ