Accepted Manuscript

“Electrochemical oxidation of organic pollutants for wastewater

treatment”

Carlos Alberto Martı́nez-Huitle , Marco Panizza

PII: S2451-9103(18)30121-2
DOI: 10.1016/j.coelec.2018.07.010
Reference: COELEC 291

To appear in: Current Opinion in Electrochemistry

Received date: 12 June 2018

Revised date: 12 July 2018
Accepted date: 13 July 2018

Please cite this article as: Carlos Alberto Martı́nez-Huitle , Marco Panizza , “Electrochemical oxida-
tion of organic pollutants for wastewater treatment”, Current Opinion in Electrochemistry (2018), doi:
10.1016/j.coelec.2018.07.010

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 ACCEPTED MANUSCRIPT

Highlights
 Outlooks of emerging electrochemical processes for the treatment of wastewaters
 Recent development of anodic oxidation via intermediates of oxygen evolution
 Indirect electro-oxidation mediated by electrogenerated active chlorine
 Emphasis on cathodic processes such as electro-Fenton and photo electro-Fenton
 Perspectives and new directions of electrochemical oxidation approach

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“Electrochemical oxidation of organic pollutants for wastewater treatment”

Carlos Alberto Martínez-Huitle1,*, Marco Panizza2,*
1
Institute of Chemistry, Federal University of Rio Grande do Norte, Lagoa Nova CEP 59078-970 -
Natal, RN, Brazil
2
Department of Civil, Chemical and Environmental Engineering, University of Genoa, Via Opera
Pia 15, 16145 Genoa, Italy.
Corresponding authors: [email protected], [email protected]
Tel/Fax.: +55 (84) 3211-9224

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Abstract
This review supplies a current opinion about the most recent works, which have been carried out

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toward the electrochemical oxidation (EO) of organic pollutants for water treatment. In particular,
the first section is focused on the direct EO or anodic oxidation, and the indirect EO by

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electrogenerated active chlorine, the most important mediated process. Meanwhile, the second
section describes the use of promising cathodic processes as well as the recent progress of emerging
photoassisted electrochemical treatments such as photoelectro-Fenton and solar electro-Fenton. The
outlooks of these emerging processes for the upcoming future finally conclude this mini-review.

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Keywords: electrochemical oxidation, water treatment, emerging electrochemical technologies,
novel targets, perspectives, renewal energies, high value added products.
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1. Introduction
Over the past decades, great progress has been made on the electrochemical technologies for the
treatment of effluents containing organic pollutants. In fact, electrochemical technologies offer an
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alternative solution to many environmental problems in the process industry, because electrons
provide a versatile, efficient, cost effective, easily automatable and clean reagent [1-8].
The electrochemical oxidation (EO) of organics for wastewater treatment can be attained in
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different ways (Fig. 1a):

(i) Direct EO, where electron transfer occurs at the electrode surface without participation of other
substances [1, 2];
(ii) Indirect EO where organic pollutants are oxidized through the mediation of some electroactive
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species generated at the anode surface, which act as intermediaries for electrons shuttling between
the electrode and the organic compounds [1-6].
In the indirect electrolysis, the redox reagent can be electrogenerated by either anodic or cathodic
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process. The most popular technique among cathodic processes is the electro-Fenton (EF), in which
H2O2 is generated at the cathode with O2 or air feeding while an iron catalyst is also regenerated on
the cathode surface [2] (Fig. 1b). Recently, other emerging technologies based on EF method [6-9]
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(Fig. 1b), such as photo-EF (PEF), solar-PEF (SPEF), coagulation based on dissolution of iron
anodes (peroxi-coagulation (PC)), ultrasound irradiation (sono-EF), dissolution of heterogeneous
catalysts that supply Fe2+ (Heterogeneous-EF) and bioremediation (bio-EF), have also received
great deal of attention. Process selection depends on the nature and structure of the electrode
material, experimental conditions, and electrolyte composition.

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Figure 1. A conceptual approach to (a) direct EO and mediated EO; (b) EF-based technologies as
well as electrochemical emerging wastewater treatments; (c) the 2.5 L pre-pilot plant (1) single one-
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compartment filter-press electrochemical cell with a BDD anode and an O2-diffusion cathode, both
of 20 cm2 exposed area, used for the SPEF degradation of organic pollutants in acid medium, (2)
power supply, (3) solar photoreactor, (4) reservoir, (5) peristaltic pump, (6) flowmeter and (7) heat
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exchangers. Adapted from ref. [72]. Copyright 2007, with permission from Elsevier; and (d) the use
of renewable energy sources together with electrochemical treatments (driven by wind and by
sunlight).
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Hence, this mini-review focuses on the very recent progress in the electrochemical processes for the
oxidation of organic pollutants, discussing the most important approaches and critically presenting
their advantages and limitations.
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2. Anodic oxidation
2.1 Oxidation via intermediates of oxygen evolution
Anodic oxidation is theoretically possible at low potentials, before oxygen evolution, but in these
conditions, the surface is rapidly deactivated due to the deposition of a polymeric layer on it on the
anode surface, that is commonly called the poisoning effect. This deactivation depends on the
adsorption properties of the anode surface and the concentration and the nature of the organic
compounds.
The poisoning effect can be avoided by performing the oxidation in the potential region of water
discharge due to the participation of intermediates of oxygen evolution:
M + H2O → M (OH) + H+ + e- (1)

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R + M (OH) → M + CO2 + H2O (2)

where M is the metal surface and R is organic specie. The efficiency of the process is affected by
operating conditions and above all by the nature of the electrode material. In particular anodes with
low oxygen evolution overpotential, such as IrO2, RuO2 or Pt have “active” behavior and favor the
partial and selective oxidation of pollutants (i.e. electrochemical conversion), while anodes with
high oxygen evolution overpotential, such as SnO2, PbO2 or boron-doped diamond (BDD) have
“non-active” behavior and so are ideal electrodes for the complete electrochemical oxidation of
organics to CO2 in wastewater treatment. Some examples of organic compounds treated using
different anodes are shown in Table 1.
In particular, BDD electrodes has received great attention because these non-active anodes exhibit
good chemical and electrochemical stability, a long life and a wide potential window for water

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discharge, and are thus promising anodes for industrial-scale wastewater treatment. Using BDD
anodes, many synthetic and real effluents were completely mineralized with high efficiency, even

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100% [1-8].
For example, Cotillas et al. [10, 11] studied the removal of Procion Red MX-5B dye from

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wastewaters using BDD anode in different experimental conditions. They reported that the initial
dye content and chemical oxygen demand (COD) were completely removed and the process
efficiency increases when low current densities were used, as well as natural pH and high flow
rates.

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Very recently, new sub-stoichiometric titanium oxide (Ti4O7) was proposed as new cost-effective
anode material for electrocatalytic oxidation of organic pollutants [12]. For example, during the
degradation of paracetamol, Ti4O7 achieved higher total organic carbon (TOC) removal efficiency
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than dimensionally stable anode (DSA), but slightly lower removal efficiency than boron-doped
diamond anode (BDD).

Table 1: Examples of the direct EO.

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Pollutant Anode Comments Ref

Real wastewater BDD Use of conventional cell microfluidic cell with or [13]
with low without supporting electrolyte.
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conductivity
Secondary-treated BDD Low charge was required to attain a total depletion of [14]
wastewater living E. coli.
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Urine BDD Complete disinfection with a consumption of [15]

2 kAh m−3
Real washing BDD and Pt BDD showed higher removal efficiency than Ti/Pt. [16]
machine effluent
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Cashew-nut DSA and BDD BDD and DSA enabled 100% and 72% of COD [17]
processing industry removal, respectively.
Pharmaceuticals BDD Degradation of ciprofloxacin, sulfamethoxazole and [18]
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salbutamol. A theoretical model was proposed.

Treatment Microcyst BDD Electrolyzes performed in continuous and in batch [19]
is aeruginosa recirculated mode.
Coumarin BDD A synergistic effect observed when UV irradiation and [20]
BDD were used together.
Ferulic acid BDD Energy consumption of 9.5 kWh m−3 for complete [21]
COD removal.
Winery wastewater BDD Total mineralization and disinfection of organics from [22]
real winery wastewater by anodic oxidation.
Safranin T BDD Use of solid polymer electrolyte. [23]
Norfloxacin BDD, Sb-SnO2 Norfloxacin was efficiently oxidized over both anodes. [24]
Perfluorooctanoic PbO2 92.1% of perfluorooctanoic acid degradation was [25]
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Acid achieved in 180 min at i= 40 mA cm–2.

Perfluorooctane PbO2 A removal ratio of 74.87% with a pseudo first-order [26]
Sulfonate kinetic constant of 0.0165 min−1.
Metronidazole Co-PbO2 Organic and COD removals of 78.09% and 21.77%, [27]
respectively.
Acid Blue 113 TiO2-nanotubes Comparison between Ti/Pt, Pb/PbO2 and Ti/TiO2- [28]
with PbO2 nanotubes/PbO2 anodes. Ti/TiO2-nanotubes/PbO2 is an
efficient non-active anode.
Aspirin La-Y-PbO2 La-Y-PbO2 electrode had higher COD and TOC [29]
removals than PbO2, La-PbO2 and Y-PbO2 anodes.
Phenol Ti/SnO2-Sb Phenol and COD abatements of 100% and 85%, [30]

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respectively.
Perfluorooctane Ti/Sb-SnO2 Organic removal higher than 99% in 120 min. [31]

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Pyridine Ti/Sb-SnO2 Pyridine removal of 98% under the optimal conditions. [32]
Tetracycline Ti/Sb-SnO2 The degradation efficiency increased with the applied [33]

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current and decreased with the inter-electrode
distance.
Propanolol Ti4O7 Efficient mineralization of propranolol with Ti4O7, [34]
compared to DSA anode.

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2.2 Indirect oxidation
The idea of indirect electrolysis is to prevent electrode fouling, avoiding the direct electron transfer
between organics and anode surface. Therefore, in indirect electrolysis, pollutants are oxidized in
the bulk of the solution by means of oxidants electrochemically generated on the anode. Among
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anodically generated oxidizing species, active chlorine is the most traditional one and the most
widely employed for wastewater treatment. Active chlorine, in the form of gaseous chlorine,
hypochlorous acid or hypochlorite ions, is anodically produced from chlorides naturally present in
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or added to the solution:

2Cl– → Cl2 + 2e– (3)
+ –
Cl2 + H2O → HOCl + H + Cl (4)
+ –
HOCl → H + OCl
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(5)
Chlorine-mediated approach has been applied in the oxidation of a wide range of model pollutants
but it is particularly suitable for the treatment of real wastewaters with high sodium chloride
concentrations (even more than 5 g dm–3), such as olive oil wastewater, textile, and tannery
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effluents [1-8]. Some examples are summarized in Table 2.

In the literature, the most used electrode materials for in situ generation of active chlorine are based
on platinum or on a mixture of metal oxides (e.g., RuO2, TiO2, and IrO2 [1-8]) that have good
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electrocatalytic properties for chlorine evolution, as well as long-term stability and low price.
For example, Klidi et al. [35] studied the direct and indirect EO of a real paper mill wastewater
using TiRuSnO2. They reported that the presence of chloride ions significantly enhanced the
oxidation rate due to the electrogeneration of active chlorine. In fact, without addition of chloride,
only 60% of COD was removed; on the contrary, in the presence of 1 or 2 g/L of chloride, the COD
removal was 87% and 92%, respectively.
A detailed study on the kinetics and selectivity degradation of different organic compounds (e.g.
municipal wastewaters, humic acid, starch, algin acid, albumin, etc.) by electrochemically generated
reactive chlorine species on IrO2 anode was performed by Chung et al. [36]. They reported that the
kinetic behavior of organic matter removal, in terms of COD, depends on the reactivity of active
chlorine and pollutants, achieving a mean current efficiency of 25-40%.

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Table 2: Examples of the indirect EO electrogenerating in situ active chlorine.

Pollutant Anode Comments Ref
Phenolic Ti/RuO2 Complete removal of the total phenolic content and [37]
wastewaters COD with 10 g L− 1 of NaCl.
Enrofloxacin BDD Adding NaCl, complete removal was ∼10 times faster [38]
than with Na2SO4; Na2CO3; NaNO3 and Na3PO4.
Rhodamine B dye RuO2-IrO2 and DSA showed better performance than SnO2 in wide [39]
SnO2 operating conditions.
Real textile BDD The oxidation rate increased linearly with applied [40]
wastewaters current, and exponentially with NaCl concentration.
Reactive Black 5 DSA® Color disappearance was achieved within 15 minutes. [41]

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Carbamazepine Nb/BDD, Indirect EO by electro-generated active chlorine [42]
Ti/IrO2 achieved the most significant removal efficiency.

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Cellulosic ethanol Ti/Sn-SnO2 Complete decolorization, 8.5% of COD and 69.1% of [43]
wastewater dissolved organic carbon removal efficiencies were

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achieved.
Indigo Carmine dye IrO2-Sb-SnO2 Mathematical model was proposed to describe the [44]
evolution of COD, color and chlorine species.
Creatinine. Pt-Ru-Ir-Ti 85.41% of pollutant degradation at optimum [45]

Indigo carmine
oxide

Ti/IrO2-SnO2-
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conditions was achieved (pH 2.4, 10.29 mA cm− 2,
NaCl 0.75 g L− 1).
Color, COD and TOC removals were 100%, 77.5% [46]
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Sb2O3 and 24%, respectively.
Disinfection of Sb-Sn-W-oxide Nearly instantaneous inactivation of 107 CFU/mL [47]
bacteria-laden water of E. coli observed at 6 mA cm–2.
Diazo dye Congo BDD The degradation was considerably faster in NaCl [48]
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Red medium than in HClO4, NaCl, Na2SO4, and H2SO4

Creatinine BDD Creatinine and TOC removals were faster in NaCl than [49]
in Na2SO4.
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Indigo Carmine PbO2 and With 825 ppm of NaCl, the TiRuSnO2 anode was more [50]
TiRuSnO2 efficient than PbO2.
Disperse yellow 3 BDD, Ti/Pt and In NaCl medium faster oxidation was achieved at [51]
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Ti/RuTiO2 Ti/RuTiO2, followed by BDD and Ti/Pt.

Triphenylmethane BDD The presence of Cl− in the solution promotes an [52]
dye efficient removal of COD and color.
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2.3 Cathodic processes

The cathode can also play an important role in water treatment, by direct pollutant reduction or by
producing energy in the form of H2, via cathodic reactions. Alternatively, the mediated
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decontamination based on the cathodic H2O2 electrogeneration can be also promoted via the oxygen
reduction reactions in acidic (6) and alkaline (7) medium, being the cathode material an essential
component in such process [3, 8].
O2(g) + 2H+ + 2e  H2O2 (6)
  
O2(g) + H2O + 2e  HO2 + OH (7)
Several carbon cathode materials have been used (mixture of technical carbon with
polytetrafluoroethylene (PTFE), reticulated vitreous carbon (RVC), carbon felts, active carbon felt,
carbon nanotubes, gauzes, etc.) as gas-diffusion electrodes (GDE) [3, 5, 8]. Nevertheless, carbon-
PTFE GDE produces highest H2O2 concentration than the other materials. If H2O2 is cathodically
electrogenerated in an undivided cell without pH control, the process is called anodic oxidation with
H2O2 (AO-H2O2, anode produces adsorbed OH, H2O2 and HO2, as well as by active chlorine when

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Cl is present). Meanwhile, if the AO-H2O2 is performed, at acidic pH (~ 3.0), in presence of iron
ions (added or already present in the effluent), EF technology occurs because Fenton’s reaction (8)
is attained in the solution bulk [3-7], producing homogeneous OH. Supported or chelated iron
catalysts have been also used to extend the working pH range or cathodes that can favor the
continuous Fe2+ regeneration from reaction (9), allowing the use of a small initial amount of iron
ions [3,7].
Fe2+ + H2O2  Fe3+ + OH + OH (8)
Fe3+ + e  Fe2+ (9)

Fe  Fe + 2e
2+
(10)

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Table 3. Degradation of several pollutants by EF-based technologies.
Pollutant/Efflu Electrodes Remarks Removal Ref.

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ent efficiency
PC

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Chlorinated SS anode/RVC 200 mL of alachlor (175 mg L–1 93%-96% COD [53]
herbicides cathode COD), atrazine (68 mg L–1 COD) or
chlorbromuron (47 mg L–1 COD) in

Textile
wastewater
Fe anode/graphite
felt cathode
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0.05 M Na2SO4, pH = 2.0, Ecell = 2.5
V, 75 min.
300 mL of wastewater (1310 mg L–1
COD, pH = 6.5), cylindrical reactor,
59% color
71% COD
[54]
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air flow rate = 2 L min–1, I = 200
mA, 120 min.
PEF
Naproxen GDE cathode (20 2.5 L of 40 mg L–1 drug solution in TOC removal: [55]
M

2
cm area) /Anodes: 0.05 M NaClO4, pH = 3.0, flow cell, 83% BDD; 80%
BDD, Pt, IrO2 and 0.50 mM Fe2+, 160 W UVA, j = 50 Pt; 78% IrO2;
RuO2 (20 cm ) 2
mA cm–2, 120 min. 76% RuO2
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Methylparaben GDE cathode (3 cm 100 mL of 158 mg L–1 in 0.025 M

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TOC removal: [56]
area)/Anodes tested: Na2SO4 + 0.035 M NaCl, pH = 3.0, 89% BDD; 43%
BDD, Pt, IrO2 and stirred tank reactor, 0.50 mM Fe2+, 6 Pt; 1.9% IrO2;
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RuO2 (3 cm2) W UVA, j = 66.7 mA cm–2, 360 min. 43% RuO2

SPEF
Dyes mixture BDD/GDE cathode 2.5 L of 100 mg L–1 DOC of food 96%-97% DOC [57]
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dyes, 0.05 M and 0.50 mM Fe2+ at

pH 3.0 using the flow plant at j = 100 85% DOC
mA cm–2, 35 C and liquid flow rate
of 200 L h-1, 300 min.
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Triclosan Ti/Pt anode/graphite- 10 L of 0.225 mM drug in 0.05 M 78% TOC [58]

felt cathode (64 cm2 Na2SO4, pH = 3.0, FM01-LC reactor
area) coupled to solar CPC photoreactor,
0.50 mM Fe2+, liquid flow rate = 180
L h–1, Ecat = -0.35 V/SHE, 300 min.
Heterogeneous-EF
Winery BDD/Ni-foam undivided cylindrical glass reactor; COD removal: [59]
wastewater 150 mL solution in 0.01 M Na2SO4; 56% Fe-AB,
Catalyts (Mn-AB, 15 V constant voltage; 1 L min–1 air 54% Mn-AB,
Fe-AB, and Fe-AC) flow; 8.7, 14.25 and 3 g of Fe-AB, 82% Fe-AC
Mn-AB and Fe-AC.

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Imidapricloprid BDD/graphite undivided reactor of 150 mL; 5 V 98% TOC [60]

–1
and chlorpyrifos voltage; air flow rate of 1 L min ;
Catalyst (Fe-Y 50 – 700 mg L–1 Fe-Y zeolite; pH 3
zeolite/ Alginate) during 120 min; reusability enhanced
embedding the Fe-Y zeolite .
AB = alginate beads, AC = activated carbon, SS = stainless steel, RVC = reticulated vitreous carbon,
UVA = long-wavelength ultraviolet, COD = chemical oxygen demand, TOC = total organic carbon,
DOC = dissolved organic carbon and CPC = compound parabolic concentrator.

A large variety of applications of EF-based processes to degrade organic pollutants has been

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performed, obtaining higher decontamination efficiencies (Table 3). In PC, release of Fe2+ from a
sacrificial Fe anode (10) and cathodic H2O2 production (6) in the effluent promotes the generation

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of OH (8), favoring the destruction of organics or coagulation of them, even operating at optimum
pH 3.0 [3-8]. PC has been successfully used to degrade different organic pollutants [53, 61], as well

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as of real wastewaters [54, 62-64]. For example, a complete COD reduction was reported for azo
dye (100 mg L−1) in sulfate medium at pH 3.0 using an iron/carbon-PTFE GDE by applying
33.3 mA cm−2 [65]. Comparable degradation efficiencies were achieved by PC and EF, indicating
that is a suitable approach to treat dye-effluents.

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PEF is based on EF treatment of the effluents by irradiating UV light in an undivided cell [2-8, 66].
Organics are destroyed not only by OH formed at the anode surface and OH produced in the bulk,
according to reactions (1) and (8), but also by the photolytic action of the radiation, producing also
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
OH from photo-Fenton reaction (11) and the photodecomposition of intermediates like generated
Fe(III)-carboxylate complexes via reaction (12).
Fe(OH)2+ + h → Fe2+ + •OH (11)
2+ 2+ •
Fe(OOCR) + h → Fe + CO2(g) + R (12)
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Fe2+can be also regenerated from cathodic reduction of Fe3+ (9) and anodic transformation of H2O2
to HO2 is also attained (13):
H2O2  HO2• + H+ + e (13)
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The superiority of photo-EF (PEF) over EF has been well proven for different pollutants [67-71].
Experiments are performed in a flow plant with the liquid flowing through a cylindrical
photoreactor with a central 160 W UVA lamp [55, 56]. Higher mineralization efficiencies are
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achieved by using BDD instead of Pt, IrO2-based and RuO2-based anodes and an inert electrolyte.
Oxidative action of BDD(OH) is higher than that of Pt(OH), IrO2(OH) and RuO2(OH) and even
superior to that active chlorine produced from reactions (3)-(5).
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Novel version of PEF is solar-PEF (SPEF), in which the solution is directly irradiated by free and
renewable sunlight as UV source [58, 66, 72-74]. Figure 1c show the schemes of a solar plant
constructed for SPEF with a solar planar photoreactor and the filter-press BDD/O2-diffusion cell
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incorporated in the setup [72]. The efficacy of SPEF is improved by using larger plants with solar-
parabolic collectors. In a recent paper, Pérez et al. [58] reported a 78% TOC reduction for the
treatment of 10 L of an erythromycin solution in a solar plant equipped with an FM01-LC reactor
with a Ti/Pt anode and a graphite-felt cathode by applying a cathodic potential (Ecat) of -0.35
V/SHE for 300 min. Comparative studies using 0.2 mM Fe2+ and 1.0 g L–1 pyrite dosage for
conventional EF and heterogeneous-EF, respectively, at 50 mA, showed that the mineralization
efficiency was 5.8 folds higher in the last one. The superior efficiency in the system by using pyrite
was attributed to the “self-regulation” of the Fe2+ ions [75].

4. Perspectives and recommendations

The next step of EO, EO-based technologies as well as electrochemical emerging wastewater
treatment approaches is to pass from academic research to large-scale (pilot plants or treatment

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stations); applying the fundamental electrocatalytic concepts already established [8]. Perhaps, the
major disadvantages in comparison with other more “conventional” treatment techniques are the
potential formation of recalcitrant by-products in some specific cases, optimization of reactor
hydrodynamic conditions as well as high operation costs due to the high energy consumption and
expensive high O2 overpotential anodes. But, it is important to remark that, there is no such thing
like “zero-cost” technology and “complete green approaches”, and consequently, several
considerations can be followed in order to the fully operational applications of the electrochemical
technologies:
1) These processes can be selective, in other words, these must have a well-defined treatment
target, e.g., microcontaminants, pathogens, industrial or domestic wastewaters [7,8].
2) A decrease on the use of oxidants, catalysts and reagents must be incentivized by battery

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treatment schemes [76, 77], coupled electrochemical technologies or hybrid advanced oxidation
processes [8, 78].

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3) The use of renewable energy sources together with electrochemical treatments (driven by
sunlight or by wind) is critical; but also for simultaneous energy production. For example,

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recent original works by Scialdone et al. [79] and by Souza et al. [80] have reported the
simultaneous generation of electricity and the treatment of wastewater by means of reverse
electrodialysis with salinity gradients coupled to EF as well as a wind-powered EO process for
removing herbicides by using BDD electrodes, respectively.

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4) Development of new materials with exciting properties must be widely explored (e.g. Ti4O7

5) Waste valorization is a relatively new and rather unexploited concept that can reduce treatment
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costs. For example, the polyphenolic structure of the biopolymer lignin qualified it as potential
sustainable and renewable feedstock for fuels and aromatic fine chemicals. For this reason, the
electrochemical degradation of Kraft lignin to vanillin (high-value added product) has been
performed on Pt, Au, Ni, Cu, DSA-O2 and PbO2 [81].
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Overall, the future for the applicability of EO processes is bright because their combination with
conventional wastewater treatment systems is conceptually feasible. Future developments will rely
upon the close collaboration of analytical chemists, engineers and electrochemists to ensure
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effective application and exploitation of these electrochemical technologies.

Acknowledgements
Financial support from National Council for Scientific and Technological Development (CNPq –
PT

465571/2014-0; CNPq - 446846/2014-7 and CNPq - 401519/2014-7) and FAPESP (2014/50945-4)

are gratefully acknowledged. Carlos A. Martínez-Huitle acknowledges the funding provided by the
Alexander von Humboldt Foundation (Germany) and Coordenação de Aperfeiçoamento de Pessoal
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de Nível Superior (Brazil) as a Humboldt fellowship for Experienced Researcher

(88881.136108/2017-01) at the Johannes Gutenberg-Universität Mainz, Germany.
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References
[1] Martinez-Huitle CA, Ferro S: Electrochemical oxidation of organic pollutants for the
wastewater treatment: direct and indirect processes. Chem. Soc. Rev. . 2006, 35: 1324-
1340.
[2] Panizza M, Cerisola G: Direct and mediated anodic oxidation of organic pollutants. Chem.
Rev. 2009, 109: 6541-6569.
[3] Brillas E, Sirés I, Oturan MA: Electro-Fenton Process and Related Electrochemical
Technologies Based on Fenton’s Reaction Chemistry. Chem. Rev. 2009, 109: 6570-6631.
* [4] Sires I, Brillas E, Oturan MA, Rodrigo MA, Panizza M: Electrochemical advanced
oxidation processes: today and tomorrow. A review. Environ. Sci. Pollut. Res. Int. 2014, 21:
8336-8367.
It is an interesting and detailed review on Electrochemical advanced oxidation processes
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* [5] Martínez-Huitle CA, Rodrigo MA, Sirés I, Scialdone O: Single and Coupled
Electrochemical Processes and Reactors for the Abatement of Organic Water Pollutants:
A Critical Review. Chem. Rev. . 2015, 115: 13362-13407.
It is a complete review on single and coupled (anodic and cathodic) electrochemical processes for
the treatment of pollutants. It presents also a part on electrochemical reactors.

* [6] Brillas E, Martínez-Huitle CA: Decontamination of wastewaters containing synthetic

organic dyes by electrochemical methods. An updated review. Appl. Catal. B-Environ.
2015, 166-167: 603-643.
It is an exhaustive review on applicability of several electrochemical processes for the treatment of

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dyes.
[7] Ganiyu SO, Zhou M, Martínez-Huitle CA: Heterogeneous electro-Fenton and photoelectro-

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Fenton processes: A critical review of fundamental principles and application for
water/wastewater treatment. Appl. Catal. B-Environ. 2018, 235: 103-129.

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** [8] Martínez-Huitle CA, Rodrigo, Manuel A., Scialdone O, Electrochemical Water and
Wastewater Treatment. Elsevier; 2018.
The authors deliver a thorough overview of the historical developments and fundamentals of
different methods, and this book offers an excellent overview of the research advances and current

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applications of electrochemical technologies for water treatment. The advantages and disadvantages
of each method are explained, along with advice on how to select the method most suitable for the
needs of specific applications.
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[9] Garcia-Segura S, Eiband MMSG, de Melo JV, Martínez-Huitle CA: Electrocoagulation and
advanced electrocoagulation processes: A general review about the fundamentals,
emerging applications and its association with other technologies. J. Electroanal. Chem.
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2017, 801: 267-299.

[10] Cotillas S, Clematis D, Cañizares P, Carpanese MP, Rodrigo MA, Panizza M: Degradation of
dye Procion Red MX-5B by electrolytic and electro-irradiated technologies using
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diamond electrodes. Chemosphere. 2018, 199: 445-452.

[11] Cotillas S, Llanos J, Cañizares P, Clematis D, Cerisola G, Rodrigo MA, Panizza M: Removal
of Procion Red MX-5B dye from wastewater by conductive-diamond electrochemical
oxidation. Electrochim. Acta. 2018, 263: 1-7.
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[12] Ganiyu SO, Oturan N, Raffy S, Cretin M, Causserand C, Oturan MA: Efficiency of plasma
elaborated sub-stoichiometric titanium oxide (Ti4O7) ceramic electrode for advanced
electrochemical degradation of paracetamol in different electrolyte media. Sep. Purif.
CE

Technol. 2018. (in press https://doi.org/10.1016/j.seppur.2018.03.076

** [13] Ma P, Ma H, Sabatino S, Galia A, Scialdone O: Electrochemical treatment of real
wastewater. Part 1: Effluents with low conductivity. Chem. Eng. J. 2018, 336: 133-140.
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The authors compared the use of a microfluidic and a conventional cell with BDD anode for the
treatment of a real wastewater characterized by low conductivity.

[14] Cano A, Barrera C, Cotillas S, Llanos J, Cañizares P, Rodrigo MA: Use of DiaCell modules
for the electro-disinfection of secondary-treated wastewater with diamond anodes. Chem.
Eng. J. 2016, 306: 433-440.
[15] Cotillas S, Lacasa E, Sáez C, Cañizares P, Rodrigo MA: Disinfection of urine by conductive-
diamond electrochemical oxidation. Appl. Catal. B-Environ. 2018, 229: 63-70.
[16] Durán FE, de Araújo DM, do Nascimento Brito C, Santos EV, Ganiyu SO, Martínez-Huitle
CA: Electrochemical technology for the treatment of real washing machine effluent at
pre-pilot plant scale by using active and non-active anodes. J. Electroanal. Chem. 2018,
818: 216-222.
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[17] Oliveira EMS, Silva FR, Morais CCO, Oliveira TMBF, Martínez-Huitle CA, Motheo AJ,
Albuquerque CC, Castro SSL: Performance of (in)active anodic materials for the
electrooxidation of phenolic wastewaters from cashew-nut processing industry.
Chemosphere. 2018, 201: 740-748.
[18] Lan Y, Coetsier C, Causserand C, Groenen Serrano K: An experimental and modelling study
of the electrochemical oxidation of pharmaceuticals using a boron-doped diamond anode.
Chem. Eng. J. 2018, 333: 486-494.
[19] Mascia M, Monasterio S, Vacca A, Palmas S: Electrochemical treatment of water
containing Microcystis aeruginosa in a fixed bed reactor with three-dimensional
conductive diamond anodes. J. Hazard. Mater. 2016, 319: 111-120.
[20] Montanaro D, Lavecchia R, Petrucci E, Zuorro A: UV-assisted electrochemical degradation

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of coumarin on boron-doped diamond electrodes. Chem. Eng. J. 2017, 323: 512-519.
[21] Ellouze S, Panizza M, Barbucci A, Cerisola G, Mhiri T, Elaoud SC: Ferulic acid treatment

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by electrochemical oxidation using a BDD anode. J. Taiwan Inst. Chem. E. 2016, 59: 132-
137.

CR
[22] Candia-Onfray C, Espinoza N, Sabino da Silva EB, Toledo-Neira C, Espinoza LC, Santander
R, García V, Salazar R: Treatment of winery wastewater by anodic oxidation using BDD
electrode. Chemosphere. 2018, 206:709-717.
** [23] Clematis D, Cerisola G, Panizza M: Electrochemical oxidation of a synthetic dye using a

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BDD anode with a solid polymer electrolyte. Electrochem. Commun. 2017, 75: 21-24.
A sandwich BDD anode/Nafion membrane/TiRuO2 cathode system was successfully tested for the
treatment of Safranin T in in aqueous solutions with very low ionic conductivity. Low energy
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consumption was obtained even in distilled water.

[24] Mora-Gomez J, Ortega E, Mestre S, Pérez-Herranz V, García-Gabaldón M: Electrochemical

degradation of norfloxacin using BDD and new Sb-doped SnO2 ceramic anodes in an
M

electrochemical reactor in the presence and absence of a cation-exchange membrane. Sep.

Purif. Technol. 2018.( in press, https://doi.org/10.1016/j.seppur.2018.05.017)
[25] Zhuo Q, Xiang Q, Yi H, Zhang Z, Yang B, Cui K, Bing X, Xu Z, Liang X, Guo Q, Yang R:
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Electrochemical oxidation of PFOA in aqueous solution using highly hydrophobic

modified PbO2 electrodes. J. Electroanal. Chem. 2017, 801: 235-243.
[26] Zhuo Q, Luo M, Guo Q, Yu G, Deng S, Xu Z, Yang B, Liang X: Electrochemical oxidation
of environmentally persistent Perfluorooctane Sulfonate by a novel lead dioxide anode.
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Electrochim. Acta. 2016, 213: 358-367.

[27] Dai Q, Zhou J, Weng M, Luo X, Feng D, Chen J: Electrochemical oxidation metronidazole
with Co modified PbO2 electrode: Degradation and mechanism. Sep. Purif. Technol. 2016,
CE

166: 109-116.
[28] Moura DCd, Quiroz MA, Silva DRd, Salazar R, Martínez-Huitle CA: Electrochemical
degradation of Acid Blue 113 dye using TiO2-nanotubes decorated with PbO2 as anode.
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Environ. Nanotechnol. Monit. Manage. 2016, 5: 13-20.

[29] Dai Q, Xia Y, Chen J: Mechanism of enhanced electrochemical degradation of highly
concentrated aspirin wastewater using a rare earth La-Y co-doped PbO2 electrode.
Electrochim. Acta. 2016, 188: 871-881.
[30] Berenguer R, Sieben JM, Quijada C, Morallón E: Electrocatalytic degradation of phenol on
Pt- and Ru-doped Ti/SnO2-Sb anodes in an alkaline medium. Appl. Catal. B-Environ. 2016,
199: 394-404.
[31] Yang B, Wang J, Jiang C, Li J, Yu G, Deng S, Lu S, Zhang P, Zhu C, Zhuo Q:
Electrochemical mineralization of perfluorooctane sulfonate by novel F and Sb co-doped
Ti/SnO2 electrode containing Sn-Sb interlayer. Chem. Eng. J. 2017, 316: 296-304.
[32] Li D, Tang J, Zhou X, Li J, Sun X, Shen J, Wang L, Han W: Electrochemical degradation of
pyridine by Ti/SnO2–Sb tubular porous electrode. Chemosphere. 2016, 149: 49-56.
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[33] Zhi D, Qin J, Zhou H, Wang J, Yang S: Removal of tetracycline by electrochemical

oxidation using a Ti/SnO2–Sb anode: characterization, kinetics, and degradation
pathway. J. Appl. Electrochem. 2017, 47: 1313-1322.
** [34] Ganiyu SO, Oturan N, Raffy S, Esposito G, van Hullebusch ED, Cretin M, Oturan MA: Use
of sub-stoichiometric titanium oxide as a ceramic electrode in anodic oxidation and
electro-Fenton degradation of the beta-blocker Propranolol: degradation kinetics and
mineralization pathway. Electrochim. Acta. 2017, 242: 344-354.
The authors used for the first time a Ti4O7 as new and promising electrode material for wastewater
treatment, and compare its performance with anode materials such as BDD and DSA

[35] Klidi N, Clematis D, Delucchi M, Gadri A, Ammar S, Panizza M: Applicability of

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electrochemical methods to paper mill wastewater for reuse. Anodic oxidation with BDD
and TiRuSnO2 anodes. J. Electroanal. Chem. 2018, 815: 16-23.

IP
[36] Chung CM, Hong SW, Cho K, Hoffmann MR: Degradation of organic compounds in
wastewater matrix by electrochemically generated reactive chlorine species: Kinetics and

CR
selectivity. Catal. Today. 2018, 313: 189-195.
[37] Fajardo AS, Seca HF, Martins RC, Corceiro VN, Freitas IF, Quinta-Ferreira ME, Quinta-
Ferreira RM: Electrochemical oxidation of phenolic wastewaters using a batch-stirred
reactor with NaCl electrolyte and Ti/RuO2 anodes. J. Electroanal. Chem. 2017, 785: 180-
189.
US
[38] Carneiro JF, Aquino JM, Silva AJ, Barreiro JC, Cass QB, Rocha-Filho RC: The effect of the
supporting electrolyte on the electrooxidation of enrofloxacin using a flow cell with a BDD
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anode: Kinetics and follow-up of oxidation intermediates and antimicrobial activity.
Chemosphere. 2018, 206, 674-681.
[39] Baddouh A, Bessegato GG, Rguiti MM, El Ibrahimi B, Bazzi L, Hilali M, Zanoni MVB:
Electrochemical decolorization of Rhodamine B dye: Influence of anode material,
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chloride concentration and current density. J. Environ. Chem. Eng. 2018, 6: 2041-2047.
[40] Zou J, Peng X, Li M, Xiong Y, Wang B, Dong F, Wang B: Electrochemical oxidation of
COD from real textile wastewaters: Kinetic study and energy consumption. Chemosphere.
ED

2017, 171: 332-338.

[41] Jager D, Kupka D, Vaclavikova M, Ivanicova L, Gallios G: Degradation of Reactive Black 5
by electrochemical oxidation. Chemosphere. 2018, 190: 405-416.
[42] García-Espinoza JD, Mijaylova-Nacheva P, Avilés-Flores M: Electrochemical
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carbamazepine degradation: Effect of the generated active chlorine, transformation

pathways and toxicity. Chemosphere. 2018, 192: 142-151.
[43] Shan L, Liu J, Ambuchi JJ, Yu Y, Huang L, Feng Y: Investigation on decolorization of
CE

biologically pretreated cellulosic ethanol wastewater by electrochemical method. Chem.

Eng. J. 2017, 323: 455-464.
[44] Cruz-Díaz MR, Rivero EP, Rodríguez FA, Domínguez-Bautista R: Experimental study and
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mathematical modeling of the electrochemical degradation of dyeing wastewaters in

presence of chloride ion with dimensional stable anodes (DSA) of expanded meshes in a
FM01-LC reactor. Electrochim. Acta. 2018, 260: 726-737.
[45] Singla J, Verma A, Sangal VK: Parametric optimization for the treatment of human urine
metabolite, creatinine using electro-oxidation. J. Electroanal. Chem. 2018, 809: 136-146.
[46] Palma-Goyes RE, Silva-Agredo J, Vazquez-Arenas J, Romero-Ibarra I, Torres-Palma RA: The
effect of different operational parameters on the electrooxidation of indigo carmine on
Ti/IrO2-SnO2-Sb2O3. J. Environ. Chem. Eng. 2018, 6: 3010-3017.
[47] Ghasemian S, Asadishad B, Omanovic S, Tufenkji N: Electrochemical disinfection of
bacteria-laden water using antimony-doped tin-tungsten-oxide electrodes. Water Res.
2017, 126: 299-307.

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[48] Jalife-Jacobo H, Feria-Reyes R, Serrano-Torres O, Gutiérrez-Granados S, Peralta-Hernández

JM: Diazo dye Congo Red degradation using a Boron-doped diamond anode: An
experimental study on the effect of supporting electrolytes. J. Hazard. Mater. 2016, 319:
78-83.
[49] Zhang Z, Xian J, Zhang C, Fu D: Degradation of creatinine using boron-doped diamond
electrode: Statistical modeling and degradation mechanism. Chemosphere. 2017, 182: 441-
449.
** [50] Labiadh L, Barbucci A, Carpanese MP, Gadri A, Ammar S, Panizza M: Direct and
indirect electrochemical oxidation of Indigo Carmine using PbO2 and TiRuSnO2. J. Solid
State Electrochem. 2017, 21: 2167-2175.
The authors compare both direct and indirect electrolysis using an active and a non active anode. In

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direct electrolysis PbO2 was during direct electrolysis, PbO2 provided a faster oxidation rate,
while in the presence of NaCl, the TiRuSnO2 anode was more efficient than PbO2.

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[51] Salazar R, Ureta-Zañartu MS, González-Vargas C, Brito CdN, Martinez-Huitle CA:

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Electrochemical degradation of industrial textile dye disperse yellow 3: Role of
electrocatalytic material and experimental conditions on the catalytic production of
oxidants and oxidation pathway. Chemosphere. 2018, 198: 21-29.
[52] He Y, Wang X, Huang W, Chen R, Lin H, Li H: Application of porous boron-doped

Electroanal. Chem. 2016, 775: 292-298. US

diamond electrode towards electrochemical mineralization of triphenylmethane dye. J.

[53] Lizama-Bahena C, Álvarez-Gallegos A, Hernandez JA, Silva-Martinez S: Elimination of

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bio-refractory chlorinated herbicides like atrazine, alachlor, and chlorbromuron from
aqueous effluents by Fenton, electro-Fenton, and peroxi-coagulation methods, Desalination
Water Treat. 2015, 55: 3683-3693.
[54] Ghanbari F, Moradi M: A comparative study of electrocoagulation, electrochemical Fenton,
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electro-Fenton and peroxi-coagulation for decolorization of real textile wastewater:

electrical energy consumption and biodegradability improvement: J. Environ. Chem. Eng.
2015, 3: 499-506.
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[55] Coria G, Sirés I, Brillas E, Nava JL: Influence of the anode material on the degradation of
naproxen by Fenton-based electrochemical processes. Chem. Eng. J. 2016, 304: 817-825.
[56] Steter JR, Brillas E, Sirés I: On the selection of the anode material for the electrochemical
removal of methylparaben from different aqueous media. Electrochim. Acta 2016, 222:
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1464-1474.
[57] Thiam A, Sirés I, Brillas E: Treatment of a mixture of food color additives (E122, E124 and
E129) in different water matrices by UVA and solar photoelectro-Fenton. Water Res.
CE

2015, 81: 178-187.

[58] Pérez T, Sirés I, Brillas E, Nava JL: Solar photoelectro-Fenton flow plant modeling for the
degradation of the antibiotic erythromycin in sulfate medium. Electrochim. Acta 2017,
AC

228: 45-56.
[59] Iglesias O, Meijide J, Bocos E, Sanromán MÁ, Pazos M: New approaches on heterogeneous
electro-Fenton treatment of winery wastewater. Electrochimica Acta 2015, 169: 134–141.
[60] Iglesias O, de Dios MAF, Tavares T, Sanromán MA, Pazos M: Heterogeneous electro-Fenton
treatment: preparation, characterization and performance in groundwater pesticide
removal. J. Ind. Eng. Chem. 2015, 27: 276–282.
[61] Zarei M, Niaei A, Salari D, Khataee AR: Removal of four dyes from aqueous medium by
the peroxi-coagulation method using carbon nanotube–PTFE cathode and neural
network modeling. J. Electroanal. Chem. 2010, 639: 167-174.
[62] Yavuz Y, Öcal E, Savas Koparal A, Ögütveren ÜB: Treatment of dairy industry wastewater
by EC and EF processes using hybrid Fe-Al plate electrodes. J. Chem. Technol. Biotechnol.
2011, 86: 964-969.
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[63] Zhao X, Zhang B, Liu H, Chen F, Li A, Qu J: Transformation characteristics of refractory

pollutants in plugboard wastewater by an optimal electrocoagulation and electro-Fenton
process. Chemosphere 2012, 87: 631-636.
[64] Daghrir R, Drogui P: Coupled electrocoagulation–electro-Fenton for efficient domestic
wastewater treatment, Environ. Chem. Lett. 2013, 11: 151-156.
[65] do Vale-Júnior E, da Silva DR, Fajardo AS, Martínez-Huitle CA: Treatment of an azo dye
effluent by peroxi-coagulation and its comparison to traditional electrochemical advanced
processes. Chemosphere, 2018, 204: 548-555.
[66] Brillas E: A review on the degradation of organic pollutants in waters by UV photoelectro
Fenton and solar photoelectro-Fenton. J. Braz. Chem. Soc. 2014, 25: 393-417.
[67] Sirés I, Garrido JA, Rodríguez RM, Cabot PL, Centellas F, Arias C, Brillas E: Electrochemical

T
degradation of paracetamol from water by catalytic action of Fe2+, Cu2+, and UVA light
on electrogenerated hydrogen peroxide. J. Electrochem. Soc. 2006, 153: D1-D9.

IP
[68] Kaplan F, Hesenov A, Gözmen B, Erbatur O: Degradations of model compounds
representing some phenolics in olive mill wastewater via electro‐Fenton and photoelectro‐

CR
Fenton treatments. Environ. Technol. 2011, 32: 685-692.
[69] Thiam A, Brillas E, Centellas F, Cabot PL, Sirés I: Electrochemical reactivity of Ponceau 4R
(food additive E124) in different electrolytes and batch cells. Electrochim. Acta 2015, 173:
523-533.

US
[70] García-Rodríguez O, Bañuelos JA, El-Ghenymy A, Godínez LA, Brillas E, Rodríguez-Valadez
FJ: Use of a carbon felt-iron oxide air-diffusion cathode for the mineralization of
Malachite Green dye by heterogeneous electro-Fenton and UVA photoelectro-Fenton
AN
processes, J. Electroanal. Chem. 2016, 767: 40-48.
[71] Flores N, Cabot PL, Centellas F, Garrido JA, Rodríguez RM, Brillas E, Sirés I: 4-
Hydroxyphenylacetic acid oxidation in sulfate and real olive oil mill wastewater by
electrochemical advanced processes with a boron-doped diamond anode. J. Hazard. Mater.
M

2017, 321: 566-575.

[72] Flox C, Garrido JA, Rodríguez RM, Cabot PL, Centellas F, Arias C, Brillas E: Mineralization
of herbicide mecoprop by photoelectro-Fenton with UVA and solar light. Catal. Today
ED

2007, 129: 29-36.

[73] Antonin VS, Garcia-Segura S, Santos MC, Brillas E: Degradation of Evans Blue diazo dye
by electrochemical processes based on Fenton’s reaction chemistry. J. Electroanal. Chem.
2015, 747: 1-11.
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[74] Garza-Campos B, Brillas E, Hernández-Ramírez A, El-Ghenymy A, Guzmán-Mar JL, Ruiz-

Ruiz EJ: Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis. J. Hazard. Mater. 2016, 319:
CE

34-42.
[75] Ouiriemmi I, Karrab A, Oturan N, Pazos M, Rozales E, Gadri A, Sanromán MÁ, Ammar S,
Oturan MA: Heterogeneous electro-Fenton using natural pyrite as solid catalyst for
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oxidative degradation of vanillic acid, J. Electroanal. Chem. 797 (2017) 69–77.

** [76] Ferreira MB, Rocha JHB, da Silva DR, de Araújo DM, Martinez-Huitle CA: Application of
electrochemical oxidation process to the degradation of the Novacron Blue dye using single
and dual flow cells, 2016, J. Solid State Electrochem. 2016, 20: 2589-2597.
The use of dual cell arrangement proved to be a very efficient electrochemical system for
treating effluents, which the authors have proposed the use in a serial mode of electrochemical
flow cells with different electrocatalytical materials to favor the electrochemical conversion
and electrochemical combustion in the first and in the second cells, respectively or vice versa.
Consequently, improving the depollution efficiency and decreasing the energy requirements.

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[77]Fajardo AS, Martins RC, Martínez-Huitle CA, Quinta-Ferreira RM: Treatment of Amaranth
dye in aqueous solution by using one cell or two cells in series with active and non-active
anodes. Electrochim. Acta 2016, 210: 96-104.
** [78]Vidal J, Huiliñir C, Salazar R: Removal of organic matter contained in slaughterhouse
wastewater using a combination of anaerobic digestion and solar photoelectro-Fenton
processes, Electrochim. Acta 2016, 210: 163-170
The combination of both technologies, biological digestion and electrochemical treatments,
allows to demonstrate that, it is not necessary the applicability of a single process when the use
of electrochemical approaches can be recommended as a pre- or post- treatment in order to
depollute efficiently the effluent from industrial wastewater plants.

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** [79]Scialdone O, D’Angelo A, Galia A: Energy generation and abatement of Acid Orange 7
in reverse electrodialysis cells using salinity gradients. J. Electroanal. Chem. 2015, 738: 61-68.

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The authors demonstrated that the simultaneous generation of electric energy and the treatment
of waters contaminated by Acid Orange 7 can be achieved by reverse electrodialysis processes

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using salinity gradients and proper redox processes. Both the utilization of electro-Fenton at the
cathode and the oxidation by electrogenerated active chlorine at the anode can be successfully
used. The financial feasibility of these applications will be significantly important for both
electric energy generation and the treatment of waste waters.

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** [80]Souza FL, Lanza MRV, Llanos J, Sáez C, Rodrigo MA, Cañizares P: A wind-powered
BDD electrochemical oxidation process for the removal of herbicides. J. Environ. Manage.
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2015, 158: 36-39.
This interesting report demonstrated that the complete mineralization of organic pollutants can
be achieved when the electrochemical system is directly fed by a wind turbine; even in non-
optimal wind conditions (only 20% of wind force was used). In this frame, this result clearly
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indicates that the combination of renewal energies with electrochemical technologies is a

promising alternative to decrease the process costs, and consequently, its applicability is
feasible.
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** [81] Möhle S, Zirbes M, Rodrigo E, Gieshoff T, Wiebe A, Waldvogel SR: Modern

Electrochemical Aspects for the Synthesis of Value-added Organic Products. Angew. Chem.
Int. Ed. 2018, 57: 6018–6041.
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The electrochemical treatment of real effluents is currently the most important target;
nevertheless, the conversion of the pollutants into high-value added products is the new
challenge to transform the visualization of the discharge methodology as well as the steps
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employed during the selective conversion/degradation.

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• Papers of special interest

•• Paper of outstanding interest.

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