Available online at www.sciencedirect.

com Current Opinion in

ScienceDirect Electrochemistry

Review Article

Electrochemical production and use of chlorinated

oxidants for the treatment of wastewater contaminated
by organic pollutants and disinfection
Onofrio Scialdone, Federica Proietto and Alessandro Galia

Abstract oxidants can be effectively produced by anodic oxidation

In the last years, an increasing attention has been devoted to of chlorides (electrochlorination) such as sodium chlo-
the use of electrogenerated chlorinated oxidants for the treat- ride, which is a rather cheap reagent often present in
ment of wastewater polluted by recalcitrant organics and/or for liquid effluents [1e6]. Furthermore, it has been
the disinfection of water contaminated by pathogen microor- demonstrated that the removal of organics and pathogen
ganisms. In this review, more recent and relevant findings were microorganisms is particularly effective when carried out
presented and critically discussed. The main advantages and in the same electrochemical cell where the oxidants are
disadvantages of this technique were commented, including generated. However, these methods present some
the potential formation of toxic chlorinated organic specie and relevant disadvantages, such as a difficult selection of
of chlorate and perchlorate or the difficult selection of proper most suitable operative conditions and, in particular, of
operative parameters, as well as the key points that should be the nature of the anode and the formation of chlorinated
addressed to enhance the use on an applicative scale. toxic compounds, that should be still completely solved.
In the last years, some interesting results were obtained
Addresses in this frame, but additional efforts are necessary to
Dipartimento di Ingegneria, Università degli Studi di Palermo, Palermo
enhance the applicative perspectives of this tool, as
90128, Italy
synthetically described in this review.
Corresponding author: Scialdone, Onofrio (onofrio.scialdone@unipa.
it)
Anodic oxidation of chlorides
As mentioned previously, reactive chlorides species,
Current Opinion in Electrochemistry 2021, 27:100682 which actively participate in the oxidation of organics
This review comes from a themed issue on Electrochemical Technol-
and of pathogens, can be electrochemically generated
ogies for Wastewater Treatement from chloride ions. The anodic oxidation of chlorides
Edited by Carlos A Martínez-Huitle, Manuel Andres Rodrigo and
involves a multistep reaction that can be synthetically
Ignacio Sirés represented by eq. (1) [1e6]. As reported in eq. (2),
For a complete overview see the Issue and the Editorial
dissolved chlorine may undergo a disproportionation
reaction, depending on the proton and chloride con-
Available online 2 January 2021
centrations, forming chlorides and hypochlorous acid, a
https://doi.org/10.1016/j.coelec.2020.100682 weak acid (pKa 7.5), that is in equilibrium with ClO

2451-9103/© 2021 Elsevier B.V. All rights reserved. (eq. (3)).

Keywords 2Cl
/ Cl2ðaqÞ þ 2e
(1)

Electrochlorination, Active chlorine species, Wastewater treatment,
Disinfection, Toxic chlorinated compounds.
Cl2ðaqÞ þ H2 O/HClO þ Hþ þ Cl
(2)

Introduction
During the recent years, one of the relevant emerging HClO%H þ ClO
(3)
topics is the development of new technologies to restore
the quality of contaminated water due to the water
scarcity which is one of the main concerns of this cen- The relative concentrations of Cl2, HClO, and ClO

tury. In this context, many kinds of waters, contami- depend on the pH solution value: Cl2 prevails at very
nated by organic pollutants resistant to conventional low pH, HClO in moderate acidic conditions, and ClO

biological processes and/or by pathogen microorganisms, in basic conditions. Furthermore, at low pH the forma-
can be treated by chlorinated oxidants, such as chlorine tion of chlorine bubbles can occur. If wastewaters are
or hypochlorous acid. In the past decades, a very large treated in the same electrochemical cell where the
number of scientific studies have shown that these chlorinated oxidants are generated, higher abatements

www.sciencedirect.com Current Opinion in Electrochemistry 2021, 27:100682

2 Electrochemical Technologies for Wastewater Treatement

of the pollutants [7e10] and more lethal impact on oxidation of water results in the formation of chem-
bacteria [9e12] are achieved with respect to that ob- isorbed hydroxyl radicals), usually give lower current
tained using chlorinated oxidants in separated reactors. efficiencies than nonactive ones, such as SnO2, boron-
Indeed, organics can be oxidized also at the anode sur- doped diamond (BDD) or PbO2 (where the anodic
face by adsorbed chloro and oxychloro radicals, as shown oxidation of water results in the formation of physical
in Figure 1, and various other reactive oxygen species, adsorbed hydroxyl radicals). Conversely, in the presence
including HO, H2O2 and O
2 , produced by water of high concentrations of chlorides, among metal oxides,
anodic oxidation, can contribute to both oxidation of active anodes, such as Ir- and Ru-based electrodes,
organics and disinfection [13,14]. usually give higher current efficiencies than nonactive
ones, such SnO2 and PbO2 [3]. In this frame, Garcı́a-
Chlorides can be converted not only into active chlorine Espinoza et al. [27] have shown that, for a concentration
[15], but also in Cl2O and ClO2 by chemical or anodic of NaCl of 14 mM, BDD gave a faster production of
routes (eqs. (4) and (5)) that can contribute as well to active chloride with respect to IrO2. However, Scialdone
the organics oxidation and to disinfection. et al. [28] found that, in the presence of high concen-
trations of NaCl and high current densities, higher
Cl
þ 2H2 O/ClO2 þ 4Hþ þ 5e
(4) current efficiencies for the removal of organics can be
obtained at Ir-based anodes with respect to that
achieved at BDD.
2Cl
þ 2H2 O/Cl2 O þ 2Hþ þ 4e
(5)
More in general, provisional results present in the
literature indicate that, for large amounts of chlorides
In particular, ClO2 is a powerful oxidant which, unlike and organic pollutants easily oxidized by electro-
chlorine, does not lead to the formation of chlorinated generated active chlorine, metal oxide anodes (particu-
byproducts [17,18] while Cl2O is likely to be one of the larly active anodes, such as RuO2 and IrO2) seem more
most active species [19]. suitable due to the high current efficiency for the active
chlorine generation, the low formation of chlorate and
Oxidation of organics and disinfection perchlorate (as detailed in the following section), high
It has been shown that electrogenerated active chlorine porosity, as well as relatively low costs. Conversely, for
can be used effectively, using suitable anodes and organics resistant to active chlorine, the utilization of
operative conditions, for various kinds of waters
including industrial wastewaters with highly refractory Figure 1
organics and high salts content [20], reverse osmosis
concentrates [21], landfill leachates [22], wastewater
contaminated by pharmaceutical residues, olive-mill,
dairy and textile wastewater [23,24], tannery effluents
[25], drinking [26] and seawater [59], and so on.
Furthermore, it has been shown that electrogenerated
active chlorine can inactivate a large variety of micro-
organisms ranging from bacteria to viruses and algae
[12].

The performances of these processes drastically depend

on various operating conditions including the nature of
the anode. In particular, metal oxide anodes yield usually
higher removal of organic pollutants with respect to
graphite and Pt. To better evaluate the role of the anode
(and in particular of metal oxide ones), it is worth to
mention that in the absence of chlorides, the organics
oxidation and the disinfection takes place mainly by
hydroxyl radicals generated by the anodic oxidation of
water (eq. (6)) [3].

H2 O / HO$ þ Hþ þ e
(6) Scheme of main reaction pathways for the electrochemical oxidation of
organics in water in the presence of chlorides [16]. Reprinted with
permission from Martínez-Huitle CA, Rodrigo MA, Sirés I, Scialdone O:
Single and coupled electrochemical processes and reactors for the
In particular, in the absence of chlorides, active anodes, abatement of organic water pollutants: a critical review. Chem Rev 2015,
such as Ir- and Ru-based electrodes (where the anodic 115:13362–13407. Copyright 2015 American Chemical Society.

Current Opinion in Electrochemistry 2021, 27:100682 www.sciencedirect.com

 Electrochemical generation and use of chlorinated oxidants Scialdone et al. 3

nonactive anodes (such as BDD), which are particularly involving the hydroxyl radicals generated by the oxida-
effective for the mineralization of a very large number of tion of water [43e46] as shown in eqs. (8) and (9).
very resistant organic pollutants, would be preferable if
the formation of toxic chlorinated products can be ClO
þ 2HO$/ClO3
þ 2Hþ þ 2e
(8)
avoided. For what concerns the disinfection, it has been
shown that various anodes can be used, involving IrO2-
and RuO2-based anodes and BDD, and, in particular, the CIO3
þ HO$/CIO4
þ Hþ þ e
(9)
employment of BDD guarantees a relevant inactivation
of microorganisms [13].
In order to enhance the applicability of electrogenerated
It was also demonstrated that many other operating active chlorine, it is mandatory to find a set of operative
parameters affect the removal of organics and pathogen conditions that allows to remove organic pollutants and/
microorganisms including pH, nature and concentration or minimize pathogen microorganisms avoiding or
of organic pollutants, current density, and flow dynamic minimizing the formation of toxic chlorinated
conditions. In particular, it has been shown that the compounds.
effect of one parameter often depends on the value of
other ones [3]. Hence, in many cases, the optimization It was shown that the formation of perchlorate strongly
of this process for a new case is rather complex, even if it depends on the nature of the anode; in particular, BDD
can be helped by the knowledge of the main removal gave drastically higher perchlorate formation with
mechanisms and of pertaining literature [16]. respect to Pt- and IrO2-based anodes [26]. Furthermore,
a significantly higher formation of total HAAs and
THMs was observed using BDD anode with respect to
Formation of toxic chlorinated compounds that achieved at both Ti/SnO2eSb and Ti/PteIrO2 for a
One relevant problem of electrochemical treatment by
similar charge passed for the electrochemical treatment
electrogenerated active chlorine consists in the poten-
of reverse osmosis concentrate [47]. In the case of Pt/Ti
tial formation of undesired toxic chlorinated de-
anodes, the formation of ClO


3 and ClO4 increased with
rivatives, including highly toxic chlorinated amines

the initial Cl concentration and with the pH [42].
[29,30], trihalomethanes (THMs), haloacetic acids
Schaefer et al. [56] have shown, in the case of the
(HAAs) [21,31e34], chlorinated oligomers [55] and
disinfection of surface waters at Ti/IrO2 anode, that
ClO


3 and ClO4 , which are suspected of exerting toxic effective disinfection can be obtained at this anode
effects on humans [35,36]. The formation of undesired
without regulatory exceedances in TTHMs, HAAs, or
halogenated organic compounds is due to reactions of
perchlorate focusing on the use of low current densities
substitution and addition between the organics and the
(0.25 or 1 mA/cm2). This group has also confirmed that
active chlorine species (Figure 2) and/or chlorine radi-
the formation of HAAs and THMs can be limited under
cals [37].
regulatory levels (THM and HAA5 levels generally
below 10 mg/L) for a 6-month pilot-scale for surface
As an example, the treatment by electrogenerated
water at Ti/IrO2 anode (surface: 500 cm2) with batch
active chlorine of a mixture of dyes with a Ti/TiO2-
treatment cycles of 49 min and a current density of
RhOx anode in 100 mM NaCl at pH 4.0 gave rise to
8 mA/cm2 [57].
the formation of a high number of mono/dichlori-
nated intermediates, such as 2-chloroethenylbenzene,
It is worth to mention that the perchlorate production
2-chloro-2-methylbutane, cis-3-chloropropanate, cis-
at BDD was decreased using a lower current density
1,3-dichlor-ocyclopentane, and trans-1,2-
and a higher flow rate, that can, however, give rise to
dichlorocyclopentane [39]. Similar results were
slower removals of pollutants [26], and a higher con-
found by many other authors; although, in many of
centration of organics [46] that causes a depletion of
these cases, organochlorinated compounds were pro-
hydroxyl radicals. In particular, for BDD anodes, the
gressively removed at long electrolysis times
group of Serrano [48] has shown that, if the applied
[10,34,38e41].
current density is close to the limiting current density,
chlorides were oxidized almost only to hypochlorite;
According to various studies [35,42], chlorate and
conversely, at higher current densities than that the
perchlorate are generated via a multistep oxidation
limiting one, ClO
was converted in ClO
4 . Similarly,
pathway from chloride, as shown in reaction (7).
the group of Rodrigo has shown that, during the
disinfection of an effluent of a municipal wastewater
Cl
/ OCl
/CIO2
/CIO3
/CIO4
(7) treatment plant by electrolysis at BDD anodes, the use
of low current densities avoids the formation of
perchlorate [49]. Furthermore, these authors have
Moreover, on some anodes (such as BDD) the formation shown that CHCl3, C2H4Cl2, C2HCl3, CHBrCl2,
of perchlorate may proceed also through reaction paths CHBr2eCl, C2Cl4 and CHBr3 concentrations were

www.sciencedirect.com Current Opinion in Electrochemistry 2021, 27:100682

4 Electrochemical Technologies for Wastewater Treatement

below the detection limit of the technique used Advantages and disadvantages and key
(2 ppb) at any electrolysis-time. aspects to be addressed
On overall, the treatment of wastewater contaminated
Another possible strategy to avoid the formation of by organic pollutants and/or pathogen microorganisms
chlorates and perchlorates may consist in the use of by electrogenerated active chlorine at suitable anodes
undivided cells equipped with carbon felt cathodes. presents various advantages with respect to chemical
These electrodes favor the cathodic reduction of oxygen chlorination routes. First, a fast removal of organic
to hydrogen peroxide that can, from one hand, matter and microorganisms occurs in the electro-
contribute to the oxidation of organic pollutants and to chemical cell due to the presence of various oxidation
the disinfection and, from the other hand, favor the routes, involving both the homogeneous phase and the
conversion of chlorates to chlorine dioxide. Indeed, as anode surface; second, the avoidance of transport and
reported by the group of Rodrigo [50], chlorine dioxide storage of dangerous chlorinated oxidants; and, third,
is considered a good disinfectant and oxidant with no the decrease of overall costs caused by the low operation
tendency to form disinfection by-products for both DSA costs that compensates the higher investment costs. In
and BDD anodes. In this frame, since the cell design is a this frame, it is useful to remember that the electrolytic
key factor [51e54], recently, the group of Rodrigo pro- production of such oxidants became more interesting in
posed another route to avoid the formation of chlorate the last years, due also to the decrease of the electric
and perchlorate consisting in the use of a PEM- energy cost in many countries and the availability of
electrolyzer, equipped with diamond anodes, which in- electrodes with good performances.
volves very short hydraulic residence time [54]. As an
alternative route, the group of Urtiaga has proposed the This method presents some advantages also with
potential utilization of a hybrid process that uses an respect to direct electrochemical oxidation (carried out
adsorption step onto activated carbon to remove the in the absence of chlorides) such as (i) the potential use
THMs generated in the electro-oxidation cell [58]. of less expensive electrodes with respect to BDD ones

Figure 2

Scheme of main reaction pathways for the reaction between organic aromatic compounds and active chlorine [4]. Reprinted with permission from Ganiyu
SO, Martínez–Huitle CA: Nature, mechanisms and reactivity of electrogenerated reactive species at thin-film Boron-Doped Diamond (BDD) electrodes
during electrochemical wastewater treatment. ChemElectroChem 2019, 6:2379–2392. Copyright 2019 Wiley–VCH Verlag GmbH & Co. KGaA,
Weinheim.

Current Opinion in Electrochemistry 2021, 27:100682 www.sciencedirect.com

 Electrochemical generation and use of chlorinated oxidants Scialdone et al. 5

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