Chemosphere 269 (2021) 129325

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

Carbonaceous cathode materials for electro-Fenton technology:

Mechanism, kinetics, recent advances, opportunities and challenges
Keerthi M. Nair a, b, Vignesh Kumaravel a, b, Suresh C. Pillai a, b, *
a
Centre for Precision Engineering, Materials and Manufacturing Research (PEM), Institute of Technology, Sligo, F91 YW50, Ireland
b
Nanotechnology and Bio-Engineering Research Group, Department of Environmental Science, Institute of Technology, Sligo, F91 YW50, Ireland

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Efficiency of EF relies on the effec-

tiveness of cathode materials.

Various carbon materials as cathodes
and their modifications are reviewed.

Cathodic modifications for both ho-
mogeneous and heterogenous EF are
discussed.

Cathodes for Metal-free EF that
eliminates iron-sludge formation are
also reviewed.

Various reactor configurations and
challenges for scaling up are briefly
discussed.

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

Article history: Electro-Fenton (EF) technique has gained significant attention in recent years owing to its high efficiency
Received 2 October 2020 and environmental compatibility for the degradation of organic pollutants and contaminants of
Received in revised form emerging concern (CECs). The efficiency of an EF reaction relies primarily on the formation of hydrogen
10 December 2020
peroxide (H2O2) via 2ee oxygen reduction reaction (ORR) and the generation of hydroxyl radicals (COH).
Accepted 13 December 2020
Available online 17 December 2020
This could be achieved through an efficient cathode material which operates over a wide pH range (pH 3
e9). Herein, the current progresses on the advancements of carbonaceous cathode materials for EF re-
Handling Editor: Jun Huang actions are comprehensively reviewed. The insights of various materials such as, activated carbon fibres
(ACFs), carbon/graphite felt (CF/GF), carbon nanotubes (CNTs), graphene, carbon aerogels (CAs), ordered
Keywords: mesoporous carbon (OMCs), etc. are discussed inclusively. Transition metals and hetero atoms were used
Carbon as dopants to enhance the efficiency of homogeneous and heterogeneous EF reactions. Iron-
Fenton functionalized cathodes widened the working pH window (pH 1e9) and limited the energy consump-
Water pollution tion. The mechanism, reactor configuration, and kinetic models, are explained. Techno economic analysis
Wastewater treatment
of the EF reaction revealed that the anode and the raw materials contributed significantly to the overall
AOP
cost. It is concluded that most reactions follow pseudo-first order kinetics and rotating cathodes provide
Kinetic models
the best H2O2 production efficiency in lab scale. The challenges, future prospects and commercialization
of EF reaction for wastewater treatment are also discussed.
© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

* Corresponding author. Centre for Precision Engineering, Materials and Manufacturing Research (PEM), Institute of Technology, Sligo, F91 YW50, Ireland.
E-mail address: Pillai.suresh@itsligo.ie (S.C. Pillai).

https://doi.org/10.1016/j.chemosphere.2020.129325
0045-6535/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Basic mechanism of EF reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Photo electro Fenton (PEF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Reactor configurations in EF process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Kinetic studies and modelling of EF reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5. Cathode materials and its modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.1. Hetero atom doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5.2. Cathode modifications for heterogeneous EF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
6. Carbonaceous materials for EF process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6.1. Activated carbon fibres (ACF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
7. Carbonaceous materials for EF process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Activated carbon fibres (ACF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Carbon/graphite felt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Carbon nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Carbon aerogels (CAs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Biochar derived carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Ordered mesoporous carbon materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Hierarchically porous carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Metal free electro Fenton cathode modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Possible Mechanism of Metal-Free Electro Fenton using N-doped graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
8. Challenges and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

1. Introduction acquired the highest relevance owing to its fast reaction rate and
strong oxidation capability(Wang and Zhuan 2020). The basic
The rate of toxic waste disposals on the global water bodies have principles of various AOPs are shown in Fig. 1. AOPs are based on the
been accelerating in a high pace, owing to the tremendous increase in-situ generation of highly reactive oxidizing agents such as hy-
in population, urbanization and industrialization. Water scarcity is droxyl radicals (COH), ozone (O3), superoxide radical anions (Oe 2 ),
identified as one of the significant challenges for the socio- etc., that non-selectively reacts with all kinds of organic con-
economic development in many regions of the world(Liu et al., taminants(Glaze et al., 1987; Oturan and Aaron 2014). COH is
2017a,b,c; Ma et al., 2020). The global demand of freshwater is highly effective in complete mineralization and degradation of
estimated as 6.9 x 106 million m3/year by 2025, which makes it an contaminants due to its high oxidizing nature. These are the second
urgent need to address the pollution which harms the quality of highest oxidising agent next to fluorine with a high redox potential
freshwater sources(Ercin and Hoekstra 2014; Ahmad et al., 2020). of E0(COH/H2O) ¼ 2.8 V/SHE. Based on the generation of oxidizing
Apart from the general organic wastes, pharmaceutical products agents, the AOPs can be divided into Fenton reaction(Pignatello
(e.g. sulfamethoxazole, trimethoprim, diclofenac, etc.), pesticides et al., 2006), electrochemical oxidation(Garcia-Segura and Brillas
(e.g. boric acid, diazinon, DDT, etc.), antibiotic resistant genes, and 2011), photocatalytic oxidation(Serpone et al., 2017), sono-
personal care products which fall into the category of contaminants chemical oxidation(Montoya-Rodríguez et al., 2020) and so on.
of emerging concern (CEC), are increasingly being detected in Incorporating the advantages of electrochemistry, such as high
wastewaters and drinking water around the world(S. Kim et al., energy efficiency, environmental compatibility, and versatility,
2018). have contributed to the development of electrochemical advanced
Therefore, water treatment technologies that remove the CECs oxidation process (EAOPs), which has gained much significance
and persistent organic pollutants (POP) from water bodies, to during the past few decades(Comninellis et al., 2008; Brillas et al.,
provide safe and clean drinking water, are urgently required. con- 2009; Chaplin 2014; Brillas and Martínez-Huitle 2015).
ventional treatment techniques such as floatation, gravity, chemical AOPs based on Fenton chemistry has been proved as an effective
coagulation, etc. are not sufficiently capable of removing highly technology in wastewater treatment. The oxidation reaction in-
toxic chemicals or CECs. However, it has been reported that volves the use of Fenton reagent (a ferrous salt and hydrogen
methods such as membrane technologies(da Silva-Rackov et al., peroxide), to generate COH(Fenton 1894). Facile operation condi-
2016; Kar and Mishra 2016; Martin et al., 2016), photocatalysis(Lee tions and improved degradation efficiency are the main advantages
and Park 2013; Yazdanbakhsh et al., 2018), adsorption(Zhang et al., of this reaction(Wang and Zhuan 2020). There are several types of
2014), ozonation(Tang et al., 2018; Vanrenterghem et al., 2018), and Fenton’s reactions reported such as chemical, electrochemical,
advanced oxidation processes (AOP)(Esplugas et al., 2007; sono-chemical and photochemical depending on the formation of
C
Martínez-Huitle and Brillas 2009; Sire
s et al., 2014; Moreira et al., OH(O’Dowd and Pillai 2020). It can further be classified into ho-
2017), are much more effective to degrade the organic mogeneous and heterogeneous Fenton process according to the
contaminants. reactive phase of the iron catalyst(Babuponnusami and
Among the other decontamination techniques, AOP has Muthukumar 2014). However, the high cost, risk associated with

2
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 1. Schematics of various advanced oxidation processes (AOPs).
handling, transportation and storage of H2O2, narrow working pH
window (pH 2e4) and the significant iron sludge formation, are
identified as the major limitations of classical Fenton process.
Electro-Fenton (EF) is superior as compared to other Fenton’s
reactions owing to the in-situ generation of H2O2, via the two-
electron oxygen reduction reaction (ORR) at the cath-
ode(Nidheesh and Gandhimathi 2012),(Asghar et al., 2015). EF re-
actions possess several advantages such as high amenability,
versatility as well as environmental compatibility. There are three
major steps involved in EF process: i) in-situ generation of H2O2 at
the cathode hence reducing its risk of storage and transport; ii)
effective generation of COH via the reaction between ferrous ion
and H2O2 generated (Fenton’s reaction); iii) regeneration of Fe2þ at
the cathode surface(Liu et al., 2007; Poza-Nogueiras et al., 2018).
However, depending on the reactive phase of the catalyst, EF could
be classified into homo and hetero EF reactions. Heterogeneous EF
is appropriate for the treatment of real wastewater effluents with a
wide range of pH(Ganiyu et al., 2018b). Photoelectron-Fenton (PEF)
reaction involves the illumination of UV/vis light onto the effluent
solution. However, the catalysts support should be stable against
the free radical attack and incident light irradiation during the
heterogenous EF reaction (Brillas 2020).
The efficiency of EF reaction strongly relies on the nature of
cathode materials. An effective cathode material should possess a
high overvoltage for hydrogen evolution reaction (HER), low cata-
lytic activity for H2O2 decomposition, high stability and con-
ductivity(Nidheesh and Gandhimathi 2012; Khataee and
Hasanzadeh 2018). Apart from the cathodic influence, stable an-
odes with high overpotential for oxygen evolution reaction (OER),
that allows the supplementary COH generation, is also significant
for the enhancement of EF process(Sopaj et al., 2016). Platinum (Pt)
metal has been used as an anode in the recent decades owing to its
high conductivity and stability. However, Pt has a strong interaction
with the COH and it could diminish the availability of COH
3
Chemosphere 269 (2021) 129325
available for the pollutant degradation. To control this, materials
such as boron doped diamond (BDD), IrO2/RuO2 coated Ti(Huang
et al., 2008), RuO2/Ti mesh(Wang et al., 2005), Iron plates(Kurt
et al., 2007), etc. have been recently employed in the EF process.
Several studies revealed that the current efficiency, energy con-
sumption and pollutant degradation of BDD was superior to that of
Pt (Sire
s et al., 2007; Nidheesh and Gandhimathi 2012). Also, the
type of reactor configuration contributes effectively towards the
current efficiency for H2O2 production and accumulation.
The significance of EF process was previously reviewed in
several perspectives such as reaction mechanism(Brillas et al.,
2009), reactor design(Nidheesh and Gandhimathi 2012), nature of
pollutants(Rosales et al., 2012; Liu et al., 2018; Monteil et al., 2019),
heterogenous EF(Ganiyu et al., 2018b; Poza-Nogueiras et al., 2018)
etc. The use of electrochemical techniques in decontamination of
wastewaters along with the generation of COH have also been
reviewed by Brillas and co-workers(Martínez-Huitle and Brillas
2009). Most of the existing reviews in EF are mainly focused on
electrodes such as BDD(Nidheesh et al., 2019), carbon aerogels
(CAs)(Gan et al., 2019), activated carbons(McQuillan et al., 2018),
and graphene composites(Nidheesh 2017) for electrochemical
AOPs. A brief discussion on the use of carbon felt materials and its
modification for several energy and environmental applications,
including EF, was reported by Le et al.(Huong Le et al., 2017). In
particular, few reviews have been reported on the characteristics of
graphene electrode materials in the EF process (Divyapriya and
Nidheesh 2020; Yu and Breslin 2020). Nonetheless, there are no
comprehensive reviews on the insights of carbonaceous electrode
materials for the EF process. Herein, the mechanism and kinetics of
EF process, nature and surface features of carbonaceous cathode
materials for homogeneous and heterogeneous EF processes were
comprehensively reviewed. Cathode modifications such as hetero
atom doping, metal/metal-oxide deposition, bio-char derived car-
bon species and metal free EF cathodes have been briefly discussed.
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

O2 þ 2Hþ þ 2e /H2 O2 (4)


Fe3þ þ e / Fe2þ Eo ¼ 0:767 V=SHE (5)

Based on the physical nature of the catalyst, EF can be classified

into homogeneous and heterogeneous processes. Homogenous EF
applications are limited by strong acidic pH conditions (pH 2.8e3.5)
and thus it requires a post treatment neutralization of the treated
water when considered from an environmental point of view(-
Ganiyu et al., 2018b; Poza-Nogueiras et al., 2018). This could be
rectified through heterogeneous EF process by widening the pH
range, reducing the iron sludge formation and improving the
catalyst stability. Fenton reaction occurs on the surface of the
catalyst and not in the aqueous medium, hence a wide range of
operating pH is required. A critical comparison of the advantages
and disadvantages between heterogeneous and homogeneous EF
are given in Table 1. At first, naturally occurring iron minerals like
pyrite, goethite, magnetite(Expo
sito et al., 2007) etc., or iron con-
taining synthetic materials either alone or supported on other
porous materials have been used as catalyst for heterogeneous EF
water treatment (Expo
sito et al., 2007; Barhoumi et al., 2016).
Fig. 2. Schematic of EF reaction for the mineralization of organic pollutants into CO2
and H2O. Lately, modified cathodic materials, functionalized with iron and/or
transition metals have gained much attention. In the last five years,
several reviews have been reported on the principles, applications
The challenges, prospects and commercialization of the EF process and advancements of heterogeneous EF systems (Nidheesh et al.,
were also discussed briefly. 2018; Poza-Nogueiras et al., 2018).

2. Basic mechanism of EF reaction 2.1. Photo electro Fenton (PEF)

The basics of Fenton reaction involve the use of H2O2 and Fe2þ in
the removal of various POPs(Brillas et al., 2009; Sire
s and Brillas
2018). H2O2 being a weak oxidant reacts with Fe2þ ions leading to
the formation of a very strong oxidizing and unstable COH, which
is considered as the core reaction of Fenton process(Haber et al.,
1934; Sun and Pignatello 1993; Gallard et al., 1998; Brillas et al.,
2009). The attack of COH on saturated (RH) and aromatic (ArH)
organic pollutants proceed via the reaction (2) and (3)
PEF is an upgraded version of EF which involves the treatment of
water in acidic medium with a simultaneous exposition to an UV
light(Brillas 2014). PEF offers an enhanced mineralization rate
owing to an increased production of Fe2þ via photoreduction of
Fe(OH)2þ (Equation (6)) and photodecarboxylation of Fe(III)-
carboxylate species (Fe(OOCR)2þ) (Equation (7)). Apart from this
additional homolysis of H2O2 also occurs in the presence of UV light
(Equation (8))(Brillas 2020).

C
Fe2þ þ H2 O2 /Fe3þ þ OH þ OH (1) FeðOHÞ2þ þ hv/ Fe2þ þ
OH (6)

C
RH þ OH/ RC þ H2 O (2) FeðOOCRÞ2þ þ hv/Fe2þ þ CO2 þ R
(7)

C
ArH þ OH/ArHOHC

The in-situ generation of H2O2 via 2e ORR is the essence of EF
process (4). The iron sludge formation has also been reduced in EF
due to the reduction of Fe3þ to Fe2þ at the cathode surface (Equa-
tion (5)). Most pioneer works in this field has been carried out by
Brillas and Oturan groups from 1990s and is still a very hot topic for
exploration(Brillas et al., 2009; Oturan and Aaron 2014). Fig. 2
shows the basic mechanism of EF reaction for mineralization of
organic pollutants.
(3) H2 O2 þ hv/2
OH (8)
However, PEF possess a drawback of the high additional elec-
trical cost of artificial UV lamp. Utilising solar energy to overcome
this drawback makes the system more economical and feasible for
commercial applications. Few reports compare the efficiency of
cathode materials in EF and PEF indicating the upper hand of PEF.
Only limited researches are available on solar PEF (SPEF), and
further innovative technologies are yet to be introduced. Imple-
menting PEF in heterogenous EF has also been addressed in the past

Table 1
A comparison on the advantages and disadvantages of heterogeneous and homogeneous EF.

Parameters Heterogeneous Homogeneous

Catalyst High quantity of solid catalyst is required A small quantity of catalysts is sufficient
pH Works effectively over a wide pH range (pH > 5) Works well only in strong acidic pH (pH 2.8e3.5)
Reusability Catalysts could be easily separated, recycled and reused Recyclability and reusability are limited
Cost Expensive Inexpensive
Operation Could be easily automated Convenient to operate
Application Highly effective towards the removal of real water effluents Treated water requires further neutralization and post-treatments

4
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

few years based on the stability of catalysts or functionalized used as a membrane to separate the anolyte and catholyte cham-
cathodes under the attack of radicals and incident light(Ganiyu bers and allows the exchange of protons to maintain the electro-
et al., 2018b). Active research on these are yet to be performed to neutrality of the solutions(Pozzo et al., 2005; Sire
s and Brillas
make them commercially viable for real effluent treatments. 2018). The anodic chamber consists of an anode (Pt, boron doped
diamond (BDD), etc.) submerged in anolyte solution whereas the
cathodic chamber contains a cathode (graphite felt (GF), carbon felt
3. Reactor configurations in EF process
(CF), etc.) in the catholyte solution in case of a two-electrode sys-
tem, or a cathode and a reference electrode in case of a three-
One of the major challenges in electrochemical oxidation pro-
electrode cell configuration. Generally saturated calomel
cess is choosing a specific reactor configuration that could enhance
the mass transfer as well the current efficiency. Hence, a wide va-
riety of cell configurations and reactor set up have been already
explored with respect to EF process (Panizza and Scialdone 2018).
Electrochemical characterizations are mostly performed using a
three-electrode cell configuration or a RRDE configuration. The rate
of H2O2 accumulation and COH formation was measured which in
turn determines the efficiency of a cathode material. The TOC
measurements were further carried out and the reusability/stabil-
ity measurements gave an insight into the practical applications of
the electrodes.

i. Batch reactors for laboratories

Majority of the EF studies have been conducted at lab-scale

using a divided or an undivided electrolytic cell. EF process uses
either a three (anode, cathode and reference electrode) or two
(anode and cathode only) electrode cell configuration, generating
H2O2 at the cathodic region. The cells can be operated with or
without a membrane separator. In most of the studies Nafion was Fig. 4. Schematic of rotating ring disc electrode (RRDE) setup in A) Single compart-
ment cell. Reprinted from ref(S. Yang et al., 2018).

Fig. 3. Schematic of a) an undivided electrochemical cell used for EF reactions. Reprinted from ref(Bensalah et al., 2013). and b) H-shaped two compartment cell.

5
K.M. Nair, V. Kumaravel and S.C. Pillai
electrode (SCE) or silver-silver chloride (AgeAgCl) electrode is used
as reference electrode. The three-electrode system possess an up-
per hand by providing a constant potential to the cathode against
the reference electrode, whereas a two-electrode system could only
record the current passing through the electrode with no control
over the applied potential (Allen and Larry, 2001). Fig. 3 (a) rep-
resents an undivided electrochemical cell used for EF treatment(-
Bensalah et al., 2013). The cell consists of a continuous supply of
oxygen to the CF cathode, a thermometer to measure the temper-
ature of the electrolyte, and a water reflux to maintain the tem-
perature of the system. CF is used as the cathode and a Pt or BDD is
used as the anode in this case.
The energy requirement and working pH of the undivided cell
configuration are more feasible as compared to the divided cells.
Nevertheless, the undivided cells possess a disadvantage of several
undesired side reactions occurring, that leads to the decomposition
of H2O2 formed, and hence complicating the entire process(Sire
s
and Brillas 2018). H-type two compartment cell with the cathode
and reference electrode in one compartment and the anode in the
other is shown in Fig. 3 (b).
In recent studies, the importance of oxygen diffusion rate as well
as its solubility on the efficiency of H2O2 production have been
widely discussed. It has been concluded that due to the low solu-
bility of oxygen in the electrolyte, the amount of oxygen that rea-
ches the electrode surface is quite less in conventional batch
reactors (Petrucci et al., 2016). This has further resulted in the low
oxygen utilization efficiency. It has been then demonstrated that a
special way of supplying oxygen to the system enables a better
mass transport between the electrode surface and electrolyte(Yu
et al., 2014). This included the use of a parallel rotating cathodes
along with an anode and a reference electrode. It was proposed that
with the increase in the rotation speed, the contact area between
the electrode and oxygen increases, improving the H2O2 production
(Yu et al., 2014; Zhang et al., 2015). However, after an optimum
rotation speed, the resistance of the electrolyte solution gets
increased which could drop the yield. Fig. 4 shows the schematic of
a rotating disc electrode setup(Y. Jiang et al., 2018; H.W. Kim et al.,
2018; S. Yang et al., 2018).
Several studies have been carried out on the effect of electrodes
geometry, proving that plate shape is more effective in terms of
lower electrical resistance and high efficiency when compared to
the rod shape(Su et al., 2013; Monteil et al., 2019). Another effective
Fig. 5. a) Schematic of a trickle bed reactor. 1: Cell body, 2: Gasket, 3: Ti/PbO2 anode, 4: Gasket ring, 5: Nylon diaphragm, 6: Cathode frame for loading graphite, and 7: Nickel plate.
b) Schematic of the electrolysis process in A) continuous flow and B) batch mode where 1: Electrolyte, 2: Pump, 3: Air, 4: Tee and 5: Trickle bed reactor(Lei et al., 2013).
6
Chemosphere 269 (2021) 129325
method includes the use of gas diffusion electrodes (GDE) that
allowed a uniform O2 pressure forming more H2O2 as well as COH.
A GDE consist of a gas diffusion layer that allows the transport of O2
towards the cathode and offers a physical support to the cath-
ode(Hernandez-Aldave and Andreoli 2020). A batch mode cell
configuration also possesses an ease to incorporate a UV lamp for
studying PEF degradation, which could then be compared with EF
efficiency.
ii. Pilot scale reactor configurations
Engineering an appropriate reactor configuration is highly
beneficial to reduce the cost and maximize the efficiency of elec-
trochemical reactions for large scale applications. Several parame-
ters are needed to be considered in order to scale up any process.
This include the size and arrangement of electrodes, temperature,
mixing, etc. (Monteil et al., 2019). Most of the large-scale applica-
tions utilize two-electrode systems owing to the difficulty of
employing reference electrodes which makes the kinetics further
sluggish. Various new reactor configurations have been developed
in the past several years based on (a) geometric parameters
(trickle-bed reactors, and tubular membranes), (b) out streaming
pattern (flow-through and flow-by), (c) pressure (pressurized
reactor) and (d) size (microreactors). A brief discussion on each of
these are listed below.
Most of the industrial and commercial applications are based on
trickle bed reactor configurations that could prevent the leakage of
electrolytes and gas bubble formations occurring in a normal batch
reactor(Ban~ Uelos et al., 2014). The configuration allows an easy
transfer of oxygen to the electrode surface, improving the rate of
H2O2 production (Lei et al., 2013; Ban ~ Uelos et al., 2014). Fig. 5 (a).
shows a trickle bed reactor assembly consisting of Ti/PbO2 anode
(3), C-PTFE-coated graphite chips as cathode (6), and a porous
nylon diaphragm (5). There are three sealing gasket rings to pre-
vent any leakages (2, 4) and the cathode is in close contact with a
nickel plate that acts as the current collector (7). The reactor con-
tains all three phases of gas (air), liquid (electrolyte), and solid
(electrodes), allowing the mixing of air in the solution before it
enters the cell (Yangming et al., 2015). This allows an easy transfer
of gases to electrode surface, improving the rate of H2O2 produc-
tion. Fig. 5 (b) represents the schematic of the electrolysis flow.
Apart from the trickle bed reactor, a tubular membrane reactor was
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 6. Schematics of a) Flow-by, b) Flow-through (Reprinted from Ref (Garcia-Segura et al. 2020).) and c) 10-compartment flow-through reactor configurations (Reprinted from Ref
(G. Ren et al. 2016).).
designed by Xu et al. using a Ti/IrO2eTa2O5 anode and carbon black-
PTFE as cathode(Xu et al., 2016). The tubular anode displayed a
better efficiency owing to the large surface area caused by the
presence of micropores. The system exhibited excellent perfor-
mance even in the absence of aeration.
The effect of the waste water flow was compared in parallel
(flow-by) (Fig. 6 (a)) and perpendicular (flow-through) (Fig. 6 (b))
directions to the electrodes(Ma et al., 2016). Flow-by system fall
under the most widely used type of flow configurations for com-
mercial electrocatalytic applications(Garcia-Segura et al., 2020). In
a flow-through system, the electrolyte could transfer directly
through the electrodes which enables the access to the micropore
spaces inside them, where as a flow by system the ions could only
migrate through the thin outer electrode coating (Remillard et al.,
2018). However, a flow through EF reactor enables an increased
mass and electron transfer. A recent study demonstrated the
degradation of methylene blue (MB) using DSA (dimensionally
stable anode) as the anode and a modified GF as the cathode. The
results suggested that the mass transport was enhanced in the
vertical flow which further increased the current efficiencies and
lowered the energy consumption when compared to that of parallel
flow (Santos et al., 2010; Ma et al., 2016; G. Ren et al., 2016). Fol-
lowed by this, a multiple flow through cell reactor with 10 com-
partments was utilised to degrade tartrazine via EF reactions (Fig. 6
(c))(G. Ren et al., 2016). A higher mineralization efficiency along
with a lower energy consumption was achieved when compared to
the flow-by system.
Another innovative configuration deals with the pressurized
electrochemical reactors, which is favourable to improve the solu-
bility of oxygen in water, enhancing the overall EF performance.
Scialdone et al. demonstrated that an enhancement of air pressure
drastically increased the generation of H2O2 leading to a maximum
attenuation of TOC and pollutant degradation(Scialdone et al.,
2015). The same group also introduced a novel microfluidic
reactor. As compared to other configurations, microfluidic reactors
possess very small distance between the electrodes and hence a
much reduced ohmic resistance, improved mass transport,
enhanced current efficiencies and as a result high degradation of
organic pollutants were observed(Panizza and Scialdone 2018).
These electrodes could also be operated in the absence of an air flux
or oxygen supply. Although inexpensive electrodes could be
employed in microfluidic reactors, there is a chance of easier
clogging and fouling due to the accumulation of trapped pollutants
7
Chemosphere 269 (2021) 129325
which reduces the number of open pores available. Combining EF
along with electro-oxidation enhanced the efficiency of micro-
fluidic systems(Scialdone et al., 2014). However, scaling up this
process for treating real water effluents in pilot scale is yet to be
tackled. The factors, such as the ferrous ion content, H2O2 con-
centration, pH, current density, oxygen sparging rate, nature of
pollutants, etc. must be considered for the scaling-up process
(Nidheesh and Gandhimathi 2012).
4. Kinetic studies and modelling of EF reaction
There are very limited studies reported on the kinetics and
modelling of EF reactions for the organic pollutant degradation. A
set of operational parameters such as electrolyte, temperature,
concentration, etc. must be considered to develop a general kinetics
for the degradation path. Majority of the existing studies on decay
kinetics fit well with the theoretical aspects of a pseudo first-order
reaction(Pimentel et al., 2008; Yahya et al., 2014; Barhoumi et al.,
2016). Under galvanostatic conditions the degradation rate of an
organic pollutant (OP) can be represented as:
d½OP
 ¼ k½ C OH½OP (9)
dt
However, COH are continuously produced and destroyed at a
constant rate indicating a steady state concentration in the bulk
solution (Brillas et al., 2009). This suggests that the rate of reaction
can be further simplified as:
d½OP
 ¼ kapp ½OP (10)
dt
where kapp indicates the apparent rate constant, kapp ¼ k[COH], k
being the absolute rate constant. The absolute rate constant (sec-
ond order rate constant) was further investigated using the
competition kinetic method, with a standard substrate whose ab-
solute second order rate constant (kabs,S) is already established
(Beltran De Heredia et al., 2001; Alvarez-Gallegos and Silva-
Martínez, 2018). Benzophenone, benzoic acid, 4-hydroxybenzoic
acid, and salicylic acid are the commonly used stand-
ards(Pimentel et al., 2008; Brillas et al., 2009). HPLC was employed
to determine the pseudo first order kinetics of both standard (kapp,S)
and pollutants (kapp,OP). The absolute rate constant of an organic
pollutant (kabs,OP) was then further calculated using the following
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

equation:
k6
H2 O2 þ organic pollutants
! products (18)
kapp;OP
kabs; OP ¼ kabs; S  (11)
kapp; S k7


!H2
þ H2 O
OH þ H2 O2  (19)
Oxidation of alcohols via EF process provides a better insight
C
into the pseudo-first order kinetic models (Pimentel et al., 2008; Assuming that the pollutants are primarily oxidised by the OH,
Babuponnusami and Muthukumar 2012). Recently, the effect of the rate of degradation can be represented as:
catalyst concentration and applied current on the oxidative
d½OP
degradation kinetics have been reported for both homogeneous  ¼ k5 ½ C OH½OP (20)
and heterogeneous EF reactions. Natija et al. demonstrated that the dt
heterogeneous EF reaction with chalcopyrite as the catalyst, obeyed From the above reactions 14, 15, 17, and 19, the rate of change in
pseudo-first-order kinetics under all variations of current density C
OH concentration is given by,
and catalyst concentration(Barhoumi et al. 2016,
2017,bib_Barhoumi_et_al_2016,bib_Barhoumi_et_al_2017). Linear d½ C OH h i h i
regression coefficients (R2) were calculated which demonstrated ¼ k2 Fe2þ ½H2 O2   k3 Fe2þ ½ C OH  k5 ½ C OH½OP
dt
that the experimental results fit well with kinetic model proposed.
 k7 ½ C OH½H2 O2 
In another study, a non-linear regression analysis was applied to
investigate the effect of key operational parameters including Fe3þ (21)
concentration, applied current, concentration of pollutants, pH and C
To further simplify the model, the term [ OH] [H2O2] has been
flow rate (FR) for PEF reaction(Khataee et al., 2014). Apparent ki- removed as the [H2O2] is much lower than [Fe2þ] and k7 is one
netic constant, kapp, as a function of operational parameters is given order smaller than k3 as proved by Duesterberg and Waite(Dues-
by: terberg and Waite 2006). As previously stated, the COH ap-
 a proaches a steady state approximation, which allows to represent
k0 Fe3þ 0 ðIÞb the Equation (20) in terms of [H2O2] and [OP](Liu et al., 1999).
kapp ¼ (12)
½AB5c0 ðphÞd ðFRÞe  
d½OP k2 Fe2þ ½OP
 ¼ k5  2þ  ½H2 O2  (22)
wherein non-linear regression analysis was employed to estimate dt k3 Fe þ k5 ½OP
a, b, c, d and e, respectively. k’ is the average value calculated from
According to the Langmuir adsorption model, the oxygen
each experimental run. The calculated results were observed to be
coverage (W) on the cathode surface can be expressed in terms of
consistent with the experimental data, with a regression factor of
the dissolved oxygen concentration [O2], with an adsorption
0.9934.
equilibrium constant Kad.
Further, a versatile kinetic model has been proposed by Liu et al.
taking into consideration the rate constants of all the major re-
Kad ½O2 
actions involved in EF process(Liu et al., 2007). The model was then q¼ (23)
1 þ Kad ½O2 
experimentally validated by a phenol degradation reaction in
aqueous medium. According to the model, seven major reactions H2O2 generation rate and its concentration in Equation (22) can
are involved in EF which are as given below(Walling 1975; Buvet further be represented in terms of current density (I/A) and oxygen
et al., 1987): coverage (W) (Equation (13)) and the decomposition rates (Equa-
tions ((14), (16), (18) and (19)).

 ! !
1  eðk2 l½Fe 0 t
2þ
½OP0  k5 k1 k5 Kad I½O2 
ln þ   ð½OP0   ½OP ¼  
t   (30)
½OP k3 l Fe2þ 0 k3 lA Fe2þ 0 1 þ Kad ½O2  k2 l Fe2þ 0

k1
O2 þ 2H þ 
! H2 O2 (13)

   
d½H2 O2  Iq  h i
k2
! Fe3þ þ
OH þ OH
Fe2þ þ H2 O2  (14) ¼k1  k2 Fe2þ þk4 Fe3þ H2 O2  k6 H2 O2 OP
dt A
 
 k7 C OH H2 O2

k3
Fe2þ þ ! Fe3þ þ OH
OH  (15)
(24)
This can further be simplified in terms of k2, as k2 [ k4, k6 and
k4
!Fe2þ þ HO
2 þ H þ
Fe3þ þ H2 O2  (16) k7, given by Equation (25). On integrating Equation (25), and
assuming that [Fe2þ] is proportional to its initial concentration at
t ¼ 0, with a fixed ratio of l, [H2O2] can be expressed as in Equation

k5 (26). This indicates that [H2O2] is a function of experimental time,
OH þ organic pollutants
! products (17)
and its maximum value can be expressed as shown in Equation
(20).
8
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Fig. 7. Phenol degradation at different current densities fitted by A) the first-order model and B) the new kinetic model. Reprinted from ref (Liu et al., 2007).

d½H2 O2  IKad ½O2  h i

¼ k1  k2 Fe2þ ½H2 O2  (25)
dt Að1 þ Kad ½O2 Þ

Fig. 8. a) Complete mineralization pathway of phenol in acidic medium and b) comparison of simulated and experimental data of phenol and its intermediates Catechol, Hy-
droquinone, and Resorcinol. Reprinted from ref (Mousset et al., 2016a).

9
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

k K I½O   
1  ek2 l½Fe 0 t
2þ
½H2 O2  ¼ h 1 iad 2 (26)
k2 lA Fe2þ ð1 þ Kad ½O2 Þ
0

k K I½O 
½H2 O2 max ¼ h 1 iad 2 (27)
k2 lA Fe2þ ð1 þ Kad ½O2 Þ
0

Equation (26) can hence be modified as:

 
½H2 O2  ¼ ½H2 O2 max 1  ek2 l½Fe 0 t
2þ
(28)

Hence Equation (28) can be used to substitute the value of

[H2O2] in Equation (22), which integrates to produce a function of
experimental time, decreasing from its initial concentration of
[OP]0 at t ¼ 0 (Equation (30)).

d½OP k5 k1 Kad I½O2   

1eðk2 l½Fe 0 Þt ½OP
2þ
 ¼ h i
dt k3 l Fe2þ
þk5 ½OP ð1þKad ½O2 Þ
0
(29)

k5
This can further be simplified by giving a ¼ ,
k3 l½Fe2þ 0
k1 k5 Kad I½O2 
b¼ , and c ¼ k2 l½Fe2þ 0 as shown below:
k3 lA½Fe2þ 0 ð1þKad ½O2 



½OP0  1  ect
ln þ að½OP0   ½OPÞ ¼ b t  (31) Fig. 9. Response surface plot for a) p-nitrophenol degradation and b) TOC removal rate
½OP c with respect to [Fe2þ] and current density. Reprinted from ref (Meijide et al., 2017).
It could be concluded that the kinetic model established a direct
relation on the concentration of H2O2 and organic pollutant
temperature of the solutions as well as negligible adsorption on CF
degradation against the reaction time. This model was further
cathode. The model was validated by calculating the model effi-
validated by carrying out phenol degradation experiments in an EF
ciency (ME), the root mean square error (RMSE) and the index of
reaction system. Three different current densities (0.04, 0.16 and
agreement (IoA), given by(Esposito et al., 2011):
0.32 mA cm2) were used to evaluate the kinetics of phenol
degradation at [O2] ¼ 0.57 mM, [Fe2þ]0 ¼ 0.20 mM and pH 2.5. PK
2
Fig. 7(A) and (B) represents the experimental data fitted against the yi  y0i
ME ¼ 1  Pi¼l
K
(32)
first-order model and the new model respectively. The results i¼l ðyi  ym Þ
demonstrated that our new model fitted more accurately with a
higher correlation coefficient when compared to first-order model vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uP  2
u K
kinetics. t i¼l yi  y0i
It can be concluded that simultaneous consideration of phenol RMSE ¼ (33)
concentration and H2O2 concentration has made the model fit well K
with experimental results. Another study was conducted using the
PK

similar parameters in the above model in a stirred tank reactor by
Regalado-Mendez et al. (Regalado-Me
ndez et al., 2010). However,
in both models, the formation and oxidation of by-products during
the EF process were not considered, which could limit its practical
applications. A complete evaluation of all intermediates is essential
to analyse the toxicity of by-products, which could be even higher
than the initial pollutants.
Mousset et al. proposed a complete mineralization pathway for
phenol oxidation using a carbon felt (CF) cathode (Mousset et al.,
2016a). A set of kinetic parameters were estimated to fit the
experimental data. Five major steps such as: (i) in-situ generation of
H2O2, (ii) Fenton reaction, (iii) Fe2þ regeneration, (iv) scavenging
reactions and (v) mineralization of organic pollutants were
considered. 10 intermediates (Fig. 8 (a)) were considered with 49
reactions and 52 kinetic constants. The simulations were per-
formed by MATLAB software. The model was established based on
several assumptions including quasi-state approximation, optimal
pH and ferrous ion concentration, constant volume and
10
0 2
i¼l yi  yi
IoA ¼ (34)
PK   0  2
i¼l yi  ym  þ jyi  ym j
where yi is the single simulated value, yi’ is the corresponding
observed value and yM is the average of the simulated values. The
model estimated the second-order rate constants using MATLAB
functions and compared the same with experimental data. An
average ME value of 0.98 was monitored for majority of in-
termediates and RMSE was observed to be lower than 0.2. Also, IoA
average was observed to be higher than 0.99, demonstrating that
the model fits well with the experimental data and hence, vali-
dating the importance of intermediate reactions observed. Fig. 8 (b)
shows the comparison between simulated and experimental data
of phenol degradation and its aromatic intermediates via EF
reaction.
In a later study, the same kinetic model approximations were
employed to examine the degradation of p-nitrophenol(Meijide
K.M. Nair, V. Kumaravel and S.C. Pillai
et al., 2017). Response surface methodology based on central
composite design (CCD) was employed to evaluate the effect of
various operational parameters such as Fe2þ concentration (x1) and
current density (x2) on the p-nitrophenol degradation and TOC
removal. The simulated results were further analysed by the coef-
ficient of determination (R2), analysis of variance and response
plots. The percentage of p-nitrophenol degradation and TOC
removal were correlated with independent variables through a
second order polynomial equation as given below:
X X X response surface plots indicating both degradation and TOC
Yi ¼ b0 þ bi xi þ bii x2i þ bij xi xj þ ε
Where, Yi is the response, b0 is a constant, bi is the slope or linear
effect of the input factor, bii is the quadratic effect, bi is two-way
linear by linear interaction effect, xi and xj are the independent
parameters and ε is the random error. Second-order rate constants
were estimated via MATLAB functions to fit the experimental data
with the simulated-model. After 15 min of EF treatment, the results
of degradation and TOC removal were described in terms of
Equation (35):
h i
p  NP degradation ð%Þ ¼ 27:42 þ 289:94 Fe2þ þ 1:96 j
h i h i2
þ 2:47 Fe2þ j  443:57 Fe2þ
2
 0:020 j
Fig. 10. Comparison of kinetic model and experimental data for various catalysts (Fe, Co, Mn, Ni, Ce). Reprinted from ref (Matyszczak et al., 2020).
Chemosphere 269 (2021) 129325
h i
TOC removal ð%Þ ¼ 5:57  39:99 Fe2þ  0:37j
h i h i2
þ 1:94 Fe2þ j þ 43:69 Fe2þ þ 4:03:103 j2 (37)
given, [Fe2þ] is the iron concentration (mM) and j is the current
density (A m2). Values over 99% of p-nitrophenol degradation and
TOC removal was obtained from regression coefficient analysis af-
ter considering significant factors. Fig. 9 (a) and (b) shows the
(35) removal increased with increasing the Fe2þ concentration and
current density. The model was also validated via EF reaction using
a commercial 3D CF cathode under optimal conditions (0.3 mM
Fe2þ and 39.50 A m2 current density). The model showed good
agreement with experimental data with deviations below 2.5%.
However, all the above models possess several disadvantages of
being complicated and applicable on to specific pathways and in-
termediates, hence limiting its applications. Very recently, a
simplified kinetic model was developed to investigate the degra-
dation of Metanil Yellow using different catalysts (Matyszczak et al.,
2020). The model was completely based on rate-limiting step
approximation with no consideration of detailed mechanisms and
intermediates. Five reactions were taken into consideration:
O2 þ 2Hþ þ 2e /H2 O2 (38)
(36) M nþ þ H2 O2 þ H þ / Mðnþ1Þþ þ H2 O þ C
OH (39)
11
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Table 2
Structural and chemical modifications employed on carbonaceous materials.

Modifications Types Materials

Structural 3D electrodes with high surface area to volume ratio
Carbon based nanomaterials with an enhanced mass transfer
Chemical Hetero atom doping to create more active sites for H2O2 production
Functionalized with iron and/or transition metals for heterogenous EF (Fe/Fe Fe2O3/ACF (Lan et al., 2016), FeCuC aerogel (Zhao et al., 2016), Fc-ErGO
containing compounds grafted on carbonaceous materials (ii) Fe/Fe-TMs
coated on carbon aerogels, and (iii) bimetallic materials on carbon)
Activated carbon fibres (ACF) (Wang et al., 2005), Carbon/Graphite
felt(Guivarch et al., 2003), Reticulated vitreous carbon (RVC) (Ramírez-Pereda
€
et al., 2018), Carbon sponge (Ozcan et al., 2008), porous GDE(Pozzo et al.,
2005).
Carbon nanotubes (CNTs) (Zhang et al., 2008), graphene oxide (GO) (Thakur
and Kandasubramanian 2019), reduced graphene oxide (rGO) (Y. Li et al.,
2017b,c), ordered mesoporous carbon (OMC) (Sheng et al., 2015), etc.
N-doped graphite felt (X. Liu et al., 2017a), NeS doped mesoporous carbon (N,
S-MC) (Perazzolo et al., 2016), etc.
(Divyapriya et al., 2018a), etc.

5. Cathode materials and its modifications

M ðnþ1Þþ þ e /Mnþ (40)
Cathode materials are commonly utilised as working elec-
trodes in EF process, and has tremendous impact on the oxidation
C
Metanil Yellow þ X OH/ CO2 þ H2 O (41) power and the H2O2 formation. The selectivity of two-electron
ORR pathway relies on the characteristic of the cathode mate-
rials employed. The oxygen gas is either directly sparged into the
2H2 O / 4Hþ þ O2 þ 4e (42)
electrolyte or injected into the gas diffusion electrode (GDE). As
M  catalyst used (Fe, Co, Mn, Ni, Ce) mentioned previously, the most important parameter to deter-
X e number of COH used. mine the effectiveness of a cathode material is the high over-
Equations 39 and 40 and the value of X are the key parameters potential for HER and selectivity towards 2e‒ ORR. The material
used to generate the model. The concentration of oxygen is should also possess good conductivity and stability, which re-
considered constant and saturated, and the amount of Hþ was mains unaffected in the acidic pH conditions. Mercury was used as
controlled using a pH meter(Tura
nyi and Tomlin 2014). The dif- the cathode in some previous studies, but this was further dis-
ferential equations derived by considering the assumptions to ex- regarded considering its potential toxic nature(Tomat and Vecchi
press the rate of change of reactants is given by: 1971). Later, carbonaceous cathode materials that are non-toxic,
inexpensive and with lower H2O2 degradation rate were utilised
d½O2  as efficient cathode material for EF process (Nidheesh and
y0 (43) Gandhimathi 2012; Khataee and Hasanzadeh 2018). The utiliza-
dt
tion of carbonaceous material as cathodes was started with
graphite particles in a trickle-bed electrochemical reactor
d½Hþ  (Oloman and Watkinson 1975, 1979,bib_Oloman_and_Watkinson_
y0 (44)
dt 1975,bib_Oloman_and_Watkinson_1979).
Several structural and chemical modifications were introduced
h i
  to improve the surface area, conductivity, catalytic sites and sta-
d Mnþ h i M ðnþ1Þþ  
ðnþ1Þþ h i
¼ k8 M  k7 M nþ ½H2 O2  ¼ bility. As a result, three dimensional electrodes with high surface
dt M ðnþ1Þþ þ ½H þ  area to volume ratio such as activated carbon fibres (ACF)(Wang
h i et al., 2005), carbon felt (CF)(Guivarch et al., 2003), carbon
d M ðnþ1Þþ €
sponge (CS)(Ozcan et al., 2008), reticulated vitreous carbon

dt (RVC)(Ramírez-Pereda et al., 2018), etc., and porous GDE(Pozzo
(45) et al., 2005) have been widely explored. Lei et al. suggested that
activated carbon fiber (ACF) electrodes produced higher amounts of
H2O2 when compared to graphite cathodes under the same reac-
d½H2 O2  I0 ½H þ   
¼ : h i  k7 M nþ ½H2 O2  (46) tion conditions (Lei et al., 2010). Studies indicated that GDE were
dt 2 ½Hþ  þ M ðnþ1Þþ efficient in ORR when compared to normal electrodes(Wang et al.,
2011; Liang et al., 2016). This is ascribed to the thin and porous
structure of GDEs that allows the easy percolation of gases to the
d½Metanil Yellow k   solutions(Khataee and Hasanzadeh 2018). In the recent decades,
¼  7 M nþ ½H2 O2  (47)
dt X various forms of carbon materials such as carbon nanotubes
Kinetic constants were then analysed for different catalysts both (CNTs)(Zhang et al., 2008), graphene oxide (GO)(Thakur and
computationally and experimentally. The kinetic model was in Kandasubramanian 2019), reduced graphene oxide (rGO)(Y. Li
good agreement with the experimental data with a mean value of et al., 2017b,c), ordered mesoporous carbon (OMC)(Sheng et al.,
9.7 COH. Fig. 10 shows the plot of experimental data fitted with 2015), etc. have been applied as cathode materials in EF process.
simulated results indicating the success of the model with very Besides, surface features such as heteroatom doping(Liang et al.,
small mean relative error values. 2012), metal/metal oxide incorporation, polymer-based composite
A thorough knowledge on various kinetic models is necessary to formations(Jiang et al., 2015), etc. have also been implemented to
scale up the EF process for commercial applications. This could also improve the surface area, conductivity, and pore size of electrode.
be favourable in determining the appropriate reactor design and An increased surface area and porosity have shown direct effect on
operational parameters. oxygen diffusion and mass transfer(Petrucci et al., 2016). The

12
 Table 3

K.M. Nair, V. Kumaravel and S.C. Pillai

Carbonaceous materials for Homogeneous EF.

Category Cathode Synthesis strategy H2O2 production rate Pollutant Efficiency Reference

Activated ACF Commercial sample 200  103 mmolL1h1 Acid Red 14 70% degradation in 360 min Wang et al.
Carbon Fibre (2005)
g-C3N4/ACF Wet impregnation- Rhodamine-B TOC removal of ~91% after 240 min of electrolysis at pH 3 He et al.
calcination (2018)
N-doped OMC on ACF (AC Surface coating and self- 40.93 mmol L1 Brilliant red X3B 75% TOC removal after 300 min [117]
F@N-OMC) template method
1
Carbon/ Porous CF Thermal Treatment 24.6 mg L Paracetamol 94% TOC removal after 600 min treatment Le et al. (2016)
Graphite Felt CNT loaded GF Assembly of CNT on GF by 10.73 mg h1 cm2 Diclofenac 91.7% TOC removal in 180 min. Yu et al.
coating (2018a)
MesoC/GF Solvent evaporation- Phenol 99.1% degradation at pH 3 in 180 min. Yue et al.
induced self-assembly (2018)
Floating GF Commercial sample 61.7 mg dm3 Ibuprofen 78.3% degradation in 120 min (Zhou et al.,
2018a,b,c,d,e,f)
1 2
Electrochemically exfoliated Mechanical coating 7.7 mg h cm Imatinib 100% TOC removal after 480 min Yang et al.
graphene eCF (EEGr-CF) exfoliated graphene and (2019a)
annealing
N-doped graphite felt Hydrothermal treatment Levofloxacin 84% TOC removal after 480 min at 400 mA (X. Liu et al.,
2017a)
N-doped porous carbon on Atomic layer deposition AO7 97% colour removal in 30 min and more than 90% TOC removal in Le et al. (2017)
CF (NPC/CF) and solvothermal 480 min
conversion
Carbon Nitrogen functionalized CNT Pulsed high voltage 145.62 mg L1 MO 72% MO colour removal in 60 min at pH 7 Zhang et al.
Nanotubes (NCNT) discharge in a gas-liquid (2008)
(CNTs) hybrid reactor
CNT-GDE Rolling method 782 mg L1 Acetyl salicylic acid 100% degradation after 10 min and 62% TOC removal in 60 min (H. Yang et al.,
2018)
13

Cu2O/CNTs/PTFE Rolling Method RheB 80.2% and 89.3% degradation at pH 7 and 3 after 120 min Ai et al. (2008)
N-doped graphene@CNT (N- Hydrothermal treatment Dimethyl phthalate 51.5% TOC removal in 180 min (T. Liu et al.,
G@CNT) 2016)
N-doped MWCNT with Mechanical coating 307 mg L1 p-nitrophenol 62.61% TOC removal after 120 min Tang et al.
nickel foam as support (2015)
CNT/g-C3N4 Mechanical coating and 17.25 mg h1 cm2 Alizarin yellow R 94.8% TOC removal in 15 min Yu et al.
calcination (2018b)
Carbon Fe3O4@Fe2O3/ACA Hydrothermal Treatment Imidacloprid 90% TOC removal during 30e60 min. Zhao et al.
Aerogels (2012)
(CAs) SWCNTs/rGO aerogels Hydrothermal Treatment 8.19 mg L1 MB and palm oil mill 100% decolouration of MB at pH 3 and 47.63% of TOC removal of Nazhif Mohd
effluent (POME) POME in 60 min Nohan et al.
(2019)
Graphene 3D graphene foam Commercially sample 4.25 ± 0.10 mgL1 cm3 Phenol 78% degradation in 180 min and 50±3.5% TOC removal in 480 min. Mousset et al.
(2016c)
PTFE-carbon cloth-GDE on Mechanical coating 450.8 mg L1 Electronic wastewater Low concentration (53.46 mg L-1) of waste: 90% TOC removal in Garcia-
electrochemically exfoliated 240 min. High concentration (299.33 mg L-1) of waste: 60% TOC Rodriguez
graphene removal after 240 min et al. (2018)
rGO-CF Electrochemical AO7 73.9% TOC removal after 120 min and 94.3% mineralization after Le et al. (2015)
deposition 480 min
Graphene@graphite-based 60 mg L1 RheB 79% COD removal and 98% removal rate after 60 min (Z. Zhang

Chemosphere 269 (2021) 129325

GDE (G-GDE) et al., 2018)
Biochar derived Magnolia flower derived Pyrolysis in N2 for 2 h 18.3  103 mmol L1 min1 cm2 BO2 98% of decolouration after 70 min and TOC removal of 55% Chen et al.
Carbon carbon (2017)
Long bean derived carbon Pyrolysis with N2 and 19.6  103 mmol L1 min1 cm2 4- 99% decolourisation in 120 min Gao et al.
KHCO3 dimethylaminobenzene (2018)
(DAB)
Dried Sophora Flowers KHCO3eMgO dual- 221.9 mg L1 Bromocresol Green 96% degradation in 105 min Tian et al.
derived carbon porogen strategy (BCG) (2019)
(continued on next page)
 K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

modifications also improve the hydrophilicity of the carbon sur-

Perazzolo et al.

Yu et al. (2019)
(Y.M. Liu et al.,
Garza-Campos
After 90 min 80.75%, 77.42% and 79. 30% TOC removal for DMP, DEP (W. Ren et al.,
faces and the introduction of the functional groups have been

et al. (2018)

et al., 2019)
proved to increase the amount of H2O2, COH production and the
Liang et al.

Deng et al.

2013a,b,c)
Reference

(D. Zhang
(Yi Wang
Hu et al.
(2019a)
rate of pollutant degradation(Basova et al., 1999; Zhou et al.,
(2018)

(2013)

(2016)
2016)

2015)
et al.,
2018a,b,c,d,e,f). Table 2 highlights the structural and chemical
modifications on various carbonaceous electrode materials.

70.8 %e92% TOC removal efficiency in 60 min and 97e100%

5.1. Hetero atom doping
53% and 85% TOC removal in 120 min via EF and SPEF
86.8% TOC removal in 30 min and 95.84% in 180 min

Doping of heteroatoms like N, O, F, P, B, etc. into the carbon

67% of initial TOC removal and degradation  90% framework influences the localized electronic structure by creating
a partial positive and negative charged groups (Y. Jiang et al., 2018).
Theoretical and experimental results suggested that doping could
90.7% TOC removal after 240 min at pH2

break the electroneutrality of the carbon network giving an

enhanced number of active sites, facilitating an increased adsorp-
85.51% of TOC removal in 180 min

tion of O2, weakening the O e O bond and thereby the rate of

80.6% TOC removal in 120 min

75% TOC removal after 60 min

60% TOC removal in 180 min

ORR(Zheng et al., 2012a,b,c; Li et al., 2014). Heteroatoms have

and DMP-DEP respectively

influenced in increasing the percentage of mesopores in the carbon

degradation in 10 min

matrix, which further influences the electrocatalytic activity(Liang

et al., 2012). Since the heteroatoms have different sizes and elec-
tronegativities, the electrochemical properties of doped carbon
materials are correlated to the content and nature of the hetero-
Efficiency

atom dopant.
N-doped carbon materials are the most widely studied cathode
under ORR. Studies revealed that nitrogen atoms being more
electronegative than carbon atoms induce charge distribution and
Perfluorooctanoic acid

p electron activation, thus weakening the OeO bonding and

Molten salt carbonization 21.7  103 mmol L1 min1 cm2 Dimethyl phthalate

Dimethyl phthalate

Phthalic acid esters

Brilliant red X3B

changing the adsorption of OOH intermediates on carbon materials

Oxcarbazepine
Sulfathiazole

favouring the H2O2 production (Sun et al. 2018a,

Amoxicillin

2018b,bib_Sun_et_al_2018a,bib_Sun_et_al_2018b). Pyridinic and

Pollutant

Phenol

graphitic-N were found to be the most highly active ORR sites.

MO

However, there is no clear evidence on whether graphitic or pyr-

idinic N is responsible for an improved ORR(Vazquez-Arenas et al.,
2016; Sun et al., 2017). Thus, the application of N-doped carbon
materials for H2O2 production has gained much attention owing to
its high selectivity and efficiency(Hasche
et al., 2016; Chen et al.,
H2O2 production rate

2018). Several techniques were shown to control the number of

52.3 mmol L1 h1

electrons in the ORR using an N-doped carbon material. It was

Hydrothermal synthesis of 31.4e47.5 mM/h
10.85 mmol L1

shown that addition of certain transition metals (TMs), varying

Waste-wood derived biochar Pyrolysis of wood-waste 18.87 mg L1

Hydrothermal synthesis of 185.8 mg L1

temperature and heating power during synthesis, etc. aid in con-

85 mg L1
Hard Template procedure 1.29 mM

trolling the number of electrons involved in the reaction(C.L. Liu

et al., 2013; Bhatt et al., 2017).
Highly electronegative fluorine atoms could easily tune the
Hard templating method

electronic structure of carbon atoms like N- doping, inducing the

HPC and spin coating of
Soft Template synthesis

Direct calcination of N-

charge distributions to create more active sites for H2O2 generation.

Synthesis strategy

Apart from halogen species, very few studies have been conducted
containing MOF
Surface coating

* The units may vary with respect to the reactor configuration.

on S (Ferna
ndez-Sa
ez et al., 2019) and B(Oturan et al., 2012) doped

Calcination

carbon to improve the efficiency of EF treatment. Furthermore, co-

doping carbon materials with different types of heteroatoms could
MOF-5

ACF

create a vast amount of coexisting active sites, which would further

improve the efficiency of ORR (Hu and Dai 2019).
HPC modified ACF (ACF-HPC)
Hierarchically porous carbon
carbon electrode (ADE-MC)
Air diffusion mesoporous

NeS doped mesoporous

Water hyacinth derived

N-doped porous carbon

5.2. Cathode modifications for heterogeneous EF

CMK-3 carbon-GDE

carbon (N, S-MC)

ACF@rGO@OMC

In the case of heterogenous EF, cathodic materials functionalized

with iron and/or transition metals have gained immense attention
ACF@OMC
Cathode

in the recent years. The major concern for heterogeneous cathode

carbon

(HPC)

(NPC)

modification is that the solid catalyst used to modify the cathodes

Table 3 (continued )

should not possess any threat to its conductivity and charge

Mesoporous

transfer. The efficiency of heterogeneous-EF reaction mostly relies

on the fabrication technique (Ganiyu et al., 2018b). Cathodes can be
Carbon
Category

Ordered

mainly classified into three categories: (i) Fe/Fe containing com-

pounds grafted on carbonaceous materials (ii) Fe/Fe-TMs coated on
carbon aerogels, and (iii) bimetallic materials on carbon. Fe
14
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 11. a) Schematic of LEVO degradation using ACF cathode, b) COD and BOD5 values of LEVO after 360 min of AO, AO-H2O2 and EF techniques, c) Time-course of COD and BOD5
values using 200 mg L1 LEVO solution. Reprinted from ref (Gong et al., 2016).
incorporation have been widely used for various carbonaceous
materials including activated CF/fiber (ACF), GF, CF, carbon-PTFE
GDE, etc. This is accredited to the high surface area to volume ra-
tio, and high mechanical stability of the 3D cathode structures
(Zhuang et al., 2010a,b,c). The functionalization of carbon tends to
improve the surface features, achieving maximum H2O2 production
rate at wide pH range. Studies also revealed that carbon materials
with multiple dopants (bi or tri-metal doped) showed maximum
catalytic activity, owing to their high surface area and electron/
charge transfer rate as compared to mono-metallic counterparts
(Zhao et al., 2016; Ganiyu et al., 2017; Cheng et al., 2018; Le et al.,
2019).
In the following section, the various types of carbon materials
for EF degradation process are discussed. Techniques such as sur-
face coating, calcination, soft/hard template grafting, hydrothermal,
atomic layer deposition, etc. have been widely employed in the
synthesis of electrodes. SEM and TEM were used to analyse the
morphology and microstructures of various carbon materials.
BrunauereEmmetteTeller (BET) surface area analysis was per-
formed to determine the surface area and pore structure. Elemental
analysis and X-ray photoelectron spectroscopy (XPS) were used to
identify the elemental composition and type of hetero atoms that
are present while chemically modifying the carbon species. The
existing functional groups were determined via FTIR and the con-
tact angle measurements were carried out to explore the hydro-
philic nature of the cathode surface. A comparison of all cathode
materials based on H2O2 generation is given in Table 3. All kind of
emerging pollutants including pharmaceuticals (such as ibuprofen,
imatinib, and amoxicillin), electronic wastewater (containing cad-
mium, mercury, and other toxic metals), organic chemicals (such as
phenol, dimethyl phthalate, etc.) were degraded under the EF
process.
15
Chemosphere 269 (2021) 129325
6. Carbonaceous materials for EF process
6.1. Activated carbon fibres (ACF)
ACF is considered as one of the most important nano porous
carbon materials with considerable advantages as compared to
other commercially available porous materials. This is ascribed to
the high surface area, adsorption, conductivity and catalytic prop-
erty of ACF. Owing to the higher surface area, the 2-dimensional
planar structure of ACF converts to a quasi-3 dimensional elec-
trode, thus increasing the diffusion-limited currents and H2O2
production rate(Wang et al., 2005; A. Wang et al., 2008; Trellu et al.,
2018). There are two major steps involved in the synthesize of ACF:
(i) carbonization of precursor below 800  C under inert atmo-
sphere, and (ii) activation of the char via physical or chemical
methods(Duan et al., 2017). The samples require a pre-treatment
with acid for increasing the yield and rate of adsorption. Physical
activation involves treating the carbon materials with carbon di-
oxide (CO2) or steam whereas chemical activation involves the
treatment with chemicals such as H3PO4, KOH, ZnCl2, etc. Chemical
activation possess several advantages such lower activation tem-
perature, higher yield, less processing time and development of a
definite pore structure(Macia
-Agullo
et al., 2004).
In the first instance, ACF was used in EF for the chemical
degradation of acid red 14 (AR14)(Wang et al., 2005). ACF exhibited
a degradation efficiency of 70% during 360 min of electrolysis. The
efficiency of ACF cathode material was further studied through a
photoelectron-Fenton (PEF) process for the mineralization of the
AR14(A. Wang et al., 2008). Results suggested that PEF exhibited a
mineralization efficiency of more than 94% after 6 h of even at
reduced current densities. In another study, ACF cathode was
applied to treat waste water containing the herbicide glyphosate by
EF process(Lan et al., 2016). The results indicate that BOD5/COD
ratio for EF process increased to > 0.3 and was attributed to the high
rate of COH formation and rapid conversion of Fe3þ ions to Fe2þ.
The degradation mechanism included the breaking of CeN and CeP
bond by COH forming acetic acid and oxalic acid. Further, all the
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Fig. 12. a) N2 adsorption-desorption isotherms and pore size distribution of ACF1 and ACF2, b) evaluation of H2O2 generation in AO and EF process of ACFs c) Schematic of
experimental setup for PEF reaction. Reprinted from ref(Y. Zhang et al., 2019).

Fig. 13. a) Schematic of submerged and floating cathode cell arrangements, b) H2O2 production using GF “floating” cathode, c) IBP removal rate in EF process by “floating” and
“submerged” cathodes, and d) Schematic of ORR using “floating” GF cathode. Reprinted from ref.(Zhou et al., 2018a,b,c,d,e,f).

16
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 14. Schematic of DMP degradation mechanism by GF-EA and GF-SA. Reprinted from ref(Li et al. 2020).
organic intermediates were decomposed into inorganic ions and
CO2.
A comparative study on the degradation efficiency of anodic
oxidation (AO), AO with the assistance of electrogenerated H2O2
(AO-H2O2) and EF reaction employing ACF felt cathode was con-
ducted for the partial degradation of levofloxacin (Gong et al.,
2016). ACF with a BET specific area of 1237 m2 g1 was used as
the cathode material for AO-H2O2 and EF whereas RueTiO2 was
employed as both anode and cathode for AO. Fig. 11(a) shows the
schematic of LEVO degradation using ACF. The efficiency of LEVO
degradation in AO, AO-H2O2 and EF process were compared. The
BOD5/COD ratio was observed to be 0.24 in the EF process whereas
only 0.03 and 0.09 were obtained for AO andAO-H2O2 after treat-
ment for 360 min (Fig. 11(b)). The concentration-time plot indi-
cated that the reaction followed a pseudo-first-order kinetics with
a rate constant of 2.37 x 102 min1. It was observed that with the
increase in electrolysis time, the COD values decreased steadily in
EF process (Fig. 11(c)). Three major pathways were included in the
degradation of LEVO such as decarboxylation, de-methylation and
hydroxylation. Three carboxylic acid namely oxalic acid, acetic acid
and formic acid, inorganic ions such as NH4þ, NO3 and F, and
eight aromatic products were formed.
Similarly, the effect of ACF cathode surface properties were
examined for the mineralization of cefalexin (Y. Zhang et al., 2019).
Two different ACF cathodes (ACF1 and ACF2) with unique physical
properties such as pore size, surface area, pore volume, etc. were
utilised in this study. The mineralization rate and kinetics of EF
were compared with PEF. Fig. 12 (a) shows the adsorption/
desorption of both ACFs indicating the presence of micropores with
small external surfaces. The inset shows the pore size distribution
of both ACFs, and the higher pore size distribution in ACF2 indicates
the presence of mesopores in addition to the micropores. This
suggests that the specific surface area and pore volume of ACF2 was
higher than ACF1. Owing to the high BET surface area, ACF2 could
provide a better contact among electrode, water and reactants. The
17
Chemosphere 269 (2021) 129325
rate of H2O2 and COH production, and mineralization ability of the
ACF cathodes were in the order of ACF1-EF < ACF2-EF < ACF1-
PEF < ACF2-PEF (Fig. 12(b)). The improved oxidation efficiency of
PEF was accredited to the photodecomposition of Fe (III)-hydrox-
ylate species and the photodecarboxylation of Fe (III)-carboxylate
complexes, yielding more COH radicals and Fe3þ in the solution(Y.
Zhang et al., 2019).
Significant efforts have been carried out to improve the elec-
trocatalytic activities of ACF cathode materials for EF reaction,
which include hetero-atom doping (polyacrylonitrile derived car-
bon fibres), grafting of mesoporous carbon on ACFs (OMC@ACF (Hu
et al., 2013)), grafting of iron/other transition metals on ACFs (Fan
et al., 2010), etc.
ACF-supported on graphitic carbon nitride (g-C3N4/ACF), was
applied in the EF degradation of rhodamine B (RheB) dye (He et al.,
2018). The cathodic performance of g-C3N4/ACF was higher than
the pristine ACF. This was attributed to the difference in electro-
negativities of N and C atoms that reduced the barrier to ORR and
the presence of six nitrogen lone-pair electrons in g-C3N4 which
could act as ideal sites for metal-ion coordination. Moreover, g-
C3N4/ACF was stable for five consecutive cycles of reaction. In
another study, N-doped mesoporous carbons were synthesized
using dicyandiamide (C2H4N4) and grafted onto activated carbon
fibres (ACF) forming a composite cathode (ACF@N-OMC), and it
resulted in an increased electrocatalytic activity and lower ORR
potential (Peng et al., 2014). ACF@N-OMC was also used for the EF
degradation of brilliant red X3B. The cathode showed a degradation
rate of 1.84  102min1 and was found to be 50% higher than the
undoped cathode samples.
In a similar study, the ACF cathodes was used to improve the
nitrobenzene (NB) mineralization via UV/EF process(C. Zhao et al.,
2017). The efficiency of pristine ACF was compared with nitric
acid treated ACF (ACFN) and ammonia treated ACF (ACFH) and Ti
plate cathode. 98% of NB mineralization was achieved in 20 min by
UV/EF (ACF0) compared to Ti cathode. NB removal efficiency of the
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 15. Schematic of the electrochemical cell set up (a) carbon felt-iron oxide air-
diffusion cathode, (b) BDD anode, (c) Ni/Cr wire electrical connection, (d) air flow,
(e) magnetic bar, (f) water from thermostat at 25  C, (g) water to thermostat, (h)
electrolyte dye solution and (9) 6 W UVA lamp for PEF experiment. Reprinted from ref
(García-Rodríguez et al., 2016).
cathode materials are in the order ACFN > ACF0 > ACFH > Ti. The
results revealed that the presence of N, H atoms on the surface of
ACF enhances NB mineralization. The hydrogen bonding and
dispersion forces between the ACF and NB resulted in an improved
NB mineralization rate. Among the three ACF cathodes, ACFN
exhibited the highest rate of in-situ H2O2 generation. This was
attributed to the existence of p-p bonding, carboxylic acid (-COOH)
groups and pore volume.
ACF cathode modifications for heterogeneous EF has also been
recently explored. In a previous study mentioned where ACF
cathode was applied to remove glyphosate, Fe2O3 particles were
further deposited on the ACF surface and was concluded that Fe2O3/
ACF could be used as the source of iron in EF process (Lan et al.,
2016). Results indicated that there was not much difference in
the pore structure of ACF as well as the cycle/reuse of ACF cathode
on Fe2O3 deposition. A sandwich film cathode (SFC) of iron-
chitosan/nickel|ACF|iron-chitosan/nickel (FeeCHI/Ni|ACF|FeeCHI/
Ni) was employed to improve the H2O2 production and RhB
degradation (Fan et al., 2010). The composite SFC was highly stable
and inexpensive. A concentration of 45.17 x 106 molL1 H2O2 was
generated after 120 min of EF reaction. 92% RheB degradation was
observed at pH 6.2, but the efficiency decreased with further in-
crease in pH.
6.2. Carbon/graphite felt
Carbon felts (CF) have been considered as one of the best can-
didates for the removal of POPs owing to their low cost and stable
physico-chemical properties. However, the applications of CF are
limited by their hydrophobicity and poor kinetics for redox reac-
tions(Huong Le et al., 2017; Le et al., 2018). Thus, several modifi-
cation techniques have been adapted to enhance the
18
Chemosphere 269 (2021) 129325
electrochemical activity of CFs which include deposition of metals
(mostly Fe in heterogeneous EF) and addition of various functional
groups such as halides, amines, etc. (Chakrabarti et al., 2014).
A number of the pioneer works using CF cathodes were per-
formed by Oturan and co-workers(Guivarch et al., 2003). One of
their initial works reported the catalytic behaviour of Fe3þ/Fe2þ
system for the decomposition of chlorophene using Pt or BDD
anode and CF or O2 diffusion cathodes (Sire
s et al., 2007). The ef-
ficiency of the electrodes was compared based on their ability to
oxidize the Fe3þ-oxalate complexes generated. The results revealed
that the complexes were poorly oxidised in the Pt/O2 diffusion cell
whereas the complete destruction was observed for BDD anode at
high current densities. However, the highest oxidizing power was
attributed to BDD/CF cell, as the oxalic acid was simultaneously
decomposed both at the BDD surface and bulk solution. Later
studies described the oxidation of phenol aqueous solution using
CF cathode with various metal cations (Fe, Co, Mn, and Cu) as
catalyst to generate COH (Pimentel et al., 2008). Ferrous cation was
proved as the best catalyst to degrade phenol with 100% TOC
reduction. The results demonstrated that high surface area, pore
volume, constant current density and pH were favourable for the
faster degradation of organic pollutants. In a similar study, a porous
CF cathode was developed to eliminate paracetamol (PCM),
through EF process (Le et al., 2016). The electroactive surface area
was improved by thermal treatment in a tubular furnace with a
mixture of N2/O2 with 1% of oxygen. The porous CF was hydrophilic
in nature and the surface area was 10 times higher than the raw CF,
indicating the strong mineralization efficiency of porous CF.
GF loaded with CNTs and carbon black were developed to
improve the yield of H2O2 and thereby increasing the degradation
of diclofenac (Yu et al., 2018a). The CNT: carbon black ratio was
optimised to 3:2 to improve the surface area and pore volume by
nearly 30 folds. The 3D morphology and increased number of meso/
micropores in the loaded GF facilitated an improved diffusion of gas
molecules through the carbon material. The modified electrode
exhibited a removal rate of 99% within 30 min, which was almost 4-
fold higher than that of bare GF electrode. Several other reports also
revealed the increase in electrochemical activity of modified CF/
GFs(Zhou et al., 2013b; Miao et al., 2014; Sklari et al., 2015; Yu et al.,
2015). In another report, a mesoporous carbon coated GF (MesoC/
GF) was employed as cathode for the degradation of phenol in a PEF
reaction (Yue et al., 2018). Micron sized g-C3N4 particles were used
as the catalyst and a metal-free visible light PEF system was
developed. The effect of g-C3N4 concentration on phenol degrada-
tion was studied. As the g-C3N4 was increased beyond 140 mg L1,
there was a decrease in phenol removal rate. This can be attributed
to the light scattering and blocking effects of increased amount of g-
C3N4. However, it was manifested that at a concentration of
140 mg L1, g-C3N4 acts as a metal-free Fenton-like catalyst with a
high rate of in-situ
OH generation. The system also eliminated the
issues related to secondary metal-residue pollution.
Several modifications have been made in the type of aeration
provided to the system to improve the diffusion of oxygen. A recent
study reported a porous “floating” GF and reticulated vitreous
carbon (RVC) foam cathodes, for the degradation of ibuprofen(Zhou
et al., 2018a,b,c,d,e,f). The experimental setup for the submerged
and floating electrode system is illustrated in Fig. 13 (a). The floating
cathode utilised O2 from air as well as the electrolyte simulta-
neously, forming a three-phase boundary consisting of gaseous
oxygen, solid cathode and aqueous electrolyte. The “floating” GF
cathode degraded 78.3% of ibuprofen, in 120 min whereas only
24.5% was achieved by conventional submerged GF electrode.
Fig. 13 (b) represents the increased rate of H2O2 generated with GF
foam “floating” cathodes. The IBP removal efficiency of the
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 16. a) Schematic of PAM degradation mechanism through heterogeneous EF reaction, b) N2 adsorption-desorption isotherm of FeeCe0.75Zr0$25O2/CF, c) pore size distribution of
FeeCe0.75Zr0$25O2/CF, d) CV of bare CF and FeeCe0.75Zr0$25O2/CF, and e) Nquist plot of bare CF and FeeCe0.75Zr0$25O2/CF. Reprinted from ref(Xie et al., 2019).
“floating” cathode in EF process is shown in Fig. 13 (c) which is
consistent with the increased H2O2 generation rate.
Recently, GF with electrode aeration (GF-EA) was designed to
treat DMP wastewater(Li et al., 2020). GF-EA showed improvement
in both H2O2 generation and DMP degradation compared to solu-
tion aeration (SA) due to the enhanced O2 supply through the
three-dimensional networks. Solid-liquid-gas interfaces, solution
exchange and hence the active sites for ORR were significantly
improved through EA. Fig. 14 shows the schematic of DMP degra-
dation mechanism using GF-EA. The cathode significantly reduced
the cost of EF reaction through in-situ iron sludge collection and
reduction in energy consumption. Electrode poisoning due to the
deposition of iron sludge was prevented, improving the reusability
of the cathode.
Chemical modifications and hetero atom doping have been
further introduced to improve the EF efficiency. Chemically acti-
vated carbon felt (ACF) and graphite felt (GF) were used for the
degradation of tetracycline (TC) using a flow-through EF and ACF
adsorption system(Y. Zhang et al., 2018). Oxygen or nitrogen-
containing functional groups were introduced on the felts to pro-
mote the efficiency of cathodic reduction (Zhou et al. 2013a,
2014a,b,c,bib_Zhou_et_al_2013a,bib_Zhou_et_al_2014a; Pan et al.,
2018). The chemical modification process on CF/GF involves two
major processing steps, namely refluxing and heating (Zhou et al.,
2014a,b,c). The consumption of electric energy was also lower for
the degradation of TC by the coupling of EF and ACF adsorption
systems (Y. Zhang et al., 2018). Moreover, the system showed wide
pH adaption and self-regeneration of ACF, which resulted in 90%
removal rate of TC.
A graphitized nitrogen doped porous carbon layer (NPC) was
synthesized on commercial CF to evaluate the adsorption and
cathodic efficiency in an EF reaction for the degradation of AO7(Le
et al., 2017). Owing to the highly ordered porous structure, surface
area and nitrogen doping, these materials could enhance the
electrical conductivity and catalytic property. NPC/CF showed a TOC
removal of 90% during 480 min for the degradation of AO7 with a
high degradation rate constant of ~0.8 min1. The NPC/CF cathode
proved to be stable even after multiple reaction for 10 subsequent
19
Chemosphere 269 (2021) 129325
cycles. The enhanced activity of NPC/CF was attributed to the
porosity of carbon derived from MOFs, and the presence of pyr-
idinic/pyrrolic/quaternary N that promotes the mass transfer and
hydrophilicity. Further, the degradation of levofloxacin, an anti-
biotic was investigated using a N-doped GF cathode, synthesized
using hydrazine hydrate and ethanol(X. Liu et al., 2017a). The
cathode showed a TOC removal rate of 92% at a current of 200 mA.
The efficiency of N-doped GF was two folds higher than that of
unmodified cathode.
A cold remote plasma (CRP) treated and glucose oxidase (GOx)
enzyme biofunctionalized CF cathode was designed to study the
effect of new functional groups on the wettability of CF for elec-
trochemical applications (Kahoush et al., 2019). CRP possess several
advantages such as short operation time and solvent free approach.
After the CRP treatment oxygenated and amino functional groups
were observed in CF. The stability and reusability of the cathode
were also improved by CRP treatment. In another study, an elec-
trochemically exfoliated graphene (EEGr) modified GF cathode was
engineered to maximize the H2O2 generation yield and reduce the
energy consumption in the EF process (W. Yang et al., 2017). EEGr
presence was advantageous for the oxygen surface reaction, elec-
tron transfer and hydrophilicity. The cathodic performance of EEGr-
CF was tested for the degradation of imatinib (IMA) (Yang et al.,
2019a). The high electrocatalytic activity, and a complete mineral-
ization was observed for 34.5 mg L1 of IMA in 8 h using the EEGr-
CF cathode whereas the pure CF showed only 75% TOC removal
under the same operating conditions. These results proved that
modified CF/GF cathodes owns a higher potential for the efficient
mineralization of POPs and shed new light on the EF process for the
removal of pharmaceuticals from water or wastewater.
Heterogeneous cathode modifications have been introduced to
further improve the EF efficiency. The synthesis of two composite
Fe/CF electrodes, through oxidizing and reduced-oxidative condi-
tions were demonstrated for the degradation of diclofenac (Sklari
et al., 2015). Fe/CF was highly stable and showed a very high
degradation efficiency of 63.7% and mineralization efficiency of
31.6% for diclofenac at low applied potential (1.0 V/Ag/AgCl),
neutral pH and an initial diclofenac concentration of ~34 mg L1.
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 17. Schematic of microtubular MWCNT-GDE cathode for EF reaction. Reprinted from ref(Roth et al., 2016).
The mineralization of malachite green (MG) dye using a CF/iron
oxide air diffusion electrode was investigated by heterogeneous EF
and PEF (García-Rodríguez et al., 2016). An open and one-
compartment reactor was used for the dye degradation. BDD film
was used as the anode and it was separated at a distance of 1 cm
from the cathode. Comparative studies on the oxidation efficiency
of heterogeneous EF and PEF were explained using the concept of
mineralization current efficiency (MCE) as follows (Skoumal et al.,
2009):
nFVs DðTOCÞexp
MCEð%Þ ¼ x 100
4:32 x 107 mIt
Where n is the number of electrons consumed, F is the Faraday
constant, Vs is the solution volume, △(TOC)exp is the experimental
TOC decay (mg L 1), 4.32  107 is a conversion factor, m is the
number of carbon atoms of the molecule, I is the applied current (A)
and t is the electrolysis time (h).
Almost complete mineralization with 98% of efficiency was
observed for the heterogeneous PEF at 50 mg L1 MG and a current
density of 21.7 mA cm2. Nearly 95% of the decolorization was
observed during the initial 15 min of electrolysis. The improved
efficiency of heterogeneous PEF was accredited to the formation of
an Fe (III) complex with the oxalate group of the dye, quick pho-
todegradation of the intermediates formed, generating more sol-
uble Fe2þ and COH. Fig. 15 shows the schematic of the
electrochemical setup used for PEF reaction.
The solvothermal synthesis of hierarchical 3D porous FeIIFeIII
layered double hydroxide (LDH) on a CF substrate was described in
a recent study (Ganiyu et al., 2018a). The cathode composed of well
oriented and highly crystallized interconnected nano walls, which
showed 90% TOC removal efficiency towards sulfamethoxazole
(SMT) at pH 9 after 8 h. The cathode was stable at high pH values
and showed only less than 17% reduction in TOC removal efficiency
over 10 cycles of 4h treatment. Fe-doped Ce0$75Zr0$25O2 on CF was
applied for the degradation of polyacrylamide (PAM) (Xie et al.,
2019). The cathode material was fabricated via a hydrothermal
method. The ratio of Ce/Zr was fixed as 3:1, and the degradation
efficiency of the cathode was investigated with Fe content (Y. Li
et al., 2017b,c). The catalyst with Ce/Zr/Fe ratio of 3:1:2 showed
the highest efficiency compared to other compositions 3:1:1, 3:1:4,
20
Chemosphere 269 (2021) 129325
3:1:8 and 3:1:10. A lower iron content failed to produce enough
amount of COH from H2O2 reduction whereas a higher Fe con-
centration led to the formation of OH reducing active COH pre-
sent. The catalyst exhibited a type IV hysteresis loop and the
presence of mesopores with high surface area led to a better
adsorption and degradation of PAM (Fig. 16 (b)e(c)). Fig. 16 (d)
shows the increased peak current and peak area values of
FeeCe0.75Zr0$25O2 when compared to CF. The Nyquist plot
(Fig. 16(e)) revealed a smaller charge transfer resistance of
FeeCe0.75Zr0$25O2 cathode which contributed to the improved
catalytic activity. CeO2 was proven to support the formation of
C
OH, like Fe based catalysts (Heckert et al., 2008). Overall, the
FeeCe0.75Zr0$25O2 showed a degradation efficiency of 86% with the
TOC removal rate reached 78% after 120 min.
Three nanostructured iron oxide/graphite cathode materials
such as FeOOH/graphite, Fe2O3/graphite and Fe3O4/graphite were
used for the mineralization of RheB dye (Sun et al., 2015). The
activity of catalysts was in the order of Fe3O4/graphite > Fe2O3/
graphite > FeOOH/graphite. This was accredited to the variations of
octahedral sites and Fe2þ ions. A hierarchical CoeFe LDH modified
CF cathode (CoeFe-LDH/CF) exhibited an excellent activity for the
mineralization of acid orange 7 (AO7) over a pH range of 2e7.1
(Ganiyu et al., 2017). The enhanced performance of CoeFe-LDH/CF
was ascribed to the following reasons: (a) surface-catalysed re-
actions that could ample the working pH window and avoid the
precipitation of iron sludge at high pH, b) improved electroactive
surface area, and H2O2 production and c) effect of Co2þ as a co-
catalyst in the LDH which could promote the regeneration and
production of Fe2þ/COH.
Other transition metals have also been employed in modifying
the carbon materials in heterogeneous EF reactions (Bokare and
Choi 2014). A roll-made GDE loaded with transition metals (M/
GDE, M ¼ Cu, Ce, Mn, Fe, Co) were fabricated for the heterogeneous
EF degradation of MO dye (Liang et al., 2016). Among the dopants,
Co/GDE showed the best performance with high stability in a wide
range of pH (3e9). The activity of a composite graphite felt (GF)
loaded with Co (GF-Co) was evaluated for the MO degradation ef-
ficiency (Liang et al., 2017). GF-Co displayed a 99% MO degradation
at pH 3 after 120 min. The material also showed 82% dye degra-
dation even at pH 9. Recently, a CF cathode modified with ordered
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 18. Rotating ring disc electrode (RRDE) voltammograms showing the oxidation of
HOe2 at the ring. Reprinted from ref (Xue et al., 2017).
mesoporous-NiMn2O4 nanoparticles was fabricated for the degra-
dation of ciprofloxacin (Sun et al., 2019). 100% of ciprofloxacin
degradation was attained in 1.5 h by CF-NiMn2O4. This was ascribed
to the presence of two redox couples (Mn4þ/Mn3þ and Ni3þ/Ni2þ)
in the CF-NiMn2O4 catalyst.
6.3. Carbon nanotubes (CNTs)
CNTs have been a material of interest in the field of 2ee ORR
owing to its unique properties such as surface area, mechanical
strength, chemical stability and outstanding electrical conductivity
(Zhang et al., 2008; H. Yang et al., 2018). CNTs are also used to
modify other cathode materials to improve the generation of
H2O2(Pajootan et al., 2014; Babaei-Sati and Basiri Parsa, 2017). The
high adsorption capability of CNTs make it an excellent candidate
for the degradation of organic pollutants (Upadhyayula et al., 2009;
Zhang et al., 2011; Gupta et al., 2016; Roth et al., 2016).
A cuprous oxide/CNTs/polytetrafluoroethylene (Cu2O/CNT/
PTFE) cathode was fabricated on a gas diffusion electrode (GDE) to
degrade RheB dye (Ai et al., 2008). The degradation was also car-
ried out with blank PTFE and CNTs/PTFE cathode. Cu2O/CNT/PTFE
showed a degradation rate of 80.2% at neutral pH in 120 min
whereas no significant degradation was observed for both blank
PTFE and CNTs/PTFE cathodes. Hence, it was concluded that Cu2O
served as an effective heterogeneous EF catalyst. Cu2þ ions were
responsible for the reduction of oxygen, in-situ H2O2 production,
and further COH generation. The cathode was stable without a
drop in its efficiency for more than 15 h, suggesting its potential
applications in real wastewater treatment.
A novel microtubular MWCNTs GDE was designed to investigate
the degradation of acid red 14 (AR14) via a periodic adsorption-EF
process (Roth et al., 2016). GDE cathode was surrounded by a cy-
lindrical anode. AR14 was initially removed via adsorption on
MWCNT-GDE and was then degraded electrochemically through EF
reaction. The dye adsorbed MWCNTs was regenerated during the EF
process. Fig. 17 shows the schematic of microtubular MWCNT-GDE
cathode for EF reaction. The simple design, and high surface to
volume ratio that resulted in high packing and energy densities
were the main advantages of the tubular reactor setup. Total
decolorization of AR14 was resulted from the cathodic reduction
and was observed to be independent of the added Fe2þ concen-
tration. However, these did not lead to the total mineralization of
21
Chemosphere 269 (2021) 129325
the dye and 50%e70% of TOC and COD removal were observed with
the increase of Fe2þ concentration from 0.5 to 07 mM via EF
reaction.
Scaling up and complicated coating techniques are the major
drawbacks for the fabrication of GDE (Panizza and Cerisola 2008;
Liang et al., 2016). To address this, CNT-GDE was commercially
engineered by a rolling method for the degradation of acetylsali-
cylic acid (ASA) (H. Yang et al., 2018). CNT, PTFE and ethanol were
mixed and rolled onto the stainless-steel mesh. The rolling method
has several advantages such as accuracy, homogeneous mixing and
coating, and improved gas transport (Dong et al., 2012). It was
confirmed that the CNTGDE led to a higher H2O2 production and
almost 100% degradation of ASA within 10 min. In a similar study,
the GDE was coated with CNTs/g-C3N4 for the degradation of aliz-
arin yellow R (AYR) by PEF reaction (Yu et al., 2018b). The decol-
ouration and TOC removal efficiency of PEF was compared with EF
and photo-Fenton (PF), respectively. The TOC removal efficiency of
PEF is 94% which is 5 times higher than PF. The results revealed that
the degradation efficiency, TOC removal rate and COH radical for-
mation was enhanced by the visible light irradiation. The formation
of an electron hole pair via PEF reaction could improve the elec-
tronic conductivity and hence H2O2 generation. EPR results were
also consistent with the degradation efficiency and the signal in-
tensity was decreased for both EF and PF. A highly graphitized
MWCNTs (g-MWCNTs) electrode was fabricated as a cathode ma-
terial for chromium (Cr) oxidation in wastewater(Xue et al., 2017).
The current density measurements revealed that the g-MWCNTs
exhibited a more positive onset potential compared to MWCNTs,
indicating the much lower over-potential and higher ORR activity
(Fig. 18). The high rate of HOe 2 generation were accredited to the
highly ordered graphitic structure, and excellent conductivity.
Further, a nitrogen-doped graphene @CNTs (N-G@CNT) GD
cathode was developed for the degradation of dimethyl phthalate
(DMP) at very low cathodic potential of 0.2 V (T. Liu et al., 2016).
The efficiency of N-G@CNTs was superior to graphite-GDE, gra-
phene-GDE and CNT-GDE. This could be attributed to the bridging
effect between graphene and CNTs, which prevents the restacking
of graphene, and increases the basal spacing, and N-doping which
synergistically improves the electrical conductivity. N-doped
MWCNTs were also utilised as a catalyst layer on GDE, by immo-
bilizing them as the diffusion layer on the surface of nickel foam
(NF) as a supporting material(Tang et al., 2015). CNT/NF/GDE was
used to investigate the degradation of p-nitrophenol (p-Np). The
activity was compared with CNT/NF/CNT GDE, and the results
indicated that the H2O2 production rate and current efficiency was
remarkably improved by N-doping, consequently the degradation
level and TOC removal efficiency were higher. Liu et al. developed a
highly energy efficient N-doped graphene @ CNT composite cath-
ode with a high reusability for the EF reaction, which significantly
improved the current density with more positive onset potential(T.
Liu et al., 2016). The material showed H2O2 generation at very low
potential (0.2V vs. SCE) with a high rate constant of 0.0322
min1 for the degradation of DMP. In a similar study, nitrogen
functionalized CNTs (NCNT) cathode was synthesized and a faster
removal rate of MO was observed as compared to raw CNTs (Zhang
et al., 2008). The nitrogen functionalities were found to be pyridine,
pyrrole, and quaternary species. It was demonstrated that 72% of
MO was degraded in 60 min at pH 7 by EF reaction. The enhanced
activity at higher pH can be attributed to two factors namely
effective regeneration of Fe2þ at NCNT cathode and the high con-
centration of H2O2 generated due to the reduced electron transfer
rate for ORR.
Reports are also available on the application of CNTs and its
modifications for heterogenous EF and Fenton-like reactions(E-
s’haghzade et al., 2017). Fe-doped multi-walled CNTs (Fe-MWNT)
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 19. Schematic of CA synthesis technique. Reprinted from ref(Zuo et al., 2015).
cathode was used for the degradation of methyl orange (MO) dye
(Fu et al., 2007). Fe-MWNT cathode exhibited a H2O2 production
rate of 110 mg L1 in 90 min and a high reusability due to the firm
adhesion of Fe2O3 grains to the electrode surface. The activity of Fe-
MWNTs was compared with graphite/gas diffusion cathode (GDC)
and the activity of Fe-MWNTs was higher than GDC. An Fe3O4
containing graphene/carbon nanotube-based carbon aerogel (Fe-
GMCA) was prepared and successfully applied for MB degrada-
tion(W. Chen et al., 2016). The results demonstrated an exceptional
increase in the H2O generation rate. This could be attributed to the
increase in electrical conductivity and surface area of the electrode
owing to the co-existence of graphene and CNTs. 99% of MB
degradation was obtained in 60 min when 5% Fe-GMCA was used.
Similarly, an iron containing MWCNT (MWCNT-Fe*) was used to
modify the glassy carbon electrode (GCE/MWCNT-Fe*) for the
degradation of benzene(Vishnu and Kumar 2016).
In another recent study, MWCNT-Al was synthesized to increase
the in-situ generation of H2O2 and glyphosate degradation (Tan
et al., 2019). H2O2 accumulation was observed to be 947 mg L1
at pH 9 and it was attributed to the direct contact between Al0 and
MWCNT in the MWCNT-Al composite. Recently, cobalt, sulphur and
phosphorous (Co, S, and P) decorated MWCNTs was synthesized on
a carbon cloth through a hydrothermal route (Ye et al., 2019). The
material was employed as an air-diffusion electrode for the PEF
treatment of bronopol. (Co, S, P)-decorated MWCNTs had higher
surface area with minimum Co leaching as compared to the bare
cathodes. Consequently, the stability and H2O2 generation of the
metal decorated MWCNTs were also higher.
Fe@Fe2O3/CNT as an oxygen-fed GDE was engineered by the
mechanical rolling of a paste made from Fe@Fe2O3 nanowires, CNT
and PTFE suspension in ethanol (Ai et al., 2007). The cathode was
used for the degradation of RheB at neutral pH. The cathode
promised a higher rate of H2O2 generation (1.65 x 102mM H2O2)
and 91.5% of RheB degradation was accomplished in 120 min at
22
Chemosphere 269 (2021) 129325
neutral pH conditions. However, among the all different CNT based
cathodes mentioned, the GDE showed highest removal rate and
H2O2 production, that can be attributed to the improved surface
area and mass transfer rates.
6.4. Carbon aerogels (CAs)
Since the extensive development of CA from early 90’s, it has
been recognized as a fascinating material for several applications
such as adsorption(Maldonado-Ho
dar et al., 2007; Bi et al. 2013,
2014,bib_Bi_et_al_2013,bib_Bi_et_al_2014), CO2 reduction(Yu et al.,
2017; Xiao et al., 2019), water treatment(Biener et al., 2011; Sui
et al., 2012; Maleki 2016; Hu et al., 2017), etc.. The major factors
contributing to the high performance of CA include large specific
surface area, abundant pore size, low density, good corrosion
resistance, electrical conductivity, and tuneable surface chemistry.
Hitherto, the use of CA has been mostly limited to adsorption and
catalysis. In the recent decades, CA has also been explored as
cathode material for EF reaction(Wu et al., 2008). In most of the
cases, iron (or any transition metals (TMs))/iron oxide incorporated
CA were used as cathode for heterogeneous EF reaction (Zhao et al.,
2012; Peng et al., 2015; H. Zhao et al., 2017).
CAs could be synthesized through a sol-gel and wet chemical
synthesis approaches. A variety of precursors such as resorcinol
with formaldehyde (RF), melamine formaldehyde (MF), phenol-
formaldehyde (PF), and several polymers like polyacrylonitriles,
polystyrenes, etc. have now been used for the synthesis of CAs. The
schematic of CAs synthesis is depicted in Fig. 19(Zuo et al., 2015).
The major steps include sol-gel formation, solvent exchange/
ageing, drying and carbonization(Maleki 2016; Gan et al., 2019).
Initially at the gelation stage, polymerization and/or crosslinking
occurs which leads to the formation of CAs. Drying the gel without
causing any dimensional shrinkage or structural collapse is the
crucial step in aerogel synthesis. The three important drying
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 20. A) Schematic of CO2 and N2 activation of FeCuC aerogel in a sequential manner, B) MB degradation rate using FeCuC aerogel and homogeneous EF system with CA and Fe2þ,
C) TOC removal of MB degradation in heterogeneous and homogeneous EF system, and D) Schematic of EF reaction on FeCuC aerogel activated using CO2 and N2 . Reprinted from
ref.(Zhao et al., 2016).
methods involved in the synthesis of aerogels are i) supercritical
drying, ii) freeze drying and iii) ambient pressure drying. Although
ambient drying is less expensive, it might lead to various structural
collapse and hence the other methods are commonly preferred. In
the final carbonization step, the aerogel is heated (in the range of
600  Ce2500  C for 3e10 h) under N2 or Ar atmosphere to
decompose oxygen and hydrogen moieties, enriching the network
with pure carbon materials(Ganiyu et al., 2018b).
Apart from CAs, reduced graphene oxide (rGO) aerogels have
also been explored recently. In a recent study, single walled CNTs/
rGO (SWCNTs/rGO) aerogel was used for the decolouration of MB
and palm oil mill effluent (POME)(Nazhif Mohd Nohan et al., 2019).
The aerogels were synthesized via a one-pot hydrothermal process
without adding any binders. The presence of CNTs and rGO aerogel
showed a synergistic effect owing to its increased surface area, pore
volume and conductivity which enhanced the degradation effi-
ciency and H2O2 production rate.
To develop an Fe/TMs coated CAs, metals precursors are added
to the homogenous solution before the sol is formed (Xiong et al.,
2015; X. Liu et al., 2017b). The combination of CAs and Fe dopants
obviously uplifts the efficiency of cathode materials in heteroge-
neous EF reaction. A 3D homogeneous ferrite carbon aerogel (FCA)
was synthesized from a metal-resin precursor and it was used for
the degradation of metalaxyl (MET) (Yujing Wang et al., 2013a,b,c).
23
Chemosphere 269 (2021) 129325
FCA demonstrated 98% TOC elimination at pH 3 in 4 h and the
cathode was stable over 10 cycles of experiments. A carbon matrix
with graphene, CNTs and Fe3O4 nanoparticles was designed by the
same researchers. 99% of MB removal was achieved in 60 min,
which was attributed to the synergistic effect of graphene and CNTs
(W. Chen et al., 2016). A highly ordered mesoporous Fe3O4@carbon
embedded composite was grafted on CA for the removal of DMP
(Wang et al., 2016). The composite cathode showed an increased
number of catalytic active sites and reduced mass transport resis-
tance due to the presence of highly dispersed Fe3O4 nanoparticles.
95% of DMP removal was achieved within 120 min. Iron oxide/
activated CA nanocomposite (Fe3O4@Fe2O3/ACA) was initially uti-
lised as cathode for the degradation of imidacloprid(Zhao et al.,
2012). ACA exhibited a high surface area of 2410 m2 g-1 with
meso and micropores, which could act as good support for H2O2
production. In a similar study, a composite FeOx/ACA cathode was
developed by controlling the reduction of Fe(III) forming a mixed
Fe2O3 and Fe3O4 crystals(Yujing Wang et al., 2013a,b,c). FeOx was
the EF catalyst in the nanocomposite. The nanocomposite displayed
maximum TOC removal efficiency (93% in 150 min) at a pH range
from 3 to 9. Moreover, the efficiency of FeOx/ACA was 1.4 times
higher than that of free Fe2þ. There are several reports regarding
the incorporation of Fe/TMs on CA (Zhao et al., 2016; H. Zhao et al.,
2017). Fe-functionalized CAs have also been used as cathode
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 21. a) Schematic of COH formation in G-GDE, b) N2 adsorption-desorption isotherm and pore size distribution of G-GDE and GDE, c) H2O2 yield at different cathode materials,
and d) SEM image of G-GDE. Reprinted from ref(Z. Zhang et al. 2018).
materials in hetero-PEF process (Peng et al., 2015).
FeeCu CA cathode was synthesized through a one step process
for the degradation of MB dye (Zhao et al., 2016). The cathode was
initially activated using CO2 and N2 at 850  C and 950  C, respec-
tively (Fig. 20 (A)). 98% MB degradation efficiency was achieved in
30 min for FeCuCA (Fig. 20 (B)). A TOC removal of 82% was observed
for FeCuCA which was 10% higher when compared to homogeneous
EF system with Fe2þ and CA (Fig. 20 (C)). The increased minerali-
zation efficiency was attributed to ultra-dispersed metallic FeeCu
nanoparticles embedded in 3D carbon matrix, and the Cu0 which
could act as a reduction promoter for electron transfer. The CO2
activation enhanced the accessibility of the aerogel’s pores, and the
secondary N2 activation enlarged the porosity and regenerated the
ultra-dispersed zerovalent iron (Fe0) with reductive carbon.
In a similar study, a FeeCu embedded CA (FeeCuC) was applied
for the selective degradation of various pollutants including
dimethyl phthalate (DMP), imidacloprid (IMI), bisphenol A (BPA)
and perfluorooctanoate (PFOA). Major studies were carried out
using DMP and was found that 93% of DMP degradation efficiency
was attained after 60 min at neutral pH. A comparative study
revealed that TOC removal of IMI, BPA, DMP, and PFOA was up to
88%, 97%, 99% and 100% in 240 min, respectively. The specific
24
Chemosphere 269 (2021) 129325
energy consumption (20-40 kW-h-(kgCOD)1) of the reaction was
minimum (Zhao et al., 2018a,b,c,d,e,f,g).
The efficiency of Fe-functionalized CA cathodes relies on the
solution pH. In an acidic pH, it is supposed to follow a Haber-Weiss
mechanism, in which the dissolved Fe ions and surface Fe (II) sites
promote the formation of COH. In basic pH range (~9), the for-
mation and deactivation of H2O2 complex at surface Fe(III) and
Fe(II) sites leads to the formation of superoxide anion and COH,
involving an in-situ recycling of iron oxide (Zhao et al., 2012). A new
bifunctional MOF(2Fe/Co)/CAs cathode was designed for the solar
PEF process for the degradation of AO7 (H. Zhao et al., 2017). The
ratio of Fe:Co on CA was fixed as 2:1, due to the interaction affinity
of FeOOH between MOF(2Fe/Co) and CAs. The enhanced ORR ac-
tivity was accredited to the availability of MOF active sites. MOF (Fe/
Co)/CAs cathode presented a high stability and degradation effi-
ciency in a wide pH window between 3 and 9.
In conclusion, effect of heteroatom doping on CAs are still left
unexplored. Fe-functionalized CAs have proved to be highly effi-
cient cathodes for both heterogeneous EF and photo-assisted het-
erogeneous EF reactions.
Apart from these carbon materials, other 3D carbonaceous
electrodes such as reticulated vitreous carbon (RVC) (Xie and Li
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 22. Schematic of the mechanism of a) ciprofloxacin degradation (Reprinted from ref(Divyapriya et al. 2018a).) b) carbamazepine degradation using Fc-ErGO in heterogeneous
EF system (Reprinted from ref. (Divyapriya et al. 2018b).
2006; Ramírez-Pereda et al., 2018; Jin et al., 2019), carbon sponge
€
(Ozcan et al., 2008; Trellu et al., 2016), graphite bead particles (C.-T.
Wang et al., 2008), etc. have also been utilised as cathode materials
for in-situ H2O2 production and pollutant degradation. Several
chemical modifications have been employed to modify the carbo-
naceous materials to shift the reduction potential of ORR towards
more positive values, enlarging the pH window, and increasing the
lifetime and stability of cathodes. Recently, a graphitized N-doped
single-walled carbon nano horns (CNHs) were synthesized via a
multistep procedure to produce H2O2 selectively in a wide pH range
(1e13) (Iglesias et al., 2018). The multi-step protocol included three
major steps:1) oxidation of CNHs to introduce COOH groups (ox-
CNHs), 2) combining ox-CNHs with dopamine hydrochloride that
polymerized on the CNHs surface (ox-CNHs@PDA) and 3) thermal
treatment at 700  C under Ar atmosphere. It was found that the
catalyst could reach 98% Faradaic efficiency (FE) in acidic pH (pH
1.0e7.4) outperforming most other carbon-based catalyst. This was
attributed to the highly N-doped graphitized carbon layer on the
graphitized single-wall carbon nano horns (g-N-CNHs). Very
recently, a new three layered self-supported CFP@PANI@Fe3O4 was
fabricated for the degradation of p-nitrophenol via EF process
(Dong et al., 2019). The results showed that CFP@PANI@Fe3O4
exhibited a 100% p-nitrophenol degradation efficiency after 60 min
of electrolysis. The improved performance was attributed to the
electrocatalytic ability of in-situ grown Fe3O4 particles on the
cathode surface.
6.5. Graphene
Although carbonaceous materials display the most excellent
performance in EF, another possible cathode material rely on sp2-
hybridized carbon atoms that are one-atom-thick with a honey
comb structure, and known as graphene (Mousset et al., 2016c;
Khataee and Hasanzadeh 2018). Graphene and its derivatives
25
Chemosphere 269 (2021) 129325
including GO, rGO, or few-layer GO, have unique morphological and
chemical characteristics(Divyapriya and Nidheesh 2020). From
various theoretical and experimental investigations, it is quite clear
that graphene and its derivatives display exceptional properties
such as high mechanical strength, surface area, thermal conduc-
tivity, etc. Graphene could be synthesized by chemical vapour
deposition (CVD), mechanical cleavage, electrochemical exfoliation,
etc. It has been successfully applied in the fields of photocatalysis
(Xiang et al., 2012; Li et al., 2016), electrochemical water treat-
ments(Hou et al., 2013; M. Li et al., 2017), energy storage (Hou et al.,
2011; Raccichini et al., 2015), electronics and sensors (Wei et al.,
2010; Lou et al., 2016), drug delivery(Sun et al., 2008; J. Liu et al.,
2013), DNA sequencing(Min et al., 2011; Heerema and Dekker
2016) and more.
The physical and chemical properties of graphene and its effect
on EF process was investigated for the degradation of phenol
(Mousset et al., 2016c). Three different forms of graphene such as,
graphene monolayer (Gmono), graphene multilayer (Gmulti) and
graphene foam (Gfoam) were used as cathodes. The results
revealed that Gfoam displayed the highest rate of H2O2 generation
yield, degradation and mineralization efficiency as compared to
Gmono and Gmulti. Electrochemical impedance spectroscopy (EIS)
results revealed that the charge transfer resistance (Rct) was in the
order of Gfoam < Gmulti < Gmono, which was responsible for the
remarkable increase in electrode conductivity and phenol degra-
dation rate. Gfoam cathode displayed an improved performance
compared to CF and it also showed an excellent stability even after
10 EF runs. In another study, an electrochemically exfoliated
graphene-ink was coated on carbon cloth with Nafion as binder and
dispersant for the degradation of phenol by EF process(Mousset
et al., 2016b). The graphene coated carbon cloth improved the
electrochemical surface area by 11.5-fold and reduced the charge
transfer resistance by 97% when compared to bare carbon cloth.
Very recently, a GDE using a graphene ink coated carbon cloth
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Fig. 23. (a) SEM image, b) TEM image of pomelo peel showing the hierarchical structure. Reprinted from ref (Y. Yang et al. 2017). c) Illustration of RFMTENG fabrication process d)
Electricity generation cycle demonstrating the working principle of RFMTENG. e) COMSOL simulation and the distribution of electric potential with the change in angles. Reprinted
from ref.(Chen et al. 2017).

treated with polytetrafluoroethylene (PTFE-CC-GDE) was devel-
oped for the degradation of industrial electronic wastewater (with
high loads of metals such as Cd, Ni, Pb, etc., inorganic ions, and
certain organic components such as acetone, isopropanol)(Garcia-
Rodriguez et al., 2018). The hydrophilicity of the cathode was
increased with the addition of graphene-ink, suggesting a higher
wettability and an improved O2 diffusion and rate of ORR. The GDE
showed a TOC removal rate of 90% and 60% for low (53.46 mg L1)
and high (299.33 mg L1) concentrations of electronic wastewater,
respectively.
Modification of carbon-based materials using graphene and its
oxides have improved the pollutant degradation and mineraliza-
tion efficiencies. Electrodeposited rGO (ErGO) on CF was evaluated
for the degradation of acid orange 7 (AO7) (Le et al., 2015). Different
methods including electrochemical, chemical, and thermal, were
employed for the reduction of GO. The results concluded that the
electrochemical reduction of GO without addition of any binder or
reductant improved the electrocatalytic behaviour by enhancing
the conductivity and lowering the charge-transfer resistance. EF
efficiency of ErGO was 2-fold higher than that of CF and reached
94.3% TOC removal after 8 h of treatment.
GCE was modified using thermally reduced GO to study the

26
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 24. a) Circuit diagram of the FM-TENG-driven EF reaction, b) CV curves of the cathode in N2 and O2 saturated 50 mmolL1 Na2SO4 solution, c) H2O2 production at the cathode, d)
EIS spectra of the cathode (inset showing the equivalent circuit model), e) UVevis spectra during the degradation of DAB, f) GC-MS spectra of the intermediates of DAB degradation,
and g) Schematic of FM-TENG assisted EF reaction using carbon materials derived from long beans as cathode. Reprinted from ref. (Gao et al., 2018).
impact of annealing temperature (250  C and 1000  C) on the H2O2
electro generation rate and the degradation of MB (C.-Y. Chen et al.,
2016).The results indicated that the degradation rate of rGO @
250  C (G250) showed the highest selectivity towards 2ee ORR
when compared to rGO@1000  C (G1000) and unannealed rGO
(G0). This could be attributed to the presence of oxygen function-
alities and preservation of the s bond in G250. In a similar study, a
GDE with graphene@graphite (G-GDE) was designed for the
degradation of RheB(Z. Zhang et al., 2018). SEM images showed a
loose framework and porous microstructure, which was ascribed to
the adhesive effect of PTFE forming graphite micro-groups during
the preparation of G-GDE (Fig. 21 d). The PTFE improved the
dispersion of graphite and formed abundant apertures for ORR.
Fig. 21 (c) indicates the improved rate of H2O2 generation at G-GDE.
The system exhibited 98% RheB removal under a current density of
20 mAcm2. Fig. 21 (b) reveals that the pore size distribution of G-
GDE and GDE respectively. COH radical formation was improved
due to the presence of micropores. Further, a graphene modified EF
catalytic membrane (EFCM) was engineered to investigate the rate
of H2O2 production and the mineralization of florfenicol (W.-L.
Jiang et al., 2018). The synergistic effect of EF and membrane-
filtration led to 60% of florfenicol mineralization. The improved
efficiency could be attributed to the faster mass transfer and higher
concentration of organics on the membrane surface.
Various graphene-based cathode materials such as hetero atom
doped graphene, Fe/other TMs (Co, Cu, Mn, etc.) doped graphene
materials, etc. have also been used in heterogenous/metal free EF
systems (Su et al., 2019) (Y. Li et al., 2017a). A nitrogen-doped
graphene (N-graphene) and N-graphene-GF were used as a metal
free electrocatalyst and cathode for the selective two electron ORR
(Li and Zhang 2019). Although graphene-GF and N-graphene-GF
exhibited similar H2O2 yield, the N-graphene-GF was proved to be
more efficient in activating H2O2 to COH.
Although the Fe/iron-oxide materials showed improvements at
a wide pH range, the activity of iron oxides is influenced by poor
27
Chemosphere 269 (2021) 129325
electrical conductivity and increased charge transfer resistance. To
address this a ferrocene functionalized electrochemically reduced
GO (Fc-ErGO) was designed for the degradation of ciprofloxacin
(Divyapriya et al., 2018a). Ferrocene being an organometallic
compound, is highly stable, and has a good reversible redox prop-
erty due to its donor acceptor conjugated structure. Fc-ErGO
exhibited ~3 times higher removal rate as compared to ErGO and
~9 times as compared to GF electrodes. The efficiency of Fc-ErGO
was also investigated using a RDE for the degradation of cipro-
floxacin and carbamazepine (Divyapriya et al., 2018b). The system
exhibited 99.96% and 99.8% removal efficiency at neutral pH for
ciprofloxacin and carbamazepine, respectively. The degradation
efficiency was found to increase significantly with an increase in
rotational speed of the disc electrode. This was ascribed to the
improved mass transfer activity, contact area between oxygen and
electrode and oxygen diffusion on the liquid film at the electrode
surface. Moreover, the oxygen functionalities, like quinone acts as
an active site for oxygen adsorption and enhanced H2O2 produc-
tion. Ferrocene could act as a Fenton catalyst by receiving electrons
via graphene network. The mechanism proposed for the degrada-
tion of ciprofloxacin and carbamazepine using Fc-ErGO RDE is
shown in Fig. 22.
In conclusion, modifying graphene materials with heteroatoms
and oxygen functionalities has significantly enhanced the rate of
H2O2 formation. Synergistic effects of favourable electronic struc-
ture, enhanced pore size, distribution of N-atoms, etc. have resulted
in an improved EF degradation. Incorporating Fe/TM modified
graphene has helps in increasing the working pH range, hence
reducing the harmful environmental impacts.
6.6. Biochar derived carbon
The sustainable transformation of biomass into carbon materials
has recently gained increasing attention. Heteroatom-doped car-
bon materials from bio-mass such as honey suckles (Gao et al.,
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 25. a) The postulated mechanism of pore-formation through KHCO3eMgO dual-porogen strategy b) The relation between amount of pyrrolic N content and degradation
efficiency. Reprinted from ref (Tian et al., 2019).
2015c), ginkgo leaves (Gao et al., 2015d), amaranth (Gao et al.,
2015a), sweet potato vines (Gao et al., 2015b), Malachium aqua-
ticum (Huang et al., 2016) and catkins (Gao et al., 2017), were suc-
cessfully applied in ORR. However, the promising potentials of the
biochar derived carbon materials in EF process has long been
overlooked.
Nano-porous N/C electrocatalyst was designed from the N-rich
pomelo peel precursor (carbon source, self-template, and hetero-
atom) by one step pyrolysis to enhance the H2O2 production (Y.
Yang et al., 2017). SEM and TEM (Fig. 23 (a) and (b)) images revealed
the typical hierarchical morphology and 3D network at the nano-
metre scale, indicating the electrocatalyst to promote mass diffu-
sion in ORR. CHN analysis showed the existence of 1.1 wt% of N,
suggesting a N-doped carbon catalyst precursor. The incorporation
of Fe3þ ions was favourable to promote ORR, alter the carbonization
process and reduce the carbonaceous defects. N/C pyrolyzed at
900  C was shown to produce 22.0g/(g[cata].h.L) H2O2 over 90 min,
which was economically highly efficient compared to other mate-
rials used till date.
A self-powered EF system with a triboelectric nanogenerator
(TENG) was developed for the degradation of basic orange 2 (BO2)
Fig. 26. Schematic of a) hard template and b) soft template-based OMC synthesis. Reprinted from ref(Eftekhari and Fan 2017).
28
Chemosphere 269 (2021) 129325
(Chen et al., 2017). The carbon material obtained from magnolia
flowers was used as the cathode for ORR. The derived carbon
possessed a large surface area of 1226 m2 g-1., which could improve
the O2 mass transfer and ORR, hence stimulating the self-powered
degradation of BO2. The working principle of RFM-TENG is sche-
matically presented in Fig. 23 (c)e(e). The electrogeneration of
H2O2 was enhanced (80 mg L1 in 2 h with 98% of BO2 decolor-
ization in 70 min) by the presence of oxygen and nitrogen group
and 3D network with abundant mesopores in the cathode material.
In a similar study, carbon materials derived from long bean were
applied as cathode material for the EF degradation of 4-
dimethylaminoazobenzene (DAB) (Gao et al., 2018). The EF sys-
tem was self-driven by a flexible multi-layered TENG (FM-TENG).
The obtained carbon showed 99% colour removal efficiency in the
decolorization of DAB. This could be attributed to the presence of
abundant number of macro-/meso-pores, improved surface area
(2270 m2 g1), excessive nitrogen content and superhydrophilicity
(contact angle of 3.8⁰), that could facilitate the dissolved O2 mass
transfer and promote the rate of ORR. The schematics of FM-TENG
assisted EF process, circuit diagram, CV curves, H2O2 production
rate and the DAB degradation rate are displayed in Fig. 24 (a)e(f).
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 27. a) EIS spectra showing for the cathode samples with different amount of GO, b) Rate of DMP and DEP removal for the different cathode materials, c) Recycle tests for EF
degradation of DMP using S30 cathode. Reprinted from ref(W. Ren et al., 2016). and HRTEM images of e) ACF, f) ACF@OMC and g) ACF@DMC. Reprinted from ref. (Hu et al., 2013).
The Nyquist plot (Fig. 19 (d)) shows that the Rct and Warburg
impedance were 105.9 U and 0.0037 U, respectively.
The cathode materials derived from the biochar has been proved
to be superior in the degradation process compared to classic
Fenton reagents. Very recently, Tian et al. tuned the pyrrolic ni-
trogen content in the nitrogen doped porous carbon derived from
sophora flowers through KHCO3eMgO dual-porogen strategy (Tian
et al., 2019). Fig. 25 (a) shows the postulated pore forming mech-
anism through dual porogen strategy. It can be concluded that the
degradation efficiency had a direct correlation with the pyrrolic
nitrogen content (Fig. 25 (b)). The cathode exhibited a high surface
area - with large mesopores, high defect degree and good hydro-
philicity. Inspired from the above works, Liang et al. synthesized a
novel nitrogen-doped carbon cathode from water hyacinth. The
cathode showed a high performance in EF reaction with a BET
surface area of 829 m2 g1, an improved H2O2 yield of 1.7 mmol L1,
and a large kinetic constant of 0.318 min1 in the degradation of
DMP, which was 4 times higher than bare graphite powder
(0.076 min1) (Liang et al., 2018).
However, most of these investigations involved multiple steps of
fabrication and various post-treatments. The search for a one step
pyrolysis ended up in a recoverable waste-wood derived carbon
cathode along with pyrophosphate (PP) as electrolyte that was used
in EF at pH 8 for sulfathiazole (STZ) degradation (Deng et al.,
2019a).The electrolyte was acquired to form an Fe2þ-PP complex
which allowed the performance of EF at near neutral pH of 8. Till
now, the studies of biochar derived materials for EF reaction have
been very limited. Most of the studies demonstrated the 4ee
reduction pathways of ORR in fuel cells and super capacitors
(Huggins et al., 2014; Gupta et al., 2015; W. Sun et al., 2016).
Nevertheless, the biochar derived carbon materials are very
economical, readily available, and highly porous for use in a wide
scale.
29
Chemosphere 269 (2021) 129325
6.7. Ordered mesoporous carbon materials
Ordered mesoporous carbon (OMC) materials with a pore size
distribution of 2e50 nm offers promising benefits in electro-
chemistry owing to its high specific surface area, broad pore size
distribution, good electrical conductivity, and a high stabili-
ty(Eftekhari and Fan 2017). OMCs were first developed by Ryoo
et al. in 1999, using sucrose (as a carbon source), cubic meso-
porous silica molecular sieves, and MCM-48 (as the template)(Ryoo
et al., 1999). The samples could be synthesized by either hard
template (from inorganic templates, such as metal-organic frame-
works (MOFs), zeolites, silicas, MgO, etc.) or soft template (phenolic
resin, some block copolymers and surfactants) techniques (Lu and
Schüth 2006; Khataee and Hasanzadeh 2018) (Fig. 26).
Lately, OMC cathode materials have gained much attention in EF
reaction by facilitating the transformation and mass diffusion of O2
at the electrode surface, hence enhancing the yield of H2O2. An
activated carbon fibre cathode grafted onto OMC (ACF@OMC) was
designed by developing a lay of OMC on the walls of ACF (Hu et al.,
2013). The cathode was used for the degradation of an anionic dye
X3B. TEM images of ACF@OMC showed many distinct stripes on the
walls, revealing the good regularity of the material (Fig. 27 (e)-(g)).
The EF activity of ACF@OMC was higher compared to ACF and ACF
with disordered mesoporous carbon (ACF@DMC). The effect of pore
size on the efficiency of ACF@OMC was also investigated for the
degradation of Orange II and RheB dyes (Ren et al., 2015). Two
ACF@OMC samples with pores size 3.7 and 5.4 and ACF@DMC with
pore size 2.6 were compared. ACF@OMC-5.4 exhibited an enhanced
performance when compared to the other two samples. The
diffusion and ORR were enhanced by large and uniform mesopores.
The cathode material showed superior stability even after 10
consecutive cycles giving promising applications in real wastewater
treatment. In another study, a GDE with OMC from “CMK-3” and
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Fig. 28. a) Schematic of NOMC synthesis. The potential configurations of N-atoms in NOMC include: pyridinic N (N1), graphitic N (N2eN3), pyrrolic N (N4) and oxidised pyridinic N
(N5) b) kinetic current density and the number of exchanged electrons at the selected potentials. Reprinted from ref(Sheng et al., 2015).

SBA-15 template was developed for the degradation of DMP (Yi
Wang et al., 2013a,b,c). The OMC displayed a BET surface area of
992 m2 g-1, and a pore size of 4.2 nm, which were very higher when
compared to carbon paper and graphite. This could minimize the
HER rate and improve the H2O2 generation for the degradation of
DMP. In another study, a composite of ACF@rGO@OMC was syn-
thesized to increase the electroactive surface area of the cathode
material for the degradation of Phthalic acid esters (PEAs),
predominantly DMP and diethyl phthalate (DEP) (W. Ren et al.,
2016). Five samples with different additive masses of GO were
developed and was denoted as S0, S15, S30, S60 and S90. S30
exhibited a highest degradation rate of DMP at a rate constant of
0.049 min1, which was 1.5 times more compared to ACF@OMC.
This could be concluded from the EIS spectra that shows the
reduced charge-transfer resistance of S30 when compared to rest of
the samples (Fig. 27 (a)). Both DMP and DEP was almost completely

Fig. 29. a) Cyclic voltammetry of all the NMCs in 0.5 M H2SO4, b) cyclic voltammetry of NMCs in O2 saturated environment, c) rotating disc electrode LSV in O2 saturated envi-
ronment g) Modelling of the functional groups present on catalytic surface. Reprinted from ref(Perazzolo et al., 2015).

30
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 30. Possible mechanism for dye degradation using Fe0eFe2O3/OMC in the heterogeneous EF catalytic system. Reprinted from ref.(Wang et al., 2018).
degraded after 45 and 60 min of treatment. Fig. 27 (b) shows the
degradation efficiency of all five cathode materials. It was
concluded that higher concentration of GO created unwanted ag-
gregation that hindered diffusion and increase the electron transfer
resistance. The cathode showed a high stability for more than 10
cycles and an increased reduction of oxygen to H2O2 (Fig. 27 (c)).
Later in 2018, an air diffusion MC electrode was designed using
resorcinol-formaldehyde (ReF) polymer as the soft template and
F127 as the structure directing agent (Garza-Campos et al., 2018).
The MC showed a diameter range of 3.6e4.6 nm and produced
10.85 mmolL1 of H2O2 at a current density of 150 mA cm2. The
electrode displayed a mineralization of 55% and 85% for amoxicillin
degradation by EF and solar-PEF (SPEF) reactions, respectively.
Since hetero atom doping enhances the catalytic activity of
cathode materials, N doped OMCs (NOMC) were prepared to study
the selective reduction of O2 to H2O2 (Sheng et al., 2015). NOMC was
prepared through a nano casting method by the pyrolysis of aniline
and dihydroxy naphthalene (DHN) inside SBA-15 (Fig. 28 (a)). Two
samples with different amounts of DHN, NOMC-L (0.36g) and N-
OMC-H (0.46g) were synthesized. Fig. 28 (b) shows that NOMC-L
consistently showed better performance compared to NOMC-H.
This could be correlated to the lower micropore volume, higher
N-content, and degree of graphitization of NOMC-L. The NOMC
proved to have higher kinetic current density when compared to
previously reported carbon materials doped with nitrogen and thus
posse a high selectivity towards H2O2 production. Further, an N-
doped mesoporous carbon derived from N-butyl-3-
methylpyridinium was designed to promote 2ee ORR and H2O2
production (Fellinger et al., 2012). The increased efficiency of the
cathode material was attributed to the high nitrogen content, the
radical nature of nitrogen-bound carbon and the sufficient amount
of pyrrolic nitrogen sites within the carbon materials.
A range of nitrogen and sulphur co-doped mesoporous carbon
(N,S-MC) was fabricated through hard template approach for the
in-situ H2O2 production and degradation of MO (Perazzolo et al.
2015, 2016,bib_Perazzolo_et_al_2015,bib_Perazzolo_et_al_2016).
The electrochemical performance of N-MC was higher as compared
SMC and N, S-MC. The effect of temperature on the electrochemical
performance of N-MC was studied in the range of 750  C to 1050  C.
31
Chemosphere 269 (2021) 129325
Several different organic precursors have been employed in the
production of N-MC, S-MC and N, S-MC. 1,10 phenanthroline (N-
MC-1) and carbazole (N-MC-2) were used for synthesizing N-MCs.
The electrochemical performance of the samples N-MC-1 @750, N-
MC-1@850, N-MC-1@950 and N-MC-1@1050 is displayed in Fig. 29.
It could be interpreted from the Fig. 29 (a), N-MC-1@750 showed
the increased capacitance out of the four N-MC-1s used. This could
be attributed to the presence of nitrogen groups which could
induce a pseudocapacitive effect due to the increased amount of
intrinsic charges and adsorption of electrolyte ions and protons in
the electrical double layer. It can be clearly seen that with the in-
crease in the treated temperatures, the redox peaks get insignifi-
cant which is due to the partial loss of hydroquinone/quinone
couple (CeOH, C]O) on the catalytic surface.
Also, the increase in temperature resulted a reduction in pore
volume and diameter and there are only micropores present in N-
MC-1 @ 1050, which could further reduce the ORR activity. Fig. 29
(c) represents the RDE potentials at a scan rate of 10 mVs1 and it
was observed that N-MC-1@1050 showed the slow electron
transfer as equivalent to commercially available MC (C-MC). The
catalytic properties were investigated in both acidic and alkaline
medium. It was found that at high pH the electronic effect of pyr-
idinic groups were deactivated reducing the impact of nitrogen
doping.
The catalytic activity and selectivity of 2ee ORR pathway solely
relied on the number of N-atoms present in the N, S-MC. This was
assumed to be due to the similar electronegativity of sulphur to
carbon and large atomic radius, unlike nitrogen with similar atomic
radius and high electronegativity, which could increase the surface
hydrophobicity. Consequently, the proton transfer rate was
decreased with respect to the S content.
Fe0eFe2O3 composite nanoparticles embedded OMC hybrid
material (Fe0eFe2O3/OMC) was designed for the degradation of
acid orange II (AOII) dye via heterogeneous EF(Wang et al., 2018).
The removal efficiency was found to be in the order Fe0eFe2O3/
OMC > Fe0/OMC > Fe2O3/OMC. The enhanced activity of the com-
posite was attributed to the accelerated Fe3þ/Fe2þ cycle, surface
area, and highly dispersive active sites. Moreover, the synergistic
effect of OMC and Fe catalytic species could increase the activity of
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Fig. 31. Schematic of EF reaction setup using ACF-HPC cathode A)H2O2 generation rate with different ratios of HPC B) H2O2 generation rate with different proportion of HPC to
carbon black C) phenol degrdation on ACF and ACF-HPC-40 D) TOC removal rate on ACF and ACF-HPC-40. Reprinted from ref (Yu et al. 2019).

Fig. 32. a) Amount of H2O2 and b) current efficiency of NPC-1000 at pH 1 and different potentials, c) Amount of H2O2 produced and d) Current efficiency of NPC-1000 at a different
starting pH, and e) Schematics of H2O2 production and mineralization of antibiotics using NPC. Reprinted from ref(D. Zhang et al., 2019).

32
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

the composite. The plausible mechanism for the degradation of carried out at different temperatures 900  C (NPC-900), 1000  C
AOII is shown in Fig. 30. (NPC-1000) and 1100  C (NPC-1100). NPC-1000 displayed a selec-
tivity of 96.4% towards H2O2 production, which is much higher than
NPC-900 and NPC-1100. NPC-1000 showed 87.7% current efficiency
6.7.1. Hierarchically porous carbon
at 0.5V vs SCE in the production of H2O2. Fig. 32 (a) shows a H2O2
HPC could also be obtained through soft and hard templating
production rate of 52.3 mmol L1 h1 at 0.6 V with a current ef-
method. HPC possess multiple levels of pore size distribution such
ficiency of 81.9%. However, the highest current efficiency is
as micro (0.2 nm), meso (2e50 nm) and macro (450 nm) (Y. Liu
observed at 0.5 V as shown in Fig. 32 (b). The influence of pH on
et al., 2015b, c; M.-H. Sun et al., 2016). Thus, they exhibit a hierar-
H2O2 production was also studied at various pH range of 1, 3, 5 and
chy in porosity and structure and display high performances in EF.
7 (Fig. 32 (c)). Fig. 32 (d) shows the maximum current efficiency of
There are only few reports on the application of HPC composites
87.8 for pH 1, demonstrating that the proton-coupled electron
in EF reactions. In 2016, HPC generated from the carbonization of
transfer could be promoted by Hþ ions during H2O2 production.
MOF-5 was employed for the efficient mineralization of per-
Moreover, the catalyst exhibited 100% efficiency in 10 min for the
fluorooctanoate (PFOA) (Y. Liu et al., 2015b,c). The improved per-
degradation of oxcarbazepine. The exceptional H2O2 production
formance of HPC towards H2O2 generation was attributed to the
rate was accredited to the large BET surface area, highly porous
high proportions of defect, sp3 C content and large surface area.
structure, significant N content and reasonable proportion of sp3 C.
PFOA degradation was 94.3% in 3 h with a TOC removal efficiency of
Similarly, a hierarchically porous F doped carbon was synthe-
90.7%, 79.5% and 70.4% at pH 2, pH 4 and pH 6, respectively. Very
sized using an aluminium based MOF (MIL-53(Al)). The carbon-
recently, HPC from MOF 5 was utilised to modify ACF for the EF
ization was conducted at 4 different temperatures ranging from
degradation of phenol (Yu et al., 2019). The samples were synthe-
700  C to 1000  C and the samples were denoted as FPC-x, where x
sized with different loading amounts of HPC including 0, 0.03, 0.05,
is the respective carbonization temperature(K. Zhao et al., 2018b).
0.09 and 0.12 g on ACF. ACF-HPC cathode with 0.09 g of HPC loading
FPC-800 showed the highest H2O2 generation rate and was attrib-
showed the highest H2O2 accumulation and a degradation effi-
uted to the lower mass transfer resistance and improved surface
ciency of 99% in 35 min for phenol degradation, which was almost 5
area. Fig. 33 (b) shows the EIS data, which clearly indicates that
folds higher as compared to ACF (Fig. 31 (a)). Also, different mass
FPC-800 showed a lower charge-transfer resistance, which further
ratios of HPC and carbon black were synthesized and was found
improved the electron transfer and diffusion rate for ORR. The
that 2:3 ratio of HPC:ACF (ACF-HPC-40) showed the highest accu-
material displayed a high selectivity of 97.5e83% towards H2O2
mulation of H2O2 (Fig. 31 (b)). The enhanced performance can be
production and a current efficiency as high as 93.6e81.6%. FPC-800
attributed to the increased oxygen solubility due to the dynamic
showed an enhancement in H2O2 generation with the shift in pH
equilibrium of oxygen on gas, solid and solution surface. As a result,
towards more negative potentials. The highest rate of H2O2 pro-
the ACF-HPC-40 showed the highest degradation efficiency with a
duction was reported as 714.1 mmol h1 g1 with the current ef-
TOC removal rate of 85.51% in 180 min (Fig. 31 (c)).
ficiency of 82.1% at 0.2 V for FPC-800. Density functional theory
Recently, a highly selective nitrogen doped porous carbon (NPC)
(DFT) calculations revealed that the high selectivity was ascribed to
was prepared through the direct calcination of the nitrogen con-
the optimum F-doping level and the suitable quantity of CF2, CF3
taining MOF-ZnPDA (D. Zhang et al., 2019). Calcinations were

Fig. 33. a) CV measurements for all FPCs and hollow porous carbon (HPC)-800, b) EIS spectra of FPCs and HPC, and c) schematics for the enhancement in electrochemical production
rate of H2O2 by FPC-800. Reprinted from ref(K. Zhao et al., 2018b).

33
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 34. EEGr-GF and N-EEGr-GF: a) Phenol degradation efficiency, b) concentration of H2O2 generation, c) ESR spectra, and d) concentration of
ref.(W. Yang et al., 2018).
species in FPC-800. The adsorption energy of OOH is the lowest for
CF2 and CF3 resulting in further protonation of OOH to H2O2.
In a similar study, F doped porous carbon (FPC) was proposed to
tune the electron transfer properties by inducing charge polariza-
tion and changes in Fermi levels (K. Zhao et al., 2018a; Zhao et al.,
2019a,b,c). This could be highly beneficial for recycling Fe2þ ions
during the EF process by tuning the electron transfer properties.
The increased electron transfer rate could accelerate the reduction
of Fe3þ ions on FPC cathodes. FPC was used to degrade various
wastewater pollutants such as refinery oil waste waters which
contained atrazine, triethylamine, dibutyl phthalate, 2,6-di-tert-
butyl-4-methylphenol and n-hexadecane as the main kinds of
pollutants. The kinetic constant for atrazine degradation and Fe2þ
equilibrium concentration of FPC were 3.6 and 1.2 folds higher than
hierarchically porous carbon (HPC). The specific energy consump-
tion for the treatment of secondary effluents was very low and the
COD was below 50 mg L1 during the discharge, which was below
China’s discharge standards.
In a recent study, Mn/Fe@porous carbon (PC) was fabricated via
the carbonization of Mn-doped MIL-53(Fe) and was used as the
cathode in heterogeneous-EF reaction for triclosan (TCS) degrada-
tion (Zhou et al., 2019a,b,c,d,e,f). Mn/Fe@PC showed a high stability
and above 99% TCS removal efficiency in 120 min for 6 cycles. The
cathode consumed a minimum energy for the degradation of TC
over a wide working pH window. The effective regeneration of the
catalyst FeII/MnII/III and direct reduction on the surface of the
34
Chemosphere 269 (2021) 129325
C
OH generation. Reprinted from
cathode promoted the utilization of H2O2 and improved the
degradation efficiency.
When compared to other carbonaceous materials, OMCs and
HPCs, exhibited an increased rate of H2O2 production as well as
pollutant degradation. However, more studies of Fe based MOFs
and other porous structures to be employed as cathode materials
would benefit heterogenous EF reactions.
It has been evident that extensive studies were carried out to
design numerous carbonaceous materials for EF reactions to
maximize the cathode performance. To our delight, tremendous
progress in both cathode fabrication and mechanism exploration
have pushed the boundary of the field to a high level. Table 3 lists
the key findings (type of material, synthesis method, efficiency, etc.)
of various cathode materials for homogeneous EF that were dis-
cussed in this review. It can be concluded from the results that OMC
and biochar derived carbon materials offer a maximum H2O2 pro-
duction rate as well as pollutant degradation owing to their large
surface area and the presence of more active sites. The biomass
derived carbon materials are characterized by the presence of
hetero atoms which add to its efficiency and reduce the further cost
of external doping. However, the synthesis techniques for these
require high temperature and controlled conditions. The hetero-
atom doped carbon materials offer a higher H2O2 production rate
and a great potential to act as metal-free catalysts for EF reactions.
Hence, detailed studies on metal-free EF catalysts and biomass
derived cathodes must be performed, which would pave a path
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

Fig. 35. Schematic of binder-free in-situ fabrication of PANI derived carbon nanofibers modified electrode. Reprinted from ref (Haider et al., 2019).

towards more environmental benign and cost-effective opportu- 6.8. Metal free electro Fenton cathode modifications
nity for real wastewater treatment.
The activation of H2O2 to COH is the most crucial step in an EF
reaction, which is achieved using iron as catalyst, leads to the

Fig. 36. a) Degradation of phenol using various catalysts, b) ESR spectrum of COH using DMPO trapping agent, and c) possible mechanism of cPANI/GF2 catalysis in a metal-free EF
system. Reaction conditions: Volume 100 mL, methanol 20 mL, 0.05 M Na2SO4 at pH 3, C0 50 mg/L, potential -0.6 V vs Ag/AgCl, Feþ2 0.2 mM. Reprinted from ref (Haider et al.,
2019).

35
K.M. Nair, V. Kumaravel and S.C. Pillai Chemosphere 269 (2021) 129325

formation of iron sludge as a secondary pollutant which causes cathode from the electrodeposition of N-doped carbon nanofibers
high environmental challenges. Although, as mentioned in the derived from polyaniline (PANI) carbonization onto GF (Haider
section above, efforts have been made to reduce the metal sludge et al., 2019). Potassium hydroxide (KOH) was used to tailor the
formation via employing heterogeneous EF catalysts (Expo
sito surface functional group of the electrodes (Fig. 35). The optimised
et al., 2007),(Ai et al., 2007), it is considered difficult to cathode cPANI/GF2 (KOH to cPANI ratio of 2) showed remarkable
completely overcome the metal wastes (Hartmann et al., 2010). As a degradation rates namely 85% for phenol, 99% for florfenicol and
result, it is important to introduce metal-free catalysts that would 100% for MO dye (Fig. 36 (a)). Fig. 36(b) shows the ESR spectra of
C
prove to be an interesting alternative towards formation of COH, OH formation. N-doped graphite cathode could act as an efficient
reduce the risk of secondary pollution and hence reducing the cost catalyst for H2O2 generation as well as COH, with no externally
of treatment. Various reports have already been available on the added chemicals, and thus a very eco-friendly mode of wastewater
efficiency of carbonaceous materials for in-situ COH formation treatment.
without any metal catalysts (Saputra et al., 2013; Dong et al., 2016).
A GF cathode was modified with nitrogen and electrochemically
6.9. Possible Mechanism of Metal-Free Electro Fenton using N-
exfoliated graphite foil (N-EEGr) for in-situ metal-free EF reaction
doped graphene
(W. Yang et al., 2018). N-EEGr-GF cathode exhibited a wide pH
range, and an improved efficiency with no iron sludge formation,
Nitrogen atoms being highly electronegative (3.04) when
suggesting a promising cathode material for metal-free EF. The
compared to carbon atoms (2.55), disrupts the sp2 configuration of
degradation efficiency of N-EEGr-GF at different experimental
graphene and produce positive charge sites for oxygen adsorption
conditions is given in Fig. 34 (a). N-EEGr-GF showed a stable phenol
and catalysis reaction. Most of the adsorbed O2 experienced 2ee
degradation efficiency of 97% and 92% in 50 min at pH 3 and 7
ORR to generate H2O2 at the cathode surface which is catalysed by
which was dramatically reduced from 99% to 42% as the pH was
the active sites, mainly the graphitic N(J. Liu et al., 2016; Su et al.,
increased from 3 to 7 in traditional EF reaction. Fig. 34 (b) indicates
2019). In-situ COH production was assisted by the pyridinic nitro-
that N-EEGr-GF showed a slightly less rate of H2O2 production,
gen that serves as active sites for the electron transfer. The zigzag
which was ascribed to the reduced electron transfer rate and sur-
edges and defects in the graphene generated during the synthesis
face area. However, DMPO spin-trapped ESR spectroscopy (Fig. 34
also function as active sites in the catalysis process (Duan et al.,
(c)) studies concluded that COH was the active species for EEGr-
2016; W. Yang et al., 2018). A small part of adsorbed O2 reacts
GF and N-EEGr-GF cathodes. Also, Fig. 34 (d) shows that the con-
with an electron to form OCe2 , but the active sites for this reaction is
centration of COH generated on N-EEGr-GF was almost 2 times
still not clear. The possible mechanism for the degradation of
higher than that of EEGr-GF. Hence, the activation of H2O2 on N-
organic contaminants by COH is shown in Fig. 36 (c) and (d).
EEGr-GF was superior, which was ascribed to the disruption of sp2
Apart from N-doped graphene, a low-cost activated carbon/
C, making it an active metal-free catalyst.
stainless steel mesh (ACSS) composite cathode was developed for
The in-situ COH generation was also examined with various
the degradation of organic pollutants (Zhou et al., 2019a,b,c,d,e,f).
ratio of EEGr/N (1:0, 1:1, 1:3, 1:7) and the cathode materials were
XPS spectra (Fig. 37 (b)) revealed the presence of C1s containing
tested for the mineralization of 2,4-dichlorophenoxiacetic acid
four component peaks which corresponds to sp2 C]C
(2,4-D) (Yang et al., 2019b). It was observed that the cathode with
(284.6e284.7 eV), sp3 CeC (285.1 eV), CeOH(286.0e286.3 eV), and
1:1 ratio of EEGr/N displayed an exceptional catalytic activity for
C]O (286.8e287.0 eV) and the oxygen containing functional
the activation of COH. At pH 7, the N1-EEGr-GF showed a total
groups (COOH and etheric) were considered as active sites for 2ee
degradation of 20 mg L1 2,4-D in 60 min and a TOC removal of 45%
ORR while the porous configuration could provide sufficient cata-
in 120 min. In a similar study, N-doped graphene was synthesized
lytic surface area. A part of H2O2 generated in the pores was acti-
via annealing melamine and graphene (Nx-GE, x ¼ the mass ratio of
vated into COH, while the remaining H2O2 was released into the
melamine to graphene), and it was used to modify GF (Nx-GE-
electrolyte. COH was also generated from the contact between the
GF)(Su et al., 2019). N3-GE showed the highest activity, with a H2O2
bulk H2O2 and AC surface, and COH formed from both sources were
generation rate of 8.6 mg h1 cm2, and selectivity of 78.02% to-
considered responsible for pollutant degradation. The ACSS cath-
wards phenol degradation in a neutral pH solution. Very recently, a
ode exhibited a long-term stability over 10 consecutive cycles of
binder free approach was developed towards the fabrication of a
reactive blue (RB19) degradation with 61.5% in 90 min and the cell

Fig. 37. a) Schematic of EF reaction occurring at the ACSS b) XPS spectra of ACSS. Reprinted from ref(Zhou et al., 2019a,b,c,d,e,f).

36
K.M. Nair, V. Kumaravel and S.C. Pillai
Fig. 38. Schematic of a) pilot EF, b) electrode stacks, and Photographs of c) pilot EF, d) electrode stacks treating 40 m3 per day of wastewater rich in organics located at the T-
wastewater treatment, in Gyeonggi-do, Republic of Korea. Reprinted from ref.(Lee et al., 2020).
voltage was continuously decreased within 90 min, indicating an
increase in the conductivity of electrolyte.
A boron-doped graphene aerogel (BGA) was synthesized to
modify GDEs, and it was employed for bisphenol A (BPA) degra-
dation (Wu et al., 2019). A complete degradation of BPA was ob-
tained for the 2.4% of doped boron. The catalyst also showed a BPA
removal rate of 89.65% and TOC elimination of 89.58% even after
five consecutive cycles. The above results indicate that the metal-
free carbonaceous cathode materials exhibit excellent stability
over wide pH range and zero metal sludge formation in comparison
to the traditional EF catalysts.
Recently, cathodes other than carbonaceous materials are also
under development. A nickel-foam (NieF) was modified with
nitrogen-doped carbon (CN/NieF) cathode material was applied for
the degradation of sulfathiazole (STZ)(Deng et al., 2019b). The
electroactive surface area of NieF was improved, and the charge
transfer resistance was reduced after modification with C and N,
thus increasing the H2O2 accumulation and STZ degradation rate as
compared to bare NieF. A 3D FeeCu/kaolin electrode was fabri-
cated for the degradation of RheB in EF system (B. Zhang et al.,
2019). Fe and Cu dopants were observed in the form of a-Fe2O3
and CuO on kaolin surface and the activity of FeeCu/kaolin (kinetic
constant of 0.0503 min1 for the degradation of RheB)
37
Chemosphere 269 (2021) 129325
outperformed both activated carbon and pure kaolin.
A metal oxide, bismuth molybdate (Bi2Mo3O12), with oxygen
vacancies modified Ti cathode was utilised to catalyse the H2O2
production and AOII degradation(He et al., 2019). The cathode
functioned as a dual electrochemical catalyst and hence faster H2O2
yield in a wide pH range. Another study utilised the low-cost Ti
electrodes as cathode for EF wastewater treatment(Lee et al., 2020).
Ti mesh with dimension 1.0  1.5 mm demonstrated the highest
COD removal and a very low specific energy consumption. In
addition to this, a pilot experimental setup was run for five months
consecutively, demonstrating a stable organic pollutant degrada-
tion with a reduced sludge formation. The pilot-scale plant installed
at the T-wastewater treatment, (Gyeonggi-do, Republic of Korea)
could treat a maximum of 40 m3 of wastewater/day. COD removal
efficiency of 86% was observed with an estimated cost of $2.48 per
kg COD removed. The pilot-scale system could reduce the reagent
use by 22% and the sludge formation by 39%, leading to a highly
efficient and economical treatment of real wastewater. Hence, the
Ti mesh cathode was found to reduce the overall operational and
maintenance cost. The schematic and photograph of pilot scale EF
are shown in Fig. 38 (a) and (c), respectively. The schematic and
photographs of the electrode stacks are shown in Fig. 38 (b) and (d).
The stacks consisted of alternative layers of twenty-one Ti cathodes
K.M. Nair, V. Kumaravel and S.C. Pillai
and twenty iridium oxide and ruthenium oxide coated titanium
mesh as anodes.
A quantitative cost analysis of the pilot-scale system was per-
formed, which concluded that the total cost of the reagents and
electricity added up to $ 10.645 for 4.71 kg of COD removal. The
analysis revealed that the cost of Fenton reagents is higher when
compared to the electricity cost. A similar study on the cost analysis
of EF reactions for the treatment of real textile wastewater using Al
cathode and Ti/RuO2 anode was reported in India(Kaur et al., 2019).
The study demonstrates that a total cost of $ 5.76/kg of COD
removal was observed, out of which only $ 0.10 fell under the
electrical energy consumed. This indicates that the cost of EF pro-
cess can be reduced by selecting cost effective electrodes and
avoiding their deterioration.
7. Challenges and future prospects
Enormous research efforts have been dedicated in the past three
decades in advancement of EAOPs, mainly EF reactions. The effi-
ciency of an EF reaction is ruled by the surface characteristics of
cathode material, reaction pH, oxygen sparging rate, applied cur-
rent density, Fe2þ concentration, etc. It is of utmost significance to
develop an efficient and economically viable cathode material for
the H2O2 production and faster generation of COH.
Although remarkable advancements have been achieved in
improving the efficiency of EF process, significant research is still
required for the advancement in the areas listed below.
(i) Development of cost-effective cathode materials
Several efforts have already been introduced to develop
constructive cathode materials for EF wastewater treat-
ments. As stated in the review, carbonaceous materials
are found to be the most promising cathodes in EF pro-
cess. However, processing and handling of carbon mate-
rials require more consideration and advanced
technologies. Most of the synthesis methods involve
complex techniques, which require immense care and
precautions and hence increase the cost of processing.
Also, more focus should be given in developing cathodes
that can be fabricated from readily accessible and cheap
materials such as biochar-derived carbon. Biomass
derived carbon cathode materials could offer large surface
area along with the presence of several heteroatoms that
can offer active sites for the improvement of ORR. With
the chemical functionalization, more theoretical and
computational studies are yet to be performed for un-
derstanding the effect of different types and combina-
tions of foreign atoms in improving the rate of H2O2
production. A fundamental understanding of doping ef-
fects on different types of carbon materials is still largely
lacking, along with specific dopant effects on electrode-
electrolyte interactions.
ii) Reaction pH
Agglomeration of the iron catalyst at high pH (pH > 3) is
one of the major challenges in homogenous EF reaction
and has led to a reduction in effective surface area and
thereby a decrease in active sites of the catalyst. Even
though researches demonstrate that iron-based catalysts
agglomerates at pH > 5, there are no comprehensive
studies at higher pH. Reports suggest the formation of
Fe(OH)n and degradation of H2O2 at higher pH, but no
clear mechanism and reasoning has yet been developed.
Supported catalyst or functionalized cathodes were
developed to solve this challenge. Albeit the introduction
of heterogeneous EF cathodes and catalysts to improve
38
Chemosphere 269 (2021) 129325
the efficiency at higher pH, the synthesis procedures for
the same is quite complex and requires multiple steps.
Hence, a clear study of the reaction mechanism at higher
pH for homogenous EF and introduction of cost-effective
techniques for fabricating heterogeneous EF catalysts are
quite necessary.
iii) Stability and recyclability
The raw materials for the fabrication of heterogenous
cathodes are highly expensive but less stable, which in
turn affects its reusability in EF process. Apart from this,
excessive leaching or catalyst fall-off was also observed
due to mechanical wearing in the electrolyte at high pH
and long-term operation. This has limited the studies of
heterogeneous EF process to laboratory scales. Long term
reusability and reduction in the cost of modifying the
carbon materials are required to achieve practical appli-
cations, especially in developing regions. This could be
solved by focusing to design inexpensive cathode mate-
rials and catalysts which would be stable in high pH and
active in real wastewater.
Extensive studies on metal-free EF catalyst and biomass
derived carbon should be performed due to its environ-
mental benignity and improved work efficiencies. High
performance anode materials other than noble metals
and BDD should be developed to reduce the cost of EF
process. A real understanding of the potential pH window
of the reaction and current efficiencies would be useful in
fabricating a low cost yet efficient electrodes for EF.
(iv) Investigation of by-products and H2O2 activation
Investigations are required to explore the mechanism of
H2O2 activation to COH, pathways and reactions involved.
In-situ spectroscopic techniques must be used to analyse
the nature of various reaction intermediates at the elec-
trode surface. Also, a better understanding of the degra-
dation pathways of the pollutants and the investigation of
exact by-products could be beneficial for real wastewater
treatments. Several by-products might be highly toxic
when compared to the real effluents. Detailed studies on
the impact of these by-products on environment will help
in improving the real-world applications. Moreover, this
can reduce any secondary pollution that might be caused
due to leaching and infiltration. The combination of EF
reactor with biological treatment is one of the best ways
to improve the degradation of by-products and minimize
the cost as well as energy consumption.
(v) Analysing the environmental impact
Most of the developments on existing carbon electrodes
are feasible only at the laboratory scale. However, it is
often challenging to scale up the materials for real life
applications. Several parameters are still needed to be
optimised to implement an industrial scale operation.
These include a better dispersion of carbonaceous mate-
rials in solvents and improved coating techniques that
prevent the agglomeration of nanoparticles. Also, the rate
of carbon leakage should be controlled as this could lead
to environmental toxicity and cause several adverse
effects.
(vi) Studies on treating biological contaminants
EF process is mostly limited to organic pollutant degra-
dation with very limited studies on microbes and viruses.
Amidst the global pandemic breakout and emergence of
various infectious diseases, it is quite essential to extend
the use of EF techniques towards microbial decontami-
nation. Introduction of techniques like PEF has however
facilitated in improving the efficiency of EF treatment. UV
K.M. Nair, V. Kumaravel and S.C. Pillai
light active inorganic nanoparticles could generate free
radicals to kill germs and could act as a successful anti-
viral coating, even for recent covid-19. The nano-
structures are said to capture the virus and further trigger
chemical reaction using UV light. In addition, the utili-
zation of direct sunlight as visible light source for PEF
could reduce the cost of UV lamps or other light sources.
Combining EF with other wastewater treatment tech-
niques such as electrocoagulation, could further improve
the degradation efficiency.
(vii) Reactor designs for large scale operations
EF reaction possesses the advantage of non-selectivity,
thus destroying almost every type of pollutants and
achieving a complete mineralization in almost all cases.
However, the treatment cost of EF process is not much
feasible for pilot scale studies. Treatment of real waste-
water is cumbersome when compared to lab-scale set-
ups due to their complex composition. Hence, they
behave contrastingly during EF treatment, in terms of the
rate of degradation and the efficiency of the whole pro-
cess. Studies should be performed in terms of designing
pilot scale reactors taking into consideration the limiting
factors such as mass transfer, electrical resistance, etc.
Flow reactors that employ heterogenous EF cathodes are
still limited and needs to be further investigated. Overall,
significant amount of research is required in terms of
commercializing the EF process without compromising
the efficiency of EF process.
8. Summary
EF is one of the most environmentally benign technologies to
address the rising issue of water contamination caused by organic
pollutants and CECs. This review provides a comprehensive over-
view on the application of various carbonaceous cathode materials
and their modifications to enhance the rate of H2O2 production in
EF reaction. It also discusses briefly on the mechanism, reactor
configuration and kinetics of EF. Besides this, several challenges
that hinder the commercialization of EF and some possible pros-
pects have also been summarized.
Important reactions involved in the process including H2O2 and
C
OH generation are explained in detail. Various reactor configu-
rations, both in lab scale and pilot scale are discussed. The rotating
disc cathodes exhibited the best performance under batch reactors.
Pilot scale configurations based on geometric parameters, out-
streaming patterns, pressure and size are also discussed and
compared. However, additional studies are required for the devel-
opment of highly efficient industrial scale reactors to address the
limiting factors such as mass transfer and electrical resistance. The
significant kinetic studies and models are also briefly summarized.
Most of the reactions followed a pseudo-first order kinetics. Very
limited kinetic models are developed especially considering the by-
products involved in the reaction.
Carbonaceous cathode materials (ACF, CNTs, CAs, CF/GF, OMCs
etc.) are inexpensive, easily available and comparatively less toxic in
nature. Carbonaceous materials are highly selective toward the 2ee
ORR and hence they are considered as the finest cathode materials
for EF process. The modifications have improved the performance
of cathode with a limited energy consumption and wider working
pH (pH 1e9) window. Recently, biomass derived carbon materials
have been widely employed in ORR. Several reports have also
addressed the issue of energy consumption in the EF system by
triboelectric nanogenerators (TENGs) which converts the me-
chanical energy to electrical energy, thus designing a self-powered
39
Chemosphere 269 (2021) 129325
EF system.
Furthermore, doping of hetero atoms such as N, F, etc. with
carbon induces a charge distribution within the sample and gen-
erates more active sites for the H2O2 production. Heterogenous EF
reactions using metal/metal oxide modified cathode materials
could provide an opportunity to explore the novel materials for
more effective reactor designs. The trouble of iron sludge formation
and limited pH window could be rectified in the heterogeneous EF
reactions. Efforts have also been put forward to eliminate the use of
iron as such from the reaction by introducing metal-free catalyst to
activate H2O2 to COH.
However, there is still no details on the design of cost-effective
large-scale cathode fabrication and the long-term stability of
cathodes under practical conditions. Techno economic analysis of
the EF reaction revealed that there is an ample opportunity to
improve the cost effectiveness of the process compared to the pre-
existing commercial treatment techniques. It was concluded that
the high-performance anode materials and the raw materials for
heterogenous catalysts contributed the most to capital costs, while
the electricity costs were much less significant. Studies on natural
water matrix and strategies of selective pollutant treatments
should be conducted to attain an accurate cost estimation. Future
studies should be focused on the following aspects, developing cost
effective cathodes, investigation of by-products and their toxicity,
treating biological contaminants, and pilot scale reactor designs.
More studies should be conducted on the kinetic and theoretical
aspects of EF process to fabricate a cathode material which is more
effective towards H2O2 production and pollutant degradation.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
This work is carried out as a part of ’PANIWATER’ project which
has received funding from the European Union’s Horizon 2020
Research and Innovation Programme under grant agreement
number 820718, and is jointly funded by the European Commission
and the Department of Science Technology of India (DST). The au-
thors would also like to thank Institute of technology Sligo, Ireland
for providing facilities to conduct the research.
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modified cathode’. Chem. Eng. J. https://doi.org/10.1016/j.cej.2019.123324, Institute of Science Education and Research, Thir-
123324, available: uvananthapuram (IISER Tvm). Currently, she is a Graduate
Zhou, W., Rajic, L., Chen, L., Kou, K., Ding, Y., Meng, X., Wang, Y., Mulaw, B., Gao, J., student under EU funded EU-Horizon 2020 PANI Water
Qin, Y., Alshawabkeh, A.N., 2019c. Activated carbon as effective cathode material PhD Scholarship, under the supervision of Prof. Suresh C.
in iron-free Electro-Fenton process: integrated H2O2 electrogeneration, acti- Pillai, at the Institute of Technology, Sligo. Her Ph. D
vation, and pollutants adsorption. Electrochim. Acta 296, 317e326. https:// work is on fabrication of new Electrode Materials for
doi.org/10.1016/j.electacta.2018.11.052 available: Electro-Fenton Reactions and electrocatalysis.
Zhou, X., Xu, D., Chen, Y., Hu, Y., 2019d. Enhanced degradation of triclosan in het-
erogeneous E-Fenton process with MOF-derived hierarchical Mn/Fe@PC
modified cathode. Chem. Eng. J. https://doi.org/10.1016/j.cej.2019.123324,
123324, available:
Dr. Vignesh Kumaravel is working at IT Sligo as a Senior
Zhou, W., Rajic, L., Chen, L., Kou, K., Ding, Y., Meng, X., Wang, Y., Mulaw, B., Gao, J.,
Research Fellow in the Renewable Engine project. He ob-
Qin, Y., Alshawabkeh, A.N., 2019e. Activated carbon as effective cathode mate-
tained his Ph.D. from Madurai Kamaraj University, India in
rial in iron-free Electro-Fenton process: integrated H2O2 electrogeneration,
2013. His research interests include the synthesis and
activation, and pollutants adsorption. Electrochim. Acta 296, 317e326. https://
utilization of various nanoparticles for hydrogen produc-
doi.org/10.1016/j.electacta.2018.11.052 available:
tion, CO2 conversion, self-cleaning, food packaging poly-
Zhou, X., Xu, D., Chen, Y., Hu, Y., 2019f. Enhanced degradation of triclosan in het-
mers, high temperature stable batteries/supercapacitors,
erogeneous E-Fenton process with MOF-derived hierarchical Mn/Fe@PC
and antimicrobial applications. He has completed various
modified cathode. Chem. Eng. J., 123324 https://doi.org/10.1016/
major research projects as Co-PI. He is currently acting as
j.cej.2019.123324 available:
a guest editor in Catalysts.
Zhuang, L., Zhou, S., Li, Y., Liu, T., Huang, D., 2010a. In situ Fenton-enhanced cathodic
reaction for sustainable increased electricity generation in microbial fuel cells’.
J. Power Sources 195 (5), 1379e1382.
Zhuang, L., Zhou, S., Li, Y., Liu, T., Huang, D., 2010b. In situ Fenton-enhanced cathodic
reaction for sustainable increased electricity generation in microbial fuel cells’.
J. Power Sources 195 (5), 1379e1382. https://doi.org/10.1016/j.jpows-
our.2009.09.011 available: 10.1016/j.cej.2013.08.044.
Zhuang, L., Zhou, S., Li, Y., Liu, T., Huang, D., 2010c. In situ Fenton-enhanced cathodic Prof. Suresh C. Pillai obtained his Ph.D. from Trinity
reaction for sustainable increased electricity generation in microbial fuel cells’. College Dublin and completed his postdoctoral research at
J. Power Sources 195 (5), 1379e1382. https://doi.org/10.1016/j.jpows- California Institute of Technology (Caltech, USA). He has
our.2009.09.011 available: joined at IT Sligo in 2013 as a Senior Lecturer and
Zuo, L., Zhang, Y., Zhang, L., Miao, Y.-E., Fan, W., Liu, T., 2015. Polymer/carbon-based currently leads the Nanotechnology and Bio-Engineering
hybrid aerogels: preparation, properties and applications. Materials 8 (10). Research Group. His research interests include the synthe-
https://doi.org/10.3390/ma8105343 available: sis of nanomaterials for energy and environmental appli-
cations. He is the recipient of a number of awards
including the Boyle-Higgins Award 2019. He is an associate
Keerthi M. Nair graduated with a dual degree of Bachelor editor for the Chemical Engineering Journal and ediotrial
of Science and Master of science in Chemistry from Indian board member for Applied Catalysis B (Elsevier).

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