water

Review
Examining Current and Future Applications of Electrocoagulation
in Wastewater Treatment
Yi Mao 1 , Yaqian Zhao 1,2, * and Sarah Cotterill 1

1 UCD Dooge Centre for Water Resources Research, School of Civil Engineering, University College Dublin,
Belfield, D04 V1W8 Dublin, Ireland; yi.mao@ucdconnect.ie (Y.M.); sarah.cotterill@ucd.ie (S.C.)
2 State Key Laboratory of Eco-Hydraulics in Northwest Arid Region, Xi’an University of Technology,
Xi’an 710048, China
* Correspondence: yzhao@xaut.edu.cn

Abstract: Electrocoagulation (EC) has gained increasing attention as an effective and environmentally
friendly technique for purifying water and wastewater. This review provides a comprehensive
analysis of the recent literature on EC and identifies new trends and potentials for further research.
Initially, the nature of EC and its operating parameters are discussed, while the research trends are
analyzed using the Scopus database and VOSviewer software. From 1977 to 2022, 2691 research
articles and review papers on EC for water/wastewater treatment were published, with the number
of publications increasing from 2 in 1977 to 293 in 2022. In the past five years, most studies focused on
treatment performance and the mechanism of EC systems. However, recent emphasis has been placed
on combining EC with other treatment processes and addressing emerging pollutants. The innovative
applications of EC are highlighted, including the removal of microplastics and per/polyfluoroalkyl
substances, the power supply of EC via microbial fuel cells (MFCs) and electro-wetlands (EWs), and
the application of power management systems in EC. The review concludes with suggestions for
further research to enhance the technology and expand its scope of applications.

Keywords: electrocoagulation; water and wastewater treatment; emerging-pollutants removal;

microbial fuel cell; electro-wetland; constructed wetland

Citation: Mao, Y.; Zhao, Y.; Cotterill,

S. Examining Current and Future 1. Introduction
Applications of Electrocoagulation in Water scarcity and pollution have become increasing global problems due to pop-
Wastewater Treatment. Water 2023, ulation growth, industrialization, and the overuse of water resources. In 2020, only
15, 1455. https://doi.org/10.3390/ 74% (5.8 billion) of the global population had access to ‘safely managed’ drinking wa-
w15081455 ter services [1,2]. This term refers to access to improved water sources, which are located
Academic Editor: Alexandre T. Paulino on their premises, available when needed, and free from fecal and priority chemical con-
tamination. However, the remaining two billion people still live without safely managed
Received: 8 March 2023 drinking water services, with 1.2 billion people lacking even a basic level of service. Ap-
Revised: 2 April 2023
proximately 80% live in rural areas, and half live in the least-developed countries. The
Accepted: 5 April 2023
United Nations Sustainable Development Goal targets 6.1 and 6.A aim to achieve, by 2030,
Published: 7 April 2023
universal and equitable access to safe and affordable drinking water and building support
to developing countries in water- and sanitation-related activities and programs, including
water harvesting, desalination, water efficiency, wastewater treatment, recycling, and reuse
Copyright: © 2023 by the authors.
technologies [1].
Licensee MDPI, Basel, Switzerland. This has prompted research into developing low-cost, easily constructed and main-
This article is an open access article tained, and sustainable technologies for water treatment and recycling in rural or
distributed under the terms and less-developed areas. Electrocoagulation (EC) is a water purification system that uses
conditions of the Creative Commons micro-electrical current to remove contaminants in aqueous environments. It is an alterna-
Attribution (CC BY) license (https:// tive to chemical coagulation (CC), which involves delivering metallic coagulants to water
creativecommons.org/licenses/by/ through the electro-dissolution of electrodes. Both methods aim to remove finely dispersed
4.0/). particles from water/wastewater by destabilizing or neutralizing the repulsive forces that

Water 2023, 15, 1455. https://doi.org/10.3390/w15081455 https://www.mdpi.com/journal/water

Water 2023, 15, x FOR PEER REVIEW 2 of 31

chemical coagulation (CC), which involves delivering metallic coagulants to water

Water 2023, 15, 1455 2 of 29
through the electro−dissolution of electrodes. Both methods aim to remove finely dis-
persed particles from water/wastewater by destabilizing or neutralizing the repulsive
forces that keep the particles suspended in the water. This process leads to the formation
ofkeep theparticles
larger particles suspended
that can settlein thebewater.
and more This
easilyprocess leads
separated to the
from the formation
water. of larger
particles that can settle and be more easily separated from the water.
EC combines the benefits of coagulation, flotation, and electrochemistry in one sys-
EC EC
tem [3,4]. combines
consiststhe benefits
of an of coagulation,
electrolytic cell with twoflotation, and
electrodes electrochemistry
(an in one
anode and a cathode)
system [3,4]. EC consists of an electrolytic cell with two electrodes (an anode and a cathode)
immersed in a conducting solution to be treated and coupled to an external electricity
immersed in a conducting solution to be treated and coupled to an external electricity
power supplier (Figure 1). There are several steps in the EC process:
power supplier (Figure 1). There are several steps in the EC process:

Figure
Figure1.1.Schematic
Schematicdiagram
diagramofofthe
theelectrocoagulation
electrocoagulationprocess.
process.

(1) When
(1) When ananelectric
electriccurrent
currentisissupplied
suppliedfrom fromananexternal
externalpower
powersource,
source,the
theactive
activecoag-
coagu-
lant cations
ulant cations (usually aluminum
aluminum or oriron)
iron)are
arereleased
releasedintointothe
thesolution
solutionbyby the
theelectrolytic
electro-
oxidation
lytic oxidationof aofsacrificial anode
a sacrificial Equations
anode Equations(1) (1)
andand
(4);(4);
(2) Simultaneously,
(2) Simultaneously,hydroxyl
hydroxylions ionsare
areproduced
produceddue duetotocathode
cathodehydrolysis
hydrolysisEquation
Equation(6);(6);
(3) The
(3) The metalcations
metal cationsreact
reactwith
withhydroxyls
hydroxylstotoform formmonomeric
monomericand andpolymeric
polymericspecies
species
Equations
Equations (2),
(2), (3)(3)
andand (5);
(5);
(4) Neutralization of the surface
(4) Neutralization of the surface charge charge ofofcontaminants,
contaminants, suspended
suspended particulate
particulate matter,
matter,
and emulsions is achieved due to its reaction with
and emulsions is achieved due to its reaction with metal hydroxyls; metal hydroxyls;
(5) Agglomeration
(5) Agglomeration ofof neutralized
neutralized particles
particles andtheir
and theircoagulation
coagulationoccurs
occursininthe
theaqueous
aqueous
phase
phase asas flocs;
flocs;
(6) Precipitation
(6) Precipitation ofof heavier
heavier flocs
flocs takesplace
takes placebybysedimentation
sedimentationvia viasweep
sweepcoagulation;
coagulation;
(7) Hydrogen bubbles are produced at the cathode by water electrolysis, resulting ininthe
(7) Hydrogen bubbles are produced at the cathode by water electrolysis, resulting the
floatation of flocs at the surface of the solution via sweep coagulation
floatation of flocs at the surface of the solution via sweep coagulation Equation (6). Equation (6).
Anodereactions:
Anode reactions:
Fe (s) → Fen+ (aq) + ne−1 (1)
Fe s) → Fe aq) + ne (1)
2+
4Fe
4Fe (aq ) ++10H
aq) 10H2 OO++OO2 (aq
aq))→ 4Fe(OH)
→ 4Fe OH)3 (s) 8H+
s)++8H (2)
(2)

2+ aq) + 2OH− → Fe OH) s)

FeFe (aq) + 2OH → Fe(OH)2 (s) (3)
(3)

Al s) → Al aq) + 3e (4)
Al(s) → Al3+ (aq) + 3e−1 (4)

Al3+ (aq) + nH2 O → Al(OH)3n−n (s) + nH+ (5)

Water 2023, 15, 1455 3 of 29

Cathode reactions:
2e−1 + 2H2 O → H2 + 2OH− (6)
The anode dissociation follows Faraday’s law Equation (7). Where, m A is the mass
of anode dissolved (g), I is the current (A), t is the operation time (s), Mw is the molecular
weight of anode (aluminum, 29.89 g/mol), F is Faraday’s constant (96,487 C/mol), and z is
the number of electrons involved in the reaction.
I × t × Mw
mA = (7)
z×F
In some cases, the actual anode dissolution does not match the theoretical anodic
dissolution calculated by Faraday’s law, which indicates that other electrochemical reactions
might be taking place at the anode. Several authors suggested that the evolution of
oxygen at the anode might take place at alkaline pH and sufficiently high anodic potential
Equation (8) [5]
2H2 O → O2 + 4H+ + 4e−1 (8)
In 1889, the first study to use electricity for sewage treatment was proposed in the
United Kingdom [6], and this gained interest and was widely applied globally from the
1970s onwards [7]. There are a vast number of published research papers from the last two
decades that sought to investigate the performance of EC for the treatment of different
wastewater. Previous studies have reported that EC is effective for the removal of contami-
nants such as heavy metals [8,9], oil droplets [10], dyes [11], suspended solids [12], natural
organic matter (NOM) [13,14], and phosphorous [15,16] in wastewaters including munic-
ipal sewage, industrial wastewater, and polluted natural water [5,17,18]. In this review
paper, the characteristics of EC and operational parameters are discussed, followed by an
analysis of research trends of publications utilizing the Scopus database and VOSviewer
software. The paper places particular emphasis on exploring novel applications of EC in
recent studies, including treating emerging pollutants, utilizing sustainable bio-current
sources (such as microbial fuel cells and electro-wetlands), and implementing power man-
agement systems. Additionally, the paper identifies gaps in current research and provides
recommendations for future investigations that can address these gaps and overcome
operational challenges.

2. Nature of Electrocoagulation and Performance-Influencing Factors

2.1. Pros and Cons of Electrocoagulation
The EC approach to coagulation has several advantages and disadvantages over
traditional physio-chemical treatment methods [4,5,18,19] (Table 1). EC has advantages
over CC for wastewater treatment, including faster and more efficient organic-matter
separation, pH control without chemicals, lower operating costs, less secondary pollution,
and easier automation. It also produces gas bubbles to facilitate pollutant removal, larger
and more stable flocs and can remove even small colloidal particles. Compared to other
electrochemical/chemical processes, such as photocatalysis (PC) and electro-Fenton (EF),
EC is relatively inexpensive due to its lower equipment and maintenance costs and because
no additional chemicals are required [20,21]. Additionally, EC can function under a wide
range of conditions, including high salt and pH levels. In contrast, PC is sensitive to
environmental factors such as pH, temperature, and the presence of organic matter [22],
while EF only operates under a narrow acidic pH range [17,23].
However, EC has some disadvantages, including cathode passivation, periodic replace-
ment of sacrificial anodes, the need for post-treatment due to high metal-ion concentrations,
high power-consumption costs in areas with limited access to electricity, and potential
sludge buildup on electrodes during continuous operation. In addition, EC utilizes elec-
trochemical methods exclusively to eliminate pollutants without relying on biological
processes, which are not very effective for breaking down biodegradable pollutants and sol-
uble organic substances [20]. However, other treatment methods, such as PC [20,24], EF [21],
Water 2023, 15, 1455 4 of 29

microbial electrolysis cell (MEC), and microbial fuel cell (MFC) [17], may be more effective
at treating water with organic pollutants. These methods involve bio-electrochemical
processes or the use of chemicals and light to support the treatment process and, therefore,
may be more efficient.

Table 1. Advantages and disadvantages of electrocoagulation over traditional physio-chemical

treatment methods.

Pros Cons
Cathode passivation can occur due to the hydroxides of calcium,
Produces larger and more stable flocs for easy filtration,
magnesium, and other substances, inhibiting the flow of current
compared with CC.
and the release of hydrogen.
pH control without chemicals. Sacrificial anodes must be replaced periodically due to corrosion.
Lower operating costs compared to CC, PC, and EF
Post-treatment may be necessary to remove high concentrations of
processes due to lower equipment and maintenance costs
iron and aluminum ions from effluent.
and no addition of chemical costs.
No secondary pollution or added chemicals means less Electrochemical methods may be costly in areas with limited access
sludge production. to electricity.
Sludge buildup on electrodes can inhibit the electrolytic process
Produces gas bubbles to aid pollutant removal.
during continuous operation.
Electrochemical methods may not be as effective as biological
Simple equipment with automation potential. processes for removing biodegradable pollutants and soluble
organic substances.
Can remove even the smallest colloidal particles through
faster collision and facilitated coagulation.
Can operate under a wide range of conditions compared
with PC and EF, including high salt and pH levels.

2.2. Removal Mechanisms

The mechanisms of coagulation–flocculation and the series of reactions and processes
in the EC and CC are similar. In Al-based EC, when the aluminum anode is dissolved into
Al3+ ions, they become hydrated and form the hexaaquoaluminium ion (Al(H2 O)6 3+ ); see
Equations (1)–(8). This ion then undergoes a series of rapid hydrolysis reactions, leading
to the formation of soluble monomeric species (Al(OH)(H2 O)5 2+ ) and polymeric species
(Al13 O4 (OH)24 7+ ), as well as solid Al(OH)3 and aluminate ions (Al(OH)4 − ) [7,25].
For the removal of organic matter, there are several mechanisms including: (1) complex-
ation; (2) charge neutralization or destabilization; (3) entrapment; and (4) adsorption [19].
The predominance of each mechanism depends on the nature of the pollutant (charge, size,
hydrophobicity, etc.), the type of coagulant and its dosage, as well as the pH and other
factors in the water matrix. It is important to note that the overall mechanism for removing
pollutants through coagulation is complex and can often involve multiple mechanisms
working together to improve the removal efficiency [19].
Natural organic matter (NOM) refers to organic material which consists of a diverse
mix of humic substances (such as humic and fulvic acids and phenolic compounds), hy-
drophilic acids, proteins, lipids, and carbohydrates. ECs have been reported to treat a
variety of NOM-containing waters, including peat water [13,26], river water [27,28], lake
water [14,28,29], and synthetic wastewater [30,31]. Low levels of NOM in water can pre-
vent chemical dissolution, pitting corrosion, and chlorine generation during electrolysis,
as there are low levels of salinity and chloride ions [32]. In the case of using iron elec-
trodes, Fe(II) can be converted to Fe(OH)3 (s) through ‘sweep coagulation’ by increasing
pH and dissolved-oxygen concentration in oxygenated water [32]. Aluminum hydroxide
is the main oxide formed during Al-based EC in natural water, and the presence of NOM
can disrupt its crystalline precipitation, similar to chemical precipitation with aluminum
chloride [32]. Oxygen was not released during the anodic dissolution of aluminum/iron,
indicating that all electrons participated in the process [32].
Water 2023, 15, 1455 5 of 29

Aluminum electrodes can remove phosphates in water through the direct adsorption
of phosphate ions, incorporation of soluble phosphates into suspended colloids, and
formation of insoluble salts with aluminum [7]. However, the system of the aluminum–
orthophosphate is complex, and the removal of phosphates also depends on hydrolysis
products of aluminum and the Al3+ ion rather than the formation of individual AlPO4 and
Al(OH)3 species [7]. The pH of the solution affects the process, with higher pH leading to the
formation of aluminum–hydroxy species that can adsorb onto positively charged aluminum
hydrolysis species or act as nucleation points for the further precipitation of aluminum
hydrolysis products. The highest removal efficiency occurs when the concentrations of
aluminum hydroxy species and phosphates are high, and the solubility of AlPO4 is low [7].

2.3. Influencing Factors

Several parameters influence electrocoagulation efficiency and its ability to remove
Water 2023, 15, x FOR PEER REVIEW
pollutants from wastewater (Figure 2). The most important parameters include electrode
6 of 31
materials and arrangement, pH and anion concentration, type of power sources, and
current density. EC-removal efficiencies, power consumption, and operating costs under
various operating conditions in previous studies are summarized in Table 2.

Figure 2. Factors
Figure Factorsinfluencing
influencingEC’sEC’sremoval
removalperformance
performance (a);(a);
Electrode arrangement,
Electrode monopolar
arrangement, par-
monopolar
parallel (MP-P), monopolar series (MP-S), and bipolar series (BP-S) [5]; (b) EH-pH diagrams °C
allel (MP−P), monopolar series (MP−S), and bipolar series (BP−S) [5]; (b) EH−pH diagrams at 25 at
of ◦aluminum
25 and iron
C of aluminum and in water,
iron the dashed
in water, lineslines
the dashed represent the the
represent electrochemical stability
electrochemical range
stability of
range
water [3]; (c) Current flow type for EC−direct current (DC), alternating pulsed current
of water [3]; (c) Current flow type for EC-direct current (DC), alternating pulsed current (AC), (AC), polar-
ity−reversal current (PRC).
polarity-reversal current (PRC).

2.3.1. Electrode Materials and Its Arrangement

Aluminum and iron are commonly used electrode materials due to their reliability
and availability [18]. Aluminum anodes dissolve as Al3+, while iron anodes dissolve as Fe2+
and Fe3+ in solutions, Equations (1) and (4). Fe2+ is highly soluble but a weak coagulant
and has a lower pollutant−adsorption capacity compared to Fe3+. Iron electrodes are suit-
able in specific pH ranges to ensure complete oxidation of Fe2+ to Fe3+ [5]. Aluminum elec-
Water 2023, 15, 1455 6 of 29

2.3.1. Electrode Materials and Its Arrangement

Aluminum and iron are commonly used electrode materials due to their reliability and
availability [18]. Aluminum anodes dissolve as Al3+ , while iron anodes dissolve as Fe2+
and Fe3+ in solutions, Equations (1) and (4). Fe2+ is highly soluble but a weak coagulant
and has a lower pollutant-adsorption capacity compared to Fe3+ . Iron electrodes are
suitable in specific pH ranges to ensure complete oxidation of Fe2+ to Fe3+ [5]. Aluminum
electrodes are more expensive but more efficient than iron electrodes [5,7]. Aluminum
anodes can be paired with other materials as cathodes, such as stainless steel [33–35] or
iron [36], for specific pollutant removal. Alternative anodic materials like copper, zinc, and
magnesium can be used instead of iron or aluminum to coagulate contaminants in water.
These materials dissolve to form hydroxides and help with coagulation [19,37]. However,
iron and aluminum require less coagulant due to their higher charge valence [19]. It is
important to note that excessive coagulant residue in treated water can be harmful to health,
and EU regulations limit aluminum (200 µg/L), iron (200 µg/L), and magnesium (50 µg/L)
concentrations to avoid potential health problems [38].
There are three types of electrode arrangements for electrochemical cells: monopolar–
parallel (MP–P), monopolar–series (MP–S), and bipolar–series (BP–S) (Figure 2a). In MP–P,
anodes are connected to each other and the power supply in a parallel configuration. In
MP–S, the internal electrodes are connected to each other in a series connection. In BP–S,
the inner electrodes are separated from each other and the power supply, forming a series
connection [4,5]. It is important to note that a series connection requires a higher potential
difference, while a parallel connection distributes the electric current among all the intercon-
nected electrodes based on their resistance. However, a parallel-connection configuration
offers significant energy savings. Thus, the MP–S connection mode uses a higher potential
difference, while the MP–P connection mode has lower energy consumption. Additionally,
the BP–S mode provides high pollutant removal [39,40], while the monopolar-configuration
mode has a lower cost of operation [40,41].

2.3.2. pH and Anion Concentration

The electrode dissolves and forms different metal ions depending on the initial pH
(pHi) of the solution. Aluminum and iron EH-pH diagrams (Figure 2b) show which
compound is thermodynamically stable under given conditions. When the cell potential
is between −2 V and +2 V, Al3+ is the major species present at pH < 3.5, Al(OH)3 (S) for
pH 4–9.5, and Al(OH)4 − for pH > 10. Al(OH)3 is the main contributor to floccule and
aggregate formation through complex precipitation processes [7,19]. Fe ion formation
is more complicated, with the ferric ion predominant in highly acidic solutions and the
ferrous ion more common in pH < 6.5. Most studies found that Fe2+ is initially formed
by iron electrolysis and then oxidized to Fe3+ by dissolved oxygen when conditions are
suitable (e.g., pH 5–9), after which it is then hydrolyzed to form insoluble Fe(OH)3 (s) and
FeOOH(s) [3,5].
In ECs, the solution around the anode is slightly acidic due to H+ formation, and the
solution around the cathode is slightly alkaline due to OH− production and H2 evolution.
The amphoteric character of Al(OH)3 contributes to a decrease in the solution pH when
an aluminum anode is used. EC with Al anode is considered pH-neutralizing and can be
used for wastewater treatment with specific pH conditions or pH-enhancement/reducing
requirements [3].
The electrolyte used in electrochemical processes is important for improving solution
conductivity and reducing energy consumption [42]. The type of cation and anion used
can affect the electro-dissolution kinetics of sacrificial anodes and the ability of coagulants
to form flocs. Sulfate and nitrate ions can inhibit electro-dissolution [3,43], while chloride
(when the ratio of chloride to sulfate ions is greater than 0.1 [7]) and nitrate ions can break
down passive films and improve EC processes [3]. However, high levels of chlorine can
cause aluminum hydroxide to dissolve into aluminum chloride and reduce treatment
effectiveness [44,45]. The supporting electrolyte can also compete with contaminants in
Water 2023, 15, 1455 7 of 29

the water, potentially affecting contaminant-removal efficiency. For example, sulfate ions
can impact fluoride removal due to their ability to form precipitates with Al3+ along with
fluoride ions [46]. Electrode corrosion can also be influenced by the type of electrolyte, with
sulfate medium causing uniform corrosion, nitrate medium causing crevice corrosion, and
chloride medium causing localized pitting corrosion [46].

2.3.3. Type of Power Sources and Current Density

EC processes rely on a power source, usually direct current (DC). Long-term use can
lead to electrode passivation, reducing efficiency [47,48]. Alternating pulsed current (AC)
or polarity-reversal current (PRC) can prevent passivation [3,5] and have been used in
previous studies to improve EC efficiency [49,50]. AC uses a sinusoidal current, while PRC
involves switching the direction of a direct current in a square-wave pattern (Figure 2c).
PRC is simpler to implement and only requires a DC time relay or manual switching of
the positive and negative terminals [3,47]. AC produces smoother electrodes [51,52], while
PRC prevents electrode fouling and allows for more uniform metal-ion distribution [31].
It is unclear how passivation is prevented or removed during these processes, but possi-
ble mechanisms include hydrogen gas bubbles mechanically removing surface layers or
dissolution of the metal beneath [48].
To reduce costs and explore more applications, onsite sustainable/renewable-energy
sources with energy-storage systems used as backup power can be employed to power
EC processes. These sources include solar photovoltaic [47,53], wind turbines [54,55],
biomass [55–57], or hydroelectricity [58]. The rate of power generation by theses energy
systems highly depends on the natural conditions, such as geographical latitude, the
intensity of sunlight, wind speed, gravitational potential, land area, hydraulic loading, etc.
Current density is crucial in the EC process as it affects the amount of coagulant
generated and the production rate, size, and density of bubbles produced. The applied
current density can vary greatly, typically between 0.01 and 880 A m−2 [40]. Increasing
current density produces more coagulant [13,59] and smaller bubbles that adhere better to
particles [60,61], increasing removal efficiency. However, excessive current can decrease
Faradaic efficiency and removal performance due to secondary reactions and electrode
passivation [3,30]. Chen et al. [62] reported that with an increase in current density from
18 mA/cm2 to 52 mA/cm2 , the Faradaic efficiency dropped from 116% to 80% in aluminum-
based electrocoagulation. A substantial decrease in Faradaic efficiencies (from ~100% to
60%) has also been observed after a 30 min reaction at a current of 1.40 A. The theoretical
dissolved rate of the anode may differ from experimental observations due to oxygen
evolution and high anodic potential [7]. Excess current may also result in wasted energy
and reduced current efficiency [5,63].
Water 2023, 15, 1455 8 of 29

Table 2. Summary of the removal efficiencies, power consumption, and operation cost of EC processes under different operating conditions.

Optimum
Pollutants or Removal Performance (%) and
EC Configuration Impactor Factors Operation Operation Cost Reference
Wastewater Power Consumption
Conditions
Batch mode; Reaction volume: 2 L; CD, initial
pharmaceuticals 48%, 44%, and 36% of DCF, CBZ, 0.1, 0.2, 0.81, and 1.57 €/m3
Electrode: Al (5 cm × 16.5 cm × 0.2 cm) concentration,
from municipal and AMX removal when the CD when CD of 0.3, 0.5, 1.15, and [33]
and SS (6 cm × 16.5 cm × 0.2 cm), 5 cm electrolysis duration,
wastewater of 1.8 mA/cm2 1.8 mA/m2
apart; Stir rate: 300-rpm and application mode
Iron system: uranium Iron system: in the United
Electrode: Fe-SS, Al-SS concentration: 5 µg/L, States: 60.0 USD/g-U, South
(70 mm × 50 mm, distance: 5 mm); uranium from RT: 101.6 min, CD: cumulative uncertainty: Korea: 55.4 USD/g-U and
CD, Reaction time (RT) [34]
Reaction Volume: 500 mL; Stir rate: mine water 59.9 mA/cm2 25 µg/L; Power consumption: Finland: 78.5 USD/g-U;
200 rpm; Voltage: 40 V; Current: 5 A. 461.7 kWh/g-U; Aluminum Aluminum system:
systerm: 96 µg/L-U; 9 747 USD/g-U)
Batch mode; Reaction volume: 500 mL,
99.7% and 97.7% of uranium
Electrode: AL-SS and Fe-SS Electrode type, uranium from CD: 70 mA/cm2 ,
removal in Fe-SS and [35]
(70 mm × 50 mm, 5 mm apart); Stir CD and RT mine water RT: 120 min
AL-SS system
rate: 200 rpm.
Batch mode; Reaction volume: 0.35 L; Initial pH, CD, initial
phosphorus from pHi: 4, CD:
Electrode: titanium, Al, Fe phosphorus 99.99% of removal; Power
domestic 20 A/m2 , RT: [36]
(4.4 cm × 4.7 cm, effective area of concentration, consumption: 3.422 kWh/m3
wastewater 80 min
62 cm2 , MP-P); Stir rate: 300 rpm and reaction
Removal of total phenolic (TPh)
Initial pH: 3.2, CD: and COD: 84.2% and 40.3% with
Batch mode (180 min); Reaction volume: pH, CD, distance
250 A/m2 , distance NaCl, 72.3% and 20.9% without
1000 mL; Electrode: Zn-SS (effective between electrodes, filtered real
between electrodes: NaCl addition; Power [37]
initial area of 33.5 cm2 , connect in nature of electrolyte, olive mill
1.0 cm and NaCl: consumption: 40 kW h/m3
parallel, distance: 5–20 mm) and kind of cathode
1.5 g/L (simulated WW) and
34 kW h/m3 (real WW)
Reaction volume: 3 L; Electrode: Four 0.38 US$/m3 (MP) and
Initial concentrations RT: 30 min, CD:
AL (0.15 m × 0.1 m × 0.002 m, distance fluoride from 0.62 US$/m3 (BP) for the initial
of fluoride, electrode 625 A/m2 , using Fluoride (1 mg/L) [39]
0.5 cm, BP/MP connection, effective drinking water fluoride concentration of
connections BP connection
surface area 4 × 10−3 m2 ). 10 mg/L1
Water 2023, 15, 1455 9 of 29

Table 2. Cont.

Optimum
Pollutants or Removal Performance (%) and
EC Configuration Impactor Factors Operation Operation Cost Reference
Wastewater Power Consumption
Conditions
Turbidity removal of 88.6% and
Reaction volume: 1L; Electrode: Al or 84.1%, Color removal 90.9% and
textile Al-based EC: 6.439 €/m3 , Fe
Fe (60 mm × 60 mm × 3 mm, effective MP-P, MP-S, BP-P MP-P mode 80.0%, COD removal of 69.3% [41]
wastewater based EC: 4.732 €/m3
area: 96 cm2 , distance: 0.8 cm). and 64.1% of Al and
Fe-based EC
EC followed by advanced oxidation by
photoelectro-Fenton (PEF) process with
Anode material, 0.05 M NaCl, pH:
in-situ H2 O2 electrogeneration and organic
supporting electrolyte, 6.3, CD: 200 mA, [43]
UVA light irradiation; EC electrode: Fe pollutants
pH, and current RT: 15 min
or Al anode (3.0 cm × 1.5 cm ×
0.25 cm), SS cathode, distance: 1.0 cm.
Batch mode; Reaction volume: 2 L; Initial NO3− Complete removal after 100 min,
Anode: 10 mesh horizontal Al, Cathode: concentration, initial 80% removal in 60 min; Power
nitrates [44]
H2 evolving Al plate (14 cm × 20 cm), pH, applied CD, and consumption: 3.9 to
distance: 0.5 cm NaCl concentration 96.17 kWh/kg nitrates
Maximum 100% removal in
Anode: Al-Mg (4.0 cm × 6.0 cm),
AL-Mg system, 97 ± 2%
cathode: SS (surface area of 35.1 cm2 , Initial concentration
phosphates removal in Al-Al; Power [45]
Constant CD of 11.0 mA/cm2 , 300 cm3 of phosphate
consumption: 3.15 to
of solution
0.15 kWh/m3
Defluoridation = 100% w/o
Batch mode; Reaction volume: 1 L;
other ions. With other ions, bulk
Electrode: seven Al electrodes (active
SO4 2− , Cl− , NO3 − fluoride reaction happens, residual [46]
area: 72 cm2 of each, distance 1 cm, BP
fluoride controlled by
connection); Stir rate: 400 rpm
Al (III) amount.
DC powered system:
DC/AC, current
Reactor size: 3 cm × 12 cm. Reaction 98.8 ± 0.2%, 0.378 kWh/m3 to
densities, voltages, and Oil from
volume: 40 mL; Electrode: Al plates 0.977 kWh/m3 ; AC powered
operation modes, synthetic bilge [48]
(thickness of 2 mm, distance of 3 mm, system: 99.2 ± 0.1%,
polarity changing water
effective surface area of 14 cm2 of each) 0.787 kWh/m3 to
frequency, AC current
0.936 kWh/m3
Water 2023, 15, 1455 10 of 29

Table 2. Cont.

Optimum
Pollutants or Removal Performance (%) and
EC Configuration Impactor Factors Operation Operation Cost Reference
Wastewater Power Consumption
Conditions
Batch mode; Reaction volume: 0.9 L; 69.1% of chloride ions removal
Electrodes: AZ31 alloy and Al plates and 90.4% of non-purgeable
polarity reversal Indigo carmine
(effective area of 76.5 cm2 and 46.6 cm2 , dissolved organic carbon [49]
frequency and chloride ions
distance of 0.5 cm), Current intensity of removal with 0 and 2 min
0.34 A polarity changes.
Removal of PFBS, PFHxS, and
Reaction volume: 400 mL; Electrodes:
PFAs from syn- PFOS: 87.4%, 95.6%, and 100%
Al-Zn (60 mm × 40 mm × 2 mm, Voltage: 12.0 V, pH:
Voltage, pH, thetic/natural in the synthetic aqueous
distance 2 cm); PREC: 9 V; reversing 7.0, and stirring [50]
stirring speed groundwater solutions, and 59.0%, 88.2%, and
period of 10 s; Stir rate: 600 r/min, speed: 400 rpm
samples 100% in the natural
electrolyte concentration of NaCl: 1 g/L
groundwater
Removal of 97.8 and 97.2% with
Reaction volume: 1.0 L; Electrode: pH, initial ion
CD: 0.025 A/dm2 , an energy consumption of
Magnesium alloy (size of 2 dm2 and concentration, CD, Copper [51]
pH: 7.0 0.634 and 0.996 kWh/m3 for
distance of 0.5 cm) co-existing ions
AC and DC
0.57 kWh/g and 90% with DC
pHi, process time, and a simple electrode;
Reaction volume: 1 L; Electrodes: Two
conductivity, initial 0.43 Wh/gand 91% with DC
L-shaped Al (surface area of 100 cm2 at
HA concentration, and a perforated electrode;
1 cm distance, and 20 pores with a HA [31]
pulse time, current 0.17 Wh/g and 85% with APC
diameter of 4 mm); Mixing speed of
type, electrode shape, and a simple electrode;
50 rpm (≈10.47 rad/s).
electrode surfaces 0.18 Wh/g and 87% with APC
and a perforated electrode
EC with AC and Fe: 96.7%,
95.2%, and 0.69 kWh/m3 of lead
removal, zinc removal and
Lead and zinc
power consumption; EC with
Reaction volume: 1 l; Electrode: 30 Fe from
Electrode type, current AC and SS: 93.8%,93.3% and
and SS rods (50 mm × 5 mm, distance battery-making [52]
type, CD, RT. 0.98 kWh/m2 ; EC with DC and
of 2 cm, MP connection) industry
Fe: 97.2%, 95.5% and 1.97 kW
wastewater
h/m2 ; EC with DC and SS:
93.2%, 92.5% and 2.53 kWh/m3
respectively
Water 2023, 15, 1455 11 of 29

Table 2. Cont.

Optimum
Pollutants or Removal Performance (%) and
EC Configuration Impactor Factors Operation Operation Cost Reference
Wastewater Power Consumption
Conditions
Reaction volume: 1.0 L; Electrode: six 90% for COD, 94.56% for
CD: 48 A/m2 ,
Al plates (distance of 1 cm, effective turbidity, and 49.78% for TDS;
municipal hydraulic
area of 0.0210 m2 , parallel connected) CD and detention time, Power consumption: [53]
wastewater detention time:
Power source: solar 2.27 kWh/m3 (20 min of RT and
16 min
photovoltaic module 40 A/m2 of CD)
Reaction volume: 50 mL; Electrodes:
SPEC removes 90% of algae and
Al-AL with a conversion circuit; Power algae wastewater,
RT 97% of organic dye with [54]
sources: a wind energy harvesting dye wastewater
self-powered treatment for 72 h.
triboelectric nanogenerator
Reaction volume: 200 mL; Electrodes: bilge water (EC)
Power sources,
two Al plates (effective electrode area of and municipal MFC stack-powered ECC
electrode area, [56]
25.3 cm2 and distance of 0.5 cm) wastewater removed 93% of oily organics
and distance
Power sources: 3 MFC cells and DC (MFC)
For synthetic wastewater
Batch mode (60 min of each run);
treatment: 95.4%, 88.4%, and
Electrode: AL-SS (surface area: 60 cm2 Synthetic and
93.8% of COD, TDS, and TSS
of each, distance: 3 cm); Power sources: real municipal 3600 $/m3 per year [57]
removal; For real municipal
6 MFCs with two 1.2 V wastewater,
treatment: 83.7%, 57.5%, and
rechargeable batteries
85.8% of each.
HRT at 40 min with 0.5 mg/L
Continuous mode; Reaction volume: US$ 0.03/m3 , 0.05/m3 , 0.08/m3 ,
HRT, drug NOM, AP exhibited the best removal
1 L; Stir rate: 250 rpm; Electrode: Al–Al 0.10/m3 in 10 min, 20 min, [60]
concentration acetaminophen efficiency for NOM (55.9%) and
(distance 2 cm, 6.3 cm × 7.9 cm) 30 min, and 40 min HRT
AP (53.4%) removal.
50% B removal from river water
Boron (B) from
(C0 = 10 mg/L, current = 0.2 A)
Reaction volume: 150 mL; Electrode: river water,
current intensity, TDS in 2 h; 80% B removal from [62]
two rods (1.2 cm × 5 cm, 2.5 cm apart). oilfield produced
produced water (C0 = 50 mg/L,
water
current = 1.0 A) in 2 h.
EC–ultrafiltration; EC: two Fe anode
(dimensions of 15 cm × 12 cm × 0.3 cm) Higher CD and operation time,
Sulfonated RT: 7 min, CD:
and two graphite cathodes RT, CD, Initial pH lower pH, and improved SHA [63]
Humic Acid 10 mA/cm2 , pH: 5.
(15 cm × 12 cm × 1 cm), distance of removal. Max removal: 89.12%.
electrode: 1.5 cm.
Water 2023, 15, 1455 12 of 29

Table 2. Cont.

Optimum
Pollutants or Removal Performance (%) and
EC Configuration Impactor Factors Operation Operation Cost Reference
Wastewater Power Consumption
Conditions
For turbidity
removal:
318 mA/cm2 ,
Batchwise mode: recirculation of the
20 min and
liquid medium at 1.0 L/min; Electrode: 98.3%, 78.5%, and 56.5% for
4.4 (pHi); for TOC
Fe plates (parallel connected, CD, RT, and initial pH, shale gas turbidity, TOC, and Ca2+
removal: 0.80 US$/m3 [64]
10 cm × 17 cm × 0.2 cm, effective area: Cl− and Fe wastewater removal under the
481 mA/cm2 ,
170 cm2 , 2.0 cm apart); CD of optimum conditions
20 min and 2.4, and
318–481 A/m2
for Ca2+ removal:
400 A/m2 , 20 min,
3.9 (pHi)
Water 2023, 15, 1455 13 of 29

2.4. Process Economy of EC

The implementation of EC technology in water and wastewater processes not only de-
pends on its technical feasibility but also on its cost-effectiveness. Therefore, it is essential to
calculate the operational costs to determine the viability of using EC technology to evaluate
not only removal efficiencies but also the economic impact of this technology. The total
EC operating costs typically (TOCTotal ) include the cost of materials (OCma , €/m3 ), chem-
icals (OCch , €/m3 ), electricity (OCen , €/m3 ), sludge generated (OCsl , m3 ), maintenance
(OCma , €), depreciation (OCde , €), and labor (OCla , €) [11,19,64], as Equations (9)–(12):

TOCTotal = a × OCme + b × OCch + c × OCen + e × OCsl + OCma + OCde + OCla (9)

mA
OCme = (10)
V ∗ 1000
mC
OCch = (11)
V
U It
OCen = (12)
V ∗ 3600000
where a is the electricity price, b is the chemical price, c is the electrode material price, e is
sludge dehydration and disposal cost. U is the applied voltage (V), I is the current (A), t
is the time of reaction(s), V is the volume (m3 ) of the sample, and mC (kg) is the mass of
NaCl addition (to increase the electrical conductivity of solutions). The mass consumption
of the electrode was calculated by a function of Faraday’s law, Equation (7).
It is clear that the TOCtotal with EC is influenced by various factors, including the prices
of consumables and costs related to sludge management, along with the cost of labor. The
cost of electrochemical cells alone is reported to account for 30–60% of the total treatment
cost in many cases [55,65]. The operating cost can be reduced by optimizing current density
and treatment time and selecting appropriate electrode material and configuration [40].
However, factors such as electrode passivation and electrode thickness can increase the
operating cost of materials and energy and need to be carefully evaluated [40]. These factors
should be considered when calculating the cost and designing the reactor for the EC process.
Additional measures such as periodically reversing electrode polarity [3,5], auto-cleaning
of electrodes, and post-treatment methods can further reduce the operating cost [40].
The cost of electricity is a significant factor in the overall operating cost, particularly
in areas where commercial energy networks are not available or where electricity is costly.
Using renewable energy for EC could be one of the viable options to reduce costs. However,
it is crucial to consider the high investment associated with some renewable energy facilities,
such as solar photovoltaics [55]. This cost has been identified as a major obstacle to the
widespread adoption of these technologies [66], especially for powering electrochemical
treatment processes like EC.

3. Process Developments in the Past and Up to Now

3.1. Earlier Work and Updated Studies
Electrocoagulation was first proposed for sewage treatment using electrochemical
processes and mixing domestic wastewater with saline water in 1887, as described in
patents from Britain and France [6]. The UK carried out the first studies on the application
of these patents to treat water in 1889 [6]. Two water treatment plants in the UK utilized
electrochemical techniques with iron electrodes and chlorine disinfection with seawater
as the source. One of these plants operated successfully for 10 years [6,67]. Thereafter,
electrocoagulation was further developed and refined by researchers in Europe and the
United States. In 1906, the electrocoagulation principle was patented by A. E. Dietrich for
the treatment of bilge water from ships [68]. In 1909, J.T. Harries was awarded a patent in
the United States for wastewater treatment by electrolysis using sacrificial aluminum and
iron anodes [6]. Later, advances in chemical coagulation saw mass-produced alternatives
Water 2023, 15, x FOR PEER REVIEW 15 of 31

Water 2023, 15, 1455

the treatment of bilge water from ships [68]. In 1909, J.T. Harries was awarded a patent in
14 of 29
the United States for wastewater treatment by electrolysis using sacrificial aluminum and
iron anodes [6]. Later, advances in chemical coagulation saw mass−produced alternatives
for chemical coagulant dosing. The EC process for wastewater treatment, however, did
forfind
not chemical coagulant
widespread dosing. The
applications EC process
worldwide forthe
due to wastewater treatment,
relatively large capitalhowever, did
investment
not find widespread applications worldwide due to the relatively large capital investment
and the cost of supplying electricity [69]. During the 1970s to 1980s, significant and grow-
and the cost of supplying electricity [69]. During the 1970s to 1980s, significant and
ing interest in the use of electrocoagulation for water treatment was generated by Russian
growing interest in the use of electrocoagulation for water treatment was generated by
scientists [7]. Thereafter, a wide range of water and wastewater applications for electro-
Russian scientists [7]. Thereafter, a wide range of water and wastewater applications for
coagulation followed.
electrocoagulation followed.
There are a total of 2691 articles published on electrocoagulation between 1977 and
There are a total of 2691 articles published on electrocoagulation between 1977 and
2022 (Figure 3). The number of papers published annually on this topic has increased from
2022 (Figure 3). The number of papers published annually on this topic has increased
just 2 papers in 1977 to 293 published in 2022. The first EC study published in 1977 (based
from just 2 papers in 1977 to 293 published in 2022. The first EC study published in 1977
on a Scopus.com search) used an EC with a continuous flow to treat fish paste manufac-
(based on a Scopus.com search) used an EC with a continuous flow to treat fish paste
turing wastewater. Since 2001, the use of EC for water and wastewater treatment has
manufacturing wastewater. Since 2001, the use of EC for water and wastewater treatment
gained significant attention. The majority of publications are from researchers in India
has gained significant attention. The majority of publications are from researchers in India
(396), followed by researchers from China (314), Turkey (292), Iran (214), and the United
(396), followed by researchers from China (314), Turkey (292), Iran (214), and the United
States
States(214)
(214)(Figure
(Figure3).
3).Around
Around7.4%
7.4%(201)
(201)of
ofthese
thesearticles
articleswere
werereview
reviewpapers.
papers.

Thenumber
Figure3.3.The
Figure numberofofpublications
publicationsper
peryear
yearand
andeach
eachof
ofthe
theproductive
productivecountries
countriesin
inEC
ECstudy.
study.

Literature reviews
Literature reviewsinclude
includeKarimifard
Karimifard et al.
et [70], whowho
al. [70], discussed the use
discussed theofuse
response surface
of response
methodology (RSM) in the treatment of dye-containing wastewater through
surface methodology (RSM) in the treatment of dye−containing wastewater through phys- physico-chemical
processes suchprocesses
ico−chemical as adsorption,
such advanced oxidation
as adsorption, processes,
advanced coagulation/flocculation,
oxidation processes, coagula- and
electrocoagulation. Samsami et al. [71] summarized the technologies
tion/flocculation, and electrocoagulation. Samsami et al. [71] summarized the technolo- commonly used
for the
gies removalused
commonly of dyes from
for the wastewater,
removal of dyes including biologicalincluding
from wastewater, methods,biological
advancedmeth-oxida-
tion advanced
ods, processes, oxidation
electrocoagulation,
processes,adsorption, membrane
electrocoagulation, technology,
adsorption, and photocatalytic
membrane technol-
reactors using nanomaterials. Peng and Guo [72] discussed the
ogy, and photocatalytic reactors using nanomaterials. Peng and Guo [72] discussed potential toxicity the
and
carcinogenicity of chromium and the various methods for removing
potential toxicity and carcinogenicity of chromium and the various methods for removing it from wastewater,
itincluding membrane
from wastewater, filtration,membrane
including chemical precipitation, ion exchange,
filtration, chemical adsorption,
precipitation, electroco-
ion exchange,
agulation, electrochemical reduction, electrodialysis, electrodeionization, photocatalysis,
adsorption, electrocoagulation, electrochemical reduction, electrodialysis,
and nanotechnology. The use of EC for the treatment of different wastewaters was reviewed
by Shahedi et al. and Tahreen et al. [73,74], including its effectiveness in removing various
pollutants, the main challenges associated with EC, and the effects of various parameters
on the effectiveness of EC. Tahreen et al. [74] also discussed emerging hybrid technologies
Water 2023, 15, 1455 15 of 29

of EC with integrated separation technologies and their limitations for enhanced wastewa-
ter treatment systems, with a focus on the hybrid EC-membrane process as a promising
future technology for wastewater treatment. Moreover, the use of EC for the removal of
arsenic and pharmaceutical contaminants in wastewater was reviewed by Kobya et al. and
Zaied et al. [75,76], respectively, which include the mechanism and theoretical aspects of
removal by EC, the effects of operational parameters on the efficiency of the process, and the
reactor configurations and operating costs. Kobya et al. [75] further discussed the amount
of sludge produced during EC and the characterization and disposal methods for it.

3.2. Application and Development Trends

To better understand research trends in the field of EC, key terms in EC research papers
(and review articles) from the past 5 years (2018–2022) were searched on the Scopus database
and analyzed using VOSviewer software. By using the keywords of “electrocoagulation”
and “wastewater treatment” or “water treatment” and limiting the document type to
“article” or “review”, the language to “English”, and the publishing year to “2018 to 2022”,
Water 2023, 15, x FOR PEER REVIEW1201 EC papers were yielded in the Scopus database. These papers were then selected 17 of 31
manually again to exclude unrelated papers. A network map showing the resultant top
100 terms of co-occurrence is shown in Figure 4.

Figure 4.
Figure 4. Key
Key terms
terms occurrences
occurrences network
network visualization
visualization map
map in
in aa study
study of
of EC
EC from
from2018
2018to
to2022.
2022.

There are
There are five
five clusters
clusters of
of terms
termsof
ofpublication
publicationofofEC
ECfor
forwastewater
wastewatertreatment, repre-
treatment, rep-
sented byby
resented different colors,
different which
colors, havehave
which been been
identified by theby
identified VOSviewer software
the VOSviewer (Figure
software
4). The size of the circles indicates the frequency of the terms in EC studies. The terms
“electrodes” (532 occurrences), “chemical oxygen demand” (215 occurrences), “pH” (175
occurrences), “Iron” (173 occurrences), “aluminium” (156 occurrences), and “current den-
sity” (161 occurrences) were most frequently studied in the past 5 years. In general, the
red cluster consists of terms primarily related to the treatment performance of EC with a
Water 2023, 15, 1455 16 of 29

(Figure 4). The size of the circles indicates the frequency of the terms in EC studies. The
terms “electrodes” (532 occurrences), “chemical oxygen demand” (215 occurrences), “pH”
(175 occurrences), “Iron” (173 occurrences), “aluminium” (156 occurrences), and “current
density” (161 occurrences) were most frequently studied in the past 5 years. In general,
the red cluster consists of terms primarily related to the treatment performance of EC
with a focus on the role of “electrodes”, “pH”, “COD”, “Iron”, “aluminum” and “anodes”.
Terms relating to the energy aspects of the EC process, such as “current density”, and
“energy consumption” also occurred frequently. The green cluster includes terms related
to the mechanisms of EC, such as “adsorption”, “oxidation”, “procedures”, “electrochem-
istry analysis”, “chemistry”, “flocculation”, and “oxidation-reduction reactions”. The blue
cluster represents the integration of EC with other water treatment technologies, such as
“bioreactors”, “membrane”, “filtration”, and “microfiltration”. The yellow cluster focuses
on the removal of specific contaminants in portable water, such as “heavy metal”, “arsenic”,
“iron compounds”, “ground water”, and “drinking water”. The purple cluster consists of
terms related to the analysis and optimization of EC operations, including “optimization”,
“response surface methodology”, and “kinetics”.
Based on the analysis through the VOS reviewer, these five clusters could represent the
five main areas of research currently being conducted on EC at a global level: (1) pollutant
removal performance and energy consumption, with a total weight of occurrences of 2719;
(2) studies to understand the mechanisms of the EC reaction, with 705 total occurrences;
(3) integration of EC with other treatment processes, with 351 occurrences; (4) the removal
of emerging contaminants, with a total of 282 occurrences; and (5) analysis and optimization
of operation, with 471 occurrences.
The development trends towards the evolution of EC studies could also be noticed
from the highly cited articles. The top-cited experiment-based studies in the last 5 years
were searched on Scopus; it can be found that most of them were conducted to assess the
effectiveness of EC in removing various contaminants from water, including the removal of
microplastics [77], phosphate [78], mental pollutants [79,80], and the treatment of textile
wastewater [81–83] and oil wastewater [80]. In 2018, Perren et al. [77] looked at the
use of EC to remove microplastic contaminants from artificial wastewater containing
polyethylene microbeads and found that EC was effective with removal efficiencies above
90% across a range of pH values. The highest removal efficiency of 99.24% was observed
at a pH of 7.5, and the optimal concentration of NaCl for the reactor was found to be
between 0 and 2 g/L. Additionally, the specific mass-removal rate was highest for the
lowest-tested current density of 11 A/m2 , indicating that a low current density is more
energy-efficient for microbead removal. After that, Hashim et al. [78] used a new aluminum-
based electrochemical cell to remove phosphate from water, and it was found that 99% of
phosphate could be removed within 60 min at certain operating conditions. Three studies
focused on the treatment of textile wastewater were also conducted [81–83] and showed
the removal of 86% to 98% of color, 82% and 83.5% of turbidity, and 18.6% to 59% of COD,
respectively, under their optimum operation conditions.
The perspective of EC studies towards the integration of EC with other water/wastewater
treatment processes, such as ozonation [84], electrochemical advanced-oxidation pro-
cess (EAOP) [85,86], and microfiltration [80], was also highly interesting for researchers.
Bilińska et al. [84] examined the use of EC and ozonation as a one-step and two-step pro-
cess for the treatment of industrial textile wastewater and found that more than 95% of
color removed could be achieved in a short treatment time. The EC and O3 combination
was found to be more cost-effective when used in a two-step process, and the purified
wastewater produced by the treatment process was suitable for recycling. When consid-
ering the coupling of EC with EAOPs for dyeing wastewater, Zazou et al. found that the
sequential EC-EF treatment was the most effective process for the degradation of organic
pollutants, achieving removals of 97% for TOC, 100% for turbidity, and 100% for color [86].
Additionally, the EAOP followed by EC was a better approach than EC followed by EAOP,
as it yielded a higher COD reduction of 93.5% with a lower specific energy consumption
Water 2023, 15, 1455 17 of 29

and less sludge generated [85]. A study by Changmai et al. utilized ceramic membranes
that were prepared locally to perform microfiltration with the aim of eliminating flocs
produced during the electrocoagulation process. The results showed that 75–85% of the
initial flux was lost when performing microfiltration on the samples that had undergone
electrocoagulation [80].

4. New Developments
4.1. Emerging Pollutants Removal by EC
4.1.1. Removal of Microplastics
Plastic is a popular polymer material used in various industries because of its light
weight, strength, durability, and low cost. A large amount of plastic waste is being dis-
charged into the environment, creating microplastics (MPs) with particle sizes less than
5 mm in diameter [23,87–89]. Microplastics can be found in various sizes worldwide,
mainly originating from household sewage discharge, plastic manufacturing, and plastic
debris fragmentation [89]. Wastewater treatment plants are a significant contributor to
microplastics release into the environment, as they cannot efficiently remove them, leading
to their accumulation in aquatic ecosystems [89]. MPs cannot be completely degraded due
to their polymeric structure and their ability to be easily transported between different
habitats [89]. In water environments, planktonic and invertebrate organisms are highly
susceptible to accumulating microplastics, which then transfer through the food chain
and the human body, and may lead to physical harm, decreased nutritional value, and
exposure to pathogens [89,90]. Additionally, raw plastics contain chemical additives such
as phthalates, bisphenol A, and polybrominated diphenyl ethers, which can cause toxic
effects when consumed by living organisms [89].
Coagulation-based processes have great potential for MPs separation from water/
wastewater [88]. The potential benefit of using the EC process to remove MPs is its simple
operation, high efficiency, and low cost [88,91]. While EC has been a well-studied area
of research, there are relatively few studies specifically focused on MPs removal. These
studies indicate that EC could effectively remove MPs, i.e., more than 90% removal in
optimum reaction conditions from real wastewater [92–95] and artificial wastewater [77,96].
EC uses metal electrodes to generate coagulants in situ, which can adsorb charged
pollutants and even degrade MPs. The main removal mechanisms of MPs by EC include:
(1) Sorption, electrical neutralization, and flotation, whereby the positive charge on the
surface of the flocculants allows for the adsorption of negatively charged ionic MPs.
The production of H2 and O2 bubbles during the EC process could also help bring the
flocs to the surface, where they can be removed through skimming [23].
(2) Oxidation reaction, where the reactive chlorine species (RCS, such as ClO− and Cl2 )
and reactive oxygen species (ROS, such as O2 , O2 •− , H2 O2 , and OH− ) and Fe(IV)
generated on the anode accompanied by the metal-ion precipitation, can oxidize the
MPs into small molecules of non-toxic substrates [23].

4.1.2. Removal of PFASs

Per- and polyfluoroalkyl substances (PFAS) are a group of synthetic chemicals com-
prised of a hydrophobic fluorinated alkyl chain at one end and a hydrophilic functional
group at the other [97,98]. The high thermal and chemical stability owing to the strong C-F
bonds, make PFAS extremely suitable in applications where they need to repel water and oil
and resist friction [97] with over 4700 different compounds in use (e.g., Perfluorooctanoic
acid (PFOA) and perfluorooctane sulfonic acid (PFOS)) [99]. PFAS are produced on a large
scale for various industrial purposes, such as the production of textiles, paper, pesticides,
leather, medical devices, metals, minerals, and oil, as well as for consumer applications
like non-stick cookware, food packaging, cosmetics, paints, inks, surfactants, waterproof
products, and firefighting foams [97]. They are known for their persistence, bioaccumula-
tion, and occurrence in drinking-water sources and the effluent of wastewater treatment
plants. A nationwide study in the US found PFAS in all 25 drinking-water treatment
Water 2023, 15, 1455 18 of 29

plants studied at levels exceeding the maximum contaminant levels in some state-level
regulations [100]. Previous studies have reported that exposure to PFAS is associated with
various acute and chronic human diseases [97,101,102], and some perfluoroalkyl carboxylic
acids have demonstrated immunotoxicity, carcinogenicity, and hormonal disorder effects
in animals [97,103,104].
EC has the ability to eliminate PFAS through either non-destructive phase separation
or destructive oxidative pathways. Compared to other PFAS treatment methods that are
destructive, such as sonolysis, ultraviolet (UV) advanced oxidation, advanced reduction,
and photocatalysis, EC requires less energy input [105]. Most studies using EC to remove
PFAS have concentrated on non-destructive methods that involve the sorption of PFAS
to metal hydroxide flocs created using sacrificial electrodes [105]. Iron and aluminum are
the commonly used electrodes, while zinc has shown greater PFOA removal compared
to iron and aluminum [106]. PFAS sorption to hydroxides was primarily attributed to
hydrophobic interactions between PFAS species and the metal hydroxide surface via multi-
layer sorption [106]. Moreover, studies suggest that EC can produce oxidation reactions
through anode-surface oxidation, reactive iron intermediates, or Fenton processes (pre-
suming there is H2 O2 in the matrix) at low pH, which may lead to PFAS degradation [105].
Recent research has demonstrated the oxidative ability of iron-electrocoagulation for PFAS
removal, which involves direct electron transfer and oxidant generation, leading to the
production of shorter-chain PFAS compounds [107]. The removal rate was independent
of pH, making it a potential oxidative process for drinking-water treatment under neutral
conditions [19].
Wang et al. [108] found that using a stainless steel rod as the cathode was more effec-
tive than those using an aluminum rod as the cathode for the removal of PFOA. Hydroxide
flocs generated in situ in the EC process in the presence of Cl− /NO3 − could effectively
remove PFOA from an aqueous solution (99.7%/98.1% and 98.9%/97.3%), while the PFOA
removal ratios were lower in the presence of SO4 2− and CO3 2− /HCO3 − (96.2%/4.1%
and 7.4%/4.6%). The study also demonstrated that Zn0.61 Al0.39 (OH)2 (CO3)0.195 ·xH2 O
and ZnO generated in situ in the electrocoagulation process using a zinc anode and alu-
minum/stainless steel rod cathode governed the sorption of PFOA. Liu et al. [109] found
that 99.6% and 79.4% of PFOA could be removed by EC with Al-Zn electrodes from a simu-
lated solution (1 mag/L PFOA) and natural groundwater in optimum conditions. PFOA
contamination was found to be adsorbed on the flocs of Zn0.61 Al0.39 (OH)2 (CO3)0.195 ·xH2 O
through the mechanism of adsorption bringing enmeshment, mainly resulting from the
hydrophobic interaction of PFOA and Al-Zn hydroxide flocs. Kim et al. [107] found that an
increase in the current density from 2.4 to 80.0 mA/cm2 in EC using an Fe electrode led
to a significant increase in the removal efficiency of PFOA from 10.0 to 100.0% within 6 h.
Formate (HCOO− ) ions and three shorter-chain perfluorocarboxylates were observed as
organic byproducts during the EC of PFOA, indicating that the C-C bond between C7F15
was firstly broken down and then degraded into short carbon-chain compounds by PFOA
decomposition. Aside from metal electrodes, air cathodes have also been applied in EC for
PFAS removal. Mu et al. [110] showed that EC with an air cathode could remove high PFOA
concentrations (99.8 ± 0.3%) with significantly less energy consumption than traditional
electrocoagulation with aeration. At low PFOA concentrations, EC with an air cathode was
found to be less effective 41.1 ± 11.6% than EC with aeration. PFOS removal rates were
generally lower (76.4–88.5%) than PFOA but were better at low concentrations due to a
higher hydrophobicity.

4.2. EC Powered by Bio-Current

4.2.1. Power Supply via Microbial Fuel Cells (MFCs)
In recent years, bio-electrochemical systems (BESs) such as microbial fuel cells (MFCs)
have received increased attention for their ability to simultaneously treat wastewater and
generate electricity [111–113]. MFCs are a promising technology that can convert chemical
energy in biomass or organic matter found in wastewater into electricity. It operates based
Water 2023, 15, 1455 19 of 29

on the principles of oxidation and reduction processes. They typically consist of two
chambers: an anode chamber (anaerobic/anoxic) and a cathode chamber (aerobic/oxic),
which are separated by a proton-exchange membrane or sufficient distance (Figure 5).
MFCs facilitate the degradation of organics or pollutants at the anode and generate
Water 2023, 15, x FOR PEER REVIEW 21 ofan31
electron flow through a series of redox potentials, where oxygen is reduced, and electricity
is produced [112].

Figure 5. Schematic diagram of the EC powered by MFC.

Figure 5. Schematic diagram of the EC powered by MFC.
Despite the advantages of using wastewater to generate energy, the voltage produced
by MFCs Despite the advantages
is limited. The maximum of using wastewater
theoretical to generatevoltage
open-circuit energy,that
the can
voltage produced
be generated
isby1.14
MFCs is limited.
V, which is theTheresultmaximum theoretical
of subtracting open−circuit
the oxygen redox voltage
potentialthat
(−can
0.32beV)generated
from the
is 1.14V,
NADH which
redox is the result
potential (+0.82ofV)subtracting
when oxygen the is
oxygen
used as redox potential electron
the cathode’s (−0.32V) acceptor.
from the
NADH redox
However, potentialapplications,
in practical (+0.82V) when theoxygen
working is used as the
voltage of cathode’s
the MFC electron acceptor.
is typically only
However,
between 0.2inVpractical
and 0.7 applications,
V. In order tothe working
increase thevoltage
overallof the MFC
voltage, is typically
MFCs only be-
can be stacked
tween 0.2V
together (i.e.,and 0.7V.
linked In order
together to increase
in series the overall
or parallel), voltage,
resulting in a MFCs
nearlycan be stacked
additive increase to-
ingether
total (i.e.,
voltage linked togetherThe
[114–116]. in series
stacking or parallel),
of pure MFCs resulting
has in
beena nearly additive increase
well-demonstrated with in
atotal
widevoltage
variety[114–116].
of examples The ofstacking
how the of power
pure MFCs has been
generated could well−demonstrated
be reused [116]. with MFCa
wide variety
stacks could beofclassified
examplesinoftwo how the power
ways: generated
electrical stackingcould be reusedstacking,
and hydraulic [116]. MFC with stacks
the
could be classified
connection arrangement in two ofways:
either electrical stacking and
of these approaches hydraulic
being either stacking, with the[116].
series or parallel con-
The resulting
nection power output
arrangement of either from the system
of these can bebeing
approaches used either
to runseries
electronic appliances
or parallel [116].andThe
sensors that require low levels of power. To improve the current
resulting power output from the system can be used to run electronic appliances and sen- output of MFCs, the
internal
sors thatresistance
require low needslevelsto of
be power.
reduced To[117,118].
improve In theacurrent
stackedoutput
configuration,
of MFCs,the theinternal
internal
resistance
resistanceof the MFC
needs to beisreduced
affected[117,118].
by factors Insuch as transport
a stacked resistance,
configuration, kinetic resistance,
the internal resistance
and ohmic
of the MFCresistance
is affected[117,118].
by factors such as transport resistance, kinetic resistance, and ohmic
There [117,118].
resistance has been only a very limited number of studies that have attempted to use
MFCsThere to powerhas beenEC. Theonlysystem
a very configuration
limited number is of
schematically
studies thatillustrated
have attemptedin Figureto use5.
Mei et al. (2019) explored the possibility of using an integrated
MFCs to power EC. The system configuration is schematically illustrated in Figure 5. Mei EC and MFC stack (three
MFCs connected
et al. (2019) in series)
explored to not onlyof
the possibility remove
using contaminants
an integrated but to achieve
EC and energy
MFC stack neutrality
(three MFCs
by using theinelectricity
connected series) toproduced by the MFC
not only remove stack to power
contaminants but tothe EC. Results
achieve energyshow that the
neutrality by
MFC
usingstack-powered
the electricityEC was ableby
produced to the
removeMFC93% of oily
stack organics,
to power the similar to theshow
EC. Results performance
that the
of an externally
MFC stack−powered (DC) powered
EC was EC. ableThe EC electrode
to remove 93% of area and
oily distancesimilar
organics, were found
to thetoperfor-
have
amance
significant impact on current generation and contaminant
of an externally (DC) powered EC. The EC electrode area and distance were found removal [56]. Safwat et al.
(2018) also investigated the potential for integrating MFCs and
to have a significant impact on current generation and contaminant removal [56]. Safwat ECs into a single system for
two types of wastewater treatment: synthetic wastewater and
et al. (2018) also investigated the potential for integrating MFCs and ECs into a single real municipal wastewater.
In contrast
system for totwo thetypes
studyofby Mei et al. (2019),
wastewater treatment:which connected
synthetic MFC stacks
wastewater and directly to EC
real municipal
via wires, thisIn
wastewater. study employed
contrast to thetwostudyrechargeable
by Mei etbatteries
al. (2019),to which
store the electricityMFC
connected generated
stacks
from
directly to EC via wires, this study employed two rechargeable batteries to storebatteries
the MFCs stacks (which were comprised of 6 cells connected in series). The the elec-
tricity generated from the MFCs stacks (which were comprised of 6 cells connected in
series). The batteries were then discharged once they were full, providing power to the
EC. The results showed that the system was able to effectively remove COD, TDS, and TSS
from both types of wastewater. The energy harvested from MFCs to power ECs was higher
Water 2023, 15, 1455 20 of 29

were then discharged once they were full, providing power to the EC. The results showed
that the system was able to effectively remove COD, TDS, and TSS from both types of
wastewater. The energy harvested from MFCs to power ECs was higher when using
synthetic wastewater. While the initial capital cost of the integrated system is high, it
is expected to significantly reduce operational costs compared to using ECs alone [57].
Nevertheless, the investigations referred to herein solely addressed the EC operations
carried out for brief periods of 7 h and 1 h in batch mode. The research used various MFCs
linked in series as energy sources, but there remains a gap in understanding the impact
that different numbers and modes of MFC connections may have. Consequently, further
research is imperative to study the energy pathways in MFCs and evaluate the EC system’s
long-term performance.

4.2.2. Power Supply via EW

MFC has the ability to convert more than 90% of bioenergy into electrical energy [113,119].
This encourages the exploration of larger-scale MFC-based systems that can extend the
technical and economic capability of MFCs [120]. The combination of a low-cost wastewater
treatment technology, constructed wetlands (CW), with MFCs [121–123], has been termed
CW-MFC [123,124], METland [125], bioelectrochemical-wetland [120] and electroactive
wetland [112], and electro-wetland (EW) [126]. EW shares a similar configuration as MFCs,
whereby the naturally existing stratified redox conditions in EW are highly consistent with
the requirements for MFCs. EW typically consist of electrodes, substrate material, and
plants (Figure 6). The cathode is typically placed in the aerobic zone or on the surface as
an air cathode, while the anode is embedded deep in the anaerobic zone. Substances such
as alum sludge, activated carbon, and graphite are the most commonly used materials
and have been proven to improve the efficiency of these systems through biogeochemical
processes [127]. Plants are also one of the key components in the system and are typically
located in the cathode area, with their roots embedded in the substrate [128]. The elec-
troactive bacteria presented in the system break down organic matter at the anode and
produce electrons that flow through external electric wires to the cathode [112,123,127].
In the cathode area, oxygen is used as the most common electron acceptor. In reduction
reactions at the cathode, hydrogen peroxide, a strong oxidizing substance, can be produced
as a by-product and used to enhance the efficiency of pollutant removal [113]. This electron
transfer creates a potential difference between the anaerobic and aerobic regions, which
allows for electricity generation in EWs [112,113,121].
Given the sustainability and wastewater treatment capabilities of EWs, it is important
to carefully consider which applications of this ‘green energy’ technology would be suitable
for retrofitting existing EWs. During the last few years, the power output of EWs has been
significantly improved [126,129,130]. However, the volumetric power densities of EWs
are still in the milliwatts range [131]. The power density of EWs tends to be lower than
MFCs, as a result of the large ohmic losses due to the internal resistance increment and the
electrode potential losses (activation losses) [132]. Therefore, a greater electricity-generation
performance may be achieved through the direct utilization of the bioenergy produced.
Some researchers have suggested that the limited energy recovered from wastewater
in EWs could potentially be used to power small electronic devices [57,133], such as
bioelectrochemical/electrochemical systems. Xu et al. (2019) also mentioned that the
energy produced by EW could possibly offset the energy consumed in the process, such
as supporting bio-current to in situ or ex situ electrically related treatment process for
electro-Fenton or bio-electrolysis process.
The application of EWs as power sources is currently very limited, with only two
related studies reported. A proposed system configuration is schematically illustrated
in Figure 6. Zhang et al. [134] used EWs stacks (2 cells connected in series) to power a
bio-electrochemical system (BES) for sulfamethoxazole (SMX) removal. The results showed
that EWs could provide enough stable electricity (between 0.84 and 1.01 volts) to support
the BES in breaking down SMX without the need for additional energy. The low current
 substrate material, and plants (Figure 6). The cathode is typically placed in the aerobic
zone or on the surface as an air cathode, while the anode is embedded deep in the anaer-
obic zone. Substances such as alum sludge, activated carbon, and graphite are the most
commonly used materials and have been proven to improve the efficiency of these sys-
Water 2023, 15, 1455 tems through biogeochemical processes [127]. Plants are also one of the key components21 of 29
in the system and are typically located in the cathode area, with their roots embedded in
the substrate [128]. The electroactive bacteria presented in the system break down organic
matter at the anode and produce electrons that flow through external electric wires to the
levels powered by CW-MFCs did not impact the degradation products but did increase the
cathode [112,123,127]. In the cathode area, oxygen is used as the most common electron
rate of SMX removal [134]. Another study was conducted by Srivastava et al. [135], which
acceptor. In reduction reactions at the cathode, hydrogen peroxide, a strong oxidizing
explored the use of a power management system (PMS) to store the power output of EWs
substance, can be produced as a by−product and used to enhance the efficiency of pollu-
and boost voltage to power a small air pump for providing oxygen in the cathode area of
tant
the EWremoval
system.[113].
WithThis electron transfer
intermittent aeration,creates a potential
the maximum difference
power between
generation theof
by one anaer-
the
obic and aerobic regions, which allows for electricity generation in EWs [112,113,121].
EW increased from 54.6 µW to 90 µW, and ammonium removal increased by 10% [135].

Figure 6. Schematic diagram of the EC powered by EW.

Figure 6. Schematic diagram of the EC powered by EW.
EC applies the micro-electrical current to remove contaminants in an aqueous environ-
ment and therefore presents the best possibility to use the power generated from EW [136].
It is reasonable to assume that the utilization of EW for powering EC could be an effective
way to reduce not only the cost of energy consumed by EC but also to maintain the high
treatment performance of both processes.

4.3. Unilizaiton of Power Management Systems in EC

A power management system (PMS) is an electronic circuit that harvests energy from
an MFC/EW and shapes it into a usable form [137]. The system could capture and store
the unstable and limited power output from MFCs/EWs and boost voltage to a relatively
higher and constant level in a certain range [116,138], and subsequently prevent voltage
reversal occurring in stacked MFCs/EWs during long-time reactions [138]. The system
usually consists of a harvesting system, including maximum power point (MPP) tracking
and an energy storage unit by means of supercapacitors [135]. It is different from external
resistors, which only show energy output potential but do not capture usable energy, as
the current flowing through the resistor is lost as heat [137,138]. Thus the combination of
PMS with MFC-based technology is essential for the functioning of EC and provides the
possibility of creating a self-sufficient power supply for EC throughout the duration of a
long-term reaction.
As mentioned before, a rise in the current density in EC leads to more efficient re-
moval. The current density also affects the bubble production rate and size [13,60,61]. A
standard potential (1.229 V) between the cathode and anode is necessary to carry out water
electrolysis in EC, resulting in floatation and enhanced treatment performance. Hence
when considering using MFC/EW to power EC, the working voltage has to be sufficient
Water 2023, 15, 1455 22 of 29

to ensure the treatment performance of EC. Considering that the power generated from
a single cell of EW is limited, using a stack of modular EWs could potentially increase
the total voltage generated and make it sufficient to power low-energy devices [57,139].
However, the bio-current generated in MFCs/EWs relies heavily on the bioactivities of
bacteria, which vary with reaction performance conditions. Increased power production
cannot be achieved simply by constructing larger MFCs/EWs or connecting MFCs/EWs
in series or parallel, owing to the non-linear characteristics of MFCs/EWs [138]. Stacked
modular EWs often experience an unpredictable voltage reversal when some of the unit
cells act as power-supplying batteries and others as power-consuming loads [140–142].
The PMS has been used with MFCs in previous studies for practical usage. Wang et al. [138]
gave a detailed description of these updated PMS for pure MFCs, and summarized them
as three energy-harvesting processes: (a) a concise process from MFCs (energy generator)
to electronic devices (energy consumer); (b) a classic and widely adopted PMS circuit
composed of a charge pump and a boost converter with accessory components; (c) a two-
layer energy-harvesting scheme, which is operated in alternative ‘charge’ and ‘discharge’
phases [138].
So far, the use of PMS with EWs is very limited, and there have only been two related
studies published. Xu et al. [129] first reported tests of a novel strategy of PMS, called a
capacitator-engaged duty cycling (CDC) strategy, to harvest energy from an open-air bio-
cathode EW. An investigation was conducted to compare the energy harvest performance
of three working regimes: (1) continuous loading mode (CL), a continuous connection
of external resistor to the circuit; (2) duty-cycling mode (DC), intermittent loading of an
external resistor; and (3) CDC, intermittent consumption of energy stored in three external
capacitors (4700 µF) through an external resistor. The results indicate that the CDC strategy
(intermittent energy consumption) leads to a 19.81% higher effective charge than the CL
(continuous loading) mode at a duty cycle value of 31.6%. With a lower duty cycle of
20%, the total charge harvested increases by 25.0%. This study is the first to use PMS to
harvest energy in EW systems, which have not previously dealt with the application of
energy from EW. Srivastava et al. [135] unitized a PMS with two supercapacitors (55 F) to
harvest and boost voltage from EWs, and to power a small air pump to provide oxygen to
the cathode area in EWs. With the connection of PMS, the voltage of EWs (394 ± 53 mV
and 307 ± 34 mV) was boosted to 1.7 V to power the air pump. The ammonium removal
and power generation of EW were subsequently increased. However, the initial energy
harvested took a long time (60 days) to reach the start-up voltage of 1.5 V. Once 1.5 V was
reached, the air pump was connected to the circuit, but every 60 s of aeration required
6 days of harvest time to withdraw power from the EW. Further studies are needed to focus
on the optimization of the PMS circuits, including smaller supercapacitors and a lower
start-up voltage to improve the system.

5. Research Gap and Further Research Direction of EC

Considering the complexities and high investments in supplying commercial energy
to a field site, the application of EC in remote locations is limited [136]. Previous studies
have explored renewable energy sources, such as photovoltaic energy, wind energy, or
hydroelectricity. However, the power-generation rate of these energy systems is largely
influenced by natural conditions, such as geographical latitude, sunlight intensity, wind
speed, gravitational potential, land area, hydraulic loading, and other similar factors. The
high cost of implementation of such technologies has limited their application [66], espe-
cially for powering electrochemical treatment processes like EC, which has only limited
lab-scale studies published. Therefore, integration with compatible and economical bioen-
ergy technologies (e.g., MFCs or EW) seems necessary and important. Compared with
other power sources (e.g., fossil fuels, solar photovoltaic, wind turbines, hydroelectricity
power), EW/MFC could recycle the ‘green’ energy in wastewater and output as electricity
energy, which owns more advantages of sustainability, easy construction/maintaining, and
lower investment. Therefore, EW/MFC may act as a capable and green energy source of
Water 2023, 15, 1455 23 of 29

EC for water/wastewater treatment in a field or rural area. There are only a few studies
of EC powered by MFC and no published studies of EW powering EC. As such, further
development is highly desirable for this proposed approach. The PMS and stacking EWs
could be considered to manage and improve the energy output. Furthermore, energy flow
pathways between the electron accepters and electron donor and their contribution on
pollutants removal and power generation/consumption in systems should be identified.
EC systems are designed to remove pollutants using electrochemical processes only,
without relying on biological processes. While this approach is effective in removing many
pollutants, it may face practical limitations when it comes to removing new biodegradable
and soluble organic pollutants. To overcome this limitation, the EC process can be combined
with other biological treatment technologies to improve the efficiency of pollutant removal.
It is crucial to select the appropriate combination of treatments to ensure optimal results.
Systems that rely on bio-electrochemical processes, such as EW or MFC, can serve as suitable
external power sources for EC systems, but they are susceptible to toxic or recalcitrant
pollutants. Hence, combining EC and EW/MFC systems into a self-powered hybrid system
can effectively enhance water-treatment performance and achieve energy neutrality in a
single treatment process (Figures 5 and 6). This combination of processes can be utilized
to optimize treatment efficiency by allowing the removal of toxic pollutants before the
EW/MFC stage, followed by the removal of biodegradable contaminants that may still
be present after the EC pre-treatment stage. The proposed method could also serve as
a sustainable alternative for treating complex wastewater, especially in scenarios where
electricity is scarce or when dealing with field applications. At present, there is a dearth of
literature on the feasibility of a hybrid EC-EW/MFC system. Hence, it may be necessary to
conduct a feasibility study on the combination of these technologies. To ensure protection
of the environment and human health, it is crucial to focus on the removal of emerging
pollutants, such as antibiotics, pesticides, surfactants, and endocrine-disrupting compounds
(EDCs). These compounds are likely to be subject to increasingly stringent water treatment
regulations and thus require further attention.

6. Conclusions
EC is a highly efficient and environmentally friendly technology for removing con-
taminants from water and wastewater. This review offers valuable insights into the current
state of EC technology and highlights opportunities for further research and development.
The paper presents an overview of the advantages and limitations, fundamental mech-
anisms, and operational factors of EC. To determine the current state of EC research, a
comprehensive literature search was conducted using the Scopus database, and relevant
keywords were analyzed and classified using VOSviewer software. The review highlights
new developments in EC, including the removal of emerging pollutants, the use of MFC
and EW for power supply, and the application of PMS in EC. The paper concludes with a
discussion of future research opportunities, including:
• Optimizing operating conditions of EC to achieve both low power consumption and
high removal efficiency;
• Exploring the techno-economic feasibility of coupling EC and EW/MFC systems;
• Identifying the energy pathways and energy application/management of hybrid systems;
• Focusing on the effective removal of emerging pollutants using a hybrid EC system.

Author Contributions: Conceptualization, Y.M. and Y.Z.; literature review, Y.M. and Y.Z.; software,
Y.M.; formal analysis, Y.M.; writing—original draft preparation, Y.M.; writing—review and editing,
Y.Z. and S.C.; visualization, Y.M., Y.Z. and S.C.; supervision, Y.Z. and S.C. All authors have read and
agreed to the published version of the manuscript.
Funding: The first author acknowledges financial support from the China Scholarship Council and
University College Dublin, Ireland, for the Ph.D. scholarship.
Water 2023, 15, 1455 24 of 29

Data Availability Statement: All data presented in this study will be available upon request to the
corresponding author via email.
Conflicts of 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.

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