Applied Catalysis B: Environmental 235 (2018) 103–129

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Applied Catalysis B: Environmental

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

Review

Heterogeneous electro-Fenton and photoelectro-Fenton processes: A critical T

review of fundamental principles and application for water/wastewater
treatment
⁎ ⁎
Soliu O. Ganiyua, , Minghua Zhoub, Carlos A. Martínez-Huitlea,c,
a
Laboratório de Electroquímica Ambiental e Aplicada, Instituto de Química, Universidade Federal do Rio Grande do Norte, Lagoa Nova, CEP 59.072-900, RN, Brazil
b
Key Laboratory of Pollution Process and Environmental Criteria (MOE), Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control,
College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China
c
Institut für Organische Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128, Mainz, Germany

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

Keywords: This exhaustive review focuses on the fundamental principles and applications of heterogeneous electrochemical
Heterogeneous electro-Fenton process wastewater treatment based on Fenton’s chemistry reaction. The elementary equations involved in formation of
Heterogeneous/solid catalyst hydroxyl radical in homogeneous electro-Fenton (EF) and photo electro-Fenton (PEF) processes was presented
Functionalized cathodic materials and the advantages of using insoluble solids as heterogeneous catalyst rather than soluble iron salts (hetero-
Bioelectro-Fenton system
geneous electro-Fenton process) (Hetero-EF) was enumerated. Some of the required features of good hetero-
Biorefractory organic pollutants
geneous catalysts were discussed, followed by the mechanisms of catalytic activation of H2O2 to reactive oxygen
species (ROS) especially hydroxyl radical (%OH) by heterogeneous catalyst in Hetero-EF system. Extensive dis-
cussion on the two configuration of Hetero-EF system vis-à-vis added solid catalysts and functionalized cathodic
materials were provided along with summaries of some relevant studies that are available in literature. The solid
catalysts and the functionalized cathodic materials that have been utilized in Hetero-EF wastewater treatment
were grouped into different classes and brief discussion on their synthesis route were given. Besides, the use of
solid catalysts and iron-functionalized cathodic materials in bioelectrochemical system (BES) especially bioe-
lectro-Fenton technology (BEF) using microbial fuel cells (MFCs) with concurrent electricity generation for
Hetero-EF treatment of biorefractory organic pollutants was discussed. In the final part, emphasis was made on
the challenges and future prospects of the Hetero-EF for wastewater treatment.

1. Introduction advantages such as high versatility, excellent efficiency, high amen-

ability and environmental compatibility, which distinguish them from
Electrochemical advance oxidation processes (EAOPs) based on other AOPs [5–11]. In general, EAOPs based on Fenton’s chemistry
Fenton’s chemistry are among the most widely applied advanced oxi- utilizes hydroxyl radical (%OH) produce from Fenton’s reaction between
dation processes (AOPs) for the removal of persistence organic pollu- in-situ generated or externally added hydrogen peroxide (H2O2) and
tants (POPs) [1–6]. These eco-friendly techniques possess some exciting Fe2+ ions (Eq. (1)) for the degradation of POPs. The prominent

Abbreviations: 2,4-DCP, 2,4-dichlorophenol; 3D, three dimension; AB, alginate beads; AC, activated carbon; ACF, activated carbon felt; ACS, activated charcoal; AOPs, advanced
oxidation processes; APHs, 4-Amino-3-hydroxy-2-p-tolylazonaphthalene- 1-sulfonic acid; APN, allophone clay; AQ, anthraquinone; ATR-FTIR, attenuated total reflectance-Fourier
transforms Infrared spectroscopy; BDD, boron doped diamond; BEF, bioelectro-Fenton technology; BES, bioelectrochemical system; BMIM, 1-butyl-3-methylimidazolium hexa-
fluorophosphate; CAs, carbon aerogels; CB, carbon black; CF, carbon-felt; CNTs, carbon nanotubes; COD, chemical oxygen demand; DFT, density functional theory; DMP, dimethyl
phthalate; DMZ, dimetridazole; DSA, dimensional stable anode; EAOPs, electrochemical advance oxidation processes; EF, electro-Fenton; EIS, electrochemical impedance spectroscopy;
Fe-CHI, Fe-chitosan; FCSW, iron contains sludge waste; FMBO, Fe-Mn binary oxide; GC, glassy carbon; GDE, gas diffusion electrode; GEF, goethite-catalyzed electro-Fenton process; Gr,
graphite; Hetero-EF, heterogeneous electro-Fenton process; Hetero-PEF, heterogeneous photo electroFenton; FCA, Fe doped carbon aerogel; MCE, mineralization current efficiency; ADE,
Ar diffusion electrode; hv, ultraviolet irradiation; LC–MS, liquid chromatography coupled with mass spectrometer; LDH, layered double hydroxide; MB, methylene blue; MFCs, microbial
fuel cells; MTBE, methyl tert-butyl ether; NPs, nanoparticles; NTs, nanotubes; %OH, hydroxyl radical; PEF, photo electro-Fenton; PEs, particle electrodes; p-NP, p-nitrophenol; POPs,
persistence organic pollutants; PPy-AQDS, polypyrrole-anthraquinone-2,6-disulfonate; Pt, platinum; PTFE, polytetrafluoroethylene; QEEG, quinone-functionalized electrochemically
exfoliated grapheme; RB 19, Reactive Black 19; Rct, interfacial electron-transfer resistance; rGO, reduced graphene oxide; RhB, rhodamine B; ROS, reactive oxygen species; SAC, sludge
derived activated carbon; SS, stainless steel; TOC, total organic carbon; UVC, short-wavelength ultraviolet; UVA, long-wavelength ultraviolet
⁎
Corresponding authors at: Laboratório de Electroquímica Ambiental e Aplicada, Instituto de Química, Universidade Federal do Rio Grande do Norte, Lagoa Nova, CEP 59.072-900,
RN, Brazil.
E-mail addresses: soliu.ganiyu@ccet.ufrn.br (S.O. Ganiyu), carlosmh@quimica.ufrn.br (C.A. Martínez-Huitle).

https://doi.org/10.1016/j.apcatb.2018.04.044
Received 29 December 2017; Received in revised form 15 April 2018; Accepted 18 April 2018
Available online 22 April 2018
0926-3373/ © 2018 Elsevier B.V. All rights reserved.
S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

members of this class of EAOPs are electro-Fenton (EF) and photo- some of these iron minerals are pH regulator, meaning that they are
electro-Fenton processes (PEF) [4,12–14]. The PEF is a photo-assisted capable of reducing the pH of the solution towards the strong acidic pH
upgrade of EF process which utilizes either ultra-violet (UVA and UVC), required for effective EF process [22,25]. In particular, pyrite and
solar or visible light photoexcitation of Fe3+ complexes formed in chalcopyrite has been successfully used to catalyze the degradation of
Fenton’s reaction (Eq. (1)) to produce both Fe2+ and %OH (Eqs. (3) and some pharmaceuticals at circumneutral pH with higher removal and
(4)), thus it increases the quantities and regeneration of %OH as well as mineralization efficiency [25–28]. Many researches have also been
the efficiency of the process [1,4,15,16]. The photogenerated Fe2+ ion tailored towards developing Fe-containing synthetic heterogeneous
can subsequently catalyzed the Fenton’s reaction, forming Fe3+ and catalysts which are either used alone or supported on microporous or
closing the cycle (Eq. (1)). mesoporous materials for application in Hetero-EF treatment of organic
pollutants in water [29–31]. Of recent, iron and/or transition metal
Fe2+ + H2O2 + H+ → Fe3+ + %OH + H2O (1)
oxides modified or functionalized cathodic materials have been pre-
Fe 3+
+ H2O → Fe(OH) 2+
+H +
(2) pared via various techniques for application in Hetero-EF process. In
this case, the cathode performs dual function – as counter electrode as
Fe(OH) 2+
+ hv → Fe 2+
+ %OH (3) well as the iron source (catalyst) during the electrochemical treatment
Fe(OOCR) 2+
+ hv → Fe 2+
+ CO2 + R% (4) process. The functionalized cathode may be obtained by: (i) supported
or immobilized iron source on a conductive materials (mostly carbo-
These processes are efficient for the complete degradation and ex- naceous material), (ii) chemically modified a conductive materials with
cellent mineralization of synthetic and real wastewater contaminated iron source or (iii) one-pot or multistep chemically prepared low den-
with different class of organic pollutants such as pharmaceuticals and sity porous solid materials containing iron and/or transition metals
personal care products, endocrine disrupt compounds, pesticides, tex- source (i.e. carbon aerogel) [19,20,32,33].
tile effluents, polycyclic aromatic hydrocarbons, surfactants and landfill Generally, the degradation of organic pollutants during Hetero-EF
leachates [1,5,7–9,12,14,16–18]. involves two mechanisms – homogeneous catalyzed process by Fe3+/
The major challenge of both EF and PEF is that both processes are Fe2+ redox couple dissolved into the solution and surface catalyzed
only optimum at strong acidic pH conditions (i.e. pH 2.8–3.5), which process at the solid catalyst-liquid interface, depending on the working
are negative and disadvantageous from the environmental point of pH and nature of the catalyst used [19–21]. Up to date, comprehensive
view, since a final neutralization step may become necessary to obtain reviews on the Hetero-EF wastewater treatment are limited in litera-
tolerable effluents [19–22]. Besides, efficiency of EF and PEF sig- ture. The only available chapter of a book on this topic recently pub-
nificantly reduced when working outside pH 2.8–3.5. For instance at lished by Oturan group [22] mainly focuses on solid catalyst/supports
pH ≤ 2.5, the formation of peroxonium ions (H3O2+) which makes the solid catalyst without addressing the heterogeneous particle electrode
electrogenerated H2O2 electrophilic and reduces its reactivity towards and functionalized cathodic materials. Therefore, in this exhaustive re-
Fe2+, in addition to the preferential H2 evolution at the cathode occurs view, the advantages of Hetero-EF and its main mechanism of pro-
at lower acidic pH; whereas at pH ≥ 4.5, there is both gradual pre- duction of %OH were firstly presented, followed by the general features
cipitation of Fe3+ (elimination of the catalyst) as ferric hydroxide and of good heterogeneous catalyst. The two main configurations of Hetero-
the decomposition of generated H2O2 into water and O2, thus hindering EF that have been reported in literature were extensively discussed and
the production of %OH [1,19]. Other challenge of homogeneous EF and a summary of relevant studies related to each configuration were pre-
PEF is the non-recyclability of the catalyst used, which made the sented. In the final section, current challenges and possible future
technique unsuitable for continuous experimental process (Table 1). strategies were discussed from the perspective of catalyst development/
Hetero-EF uses solid catalyst source for the decomposition of H2O2 synthesis and process design. It is in our view that this review we in-
to form %OH. It has been investigated as a promising alternative to crease the attention given to Hetero-EF for wastewater treatment and
homogeneous EF to overcome necessities for catalyst quantity optimi- bring about further expansion of knowledge in this exciting area of
zation as well as widening the pH range at which EF process can be electrochemical wastewater treatment.
performed. This is beneficial because most real effluents encounter in
nature are of wide and variable pH ranges and compositions, thus not
suitable for EF and PEF treatments without adjusting the pH to strong 2. Advantages of heterogeneous electro-Fenton process
acidic pH values [19]. Earlier effort to overcome the challenge of
narrow pH window in EF resulted in the use of some naturally occur Considering the challenges of homogeneous EF process for the re-
iron bearing minerals such as goethite and magnetite as heterogeneous mediation of organic pollutants, the most important advantage of
catalysts for the treatment of synthetic wastewater [23,24]. Besides, Hetero-EF is its application over a wide pH range. In essence, several

Table 1
Comparison of advantages and drawbacks of Heterogeneous EF (Hetero-EF) and Heterogeneous PEF (Hetero-PEF) with other EAOPs.
Technology Advantages Drawbacks

Hetero-EF/Hetero-PEF Efficient over wide pH working window Possible additional cost due to solid catalyst production
Easy post treatment separation, reusability and recyclability of Requires more careful materials/catalysts selection to avoid negative
the catalysts environmental impacts
Possible regulation of solution pH towards strong acidic region
Easy automation
Suitable for the treatment of real wastewater

Homogeneous EF/PEF Low quantity and cheaper catalyst source Efficient only at narrow pH window (pH 2.8–3.5)
Easy to operate compared to Hetero-EF/Hetero-PEF Requires post-treatment neutralization of treated wastewater
Limited reusability and recyclability of the catalyst neutralization

Electrooxidation/Anodic oxidation Requires no catalyst and less chemicals for operation Higher electrical energy consumption
Requires very expensive electrode material (i.e. BDD)
Efficient over wide pH window Inferior efficiency compared to analogous EF/PEF and Hetero-EF/Hetero-
Suitable for the treatment real wastewater provided non-active PEF
electrode is utilized

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S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

Table 2
some real wastewater/effluent with their pH.
Type of real wastewater pH range

Building and construction chemical factory 6.1–9.5 [34]

Plastic shoes manufacturing factory 5.6–7.8 [34]
Industrial dyeing effluent - Poland 11.2 [35]
Textile wastewater – India 10–12.2 [36]
Pharmaceutical wastewater 3.9–9.2 [37]
Olive oil mill wastewaters 4.5–6.5 [38]
Petrochemical wastewater ≈5.6 [39]
Landscape water 7.2 [40]
Brewery wastewaters 7.5 [41]
Alcoholic wastewater 4.5–4.8 [42]
Wastewater from almond industry 6.2 [43]
Reverse osmosis concentrate 8.3 [44]

Hetero-EF configuration and design have been reported to be practi-

cally pH independent. The circumventing of the pH limitation of clas- Fig. 1. Effect of pyrite suspension loading on the pH of 250 mL solution of
sical EF process can ensure the easy application of Hetero-EF to wide 175 mg L–1 APH synthetic dye in 0.05 M Na2SO4 after 15 min.
Printed with the permission of Ref. [25].
range of real effluents without prior pH adjustment. Indeed, real was-
tewater or effluents are not only multi-components but also have wide
pH variation depending on the industrial setup or origin. The pH of real because the elimination of sludge could enhance the efficiency of the
effluents from some industrial plants and municipal wastewater are process (i.e. increases the availability of the catalyst) as well as reduced
summarized in Table 2. both energy consumption and overall cost of the process [21]. The
As seen in Table 2, majority of the effluents from industrial plants formation of the sludge during conventional EF treatment implies the
are either at strong basic or circumneutral pH, thus, homogeneous EF is loss of the Fenton’s catalyst, which has adverse effect on the process
not appropriate for the treatment of these wastewaters without prior pH efficiency, whereas sludge formed during post-treatment neutralization
adjustment. However, Hetero-EF is well suitable and efficient treatment of solution treated with EF may require further proper disposal. The use
technique for such pH-multi-variant effluents either as a single or of Hetero-EF especially with iron supported or functionalized cathodic
mixture from different plants since the efficiency of most Hetero-EF materials eliminate the formation of the sludge during the treatment
design are pH independent. Based on previous studies [19–21], the regardless of the working pH conditions. Besides, Hetero-EF using solid
independence of the efficiency of Hetero-EF has been achieved via to catalyst or functionalized cathode allows easy separation and possible
mechanisms: (i) using pH regulator as heterogeneous catalyst in the recycling of the iron promoter. This is an important parameter which
presence of O2 and (ii) surface catalytical decomposition of H2O2 to % ensures continuous operation of the treatment system unlike in homo-
OH. In the case of pH regulator, the catalyst undergoes oxidation in the geneous EF where the catalyst cannot be separated from the treated
presence of O2 with the accumulation of H+ in the solution, thus de- solution. Indeed, some studies have shown that functionalized cathodic
crease the solution pH towards the acidic values required for efficient materials like ferrite and Fe-Cu carbon aerogel and Fe-modified carbon-
EF process. The most common example of such catalyst is natural pyrite felt and graphite-felt can be repeatedly used in several cycles without
and chalcopyrite, which act as both iron ions source dosage and pH significant reduction in the efficiency of the process, even up to ten (10)
regulator and the mechanism is summarized in Eqs. (5)–(8) [25,28]. cycles [19,20,46]. The reusability and recyclability in Hetero-EF dis-
tinguished the process from homogeneous EF and enhance the effi-
2FeS2 + 7O2 + 2H2O → 2Fe2+ + 4SO42– + 4H+ (5) ciency of the system. It can also reduce the overall cost for the treat-
2FeS2 + 14H2O2 → 2Fe 3+
+ 14H2O + 4SO4 2–
+ 2H +
(6) ment of wastewater since the process can be easily adapted to
automation.
FeS2 + 14Fe 3+
+ 8H2O → 15Fe 2+
+ 2SO42– + 16H+
(7)

CuFeS2 + 16Fe 3+
+ 8H2O → Cu 2+
+ 17Fe 2+ 2–
+ 2SO4 + 16H +
(8) 3. Mechanism of heterogeneous electro-Fenton
A typical pH regulating effect of natural pyrite is shown in Fig. 1 as
According to literatures [47–49], the decomposition of H2O2 by
reported by Labidha et al. [25].
solid mono/mixed iron oxides, iron/transition metals containing com-
On other hand, the catalytic decomposition of H2O2 to %OH at the
pound and Fe-functionalized cathodic materials generally involves two
surface of solid heterogeneous catalyst has been the main mechanism of
situations according to the pH conditions at which electrolysis is being
degradation of organic pollutants at circumneutral and basic pH values
performed. At lower pH conditions (pH < 4.5), the process is con-
because iron and/or transition metal used in catalytic Fenton’s reaction
trolled by the redox cycling of dissolved Fe3+/Fe2+ and surface FeIII/
are indissolvable at neutral or alkaline pH conditions [20]. This implies
FeII couples (Fig. 2a and b). The dissolved Fe3+/Fe2+ released from the
that with solid iron/transition metal source, the Hetero-EF can be ef-
leaching of significant quantities of iron ions for the solid catalyst or Fe
ficiently carried out over a wide pH range. In particular, iron-supported
– functionalized cathodic materials due to the acidic working pH con-
catalyst and functionalized cathodic materials such as iron/transition
ditions. Other transition metals redox couples such as Cu2+/Cu+,
metal containing carbon-aerogel exhibited such properties and de-
Co3+/Co2+ and others could also catalyze the decomposition of H2O2
monstrated to achieved excellent mineralization efficiency during
to %OH if leached from solid catalyst into treated solution (Fig. 2c)
Hetero-EF treatment of different class of organic pollutants over wide
[19,50–53]. Besides, the presence of other transition metals in addition
pH range, including strong alkaline pH conditions of around 12 [45].
to iron in the solution may provoke reduction of Fe3+ to Fe2+ in con-
Detail of the surface catalyzed decomposition of H2O2 to %OH is given
junction with the catalytical decomposition of the H2O2 as shown if
in the Section 3.
Fig. 2c, thus enhance the efficiency of the electrolytic system [54–57].
Related to the application over wide pH window is the elimination
At the same time under lower acidic pH conditions, H2O2 decomposi-
or inhibition of formation of iron hydroxides sludge during Hetero-EF
tion could also be achieved by the surface alkalescent ^FeIII/FeII eOH
process or post-treatment neutralization stage. This is important
at the surface of the solid catalyst [58,59]. Therefore, the predominant

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S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

Fig. 2. mechanism of catalytic activation of H2O2 at acidic pH (pH ∼ 3) using (a) supported or non-supported iron/iron-containing solid catalyst, (b) iron-func-
tionalized cathodic materials (I: adsorption of dissolve O2 and leaching of iron ions; II: electrogeneration of H2O2 and regeneration of Fe2+ from reduction of O2 and
Fe3+ respectively and III: Fenton’s production of %OH) and (c) proposed participation of other transition metals in redox recycling of iron ions and catalytic
decomposition of H2O2 (M = Cu, Mn, Co, V, Ti, Ni or Nb).
Adopted from Refs. [60,21,57,83] respectively.

catalytic process not only depends on the working pH but also on the metal containing carbon-aerogel and layered double hydroxide mod-
solubility of the solid catalyst at lower pH [31]. Solid catalysts such as ified carbon-felt exhibited relatively good stability at acidic pH and the
natural iron minerals [23,27,60–62] as well as synthetic nanoparticles leached iron ions concentration are usually relatively minimal
of iron and iron supported catalysts [21,29,58,63–74] undergoes ex- [19,45,84]. As such, surface catalyzed decomposition of H2O2 by FeIII/
cessive leaching of iron ions at acidic pH especially pH ≤ 3 at which FeII is relatively significant when those functionalized cathodic mate-
Fenton’s reaction is optimum, thus H2O2 decomposition is majorly by rials are utilized in Hetero-EF at low acidic pH conditions. In summary,
homogeneous Fe3+/Fe2+ catalyzed mechanism. Depending on the under these circumstances, the catalytic decomposition of H2O2 to %OH
cathode materials used, the homogeneous redox couples may be con- is by homogeneous Fe3+/Fe2+ and surface FeIII/FeII redox couple, but
tinuously regenerated at cathode (Eq. (9)), thus making the system a the predominant process is determined by the nature of the solid cat-
close lop [75–79]. alyst used (i.e. solubility with pH).
In contrast, at neutral and alkaline pH values, the contribution of
Fe3+ + e− → Fe2+ (9)
dissolved iron ions to the H2O2 activation is expected to be negligible
Similar behavior has been reported for some iron/transition metal since FeIII is insoluble [85,86]. Although the kinetics of Hetero-EF is
containing functionalized electrode such as Fe- bentonite particle complex and involved several parameters, but the most critical step is
electrode, Fe@Fe2O3/ACF, Fe-Carbon-felt, Fe and Fe-Cu allophane na- surely the production rate of %OH from H2O2, which in this case is
noclays with large quantities of leached iron ions, which can catalyze controlled by the solid catalyst properties, H2O2 generation and solu-
the H2O2 decomposition in the bulk with minimum surface decom- tion pH [87–91]. Till date, no consensus reaction mechanisms is
position of H2O2 [21,33,80–82]. It is important to note that there is available in literature for the entire oxidation process, however, it is
possibility of oxidation of Fe2+ and other transition metals ions at the widely accepted that the Hetero-EF catalysis can fit the Haber-Weiss
anode surface during the electrolysis, however, this reaction is very circle mechanism, which is similar to those observed in the classical
insignificant and rarely reported in literature. homogeneous Fenton’s reaction [20,92,93]. The surface-based me-
Other functionalized cathodic materials especially iron/transition chanism is summarized by reactions in Eq. (10)–(20).

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S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

metal-co-catalyst provided two added advantage in Hetero-EF: (i) ac-

celerate the production of the ^FeIIeOH for H2O2 decomposition (Eqs.
(18) and (19)) and (ii) increased the rate of catalytic decomposition of
H2O2 to %OH like in the case of homogeneous EF [19,98–100].

^CoIIeOH + ^FeIIIeOH → ^CoIIIeOH + ^FeIIeOH (18)

^Cu eOH + ^Fe eOH → ^Cu eOH + ^Fe eOH

I III II II
(19)

^Co eOH + H2O2 → ^Co eOH + %OH + OH–

II III
(20)

^Cu eOH + H2O2 → ^Cu eOH + %OH + OH–

I II
(21)

Studies have shown that the production rate of %OH in homo-

geneous Fenton reaction catalyzed by Fe2+ is 104–105 folds faster than
Fe3+ catalyzed Fenton-like process [20]. On the other hand, the surface
catalytic centers of Fe in iron oxide nanoparticles were reported to be at
least 50-folds more effective for %OH generation than dissolved Fe3+
ions at circumneutral pH [83,101]. This implies that the reduction of
FeIII to FeII at the surface of the catalyst is the rate-limiting step of the
Fig. 3. mechanism of surface catalyzed activation of H2O2 to %OH at neutral whole Hetero-EF reactions [20]. Previously, Costa et al. [102] and
and basic pH on Fe-functionalized cathodic materials (here ferrite-carbon Moura et al. [88] have drawn similar conclusions when zero valent iron
aerogel). (Fe°) and iron oxides encapsulated composite were studied, which had
Adopted from Ref. [20]. higher reactivity in oxidation of organic pollutants than Fe° or iron
oxides alone due to the Fesurf2+ species formation via electron transfer
from Fe° to Fe3+ within the composite and increased oxygen vacancies
O2 + 2H+ + 2e– → H2O2 (10) [103]. In 2013, Wang and co-workers [20] have also shown that the
formation of FeII mediator with high catalytic activity for H2O2 de-
^Fe eOH + e– → ^Fe eOH
III II
(11)
composition to %OH was via reversible redox by electron transfer among
^Fe eOH + H2O2 ↔ ^Fe eOH(H2O2)(s)
III III
(12) the iron species with different valences (Eq. (22)) in a ferrite-carbon
aerogel containing mix phase of Fe° and α-Fe2O3.The higher catalytic
^Fe eOH(H2O2)(s) → ^Fe eOH(HO2%)(s) + H
III II +
(13)
activity of Hetero-EF process arises from the formation of more ^FeII
^Fe eOH(HO2%)(s) → ^Fe eOH + HO2% + H
II II +
(14) mediator via electron transfer among the iron species as shown in Fe°
and iron oxides composite and ferrite-carbon aerogel. This can also
^Fe eOH + H2O2 → ^Fe eOH + %OH + OH–
II III
(15) explain the higher catalytic activity and role of Co and Cu co-catalyst in
%OH + organic pollutants → byproducts → CO2 + H2O (16) Fe/Cu and Fe/Co functionalized cathodic materials since the addition
of Co or Cu led to the formation of more ^FeII mediator as depicted in
%OH + H2O2 → HO2% + H2O (17) Eqs. (23) and (24).
The surface-catalyzed mechanism (Fig. 3) is initiated with the ^Fe° + 2^FeIII → 3^FeII (22)
generation of H2O2 at/within the cathode and simultaneous partial
reduction of ^FeIIIeOH at the surface of the Fe-containing catalyst to ^Co + ^Fe → ^Fe + Co
II III II II
(23)
^FeIIeOH by obtaining one electron (Eqs. (10) and (11)) as current is ^Cu + ^Fe → ^Fe + Cu
I III II II
(24)
applied across the system [20,45,94]. The generated H2O2 can interact
strongly with the negatively charged catalyst surface, forming a pre-
cursor surface complex ^FeIIIeOH(H2O2) within the inner and outer
surface of the cathode matrix [95]. More so, the surface H2O2 complex 4. Required features of efficient heterogeneous catalyst
may be transformed into ^FeIIeOH(HO2%) via reversible ground state
electron transfer from the ligand to central atom (Eq. (13)), followed by Wide varieties of substrates/materials can be selected as model
deactivation to form ^FeIIeOH (Eq. (14)) [20,61,62,92,93]. It is ob- catalyst and range of reaction conditions may be involved, therefore it
vious that the rate of reactions in Eqs. (13) and (14) can be significantly is necessary to enumerates what would be the most important para-
accelerated by increasing the pH towards alkaline conditions, since the meters that should be determined in order to rate different materials
rapid consumption of H+ will swiftly shift the equilibrium towards the based on their activity to catalyze the decomposition of H2O2 in
formation of more ^FeIIeOH [30]. After that, H2O2 is directly and Fenton’s or Fenton’s-like reaction [104]. The most important parameter
catalytically decomposed by FeII to %OH, which can oxidize the organic is the catalytic activity and stability of the material over wide experi-
pollutants until their complete mineralization to CO2 and H2O. The % mental conditions. The material should possess good catalytic activity
OH can also react with excess H2O2 (quenching) to produce hydro- which must be less affected by experimental conditions, especially pH,
peroxyl radical (HO2%) (Eq. (17)), which is a much weaker oxidant and high stability to ensure the reusability in several runs
compared to %OH, thus reducing the efficiency of the process. [83,91,104–106]. It is important to note that reusability in several runs
Other transition metal especially Co and Cu may also catalyzed the is not a good criterion to assess stability of the catalyst because pollu-
decomposition of H2O2 via surface mechanism as reported for tant-to-catalyst ratio usually determines the reusability of the catalyst
CoIIFeIIILDH modified carbon-felt [19], Fe3-xCuxO4 nanoparticles [96], [107]. This implies that for solid catalyst with high stability, large ex-
Fe-Co and Fe-Cu carbon-aerogel [84,97]. It this case, ^FeIIeOH re- cesses quantities would allow possible reusability of the catalyst in
duzate could be formed by an electron reduction of ^FeIIIeOH by both several consecutive reactions runs, whereas less amount of solid cata-
CoIIeOH and CuIeOH according to Eqs. (18) and (19). Additionally, lyst may make reusability more difficult. Optimization of the quantities
direct decomposition of H2O2 through CoIIeOH and CuIeOH catalysis of the catalyst may be necessary because excess material could enhance
to generate %OH could be also achieved at the surface of the transition the destruction of the generated %OH by its destructive attack on the
metals-containing solid catalyst (Eqs. (20) and (21)). Overall, transition catalyst especially when utilizing materials with low stability
[104,108]. The optimum quantity of solid catalyst required for certain

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wastewater treatment is closely related to the catalytic activity/prop-

erties of the solid, treated volume as well as organic matter content of
the wastewater. The measurement of the maximum productivity of the
catalyst may also be necessary considering the varieties and amount of
solid catalyst used in Hetero-EF. Navalon et al. [104] has proposed a
simple test in which a large excess substrate is used in a prolonged
experiment until total deactivation of the catalyst. The data obtained
will not only provide the maximum productivity but also information
about the causes of deactivation of the catalyst. It may also necessary to
wash the catalyst under alkaline conditions because the metal ions may
form complexes with carboxylic acids, which are usually the final end
organic products of electrochemical oxidation of organic pollutants.
Besides in Hetero-PEF, the support material on which the catalysts
(catalyst supported or impregnated on substrates) are deposited must
be photo-resistant and non-radical scavenger to avoid degradation of
the support.
Closely related to the stability of the catalysts as well as reusability
is the absence of leaching of metal species from solid catalyst or de- Fig. 4. EIS spectral of raw and CoFe-LDH modified carbon-felt performed in
50 mM Na2SO4 solution at voltage amplitude of 10 mV in the frequency range
activation/mechanical wearing of catalyst from the solid support into
of 50 kHz to 100 MHz.
the aqueous phase, which is one key issue because it determines the
Adopted and printed with the permission of Ref. [19].
contribution of homogeneous EF to the catalysis of the H2O2
[104,109,110]. Minimum concentration of metal species could be af-
forded in the solution because the species can act as homogeneous experiments are required to evaluate either the decomposition of the
catalyst. In the case, where there is significant leaching or mechanical H2O2 by the substrate used as support for the catalyst and products
wearing of the solid catalyst, the overall catalytic activity could be the formed or the capacity of functionalized cathodic material for produc-
combination of the activity of the leached species and solid catalyst. tion of H2O2.
This was the case observed at pH 2 for CoIIFeIIILDH functionalized Further, the toxicity and environmental compatibility of the solid
carbon-felt [19,111], electrochemically prepared iron-modified acti- catalyst are other important parameters that should be considered for
vated carbon electrode [112] and other solid catalysts [113,114]. On materials selected as catalysts or as supports for the catalyst. Iron oxides
the other hand, excessive leaching of metal species from solid catalyst and supported Fe-compounds are considered more environmental
may enhance the efficiency of Hetero-EF process especially at acidic pH friendly and exerted no toxicity in environment; as such leaching of
conditions, at which Fenton’s reaction is optimum, thus the system iron ions into the solution and its subsequent disposal and the residual
proceeds like a typical homogeneous EF process. The major dis- solid catalyst into surface water and/or environment has limited en-
advantage of leaching is depletion of the active metal sites in the solid vironmental consequences to ecosystem. However, recently other
catalysts which decreases the reusability, and if persisted for long time, transition metals like copper, manganese, vanadium, nickel and cobalt
it will cause the loss of the solid catalytic activity [104,115]. have been used along with iron/iron oxides as solid catalyst in Hetero-
In the case of functionalized cathodic materials, the electrochemical EF [96,116]. In this case, the disposal of the treated solution or the
properties of the modified material are an important parameter which residual solid catalysts may have serious environmental implications
can influence the performance of the Hetero-EF system. The nature and since these metals ions are considered toxic especially cobalt. There-
quantity of the solid catalyst grafted on the cathode material as well as fore, careful selection of catalyst/support materials is needed to avoid
the preparation route should have minimum negative effect on its use of materials with questionable environmental compatibility as solid
conductivity since this could affect the charge transfer at liquid-solid catalyst/support in Hetero-EF system. Additionally, exclusive descrip-
interface and may reduce the potential of the material for production of tion of the preparation procedure and explicit characterization data are
H2O2. Most iron/transition metals compounds have lower conductivity other parameters that should be considered in order to ensure re-
than minimum required for EF cathode materials, as such reduces the producibility of the material and the catalytic performance [104]. The
electrical conductivity (increased electron-transfer resistance) of car- catalyst/supported catalyst or functionalized cathodic materials for
bonaceous materials commonly used in EF when grafted or functiona- Hetero-EF should have easy production or fabrication route as well as a
lized with these oxides. In most cases, the reduction in the conductivity cost effective for possible adaption on commercial scale. Studies on
is very significant but still within the limit required for successful catalyst/supported catalyst or functionalized cathode materials with
electrochemical process, even though the effect of cathode modification complex and expensive route may only end-up on laboratory or pilot
on electron-transfer resistance depends on the compound grafted on the scale, because treatment of organic pollutants in wastewater or re-
cathode. For instance, interfacial electron-transfer resistance (Rct) for cycling water system is considered as a non-profit but essential stage of
raw carbon-felt determined by electrochemical impedance spectroscopy production, which may only become necessary in order to comply with
(EIS) was 2.3 Ω but it reduced to 0.97 Ω after modification with environment regulation of the country. As such techniques or processes
CoIIFeIIILDH (Fig. 4), indicating a substantial reduction in electron- with minimum cost implication are usually preferred even if it is less
transfer resistance of the cathode and consequently, improving the effective.
electrochemical properties of the cathode [19]. Contrast results were Finally, based on the above explanation, it is clear that to propose a
observed for carbon-aerogel with the Rct values of 3.8 Ω and 75.8 Ω material as potential heterogeneous catalyst/supported catalyst or
obtained for pure and ferrite–doped carbon-aerogel respectively, de- functionalized cathodic materials, extensive studies are required to
monstrating a reduction in electrochemical properties of prepared determine the experimental conditions range in which the materials can
cathode [20]. exhibit catalytic activity and stability, extent of leaching at these con-
Additionally, the substrate used to support the solid catalyst or the ditions, interaction of support with the H2O2 and the environmental
cathode material modified by iron compound should be non-reactive compatibility of the solid catalyst and/or support. For functionalized
(physically or chemically) with H2O2 since the efficiency of the Hetero- cathodic materials, it is advisable to present the electrochemical prop-
EF system is not only determined by the activity of the catalyst but also erties along with description of synthesis procedures and well-founded
on the concentration/production rate of H2O2. Therefore, prior characterization data.

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5. Hetero-EF with catalytic addition groups, natural pyrite and chalcopyrite have been studied as a sus-
tainable solid heterogeneous catalyst and pH regulator for the miner-
Hetero-EF process with catalytic addition utilized solid catalysts alization of different classes of organic pollutants [26]. For instance,
which are natural or synthetic, relatively insoluble iron or iron-con- Labiadh and co-workers [25] studied natural pyrite as heterogeneous
taining compound with or without supported on substrate to catalyze solid iron dosage for the mineralization of new synthetic dye 4-Amino-
the decomposition of H2O2 to %OH. As stated earlier, the overall aim is 3-hydroxy-2-p-tolylazonaphthalene- 1-sulfonic acid (AHPS) in an un-
to achieve reusability of the catalyst, easy separation after EF treatment divided reactor equipped with boron doped diamond (BDD) anode and
and widening the pH window at which EF can be perform. The catalytic carbon-felt cathode. The authors observed that the dissolution of the
activity is usually the combination of homogeneous metal-ions and pyrite sharply reduced the pH of the solution from 6.07 to between
heterogeneous surface catalyzed process because extensive leaching of 4.03–3.0 within the first 10 min after adding 0.5–6.0 mg L–1 pyrite; and
metal ions into the solution occurs especially when perform Hetero-EF it further decreases to 3.9–2.8 after 15 min at similar dosage using
at around pH 3 [22,117]. The solid catalysts that have been in- 230 mL of solution. Over 90% mineralization efficiency was attained
vestigated in literature are grouped into two – natural minerals and after 5 h of electrolysis with 2.0 g L–1 of pyrite dosage at applied current
synthetic iron-containing nanoparticles/iron-supported solid catalysts. of 300 mA, whereas analogous studies with homogeneous EF using
The details of the studies are provided in Sections 5.1 and 5.2. 0.45 mM Fe2+ could only attained 70% mineralization at the same
electrolysis time. Further studies by the same group [28] have shown
5.1. Natural minerals that the addition of 1.0 g L–1 pyrite dosage to aqueous solution of tyr-
osol adjusts easily the solution pH to around 3 and provided approxi-
Several studies have demonstrated the potential of some solid iron- mately 0.2 mM Fe2+ to catalyze the so called EF-pyrite system. Com-
bearing natural minerals to catalyze the decomposition of H2O2 to %OH parative studies using 0.2 mM Fe2+ and 1.0 g L–1 pyrite dosage for
and in turn, mineralization of different class of organic pollutants. In conventional EF and EF-pyrite, respectively, at 50 mA, showed that the
most cases, the systems allow expanding the working pH window to mineralization efficiency attained by EF-pyrite was approximately 5.8
neutral media and preventing the accumulation of iron sludge. Pioneer times higher than that obtained in conventional EF. The superior effi-
studies investigated the viability of goethite (α-FeOOH) as a solid ciency of EF-pyrite was attributed to the “self-regulation” of the Fe2+
heterogeneous iron catalyst source for the mineralization of aqueous ions in the system by the pyrite as explained in Section 2. In related
aniline solution in a modified EF process termed “goethite-catalyzed EF studies, the EF-pyrite process was also investigated for the miner-
(GEF) process [23]. At optimum EF conditions, 95% mineralization was alization of antibiotics levofloxacin [27], sulfamethazine [26], tetra-
attained with the GEF process, suggesting α-FeOOH as a suitable solid cycline [61,118] and phenolic compound, vanillic acid [119] with the
iron dosage source for Hetero-EF process. Subsequent work [24] by the TOC removal efficiency always higher for EF-pyrite compared to con-
same group reported the catalytic behavior of other iron oxides mi- ventional EF, at similar experimental conditions for the pollutants
nerals such as wustite (FeO), magnetite (Fe3O4) and hematite (α-Fe2O3) studied. In particular, the mineralization efficiency obtained in EF-
for the catalytic decomposition of H2O2 in both EF and PEF processes. pyrite with Pt was quiet similar to those attained in convention EF with
Graphical representation of TOC removed after 5 h of EF treatment of BDD anode during the treatment of sulfamethazine, which is very ex-
100 mg L–1 aniline solutions with 1 g L–1 of these solid catalysts or citing consider the cost of BDD anode (Fig. 6a). The group [60] also
0.5 mM Fe2+ using Pt/GDE cell is shown in Fig. 5. It was observed that shown that complete detoxification of sulfamethazine and tetracycline
only wustite (62%) and magnetite (58%) achieved more TOC removal could be achieved at optimum experimental conditions and the pyrite
than Fe2+ (54%) during the EF treatment, whereas the catalytic effi- itself have exhibited no toxicity/inhibition to bacteria V. fischeri used
ciency of goethite and hematite was much lower. The trend in the TOC in microtox® analyses (Fig. 6b).
removal efficiency was related to the ability of the solid iron oxides to
release Fe2+ to the bulk to catalyze the activation of electrogenerated 5.2. Synthetic iron/iron-containing nanoparticles/supported solid catalysts
H2O2 through Fenton’s reaction (Eq. (1)), so the system behave as pure
homogeneous EF process with the solid catalyst acts as self-regulator of Synthetic iron oxides and iron-contained nanoparticles and sup-
iron dosage. ported solid catalysts have been investigated for the Hetero-EF treat-
In a recent collaboration works between Oturan, Brillas and Ammar ment of different classes of organic pollutants. The mechanism of de-
composition of H2O2 to %OH is similar to that of natural iron mineral
catalyst, which is a combination of homogeneous catalyzed process by
leached/dissolved Fe2+/Fe3+ redox cycle from the solid catalyst and
surface catalysis at the solid-liquid interface with some few exceptions.
The synthesis techniques varies from one solid catalyst to other and
extensive characterization of these catalysts are most studied along
with their catalytic activity [91,120]. For instance, Hou et al. [29] in-
vestigated synthetic nano-Fe3O4 for the Hetero-EF oxidation of catechol
with the aim of evaluating the effect of operating parameters such as
temperature, pH, current density, catalyst loading, initial catechol
concentration as well as reusability of the nano-Fe3O4. The degradation
efficiency of catechol was found to decreases with pH, but satisfactory
efficiency was still attained at pH 6. Initial catechol concentration did
not affect its removal efficiency, but the efficiency increases with the
Fe3O4 loading within the range studied (0.25–2.0 g L–1). Besides, less
than 10% of reduction in degradation and mineralization efficiency was
observed after 8 cycles of reuse, demonstrating the high stability and
Fig. 5. comparison of TOC removal achieved after 5 h of EF and PEF treatment reusability of the nano-Fe3O4 in Hetero-EF process. Other research
of 100 mg L–1 aniline solutions containing 0.2 M Na2SO4 at pH 3, 0.5 L min–1 air groups [121–125] have also utilized Fe3O4 nanosphere supported Pd
flow, and 250 mA applied current in Pt/GDE cell using 0.5 mM of Fe2+ or (i.e. Pd/Fe3O4) as solid heterogeneous catalyst for the simultaneous
1 g L–1 of solid iron catalyst. generation of H2O2 and catalytic decomposition of H2O2 to %OH
Reprinted with the permission of Ref. [24]. (Fig. 7). The synthesized Pd/Fe3O4 showed efficient mineralization of

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S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

Fig. 6. (a) TOC decay vs electrolysis time for the mineralization of 200 mL of 0.2 mM sulfamethazine solution in 0.05 M Na2SO4 at pH 3, 300 mA and room
temperature using undivided ( , ) Pt/CF and (■, ) BDD/CF cells with ( , ■) 1 g L–1 pyrite and ( , ) 0.2 mM Fe2+. The corresponding MCE is shown in the inset
panel. (b) Evolution of solution toxicity assessed in terms of percentage inhibition of the luminescence of V. fischeri bacteria after 15 min of exposure during
electrolysis at the same conditions as (a) using BDD/CF cell.
Reprinted with the permission of Ref. [26].

Pd loading. Meanwhile, the catalytic activity of the Pd/Fe3O4 deterio-

rated severely with use due to difficulty in recovery of the nano-
particles, thus limited the reusability of the catalyst. The catalyst has
also been studied for the degradation of phenol [123], 4-bromophenol
[121], Rhodamine B [126] and trichloroethylene in groundwater [127].
Other studies have utilized nanostructured Pd/Fe modified graphene
[128] and Pd/Fe nanoscale particles [129] for degrading chlorinated
phenols. In most cases, the Pd nanoparticles catalyzed the combination
of H2 and O2 electrogenerated at the cathode and anode respectively to
H2O2 according to Eqs. (25)–(28) [122–124,130], which is an im-
portant reagent for Fenton’s reaction.
Pd
H2 + O2 → H2 O2 (25)
Pd 1/2
H2 O2 + O2 → H2 O + O2 (26)
Pd
H2 O2 + H2 → 2H2 O (27)
Pd
O2 + e– → O•2− (28)
Some authors have also studied Fe2O3/supported-Fe2O3 nano-
particles or solid catalysts for Hetero-EF degradation of organic pollu-
tants. For example, Yue et al. [131] investigated α-Fe2O3/γ-Al2O3 na-
Fig. 7. Proposed mechanism of humic acids and Cr (VI) removal using Pd/ nocatalyst for degrading 500 mg L−1 of Acid Red 3R and the
Fe3O4catalyst. decolorization efficiency of 77.2% was attained in 100 min at optimum
Adapted from Ref. [122]. conditions of pH 3, 0.2 m3 h–1 airflow and 20 V applied constant vol-
tage. The LC–MS analysis of the treated solution showed that the azo
pentachlorophenol [124] as well as simultaneous removal of Cr (VI) dye was firstly degraded into aromatic intermediates, followed by ring
and degradation of humic acids in aqueous solution [122]. Complete opening into carboxylic acids before final mineralization to CO2. Re-
removal of pentachlorophenol was attained in 30 min at applied voltage cently, Ozcan and co-workers [132] reported the efficiency of Fe2O3
of 5 V, pH 2.8 and 288 k with Pd/Fe3O4 compared to 17.2% obtained modified kaolin for Hetero-EF degradation of antibiotic enoxacin. The
with electrochemical oxidation treatment alone; and approximately mineralization rate of enoxacin attained its maximum value at 0.3 g
90% of mineralization of humic acids and higher Cr (VI) removal effi- Fe2O3-kaolin loading, pH 2.0–3.0 and applied current of 300 mA. In-
ciency was attained at the optimal experimental conditions. The Pd/ teresting, complete mineralization of enoxacin were also obtained at pH
Fe3O4 nanocatalyst acts as electron and hydrogen atoms transfer carrier 5.1 and 7.1 and less than 0.5% reduction in mineralization efficiency
and the oxidation of organics was performed by the participation of O2% was observed after 5 cycles of reuse, demonstrating the efficiency of the
and %OH, whereas the reduction of Cr (VI) was attribute to the con- catalyst over wide pH range and it high recyclability.
tribution of Pd/Fe3O4 nanocatalyst and the atomic hydrogen on the Two Chinese research groups have also studied iron containing
catalyst surface (Fig. 7). The Pd nanoparticles anchor on the Fe3O4 perovskite-like solid catalysts ZnFe2O4 [133] and Bi2Fe4O9 [134] for
nanosphere was found to enhanced the atomic hydrogen and H2O2 the Hetero-PEF and Hetero-EF degradation of benzotriazole and 1-
production and in turns Cr (VI) and humic acids removal efficiency up diazo-2-napthol-4-sulfonic acid, respectively. Heterogeneous PEF using
to 5 wt%, whereas no essential change in efficiency was found at higher ZnFe2O4 showed high catalytic activity for degrading benzotriazole

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with 91.2% and 85.3% for degradation efficiency and COD removal, limited desorption.
respectively, after 180 min of treatment at optimum experimental Some studies have utilized solid Fe-containing compound in bioe-
conditions with graphite electrodes. The benzotriazole degradation ef- lectrochemical system/bioelectro-Fenton technology (BES/BEF) using
ficiency and COD removal decreased with an increase in pH and initial microbial fuel cells (MFCs) [139,140]. In MFC, the biooxidation of or-
benzotriazole concentration; but increased with ZnFe2O4 dosage in the ganic substrate in the anode chamber by microorganisms produces
range of 0–0.067 g L–1 and applied negative voltage between –0.3 to electrons that are transfer via external circuit to the cathode, where it
–0.6 V. Similar results were observed during the Hetero-EF process in a reduces electron acceptor mostly oxygen to H2O2 [141–143]. The flow
reactor equipped with Ti/GDE electrodes using Bi2Fe4O9 as catalyst, electrons produced electricity in the circuit due to drop in potential
however, the degradation efficiency of 1-diazo-2-napthol-4-sulfonic difference (Fig. 9). In essence, MFC converts chemical energy of organic
acid and COD depletion depended on the solution pH, Bi2Fe4O9 dosage substrate to electrical energy [144–146]. By addition of suitable iron
and applied current. At optimum conditions, almost complete COD source in the cathodic chamber of MFC, the produced H2O2 can be
removal (89%) was achieved after 200 min of treatment, whereas catalytically activated to %OH in a process called bioelectro-Fenton
comparative electrochemical oxidation (without Bi2Fe4O9) and ad- process (BEF) (Fig. 9) [147–149], thus utilizing the produced electricity
sorption (with Bi2Fe4O9) studies merely attained 39% and 32% COD to driven electrochemical system. Several studies have reported effi-
removal, respectively, at similar treatment time. Other group [95] has cient mineralization of biorefractory organics in the cathode chamber
also investigated the catalytic activity of Fe3-xCuxO4 (0 ≤ x ≥ 0.25) of MFCs using BEF along with concurrent production of electricity.
nanoparticles prepared by co-precipitation method for the Hetero-EF For instance, efficient removal of p-NP was reported by Tao et al.
treatment of amaranth food dye solution at strong alkaline conditions [139] in BEF using a dual chamber MFC with continuous injection of
(pH 13.4) in a three-electrode cell that consists of GDE as working limonite (α-FeOOH) powder into the cathode chamber as main source
electrode and Pt and Ag/AgCl as counter and reference electrodes, re- of iron dosage. Up to 96% of p-NP (0.25 mM) was removed in 6 h at
spectively. The degradation and mineralization of the azo dye was so- optimal conditions and a limonite dosage of 112 mg per 50 mL of p-NP
lely by surface catalyzed process without contribution from homo- (0.25 mM) was found to sustained 7 cycles of BEF operation with p-NP
geneous catalysis since the catalyst is insoluble at the working pH. removal efficiency > 94%. The mechanism of degradation of p-NP was
Almost complete color removal and degradation efficiency (98%) and by %OH generated from catalytic decomposition of H2O2 electro-
high mineralization efficiency (70%) was achieved after 90 min of generated at the carbon-felt cathode by homogeneous Fe2+ released
treatment at 0.15 mM dosages and –1.1 V applied voltage. into the bulk via partial dissolution of α-FeOOH. Other studies related
Similarly, Zhou’s group [135–137] have studied Fe-C modified by to Hetero-EF with iron/iron-containing nanoparticles and supported
polytetrafluoroethylene (PTFE) as solid catalyst for Hetero-EF de- iron catalysts including BES/BEF are summarized in Table 3.
gradation of 2,4-dichlorophenol (2,4-DCP) at circumneutral pH with
much emphasis on the influence of operating factors on degradation
6. Heterogeneous electro-Fenton with Fe-functionalized cathodic
and mineralization of the pollutant, mechanism of degradation and electrodes
degradation pathway. The catalytic activity of the Fe-C was well
maintained after PTFE coating with much lower iron leaching; and the Fe-functionalized cathodic materials have been recently developed
degradation efficiency of 2,4-DCP exceeded 95% within 120 min of for application in heterogeneous electrocatalytic oxidation of refractory
treatment at current intensity of 100 mA, initial pH 6.7 and 6 g L–1 organic pollutants. In this context, the functionalized material serves
catalyst dosage. A synergetic effect between anodic oxidation at the dual purpose of electrode as well as the catalyst source in Hetero-EF
surface of the Ti/RuO2-IrO2 and heterogeneous catalysis on the single system. In many cases, the catalysts are impregnated or loaded on
Fe-C was observed for the degradation and mineralization of the 2,4- materials with higher capacity to generate H2O2, such as active carbon/
DCP (Fig. 8). The catalytic activity of PTFE modified Fe-C was highly fiber, carbon-felt, graphite felt, and recently carbon aerogel. The cata-
stable and there was only negligible reduction in 2,4-DCP degradation lytic performance in most cases is due to combination of both homo-
efficiency over 15 cycles of consecutive runs with relatively low iron geneous oxidations in the bulk of the solution because of leaching of the
leaching ratio. Meanwhile, Ramírez et al. [138] utilized Fe – supported catalyst and heterogeneous oxidation at the surface of the cathode at
on Nafion membrane and ion-exchange amberlite and purolite resin as low pH values, whereas surface catalyzed process is predominant as pH
a catalyst in PEF process for degradation of aqueous orange-II dye so- increases (as explained in Section 3). However, the properties of the Fe-
lution. While up to 60% TOC removal was achieved under experimental functionalized cathodic material especially the chemical stability in
conditions employed, the Fe was relatively fixed on the supports with acidic solution play a key role in determine the contribution of the

Fig. 8. Proposed mechanism and degradation pathway of 2,4-DCP during the Hetero-EF treatment using Fe-C catalyst.
Reprinted with the permission of Ref. [136].

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Fig. 9. Microbial fuel cell-bioelectrochemical system (bioelectro-Fenton process) for the concurrent generation of electricity and heterogeneous EF treatment of
organic pollutants.
Adopted from Ref. [139] with modification.

homogeneous EF in the overall mineralization of organic pollutants electrodes could activate molecular oxygen to produce (O2%)– via a
during Hetero-EF process. Additionally, the efficiency, stability and single electron transfer to subsequently generate more H2O2 and in turn
reusability of the catalyst impregnated electrodes/functionalized %OH. Synthetic RhB solution has been also treated by 3D EF using iron-
cathode are largely affected by the technique by which the catalyst is slag/clay particle electrodes in a micro-electrolysis cell equipped with
grafted onto the carbon matrix. The technique used controls the ad- Pt anode and stainless steel cathode [172]. The particle electrodes with
hesion and mechanical wearing of the catalyst from cathode matrix. particle size 3–5 cm was prepared from pot milled steel slag powder
Several Fe-functionalized cathodic materials have been reported in mixed with clay and pore forming agent and calcinated at 1050 °C for
literature with widely varying properties and synthesis/preparation 30 min. The 3D EF treatment of RhB solution with the iron-slag/clay
techniques/routes, as such there is no consensus or generalized method particle electrodes could achieve 82.4% and 65.45% removal efficiency
to obtain the functionalized cathodic materials. However, based on the with or without the airflow in 60 min. Additionally, the particle elec-
existing literature, these functionalized cathode materials can be trodes was found to exhibited satisfactory cyclic performance over 8
broadly grouped into three classes according to the nature of the bulk cycle of reuse. A typical degradation scheme involving particle elec-
material on which the Fe/Fe-containing compounds is loaded. These trodes and removal efficiency of Fe-Cu allophane clay particle elec-
groups are: Fe/supported Fe- containing particle electrodes, Fe/Fe- trodes for the mineralization of phenol are shown in Fig. 10a and b
containing compound modified carbonaceous cathode and Fe/Fe-tran- respectively.
sition metals carbon-aerogel and are discussed vividly in the next three A Chinese group has also studied a neutral 3D EF system with
sections. various bentonite-based Fe particle electrodes for the degradation of
phenol [80], Acid Orange II [174] and pulp and paper mill wastewater
6.1. Fe-particle electrodes [175]. The group showed that at optimal condition and pH 6.24, Fe3O4-
bentonite, Fe2O3-bentonite and Fe°-bentonite could achieve 13.28%,
Several studies have reported the use of 3D Fe-containing particle 57.8% and 67.48% COD removal respectively after 4 h of treatment of
electrodes for heterogeneous electrochemical treatment of refractory phenol solution. Analysis of the Fe leaching behaviors from the particle
organic pollutants. In most cases, the particle electrodes with high ac- electrodes during the degradation of phenol revealed that both homo-
tivity and stability are packed in between the anode and cathode of geneous and heterogeneous EF reactions contributed to the degradation
electrochemical cell for the degradation of the pollutants. The particle of the phenol. Similar results were reported for Fe-bentonite particle
electrodes have been also demonstrated to enhance the conductivity of electrodes for the degradation of Orange II with COD removal and
the solution and the mass transfer of substances during electrolysis decolorization efficiency of 71.57% and 98.89%, respectively [174].
[171]. Fe/Fe-compounds supported on mesoporous materials especially Other relevant studies on the application of Fe-particle electrodes for
clay minerals are the most studied particle electrodes reported in lit- 3D heterogeneous EF degradation of organic pollutants are summarized
erature, majorly because clay materials are largely abundant and in- in Table 4.
expensive as a support material. Liu and co-workers [171] studied Fe-Ni
foam particle electrodes for 3D EF treatment of RhB solution using Ti/ 6.2. Fe-functionalized carbonaceous cathode material
RuO2-IrO2 and activated carbon as anode and cathode, respectively.
The 3D EF system was able to achieve higher RhB removal efficiency Fe-functionalized cathode based on carbonaceous materials are the
(99%) compared to analogous electrochemical system (without Fe-Ni most widely studied functionalized cathodic materials for Hetero-EF
foam) (33%) and EF system (13%) at neutral pH conditions in 30 min. treatment of organic pollutants because of the high capacity of carbo-
The enhanced degradation efficiency was attributed to the production naceous materials for the in-situ production of large quantities of H2O2
of more %OH in the 3D EF system because the Ni-foam particle (Fenton reagent) during electrolysis. Indeed, several studies and

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 Table 3
Summary of some relevant studies on Hetero-EF system catalyzed by Fe/Fe-supported solid catalysts.
catalyst pollutants electrodes Technology operation main results
conditions
S.O. Ganiyu et al.

Iron rich sludge 1,4-dioxane Ti/RuO2/SS EF undivided glass stirred tank reactor connected to Peristaltic pumps; 5.3 mM 1,4-dioxane removed at current efficiency over 70%
1000 mL solution; j = 2.8 A cm–2 for 120 min; pH 2.0–3.0 [150]

Fe-AB Lissamine green B Azure B Gr EF undivided cylindrical glass reactor; 150 mL solution;14.19 V applied 98–100% removal efficiency for both dyes; catalytic activity
potential for 30 min; 8.69 g Fe –AB; pH 2–8. unchanged after 3 cycles [151]

Gr EF airlift continuous flow reactor; 1500 mL solution; 115 g Fe–AB; 81% and 87% decolorization for Lissamine green B and Azure B
1.5 L–min–1 air flow; 3 V constant voltage; pH 2 respectively [152]

Imidapricloprid BDD/Gr EF undivided glass reactor; 150 mL solution; 5 V constant voltage for 30 min; 98–100% removal efficiency in successive batches; efficiency
4.27–16.84 g Fe-AB; pH 2 – 7. decreases with increased pH and Fe-AB dosage [153]

Indole Pt/CF EF/PEF undivided closed glass reactor; 250 mL solution; j = 0.13 – 0.8 mA cm–2; 90% TOC removal in 7 h at pH3, 0.53 mA cm–2, and 200 mg L–1
50 – 250 mg L–1 Fe-AB; pH 3; 25 °C Fe-AB; UVA-PEF only achieve slight increase inefficiency [31]
Reactive Black 5 Gr EF undivided glass reactor; 150 mL solution; 5.69 V constant voltage; 65% COD removal [154]
2.68 mM of Fe-AB beads; pH 2.24
Mn-AB Reactive Black 5 Gr EF undivided cylindrical glass reactor; 150 mL solution; 5 V constant voltage; 75% removal efficiency after120 min; stable catalytic after four
6–14 g Mn-AB dosage; pH 2 cycle of reuse [155]
Mn-AB, Fe-AB, and Fe- Winery wastewater BDD/Ni-foam EF undivided cylindrical glass reactor; 150 mL solution in 0.01 M Na2SO4; 56%, 54% and 82% COD removal efficiency for Fe-AB, Mn-AB
AC 15 V constant voltage; 1 L min–1 air flow; 8.7, 14.25 and 3 g of Fe-AB, Mn- and Fe-AC respectively after 24 h [156]
AB and Fe-AC respectively; natural pH
Iron oxide- allophane Atrazine Pt/GC EF three electrode undivided glass reactor; 8 mL of 46 mM atrazine solution; 100% and 76% removal efficiency at pH 3 and 6 respectively
clay –1.04 V constant voltage; pH 3–6; 25 °C [81].

Fe-sepiolite Reactive Black 5 BDD/Gr EF undivided reactor; 150 mL of 100 mg L–1 Reactive Black 5 solution; 3 g Fe- 97.2% decolorization after 90 min; stable catalytic activity after
sepiolite; 5 V constant voltage; pH 2 4 cycle [157]

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Fe-Y zeolite/ Alginate Imidapricloprid and BDD/Gr EF undivided reactor; 150 mL solution; 5 V constant voltage; air flow rateof 98% removal efficiency in 120 min; low reusability but can be
chlorpyrifos 1 L min–1; 50–700 mg L–1 Fe-Y zeolite; pH 3 enhanced by embedded the Fe-Y zeolite in alginate [158]
Fe3O4 NPs RB 19 Pt/ACF EF undivided cylindrical glass reactor; 200 mL of 100–300 mg L–1 of RB19 in 87% TOC removal efficiency in 120 min [159]
0.05 M Na2SO4 solution; 1.0 g L–1 Fe3O4 NPs; j = 3 mA cm–2 and pH 3
4,6-dinitro-o-cresol Gr EF undivided cylindrical cell; 200 mL of 11.4 μg L–1 of DNOC in 0.08 M 100% removal of DNOC in less than 60 min at pH 2.8 [160]
(DNOC) Na2SO4 solution; 1 g of Fe3O4; I = 0.025 A; O2 flow of 40 mL min–1

rGO-Fe3O4 Methylene blue Ni-foam EF undivided reactor; 150 mL of 10 mg L–1 solution; I = 0.5 mA; O2 flow rate 97% decolorization after 24 min [131]
of 40 mL min–1; 30% wt rGO- Fe3O4; pH 2

Pd-Fe3O4 phenol Pt EF undivided reactor; 200 mL of 20 mg L–1 solution; 1 g L–1 Pd/Fe3O4; I 98% degradation efficiency in 60 min; stable catalytic activity
= 50 mA; pH 3; 25 °C over ten cycle of reuse [123]

Pd-Fe MTBE Ti/IrO2-Ta2O5 EF undivided cell; 400 mL of 20 mg L–1 solution; 2 mA cm–2; pH 3; 25 °C 70% removal efficiency in 20days [125]

Fe-AC m-cresol BDD/Ni-foam EF undivided glass reactor; 150 mL of 100 mg L–1 m-cresol solution; 28 mg L–1 83% TOC removal in 2 h; removal mechanism was by adsorption
Fe in Fe-AC; air flow rate of 1 L min–1; 5 V constant voltage; pH 3 onto Fe-AC followed by oxidation [161]

α-Fe2O3 and α-Fe2O3/ Phenol Ni/TiO2 NTs PEF undivided glass reactor; 100 mL solution of 10 mg L–1 phenol solution; 5 V 100% phenol removal in 60 and 120 min for dispersed α-Fe2O3
TiO2 NTs constant voltage; pH 3 and fixed α-Fe2O3/TiO2 NTs respectively [162]
CuO/γ-Al2O3 Amaranth Pt/AQS-PPy EF Undivided electrolytic cell; 200 mL of 80 g L–1 amaranth in 0.1 M Na2SO4 56.35% TOC removal efficiency after 5 h [163]
solution; 1.25 g L–1 of CuO/γ-Al2O3; − 0.4 V cell voltage; pH 4.3
Fe scrap p-NP CF BEF divided glass reactor; 300 mL of 1 mM p-NP; 10 g of scrap iron; pH 2 complete removal of p-NP in 12 h and 85% TOC decay in 96
[164]

FeVO4 Orange II (AO7) C-cloth/CF BEF divided glass reactor; 200 mL of 50 mg L–1 of AO7 solution; 1 g of FeVO4 89% and 81% AO7 and COD removal efficiency respectively
powder; pH 3 [165]

γ-FeOOH AO7 PPy-AQDS/CF BEF divided glass reactor; 75 mL of 0.2 mM of AO7; 1 g L–1 of γ-FeOOH; pH 7 Higher H2O2 electrogeneration and complete mineralization of
AO7 in 60 h [166]
(continued on next page)
Applied Catalysis B: Environmental 235 (2018) 103–129
S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

Note: SS – stainless steel; Gr – graphite; CF – carbon-felt; GC – glassy carbon; AB – Alginate beads; rGO – reduced graphene oxide; MTBE – methyl tert-butyl ether; FCSW – iron contain sludge waste, GDE – gas diffusion
substantial review works [4,79,183–185] have detailed the structural

0.18 A; pH 3 and 1 g L–1 and 0.6 g L–1 Fe3O4-NPs for AR14 and

98% and 99% removal for MB and AR 14 respectively [168]

and physicochemical properties of most carbonaceous materials as
93.35% and 84.46% AR14 and AB92 removal efficiency at
electrodes for energy and environmental applications. They possess
some distinguished characteristics such as good electronic conductivity
and mechanical stability, excellent chemical stability, high surface
areas and porosity which can provide abundant redox reaction sites and

< 96% RB 5 removal after 120 min [169]

excellent electrolytic efficiency at relatively low cost [79,186–188].
Their high abundance in nature, inexpensive and easy accessibility
100% phenol removal in 30 min [170]
make them most studied cathode materials in electrochemical waste-
water treatment. Additionally, carbon is nontoxic and exhibits a high
over-potential for H2 evolution and low catalytic activity for H2O2 de-
AB92 respectively [167]

composition [4,189]. Three dimensional carbonaceous materials, such

as, activated carbon felt/fiber (ACF), graphite felt (Gr), carbon-PTFE O2
diffusion (GDE) and carbon-felt (CF) are the most widely used material
for the preparation of Fe-functionalized cathode due to their high ratio
of surface area to volume, combined with high mechanical stability
which is necessary for effective modification process [190]. Several
modification methods at different experimental conditions have been
reported for the preparation of Fe-functionalized carbonaceous cathode
electrode; AC – activated carbon, NTs – nanotubes, PPy-AQDS – polypyrrole-anthraquinone-2,6-disulfonate; CNTs- carbon nanotubes; NPs – nanoparticles.
Undivided glass reactor; 250 mL of either AR14 or AB92 in 4 g L–1 Na2SO4

Undivided reactor; 1 L of 200 mg L–1 phenol in 1 g L–1 of Na2SO4; 0.5 g L–1

for the application in Hetero-EF treatment of organic pollutants. After

Undivided cylindrical reactor; 150 mL of dyes in 0.01 M Na2SO4; 5 V

modification process, the electrochemical activity of the carbon mate-

rial could be significantly changed [19]. As stated earlier in Section 1,
the Fe- functionalized carbonaceous materials acts as cathode or
working electrode in the electrolysis cell on which dissolved oxygen is
reduced to produce H2O2 as well as iron source for the release of Fe-
species required for the activation of H2O2 to %OH. Besides, the me-
chanism of the decomposition of H2O2 to %OH depends on the prop-
constant voltage; air flow rate of 2 L min–1

erties of the solid iron source loaded on the cathode and the working pH
of the solution.
The functionalized cathode materials have been used both in con-
Fe° NPs; 500 g L–1 H2O2; pH 6.2

ventional Hetero-EF as heterogeneous catalyst system and bioelectro-

Fenton’s system in MFCs for degradation of biorefractory organic pol-
lutants. Especially worth nothing is the pioneer works which utilized
Fe@Fe2O3/CNT as an effective oxygen-fed gas diffused cathode for a
neutral EF system [63]. The Fe@Fe2O3 nanowire was first synthesized
main results

by reaction between FeCl3 and NaBH4. The Fe@Fe2O3/CNT cathode

was prepared by mechanical rolling of paste made from a mixture of
solution

Fe@Fe2O3, CNT, and PTFE suspension in ethanol to form a 0.5 mm thin

–

electrode. The prepared electrode was found to be efficient for H2O2

electrogeneration; and the degradation of RhB with this electrode was
Technology operation

91.5% in 120 min at neutral pH conditions, demonstrating that the

system was very promising for wastewater treatment. Subsequent stu-
dies by the same group investigated Fe@Fe2O3/ACF cathode because
conditions

ACF can easily adsorb iron ions that can be reduced to Fe@Fe2O3 by
EF/PEF

NaBH4 [165]. It was found that the Hetero-EF system with Fe@Fe2O3/
EF

EF

EF

ACF cathode showed higher catalytic activity than EF systems catalyzed

with commercial Fe° powders and ferrous ions (Fe2+) for degrading
Gr/Gr-CNTs

RhB. Since then, several other studies have utilized Fe- modified ACF/
electrodes

rGO-Gr

AC for the Hetero-EF treatment of several pollutants such as m-cresol

and RhB using iron-loaded AC [160] and methyl orange using Fe@
Gr

SS

Fe2O3/ACF cathode in bioelectro-Fenton’s system with MFCs [191].

Excellent production of H2O2 and high catalytic activity was also re-
Methylene blue (MB)

ported for electrochemically prepared iron-modified AC electrodes in

Acid blue 92 (AB92)
Acid red 14 (AR14)

Hetero-EF and Hetero-PEF treatment of synthetic methyl orange solu-

Reactive black 5
Blue Sella solid

tion [113]. Almost total decolorization (96%) and TOC removal (88%)
pollutants

was attained during Hetero-EF treatment in 30 min of treatment,

Phenol

whereas complete decolorization (100%) and TOC removal (98%) was

AR14

achieved in similar treatment time using Hetero-PEF process.

CF electrode has a high specific surface area that favors the fast
generation of both Fenton’s reagent (H2O2 and Fe2+) and can be easily
Table 3 (continued)

modified with Fe and/Fe-containing compounds for application in

Hetero-EF system. Sklari et al. [33] investigated Fe-loaded CF compo-
Fe-hydrogel

sites prepared under oxidizing condition by immersing the CF in

Fe3O4-NPs

Fe°-NPs
catalyst

ethanolic solution of FeCl3.6H2O or reducing condition with continuous

flow of N2. The Fe-CF prepared under reduced condition was found to
have high stability and catalytic activity during Hetero-EF process,

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S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

– 4
Fig. 10. (a) Scheme for degrading organics by particle electrodes and (b) COD removal efficiency at pH 3 and 5 for the mineralization of 100 mL of 5 × 10 M
phenol in 0.05 M Na2SO4by Fe-Cu allophane (APN) clay with different composition of Fe and Cu (Fe6-xCux) at –0.6 V.
Adopted from Refs. [173,82] for (a) and (b), respectively, with modification.

achieving diclofenac degradation and mineralization efficiency of loaded with trace transition metals (M/GDE, M]Cu, Ce, Mn, Fe, Co) as
63.7% and 31.6%, respectively, at low applied potential of 1.0 V vs Ag/ an effective cathode/catalyst for Hetero-EF (Hetero-EF-like) degrada-
AgCl, pH 7 and 34 mg L–1 initial diclofenac solution. Similar studies was tion of methyl orange. The prepared rolling-made GDE demonstrated a
reported by Brillas group [192] where CF/iron oxide air-diffused good catalytic activity and stability for H2O2 production, with a max-
cathode prepared by Fe3+ electrodeposition was utilized for the mi- imum H2O2 concentration of 595 mg L–1generated after 120 min and
neralization of malachite green dye in a Hetero-EF and UVA Hetero-PEF variation of less than 3.36% after 10 cycle of reuse. Among the cathodes
processes. It was observed that the oxidation of the malachite green at studied, Co/GDE showed the highest activity at Co loading of 0.7 wt%
pH 3 was by hydroxyl radicals formed at the BDD anode surface from with highly stable catalytic activity towards pH variation (pH 3–9). It
water oxidation and at the cathode or in the bulk from Fenton’s reaction was confirmed that the degradation of methyl orange was majorly by %
between the deposited or leached Fe2+ and electrogenerated H2O2 in OH produced from the catalytic activation of H2O2 in a Fenton or
both treatment, along with the photo-oxidation by UVA light in het- Fenton-like reaction. Table 5 summarizes some other relevant studies
erogeneous PEF. Complete decolorization of the dye was attained in that have applied Fe-functionalized carbonaceous cathode materials for
both processes, whereas mineralization efficiency of 85% and 98% was Hetero-EF/Hetero-PEF treatment of wastewater.
achieved at 50 mg L–1 malachite green, pH 3 and current density of
21.7 mA cm–2 for Hetero-EF and UVA Hetero-PEF treatment respec- 6.3. Fe-containing carbon-aerogel
tively, after 6 h. Recently, we reported CoFe-layered double hydroxide
(CoFe-LDH) modified CF as an efficient heterogeneous catalyst/cathode Aerogel is a general term used to describe a class of material derived
for mineralization of orange II [19]. The modified cathode synthesized from organic, inorganic or hybrid molecular precursors that are nor-
by in-situ solvothermal process showed highly crystalline, porous and mally prepared by sol-gel process and retain it three-dimensional and
anisotropic CoFe LDH grown on CF (Fig. 11a–d). highly porous network after appropriate drying technology [208].
Electrochemical characterization using cyclic voltammetry and EIS Aerogel was first developed in 1930’s by S. Kistler using supercritical
showed that the prepared cathode was highly stable at neutral pH drying approach to extract pore-filling liquid of wet gels to obtain air
conditions with almost zero percent Fe or Co leaching and good con- filled solid structure with approximately same dimension as their initial
ductivity for electrochemical process. Excellent mineralization of or- wet gel [209,210]. Although, pioneer studies mainly focused on robust
ange II was obtained at all pH values studied and superior miner- aerogels with different stating molecules, the subsequent studies in-
alization efficiency was always achieved in Hetero-EF with CoFe LDH/ vestigated silica (SiO2) type aerogels [211–214]. Due to complex and
CF compared to conventional EF with added Fe2+ and/or Co2+with intricate multistage synthesis procedures, aerogel as a porous material
relatively good reusability (Fig. 11e and f). The mineralization of or- was abandoned and studies about it synthesis and applications were
ange II was via the formation several intermediates and carboxylic acids forgotten for over 30 years. However, different types of aerogels in-
which were later mineralized to CO2 (Fig. 12) cluding inorganic (e.g. SiO2 derived from alkyoxysilanes, TiO2, Al2O3,
Other studies have reported Fe-modified graphite electrodes pre- ZrO2 and others) [211,215–218], organic (polyamide, polystyrene,
pared with various iron sources and techniques for Hetero-EF treatment polyurethane, etc.) [219,220], carbon (carbon, carbon –nanotube, gra-
of different organic pollutants. Graphite electrodes have been ex- phene) [221–224], semiconductor chalcogenide [225], natural based
tensively studied as suitable electrode (both anode and cathode) in aerogels [226–228] and SiC aerogels [222,229–232] have been devel-
electrochemical wastewater treatment owing to their excellent con- oped in the last decades due to advances in synthesis and drying
ductivity and mechanical integrity which can enhance their modifica- technologies. In general aerogel are light material with overwhelming
tion [185,193]. For instance, nanostructured iron oxide/graphite majority of it volume being air, which endows it with interesting
(FeOOH/graphite, Fe2O3/graphite and Fe3O4/graphite) electrodes physicochemical properties, such as high porosity and easy to modified
fabricated from synthetic acid mine drainage was reported to have or functionalized for excellent mass-transfer of reactants/substances
shown high stability and catalytic activity for the degradation of RhB in [233–235].
Hetero-EF system [194]. It was found that EF system using raw graphite Carbon aerogels (CAs) were extensively developed in early 90’s with
could only achieve 30% RhB removal in 120 min whereas up to 62.5%, multi-facet properties and additional functionality such as mechanical
94.5% and 95.6% was attained with FeOOH/graphite, Fe2O3/graphite strength, hydrophobicity and catalytic features for high performance
and Fe3O4/graphite, respectively, at the same treatment time. More applications [236–239].They possess exclusive properties such as low
recently, Zhou group [46,116] investigated a novel roll-made GDE density (∼0.003–0.5 g cm–3), relatively high surface area

115
 Table 4
Summary of some relevant studies on the application of Fe/Fe-supported particle electrodes in Hetero-EF wastewater treatment.
particulate pollutants electrodes technology operation main results
electrodes conditions
S.O. Ganiyu et al.

Fe-Mn – Nitrobenzene Pt// EF Open, undivided 1.3 μM W–1 cm–2 of %OH produced at pH 7; 80 ± 3% and 42 ± 7% NB removal for Pt//FMBO/AC/CB and 0.1 Fe2+ EF respectively after 120 min [176]
carbon FMBO/ glass reactor;
black ACS/CB 400 mL of
100 mg L–1 of NB in
0.05 M Na2SO4
solution; O2 flow
rate of 0.3 L min–1;
8.33 mg cm–2
FMBO/AC loading;
pH = 7
Martite- Paraquat Gr/Pt EF Undivided glass 85.78% and 41.03% paraquat removal efficiency in 150 min for plasma modified and unmodified martite particles [177]
particles cell; 100 mL of
20 mg L–1 paraquat
in 0.05 M Na2SO4
solution; 1 g L–1
plasma modified
martite catalyst;
300 mA applied
current; pH 6
Fe-clay Atrazine Fe-Clay- EF Undivided cell 100% and 76% atrazine degradation efficiency attained at pH 3 and 6 respectively after 8 h treatment [81]
allo- GC//Pt// equipped with
phane Ag/AgCl three electrodes;
30 mL of 45 mM
atrazine in 90% 0.1

116
Na2SO4 and 10%
methanol solution;
− 1.04 V constant
voltage; pH 3–6
Fe2(MoO4)3- Methyl Gr/Gr EF Undivided glass 97% decoloration in 10 min and 92.48 COD removal in 60 min at pH 3 and current density of 68 mA cm–2 [173]
kaolin Orange cell; 300 mL methyl
450 (FM- orange solution in
kaolin- 0.05 M Na2SO4; air
450) flow rate of
1 L min–1; pH 2 –
6.7
Fe-Cu Phenol Fe-Cu/ EF Undivided cell 100% phenol in 2 h and 80% COD removal at pH 3 in 4 h was attained with Fe-Cu allophane [82]
allo- GC//Pt// equipped three
phane Ag/AgCl electrodes; 100 mL
clay of 0.5 mM phenol
in 0.05 M Na2SO4
solution; −0.6 V;
pH 3–5.5
Nano-Fe°/AC Methyl Pt/ EF undivided cell; 80% decolorization in 10 min, and 40% TOC removal after 2 h [178]
orange graphite 130 mL of 60 mg/L
felt solution; cathode
potential −0.65 V,
pH = 3, O2 flow
rate 0.4 L/min
Fe-Slag – clay RhB Pt/SS EF 82.4% and 65.45 RhB removal efficiency with and without particulate respectively [172]
particles
(continued on next page)
Applied Catalysis B: Environmental 235 (2018) 103–129
 Table 4 (continued)

particulate pollutants electrodes technology operation main results

electrodes conditions
S.O. Ganiyu et al.

Undivided cell;
50 mL of 0.01 mM
RhB in 0.1 M
Na2SO4; 15 g of the
particulate;
V=3V
SAC-Fe or Coal Ti/SnO2/ EF Undivided cell; 1 L 78.1% and 37.1% COD removal with SAC-Fe and Fe3O4 NPs respectively in 2 h [179]
Fe3O4 gasification ACF of CGW containing
NPs wastewater 173.3 mg L–1 COD
(CGW) and 48.3 mg L–1
total phenol;
5.0 g L–1 SAC-Fe
and 1.07 g L–1
Fe3O4 NPs; air flow
rate of 4 L min–1;
pH = 6.8
CTAB-bent/ Paper and SS/SS EF Undivided tank 84.3 % and 93% COD and color removal efficiency respectively [175]
OH-Al- pulp mill reactor; wastewater
CTAB- wastewater contain 256 mg L–1
bent COD and UV254
4.183 cm–1;
working volume of
500 mL; air flow
rate of 2.5 L min–1;
applied current of

117
0–3 A
Fe-bentonite Orange II Gr/Gr EF Undivided glass 98.89% and 71.75% decolorization and COD removal efficiency after 1 h of treatment [174]
(Fe-bent) reactor; 400 mL of
100 mg L–1 Orange
II in 0.05 M Na2SO4
solution;
14.29 mA cm–2
current density;
0.5 g PEs; pH 6.4
α and γ- RhB AQ/rGO// EF Divided glass cell 100% RhB removal in 120 min [30]
FeOOH Pt/Ag/ with cation
AgCl exchange
membrane
separator; 0.01 M
NaClO4 as anolyte;
200 mL of
10 mg L–1 RhB in
0.5 M Na2SO4 or
MgSO4 catholyte;
100 g L–1 of PEs;
Oxygen flow rate of
0.6 L min–1; −
0.5 V constant
voltage
Pd-Fe/Ni- DMZ Pt/Pt EF 96.5% DMZ removal achieved in 60 min with Pd-Fe/Ni-foam PEs [180]
foam
(continued on next page)
Applied Catalysis B: Environmental 235 (2018) 103–129
 Table 4 (continued)

particulate pollutants electrodes technology operation main results

electrodes conditions
S.O. Ganiyu et al.

Undivided reactor;
400 mL of
50 mg L–1 DMZ in
5 g L–1 Na2SO4
solution; air flow
rate of 1 L min–1;
12.5 g L–1 of PEs;
current density of
31 mA cm–2; pH 3
AuPd/Fe3O4 BMIM DSA EF Undivided 100% removal of 10 mM BMIM in less than 40 min [181]
cylindrical glass
reactor; 150 mL of
BMIM containing
2.13 g Na2SO4 and
1.5 g of AuPd/
Fe3O4; applied
current of 300 mA;
pH 3

FCSW PE p-NP PbO2/ EF Undivided reactor; 94.31% p-NP removal in 60 min and 78.96% TOC removal in 180 min [182]
GDE 50 mg L–1 p-NP in
0.05 M Na2SO4
solution; air flow
rate of 0.2 L min–1
3 g L–1 of FCSW
PEs; current density

118
3 mA cm–2; pH 3;

Note: FMBO – Fe-Mn binary oxide; ACS – activated charcoal; CB – carbon black; SS – stainless steel; ACF – activated carbon felt; AQ – anthraquinone; DSA – dimensional stable anode; SAC – sludge derived activated
carbon; BMIM – 1-butyl-3-methylimidazolium hexafluorophosphate; GDE – gas diffuse electrode; FCSW – fluffy clump steel wire; PEs – particle electrodes.
Applied Catalysis B: Environmental 235 (2018) 103–129
S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

Fig. 11. SEM image of (a) raw CF and (b) CoFe-LDH/CF; (c) X-ray diffraction pattern of (a) CoFe-LDH powder and (b) CoFe-LDH/CF; (d) Cyclic voltammetry of CoFe-
LDH/CF performed in 50 mM Na2SO4 at (a) pH 5.83, (b) pH 3 and (d) pH 2; (e) comparison of TOC removal efficiency of ( ) 0.2 mM Co2+, (■) 0.2 mM Fe2+, ( )
0.2 mM (Fe2+ + Co2+) (1:1),( )0.2 mM (Fe2+ + Co2+) (2:1) and ( ) CoFe-LDH/CF during the mineralization of 150 mL of 0.1 mM AO7 solution in 0.05 M Na2SO4
at pH 3 and applied current of –40 mA using Pt anode; and (f) TOC removal efficiency with number of cycle using CoFe-LDH/CF at similar conditions as (e).
Reprinted with the permission of Ref. [19].

(∼500–1200 m2 g–1), high porosity (∼88–99.8%) with tunable surface and Hetero-PEF processes, in the last four years.
chemistry combined with ability of being processed into a variety of CAs is prepared by wet chemical synthesis approach, sol-gel reac-
morphologies and sizes to suit different applications [240,241]. CAs is a tion, but through different starting precursors, operating and provision
hybrid aerogels which could well combine advantages of several ma- requirement [214]. The complete steps involved in CAs preparation
terials to achieve specific function. Among other properties, CAs is include sol-gel formation, solvent exchange, ambient pressure drying
characterized by high electrical conductivities and good corrosion re- and pyrolysis (Fig. 13) [246–248]. Firstly, mixture solutions of pre-
sistance especially under the strong oxidizing conditions cursors, water and catalysts are transformed into highly dispersed so-
[222,242–244]. The mechanical robustness and thermal stability of CAs lution of colloidal primary particles or monomers via hydrolysis and
could be tremendously enhanced when hybridized with iron aerogel, polycondensation reactions to form sols. The colloidal particles of the
which is known for its strong mechanical and thermal strength. This sol can connect to one another to form three-dimensional and inter-
type of hybrid aerogel, containing carbon and iron network, has been connected network upon addition of chemical cross-linker or by chan-
developed as a prospective candidate for catalytic applications ging the conditions of reaction (i.e. pH, temperature) [249–252]. The
[32,236,245]. Indeed, several studies have demonstrated the suitability formation of the porous three dimensional networks is the most critical
of this material as Fe-functionalized cathodic material for Hetero-EF and determinant aspect of aerogel [209]. The pore-filling solvent of the

119
S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

Fig. 12. Reaction mechanism for complete degradation of orange II by %OH.

Reprinted with the permission from Ref. [19].

wet gel is exchange with volatile solvent to form the highly porous coarsening and there are changes in textural properties of the gel such
network. To prepare functionalized CAs (i.e. Fe-functionalized CAs), as pore size, porosity and surface area during the ageing process
iron/transition metal containing compounds are added to the homo- [258–262]. Drying the gel without collapsing the original porous 3D
geneous precursor solution prior to the formation of sol [251–255]. The structure is a critical step in aerogel preparation process [262–265].
wet gel is subjected to curing and ageing because the chemical reactions Supercritical drying (using alcohol, acetone, or CO2) is the most pop-
are not finished with gel formation [256]. In fact during the ageing, the ular conventional method for drying wet gel, but it requires reactors
reactive species such as eOH or unreacted monomers contained in the withstanding high pressure, which greatly increase the production cost
gelation solvent inside the pores are condensed onto the network. The [266,267]. Ambient pressure drying and freeze-drying are some of
curing or ageing process is commonly performed by soaking the gel in other prominent drying method reported in literature, however, most
the initial sol or suitable solvent under controlled conditions (pH, time studies on Fe-functionalized CAs utilized ambient pressure drying,
and temperature) for long period ranging from hours to days which is easy and inexpensive [268–270]. The final step of CAs pre-
[212,246,256,257]. The 3D networks of the gel is strengthening and paration is carbonization of the dry gel at high temperature (> 600 °C)

120
 Table 5
Summary of some relevant studies on application of Fe/transition metals modified carbonaceous cathode for Hetero-EF wastewater treatment.
Functionalized Preparation method pollutant technology Operation conditions Main results
cathode
S.O. Ganiyu et al.

Fe/AC Electrochemically, using three MO EF/PEF Undivided glass cell equipped with EF - 96% decolorization and 88% TOC in 30 min, PEF - 100% decolorization and 98% TOC
electrode cell with AC suspended in three electrodes; 25 mL of 10 ppm of removal in 30 min [113]
H2SO4 and addition of FeCl3 in drops MO solution; − 900 mV cathode
potential; pH 3; 25 °C
Fe3O4/GDE Fe3O4/AC was prepared by Tetracycline (TTC) EF Undivided glass cell; 100 mL of 94.2% TTC removal in 100 min [195]
precipitation method; then mixed 50 mg L–1 TTC in 0.05 M Na2SO4
with PTFE, ethanol and Na2SO4 solution; −0.8 V potential vs SCE; pH 3
before forming under in hydraulic
machine
Fe2O3-C/graphite i) pretreatment of Gr membrane; ii) Flutriafol EF Flow reactor; working volume of 79.6% flutriafol removal [196]
membrane deposition of active layer containing 54.84 cm3 at 82.9 L m–2 h–1 flux;
cathode carbon black (CB) and Fe 100 mg L–1 of flutriafol in 0.05 M
iii) deposition of reductive and Na2SO4; current density of 13 mA cm–2;
protective layer using CB and PTFE CB/Fe of 6.2: 1; pH 6.7
γ-Fe2O3-Fe3O4/CF oxidizing condition - soaking of CF in Diclofenac EF Flow reactor with 3 pair of anode/ 85% and 36% diclofenac and TOC removal efficiency respectively [197]
(Fe-NPs/CF) FeCl3.6H2O and dried or reducing cathode; flow rate 40 L h–1; V = 2 V per
condition – passing N2 into solution anode/cathode;
prior soaking
FeCx/N-doped FeCx was prepared by Dimethylarsinate EF Undivided cell, 100 mL of 5 mg L– 1 96% DMA removal in 6 h with residual As (V) concentration less than 0.01 mg L–1 [198]
carbon fiber electrospinning using iron (III) (MDA) DMA in 0.05 M Na2SO4 solution; O2
(FeCx/NCNFs) acetylactonate, N,N- flow rate of 50 mL min–1; applied
dimethylformamide and current of 0.15 A; pH 3
polyacrilonitrile solution
Fe3O4/graphite felt MFC treatment of acid mine drainage RhB EF Undivided reactor; 175 mL of 50 mg L– 1 100% decolorization and mineralization in 10 and 70 h respectively [199]

121
(Fe3O4/Gr) using Gr anode; after operation, Gr RhB in 50 mM Na2SO4 solution; O2 flow
anode was remove and calcined rate = 1.5 L min–1; pH 6.8
QEEG/Fe3O4 Co-precipitation of pre-hydrolyzed Bisphenol EF Undivided cell; 60 mL of 5 mg L–1 Complete bisphenol removal in 90 min [200]
composite ferric and ferrous salt in the presence bisphenol in 0.05 M Na2SO4 solution; air
of QEEG flow rate = 1 L min–1; V = −1.2 V; pH
3
Fe2O3/Gr Precipitation using FeCl3.6H2O and Alcohol wastewater EF Undivided glass reactor; 250 mL of 66.15% COD removal in 69.29 min [42]
NaBH4 solution added in drop wastewater; applied current of
51.54 mA; pH 2.84
Fe@Fe2O3/ACF Precipitation using FeCl3.6H2O and MO BES-EF Divided reactor (MFC); 500 mL of 73.9%–86.7% MO removal efficiency for eight successful cycle [191]
NaBH4 solutions 5 mg L–1 of MO in 0.05 M Na2SO4; O2
flow rate of 750 mL min–1; pH 3
Fe@Fe2O3/CF Precipitation using FeCl3.6H2O and RhB BES-EF Divided reactor (MFC); 75 mL of 95% and 90% RhB decoloration and TOC removal respectively in 12 h [201]
NaBH4 solutions 15 mg L–1 of RhB solution; p H 3
Swine wastewater BES-EF Divided flow reactor at 3.1 or 62.2%–95.7% COD removal efficiency [141]
1.24 L day–1 with organic loading 1.1
and 4.6 g COD L–1 day–1; pH 3
E2 and EE2 BES-EF Divided reactor; 75 mL of 20 mg L–1 81% and 56% removal for E2 and EE2 after 10 h [202]
each of E2 and EE2 in 0.1 M NaCl; air
flow rate of 100 mL min–1; pH 3
Fe@Fe2O3/Gr felt Precipitation using FeCl3.6H2O and Triphenltin chloride BES-EF Divided reactor; 30 mL of 100 mg L–1 of 78.32 ± 2.07% TTCT degradation efficiency at rate of 0.775 ± 0.021 h–1 [203]
NaBH4 solutions (TTCT) TTCT solution; air flow rate of
100 mL min–1; pH 3; 30 °C
Medicinal herb BES-EF Divided cell; 450 mL of wastewater; pH 84.02% COD removal [204]
wastewater 3
FeOOH/TiO2-GAC Sol-gel preparation of TiO2 with Tetracycline BES-EF Divided cell with MBR; 78.75 mL of 90% and 80% COD and NH4-N removal respectively [205]
addition of FeOOH/GAC tetracycline with continuous air flow
Pyrrhotite/Gr Grafting using conductive silver Landfill leachate BES-EF Divided cell; 250 mL of landfill leachate; 77% and 78% color and COD removal respectively [206]
paste pH 5.4
(continued on next page)
Applied Catalysis B: Environmental 235 (2018) 103–129
S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

and ambient pressure under an inert atmosphere of N2 or Ar to de-

compose oxygen and hydrogen moieties in the polymeric chain and
enriches the network with the pure carbon moieties [271,272]. The

100% and 99.5% removal of 4-bisphenol in catholyte and anolyte respectively [121]
synthesis procedure for modified CAs preparation is presented in
Fig. 13.
The earlier studies on the potential of CAs in electrochemical was-
tewater treatment utilized CA as particle electrodes for electrocatalytic
degradation of RBRX dyes [273] and synthetic phenol wastewater
[244]. The CA particle electrodes prepared by ambient pressure drying
technique showed excellent degradation (∼98%) of RBRX and phenol
as well as high catalytic stability up to 20 cycles of reuse. Most studies
100% decolorization and mineralization efficiency [140]

on application of Fe – functionalized CAs cathode for 3D Hetero-EF/PEF

system were conducted by Zhao group with focus on homogeneous
Fe3O4@Fe2O3 [45], ferrite [20], Fe3O4@C, and Fe-Cu [274] CAs. In all
their studies, Fe-functionalized CAs was prepared by sol-gel formation,
solvent exchange, ambient pressure drying and pyrolysis as described
above and the prepared cathodes always exhibited good conductivity,
93% degradation in 120 min [207]

high catalytic efficiency and distinguish stability. For example, Fe3O4@

Fe2O3 CAs composite cathode was reported to achieve excellent effi-
ciency for the degradation of pesticide imidacloprid during Hetero-EF
treatment in pH range of 3–9. Approximately 90% imidacloprid and
TOC removal was attained in 30 and 60 min of treatment respectively,
at current density of 10 mA cm–2 and pH 3 [45]. The catalytic activity of
Main results

Fe3O4@Fe2O3 CAs was satisfactorily stable with pH as the change in

TOC removal efficiency values was less than 3% for treatment per-
Note: QEEG – Quinone-functionalized electrochemically exfoliated graphene; BES – bioelectrochemical system; Fe-CHI – Fe–chitosan.

formed between pH 3–pH 9. Similar results were obtained during the

Hetero-EF treatment of an active ingredient of conventional fungicide
current density of 25 mA cm–2; pH 7 and

Divided cell; 5 mg L–1 in 0.05 M Na2SO4;

air flow of 0.1 m3 min–1; applied current
Divided cell; 75.6 mL of 0.1 mM orange

metalaxyl with homogeneous ferrite CA [20]. The prepared ferrite CA

Divided cell; 150 mL of 100 mg L–1 4-
bisphenol in 0.03 M Na2SO4 solution;

was able to achieve 98% of TOC elimination in 4 h at pH 3 and stable

catalytic activity over ten (10) cycles of reuse at pH 6, with less than 2%
difference in TOC removal (Fig. 14). The same group reported similar
behavior for continuous bulk ultradispersed Fe-Cu CA cathode during
Operation conditions

the Hetero-EF degradation of MB dye with high TOC removal achieved

of 10 mA; pH 6.2

at wide range of pH values (pH 3–9) [97]. It was demonstrated that the
COD of the treated real dyeing wastewater was below China’s discharge
t = 60 min

standard after just 30 min of treatment with very low power con-
II; pH 3

sumption (0.34 k W h per ton of wastewater). In a related study [275],

Fe-Cu embedded CA was reported to have achieved efficient TOC re-
moval (88–99%) in 240 min during the Hetero-EF treatment of di-
technology

methyl phthalate, imidacloprid, bisphenol A and perfluorooctanoate.

BES-EF

Successful decontamination of five sanitary sewages were also ex-

EF

EF

hibited by the same cathode with the residual COD less than China
national discharge standard (< 50 mg L–1) at low specific energy con-
sumption. Similar results was achieved for the treatment of dimethyl
phthalate (DMP) using highly ordered mesoporous Fe3O4@C CA with
4-bisphenol

95% and 65% DMP degradation and mineralization efficiency attained

Orange II
pollutant

in 120 min respectively [274].

RhB

Fe-functionalized CA has also been studied as cathode material in

Hetero-PEF process for the degradation of RhB and DMP using 2Fe/
Forming at high pressure using paste

Co–CA [276] and imidacloprid using Fe2O3 –CA [92]. 100% and 80%
Deposition of Fe2+-CHI on Ni foam
followed by fastening with elastic
made from a mixture of CNT, γ-

removal efficiency was obtained at 45 and 120 min for RhB and DMP
respectively in solar Hetero-PEF treatment, whereas complete de-
FeOOH, PTFE and ethanol
Photo-induced reduction

gradation of imidacloprid could be only reached in 180 min under si-

milar solar Hetero-PEF treatment. Other studies have also reported high
Preparation method

catalytic activity and stability for iron oxide-graphene/CNT – CA

composite cathode for the Hetero-EF degradation of MB [32]. The au-
thors showed that 99% removal efficiency of MB can be achieved in
60 min at pH 3 and applied current of 15 mA using 5% Fe containing
rope

graphene/CNT – CA. In all studies that involve Fe-functionalized CA

composite cathode, two mechanisms was always proposed for the ac-
Table 5 (continued)

Fe-CHI/Ni|ACF| Fe-

tivation of H2O2 to %OH during the Hetero-EF process as described in

Section 3, depending on pH of the treated solution. At acidic pH values,
Functionalized

CNT/γ-FeOOH

there was slight leaching of Fe and/or Cu/Co from the functionalized

Pd-Fe/GrO

CHI

CA cathode into the solution, thus the activation of H2O2 to %OH is

cathode

controlled by cycling of Fe3+/Fe2+ and/or Cu2+/Cu+//Co3+/Co2+

redox couple in the solution and at the surface of CA cathode. However

122
S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

Fig. 13. Scheme for the synthesis of CAs.

Adapted from Ref. [20,208].

at neutral and alkaline pH values, only surface catalyzed activation recycling Fe3+/Fe2+ redox couple. In this case, the efficiency of the
should be predominant because Fe and or Cu/Co are not soluble at such electrochemical system usually depreciates significantly with increase
pH conditions. Besides, photo-assisted Hetero-EF usually gives better in pH because the contribution of homogeneous EF diminishes with rise
mineralization and current efficiency compared to analogous Hetero- in pH conditions. Additionally, the mechanical wearing or fall-off of the
EF, thanks photo-degradation of carboxylic complex as well as gen- catalyst from the support or cathode may increase with electrolysis time
eration and regeneration of additional %OH and Fe2+ respectively from as the solution weakens the adhesive bond between the catalyst and the
the photo excitation of Fe-complexes. support regardless of operating pH values. This phenomenon was ob-
served during Hetero-EF treatment of AO7 using solvothermal synthe-
sized CoFe-LDH/CF cathode at pH 5.83, with mechanical fall off of the
7. Challenges and future prospects
CoFe-LDH from the CF substrate after 6 cycles of 2 h repeated reuse due
to the strong agitation of the solution and weakening of the bond be-
Some of the main challenges encounter in Hetero-EF/PEF are mostly
tween the CoFe-LDH and the CF [19]. The same thing could be in-
related to the heterogeneous catalyst itself, especially supported cata-
dicated for Fe-loaded clay materials, ACF and iron sludge. However,
lyst and functionalized cathode used in Hetero-EF and Hetero-PEF
this problem is limited or completely eliminated in functionalized CAs
system, though a cost-effective production of hydrogen peroxide on the
because the catalyst (Fe/Fe-compounds or Cu/Co) are not only em-
cathode is essential [277,278]. Among these problems, catalyst fall-off
bedded in the bulk of the CAs but also form the integral part of the 3D
from the support due to mechanical wearing in the solution and dis-
network of the CAs as explained in Section 6.3.
solution/excessive leaching of the catalyst at strong acidic pH are the
Agglomeration of the catalyst is another challenge that is commonly
most detrimental challenge that affects both catalytic stability and
encountered in Hetero-EF and Hetero-PEF systems, especially with non-
reusability efficiency of heterogeneous catalyst. Except in few cases like
supported catalyst. Most synthetic non-supported heterogeneous cata-
functionalized CAs, rolling made GDEs and some Fe-modified carbo-
lysts such pure Fe2O3, Fe3O4 or Fe° or their doped/modified form are
naceous cathodes, excessive leaching or dissolution were usually ob-
usually prepared and used as nanoparticles, as such there are usually
served when operating at strong acidic pH values (< pH 4), as such the
tendency of agglomeration of these particles with treatment time,
overall electrolysis system is controlled by homogeneous catalysis by

Fig. 14. (a) comparison of TOC removal efficiency at different pH for Fe@Fe2O3/CA and CA with 1 mM L–1 Fe2+ during the treatment of 100 mL of 500 mg L–1
metalaxyl solution in 0.1 M Na2SO4 at 10 mA cm–2 using BDD anode and (b) reusability of Fe@Fe2O3/CA during the 4 h a cycle at similar condition as (a).
Reprinted with the permission of Ref. [20].

123
S.O. Ganiyu et al. Applied Catalysis B: Environmental 235 (2018) 103–129

which reduces the effective surface area and active site of the catalyst 8. Conclusion remarks
and in turn the efficiency of the system. This is particularly the case of
magnetic Fe-containing nanocatalyst like Fe3O4 and Fe° where the na- Heterogeneous electrochemical wastewater treatment system based
noparticles not only attached to one another but also very difficult to on Fenton’s chemistry is one of the most exciting and efficient emerging
agitate the electrolytic system, even though such system has an ad- technologies for wastewater treatment owing to its applicability over
vantage of easy separation of the catalyst for possible reuse. More so, wide pH widows and reusability of the catalysts in several runs. The
most synthetic supported or non-supported catalyst as well as Fe- desirable features for potential heterogeneous catalysts include high
functionalized cathode requires either multi-steps or complex pre- catalytic efficiency and stability over wide pH range, easy separation
paration techniques which has limited most studies on Hetero-EF and reusability as well as environmental compatibility. The catalytic
system to laboratory or pre-pilot scale. A typical example is functio- activation of H2O2 to reactive oxygen species, especially %OH, was by
nalized CAs whose preparation involves at least four different non-re- either homogeneous catalysis by dissolved Mx+1/Mx (M]Fe, Cu or Co)
lated steps, thus makes the preparation route a bit complex, even redox couple or surface catalyzed process by surface metal species
though functionalized CAs remains one the most efficient hetero- ^MxeOH (M]Fe, Cu or Co) and its one-electron reduzate
geneous catalyst/cathode based on literature. (^Mx−1eOH) or both depending on the working pH at which the
Future studies in Hetero-EF and Hetero-PEF approaches should be system operate and partly on the properties of the solid catalyst. Two
tailored towards developing low-cost solid catalyst with improve sta- known configurations of Hetero-EF and Hetero-PEF systems vis-à-vis
bility in acidic pH, treatment of real wastewater, scale-up/pilot plant solid catalysts (bare or supported iron/transition metal containing
and flow-reactors based on these systems and in-situ spectroscopy compounds) and Fe/Fe-compound functionalized cathodic materials
studies of the H2O2 activation mechanisms at the surface of the solid were vividly examined. Relevant studies on Hetero-EF and Hetero-PEF
catalyst. It is important to enhance the stability of the solid catalyst at approaches by using both solid catalysts and functionalized cathodic
acidic pH values as studies have shown that most of the existing cata- materials were summarized and it is safe to say that the latter is a more
lysts undergo significant leaching at strong acidic pH values, which exciting treatment technique because of easy separation and reusa-
make the system, behave like homogeneous EF and PEF processes. The bility.
economic cost and environmental impacts of both existing and future Catalytic fall-off, dissolution at strong acidic pH and agglomeration
solid catalysts and functionalized cathodic materials should be con- as well as multi-step/complex techniques for catalyst/functionalized
sidered in forthcoming studies. Previous studies on Hetero-EF has failed cathode preparation are some of the major challenges encounter in
to address these key issues especially the environmental impact of the Hetero-EF and Hetero-PEF treatments of organic pollutants. It can be
nanocatalysts on biotic component of the ecosystem of the receiving anticipated that more studies and research groups will consider Hetero-
water bodies, where wastewaters are disposed after treatment. This systems in future due to it exciting features and logical growth in en-
information is crucial to engineers and regulatory agencies/bodies in vironmental concern and pollution remediation. Therefore future stu-
charge of adapting new technologies. Besides, more studies are still dies should be focused on improving the stability of the solid catalyst at
required on the application of Hetero-EF for the treatment of real acidic pH, investigating the use of Hetero-EF/PEF system on pilot scale
wastewater with complete cost analysis because there is a significant and flow reactors and complete analysis of the economic and environ-
difference in the behavior of real and synthetic wastewater during the mental impact of Hetero-EF treatment on biotic component of eco-
electrochemical treatment. Real wastewaters are complex in composi- system as well as treatment of real wastewater.
tion and properties; as such their electrochemical treatment may be-
have differently in terms of efficiency and removal mechanisms when Acknowledgements
compared to synthetic wastewater. Both the %OH scavenging effect of
the inorganic ions and natural organic matters in the real wastewater as Financial support from National Council for Scientific and
well as synergistic effect of the different organic pollutants on the ef- Technological Development (CNPq - 465571/2014-0; CNPq - 446846/
ficiency of the Hetero-EF process require further studies. 2014-7 and CNPq - 401519/2014-7) and FAPESP (2014/50945-4) are
The mechanisms of activation of H2O2 to %OH have not been ex- gratefully acknowledged. The authors also acknowledge Natural
tensive studied and no consensus on reactions involved till date in lit- Science Foundation of China (nos. 21773129 and 91545126), and
erature. Therefore, more detail investigations are still require to un- China National Water Project (no. 2015ZX07203-11) for their financial
derstand the mechanisms and reactions involved in heterogeneous support in carrying out this review work. Carlos A. Martínez-Huitle
catalytic decomposition of the H2O2. In situ spectroscopic techniques acknowledges the funding provided by the Alexander von Humboldt
such as ATR-FTIR, EIS and DFT simulations and microscopy studies Foundation (Germany) and Coordenação de Aperfeiçoamento de
about the treated solution may be of good assistance in understanding Pessoal de Nível Superior (Brazil) as a Humboldt fellowship for
the mechanisms and reactions involved in H2O2 activation as well as Experienced Researcher (88881.136108/2017-01) at the Johannes
those responsible for the transformation of the pollutants, thus allows Gutenberg-Universität Mainz, Germany.
adequate design of the electrochemical reactors and optimization of
operating conditions. More importantly, there is need for pre-pilot, pilot References
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