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Electrochemical technologies for wastewater


treatment and resource reclamation
Cite this: Environ. Sci.: Water Res.
Technol., 2016, 2, 800 Yujie Feng,*a Lisha Yang,a Junfeng Liua and Bruce E. Loganb

Research developments in environmental electrochemistry and their potential to contribute to a cleaner


environment are reviewed here for wastewater treatment applications. Most environmental pollutants can
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Received 9th December 2015, be successfully eliminated or converted to non-toxic materials by one or more processes, including
Accepted 5th May 2016
electrochemical oxidation, electrochemical reduction, electrocoagulation and electrocoagulation/flotation,
electrodialysis, and electrochemical advanced oxidation processes. Specific examples of applications for
DOI: 10.1039/c5ew00289c
pollutant removal and reclamation of wastewater are given for the different processes, along with research
rsc.li/es-water needs and improvements for commercial application of these electrochemical processes.

Water impact
Electrochemical treatment of pollutants in water can be accomplished in many different ways, for example, by direct oxidation and reduction reactions,
through the production of reactive chemical species, or by releasing chemicals that achieve physical removal. These different electrochemical processes are
critically reviewed here, noting specific challenges to advance existing and new technologies for cost-effective water treatment.

1. Introduction
a
State Key Laboratory of Urban Water Resource & Environment, Harbin Institute
As a consequence of industrial development activities, tech-
of Technology, Harbin 150090, PR China. E-mail: yujief@hit.edu.cn;
Fax: +86 451 86287017; Tel: +86 451 86287017, +86 451 86283068
nological progress and profit have sometimes prevailed over
b
Department of Civil and Environmental Engineering, The Pennsylvania State environmental concerns, resulting in an increasing number
University, 212 Sackett Building, University Park, PA 16802, USA of detrimental pollutants that have found their way into the

Prof. Yujie Feng obtained her Lisha Yang is a Ph.D. student at


Ph.D. and M. Phil. from Harbin Harbin Institute of Technology
Institute of Technology and (2013–present). She received her
Bachelor's degree from Tianjin Bachelor's degree and Master's
University. She has been working degree in Environmental Science
at Harbin Institute of Technol- and Engineering at Heilongjiang
ogy as a Lecturer (1994–1998), University. Her research interest
Associate Professor (1998–2002) is in the development of new
and Professor (since 2002–pres- routes for preparation of nano-
ent). She is currently the Deputy sized coating electrode materials
Director of the State Key Labora- for applications in electro-
tory of Urban Water Resource chemical technologies for waste-
Yujie Feng and Environment (HIT) of the Lisha Yang water treatment and resource
National Ministry of Science & reclamation.
Technology. She is also a Visiting Professor at Penn State Univer-
sity, USA and Liaoning University, China and a Fellow of Interna-
tional Water Association (IWA). Her research is focused on waste-
water treatment and energy recovery, and risk evaluation of toxic
compounds or nano-materials in engineering systems.

800 | Environ. Sci.: Water Res. Technol., 2016, 2, 800–831 This journal is © The Royal Society of Chemistry 2016
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Environmental Science: Water Research & Technology Critical review

environment. Thus, the removal of environmental pollutants


has become a major issue and a crucial factor for the sustain-
able development of modern industrial processes, which
must comply with regulations to ensure clean environments.
Industrial electrochemistry has undergone development
towards cleaner processes and more environmentally friendly
products, which is one of the strategies for environmental
protection. As a consequence, a special research field of envi-
ronmental electrochemistry has been developed, which is
based on using electrochemical techniques to remove impuri-
ties from gases, liquids, or soils, to prevent or minimize envi-
ronmental pollution. The first book devoted to the potential
of electrochemistry for environmental protection appeared
four decades ago by Bockris.1 Since then, several books and
reviews have been devoted to this topic,2–20 which have indi-
cated the inherent advantages of several different electro-
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chemical technologies based on their environmental compat-


ibility, due to the fact that the main reagent, the electron, is
a ‘clean reagent’. Other attractive advantages are related to
versatility, high energy efficiency, amenability to automation,
and cost-effectiveness.
From the viewpoint of high efficiency and low resource con-
sumption, electrochemical technologies can be used either as a Fig. 1 Flow diagram of combined electrochemical processes: (A) two-
pretreatment step to increase the biodegradability of a pollutant phase anaerobic (CSTR + EGSB)–aerobic (SBR)–electrocatalytic oxida-
tion (1. electroflocculation reactor, 2. electrochemical reactor, 3. CSTR,
or as an advanced treatment method further to reduce COD
4. EGSB, 5. SBR, 6. electrochemical reactor); (B) coagulation–electrocat-
or color in the water to achieve relevant effluent standards. alytic oxidization–biological contact oxidation combined process (1. ad-
Based on analyzing the characteristics of the wastewater justable water tank, 2. electrocoagulation, 3. sedimentation tank, 4. reg-
quality, two combined electrochemical processes have been ulating tank, 5. three-dimensional fixed bed electrochemical device
proposed by the research group of Feng and co-workers,21,22 system, 6. regulating tank, 7. biological contact oxidization device sys-
tem, 8. effluent trough, 9. pump, 10. valve, 11. DC power supply, 12.
as shown in Fig. 1.
aeration system, 13. sludge collection system).21,22
In this paper, we reviewed the electrochemistry-based ap-
proaches for removal of pollutants in wastewaters, such as
electrochemical oxidation, electrochemical reduction, electro- ative advancements and recent achievements. The fundamen-
coagulation and electrocoagulation/flotation, and electrodial- tals of each technology are briefly discussed in order to better
ysis processes. Emerging technologies such as electro-Fenton understand their advantages and limitations for practical ap-
and photoelectro-Fenton processes, photoelectrocatalysis, plications in the removal and treatment of environmental
and sonoelectrocatalysis are also discussed along with the rel- pollutants in water and wastewater.

Dr. Junfeng Liu obtained his Ph. Dr. Logan earned his B.S. and
D. and M. Phil. from Harbin In- M.S. in Chemical Engineering
stitute of Technology. Dr. Liu is and Environmental Engineering,
currently a lecturer at the School respectively, at Rensselaer Poly-
of Municipal and Environmental technic Institute and his Ph.D. in
Engineering, Harbin Institute of Environmental Engineering at
Technology. His research inter- University of California, Berke-
ests are in the fields of environ- ley. He started his career as an
mental electrocatalytic mate- Assistant Professor at the Univer-
rials, photocatalytic materials sity of Arizona, and became an
and wastewater refractory or- Associate Professor, then a Pro-
ganic pollutant removal technol- fessor before moving to The
Junfeng Liu ogy. He has published more than Bruce E. Logan Pennsylvania State University.
30 papers, including 14 papers Dr. Logan is currently an Evan
indexed by SCI. Pugh Professor and the Stan and Flora Kappe Professor of Envi-
ronmental Engineering in the Department of Civil and Environ-
mental Engineering at The Pennsylvania State University.

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2. Electrochemical oxidation
Electrochemical oxidation is considered to be a very powerful
tool for breaking up even the most resistant organic com-
pounds.23 Anodic oxidation of organic contaminants can be
performed in several different ways, including both direct
and indirect oxidation.

2.1 Direct anodic oxidation


In direct anodic oxidation (or direct electron transfer to the
anode), the pollutants are destroyed after adsorption on the
anode surface, without the involvement of any substances Fig. 2 Scheme of the electrochemical oxidation of organic
other than the electron. Such oxidation is theoretically possi- compounds on (a) “active” and (b) “non-active” anodes.
ble at more negative potentials than those needed for water
splitting and oxygen evolution. However, this process usually
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results in electrode fouling due to the formation of polymeric


layers on its surface and consequently leads to very poor The oxidation of a wide range of biorefractory organic
chemical decontamination.24,25 Gattrell and Kirk investigated compounds on platinum anodes has been reported in many
the electro-oxidation of phenol with platinum and studies.31–38 Platinum electrodes have a relatively low oxygen
peroxidized platinum anodes using cyclic voltammetry and evolution overpotential (i.e., 1.6 V vs. SHE in 0.5 M H2SO4)
chronoamperometry. Their studies demonstrated that phenol which can enable selective conversion of pollutants at a low
can be irreversibly adsorbed on metallic platinum, quickly current efficiency. In a study by Feng et al.30 on the electro-
passivating the electrode.26 oxidation of phenol using platinum electrodes, it was found
that the concentration of phenol rapidly decreased to zero,
but residual TOC concentrations suggested that the overall
2.2 Indirect anodic oxidation via intermediates of oxygen degradation reactions significantly slowed down due to the
evolution formation of intermediate products.
To avoid the drawbacks of direct oxidation, the indirect oxi- The electro-oxidation of phenol on platinum anodes was
dation method based on the oxygen evolution region can be investigated in depth by Comninellis and Pulgarin.29,33 Their
used, which has an advantage over direct electrolysis in that experimental results indicated that aromatic intermediates
it does not need addition of oxidation catalysts to the solu- (hydroquinone, catechol, benzoquinone) initially were formed
tion, and it does not produce by-products. during electrolysis, and subsequently the aromatic ring op-
In this process, the electrochemical reaction leads to par- ened with the formation of aliphatic acids (e.g., maleic,
tial or total decontamination of the electrogenerated species fumaric, and oxalic acid) which resisted further electro-oxida-
at the anode due to physically adsorbed “active oxygen” tion. Thus, complete TOC removal could not be achieved,
(adsorbed hydroxyl radicals ˙OH) or chemisorbed “active oxy- and the current efficiency decreased during the electrolysis
gen” (oxygen in the lattice of a metal oxide (MO) anode).27,28 process (Fig. 3).
This physisorbed ˙OH is the second strongest oxidant known 2.2.2 Ruthenium- and iridium-based oxide electrodes. Di-
after fluorine, with a high standard potential (E 0 = 2.80 V vs. mensionally stable anodes (DSAs) consist of a titanium base
SHE) that ensures the complete combustion of organic com- metal covered by a thin conducting layer of metal oxide or
pounds, and the chemisorbed “active oxygen” participates in mixed metal-oxide oxides, and were invented by Beer in the
the formation of selective oxidation products. late 1960s.39 RuO2- and IrO2-based anodes have been widely
As has been established in many studies,29,30 the nature of used due to their mechanical resistance as well as being rela-
the anode material influences not only the efficiency of the tively inexpensive (compared to Pt) and successful scale-up
process, but also the electrode selectivity. For example, “ac- demonstrated in some electrochemical industries, such as
tive anodes” with low oxygen evolution overpotentials such as the chlor-alkali industry, water electrolysis, and metal
IrO2, RuO2 or Pt favor the partial and selective oxidation of electrowinning.
pollutants, while “non-active anodes” with high oxygen evolu- During the past two decades, DSA-type anodes coated with
tion overpotentials such as SnO2, PbO2 or boron-doped dia- a layer of RuO2 and IrO2 have begun to be extensively
mond (BDD) can facilitate complete combustion, and thus employed in the field of wastewater treatment.30,40–47
they are regarded as ideal electrodes for the complete oxida- However, when these electrodes are used at high current
tion of organics to CO2 in wastewater treatment (Fig. 2). densities, organic oxidation can yield low current efficiencies
2.2.1 Platinum electrodes. Platinum anodes have a long for complete combustion since they favor the secondary reac-
history of use as electrode materials for the oxidation of or- tion of oxygen evolution. Electrochemical destruction of
ganics because of their good conductivity and chemical 4-chlorophenol in an aqueous medium using a platinum an-
stability. ode coated with a RuO2 film has been studied by Johnson

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et al.27 They found that this type of electrode was stable and
active when used in a cell with a solid Nafion membrane
without the addition of a soluble supporting electrolyte. How-
ever, the time required for complete COD and TOC removal
was too long and the current efficiency was low.
Titanium is also used as an inexpensive coating on
electrodes. The electro-oxidation of 1,4-benzoquinone in water,
in which the benzoquinone concentration and intermediate
products during oxidation with Ti/IrO2 and Ti/SnO2 anodes
were monitored, has been investigated by Pulgarin et al.48 It
was found that the most important factor was the composition
of the anode. With the Ti/IrO2 anode, the primary oxidation
step was easily achieved (benzene ring rupture), resulting in
the accumulation of carboxylic acids formed as the final non-
toxic products. With the Ti/SnO2 anode, carboxylic acids were
formed at a much faster reaction rate and then oxidized, pro-
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ducing only CO2 as the final product.


Electro-oxidation of Reactive Blue 19 solutions in a three-
electrode quartz cell equipped with a Ti/Ru0.3Ti0.7O2 anode
was investigated by Pelegrini et al. They obtained 35% decol-
orization efficiency and 9.6% TOC removal after 2 h of
electrolysis.49
Fig. 4 Electrochemical degradation of 100 ppm phenol in 60 ml of
Electrochemical degradation of phenol with five different
electrolyte as a function of charge passed for different electrode
types of anodes (three RuO2-based electrodes, Ti/PbO2 and Pt materials, i = 10 mA cm−2 (–■–) Ti/RuO2; (–▲–) Ti/Sb–Sn–RuO2; (–●–)
electrodes) was evaluated by Feng et al.30 Ti/Sb–Sn–RuO2–Gd; (–□–) Ti–PbO2; and (–○–) Pt.30
As shown in Fig. 4, the relative performance for phenol
degradation of the three RuO2 electrodes decreased in the
order: Ti/Sb–Sn–RuO2–Gd > Ti/Sb–Sn–RuO2 > Ti/RuO2. How-
ever, these electrodes were less efficient than Pt or Ti/PbO2 DSA-type anodes coated with a layer of RuO2 or IrO2 can
electrodes. Aromatic ring opening occurred using all these be used efficiently for organics degradation by indirect
electrodes, but with the three RuO2-based electrodes, phenol electrolysis by in situ generation of active chlorine through
was decomposed into aromatic intermediates, such as benzo- the oxidation of chloride ions present in the solution.45,50–54
quinone and hydroquinone, or several carboxylic acids, such For example, Kraft55 showed that DSA-type electrodes (IrO2
as maleic acid, succinic acid, and oxalic acid. Full mineraliza- and IrO2–RuO2) gave higher current efficiencies during
tion to CO2, or complete TOC removal, only was obtained for electrochemical chlorine production than boron-doped dia-
the Ti/PbO2 anode (Fig. 4). mond (BDD) and platinum (Pt) anodes (Fig. 5).
Scialdone et al. investigated the electrochemical oxidation
of organics on IrO2–Ta2O5 anodes in the presence and

Fig. 5 Dependence of the electrochemical free chlorine production


Fig. 3 Evolution of (1) phenol, (2) aromatic intermediates, (3) aliphatic efficiency on the chloride content of electrolyzed water under
acids, and (4) CO2 during oxidation of phenol at the Pt anode: i = 50 standard conditions using four different anode materials (iridium oxide,
mA cm−2, T = 70 °C.29,33 mixed iridium/ruthenium oxides, platinum, doped diamond).55

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absence of NaCl, in a continuous batch recirculation reaction PbO2 was largely a function of the resulting morphologies
system equipped with a parallel plate undivided electro- and microstructures on the electrodes.82
chemical cell. Their results showed that in the presence of In order to reveal the mechanism of the enhanced electro-
NaCl, high current efficiency (CE) was generally obtained chemical performance of the TiO2-NTs/SnO2–Sb/PbO2
using DSA anodes at high current densities and low flow electrode, the interlayer of Sb-doped SnO2 (SnO2–Sb) and
rates.56 TiO2 nanotubes (TiO2-NTs) on Ti were introduced into the
An electrochemical oxidation approach for the treatment PbO2 electrode system.83 This electrode with nanotubes had
of a high-salinity reverse osmosis (RO) concentrate was inves- a more regular and compact morphology than previous Ti/
tigated using boron-doped diamond (BDD) and titanium- SnO2–Sb/PbO2 electrodes, as well as better oriented crystals
based dimensionally stable anodes (Ti/IrO2–RuO2). The re- with smaller sizes (Table 1). Kinetic analyses indicated that
sults showed that both direct oxidation and indirect oxida- the electrochemical oxidation of nitrobenzene on the PbO2
tion by active chlorines played a role in the treatment of the electrodes followed a pseudo-first-order reaction, and mass
RO concentrate, but the contribution was different for the an- transport was enhanced at the constructed electrode.
odes. The highest COD removal was observed using the BDD An alternative approach for stabilizing Pb electrodes was
electrode at the same current density as that of the other to position an interlayer of TiO2 nanotubes (NTs) between a
electrode, but the least energy consumption was obtained fluorine resin (FR)-doped PbO2 coating and the Ti sub-
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using the Ti/IrO2–RuO2 electrode.57 strate.88 The improvement in surface properties and micro-
2.2.3 Lead dioxide electrodes. PbO2 electrodes have been structure was investigated by comparison to traditional PbO2
used for the production of perchlorate since 1934. In the past electrodes. This treatment improved the electrochemical re-
30 years, the development of PbO2 anodes for the oxidation sistance of the electrode in a Na2SO4 solution to 12.2 Ω with
of organics has gained great interest in environmental appli- PbO2/TiO2-NTs/Ti, compared to 147 Ω with PbO2/Ti. The ser-
cations because of their good conductivity and large vice life of PbO2/TiO2-NTs/Ti was increased to about 335 h,
overpotential for oxygen evolution in acidic media, which en- which was 7.1 times that of the PbO2/Ti electrodes. Pb4+ was
able the production of hydroxyl radicals during water detected in the electrolyte after a 50 h electrochemical degra-
discharge.58–65 However, practical applications in the oxida- dation test using PbO2/Ti (1.1 × 10−5 M) and PbO2/TiO2-NTs/
tion of organics with this type of electrode have been limited Ti (3.4 × 10−6 M) electrodes, but none was detected with the
due to its relatively shorter electrode service life, as well as FR-PbO2/TiO2-NTs/Ti electrodes. This suggests that firm
concerns over the possible release of Pb4+ ions into water. bonding between PbO2 and the substrate was achieved, with
The release of Pb4+ can occur due to the formation of cracks the PbO2 stably deposited onto TiO2-NTs, and this associa-
in the coating from increased internal stress generated from tion was improved with FR doping. Contact between SO42−
the electrode position of PbO2. and Pb4+ was likely blocked by the FR, inhibiting the anodic
In order to improve the stability of Pb electrodes, one ap- dissolution of the PbO2 coating.
proach that is being investigated is the incorporation of me- To gain better knowledge on the ability of these Pb anodes
tallic or nonmetallic species such as Fe2+,66–70 Bi3+,71–75 to eliminate pollutants, many researchers have undertaken
Co2+,76,77 and F− (ref. 69, 76, 78–80) into the PbO2 crystalline comparative studies on the performance of electrochemical
matrix. oxidation with boron-doped diamond (BDD) and PbO2 an-
Andrade et al. showed that incorporation of F, Fe, and Co odes. A comparative study between PbO2 and BDD anodes for
ions into the PbO2 film enhanced its chemical stability com- electrooxidation of cresols (o-, m- and p-cresol) showed that
pared to that of pure PbO2 in the oxidation of simulated complete electrochemical incineration was achieved at the
wastewaters containing Blue Reactive 19 dye or phenol.69,76 same time as the initial pollutant was removed, since
Another approach for stabilizing lead electrodes is based BDDIJ˙OH) simultaneously destroys all oxidation by-products
on introducing a transition layer between the coating and the formed. The mineralization process of the m-cresol effluent
substrate. Antimony-doped tin oxide has been widely investi-
gated as a transition layer for PbO2 elecrodes.81–87 The lattice
size of SnO2 is between β-PbO2 and TiO2, and therefore, the Table 1 Lattice parameters (a = b and c) and unit cell volume (V) for Sb-
Sb-doped SnO2 transition layer can enhance the solid solubil- doped SnO2 and PbO2 from XRD patterns83
ity and hence reduce the internal stress of the Ti/SnO2/β-PbO2
Unit cell parameter
electrode and improve the binding force between the PbO2
Electrode a (Å) c (Å) V (Å3)
coating and Ti substrate, and it also inhibits the formation of
a
a TiO2 layer. (Standard SnO2) 4.738 3.187 71.54
SnO2–Sb in Ti/SnO2–Sb interlayer 4.727 3.185 71.17
Bi et al. explored the electro-deposition of PbO2 on the Ti
SnO2–Sb in TiO2-NTs/SnO2–Sb interlayer 4.704 3.173 70.21
substrate with an Sb-doped SnO2 undercoating, using a tradi- (Standard PbO2)b 4.955 3.383 83.06
tional acidic nitrate solution. They investigated the morphol- PbO2 in Ti/SnO2–Sb/PbO2 electrode 4.952 3.380 82.88
ogy and microstructure of the PbO2 coatings by varying the PbO2 in TiO2-NTs/SnO2–Sb/PbO2 electrode 4.950 3.379 82.79
electro-deposition temperature and time. Their results indi- a
The lattice parameters of SnO2 (JCPDF 41-1445). b
The lattice
cated that the electrochemical performance of the deposited parameters of PnO2 (JCPDF 65-2826).

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on PbO2 under comparable conditions is much less efficient Titanium anodes coated with Sb-doped tin oxide have
due to the lower oxidation ability of PbO2(˙OH). Despite this been considered as one of the most suitable electrodes in the
fact, a shorter electrolysis time is needed for the total disap- electrochemical oxidation of refractory organics because of
pearance of m-cresol with PbO2 than with BDD.89 Electro- their large overpotential for oxygen evolution (1.9 V vs. SHE)
chemical oxidation of ibuprofen (Ibu) using a Ti/Pt/PbO2 and high yield of hydroxyl radicals.30,96,97
electrode and a boron-doped diamond (BDD) electrode was In general, two different mechanisms can be distin-
investigated by Ciríaco et al., showing a much higher degra- guished for the oxidation of organic pollutants on SnO2 an-
dation efficiency for the BDD anode of 20 mA cm−2 than that odes. One is direct oxidation, and the other is indirect oxida-
for the PbO2-based electrode.90 tion. Direct oxidation can only take place on the surface of
In contrast, work by Zhao et al.88 showed that a FR-PbO2/ SnO2 anodes. Indirect oxidation can occur via hydroxyl radi-
TiO2-NTs/Ti anode had similar morphology and surface wet- cals, which are generated by oxygen vacancies on the SnO2
ting properties, a higher OEP, and better electrochemical per- anodes.98 Electrochemical oxidation of organic pollutants on
formance than a boron-doped diamond film (BDD) electrode SnO2 anodes mainly depends on indirect oxidation.
(Table 2). The improved surface hydrophilic properties of Research has shown that the electrochemical characteris-
PbO2 electrodes could produce better conditions leading to tics and service life of SnO2 anodes are influenced by the
the increased chemical adsorption ability on the surface and preparation method as well as other factors. Ti metal is often
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subsequently lower utilization of ˙OH than BDD anodes. The used as a base material for SnO2 electrodes because of its low
physical resistance of the PbO2 electrode was much lower cost and stability. The key aspect of SnO2 anode preparation
than that of BDD, and therefore it had higher conductivity. is achieving a stable catalytic coating on the Ti base, while
Hydroxyl radical utilization is significantly enhanced on a also ensuring that the catalytic coating is stable and well ad-
PbO2 electrode, which has been shown to produce a higher hered to the base material.
oxidation rate and higher removal efficiency for 2,4- The particle size of the SnO2 crystal has a great influence
dichlorophenoxyacetic acid than a BDD electrode.91,92 on the electrochemical characteristics of SnO2 anodes.
A comparative study of the electrochemical mineralization Smaller particle sizes means larger surface areas, which will
of environmentally persistent long-chain perfluorinated car- improve the overall electrocatalytic reaction rates. The parti-
boxylic acids (PFCAs) with Ti/SnO2–Sb/Ce–PbO2 and Ti/BDD cle size of SnO2 crystals prepared by electrodeposition and
anodes was carried out using galvanostatic control at room sol–gel methods is on the nanometer scale, which provides a
temperature.93 The results showed that the performance of very high specific surface area. Of all preparation methods,
the PbO2 electrode was comparable with that of a BDD the sol–gel method is a relatively simple, effective, and conve-
electrode. After 180 min of electrolysis, the PFNA removal ef- nient way to produce effective SnO2 nanocoatings.97
ficiencies on the BDD and PbO2 electrodes were 98.7 ± 0.4% The performance of Sb-doped SnO2 anodes has been previ-
and 97.1 ± 1.0%, respectively, while the corresponding PFDA ously investigated using phenol. It has been shown in the work
removal efficiencies were 96.0 ± 1.4% and 92.2 ± 1.9%. of Stucki and co-workers that doped SnO2 anodes oxidized a
Other authors have reported similar performance using wide range of organic compounds with an efficiency about five
PbO2 and BDD anodes during oxalic acid incineration.52,94 times higher than that of platinum anodes.34,99 Similar results
There is a strong interaction between this compound and PbIJIV) were also obtained by Comninellis and Pulgarin,96 in their
sites which promotes anodic oxidation, and the rate of oxida- studies on the electrochemical oxidation of phenol on doped-
tion was only limited by mass transfer to the electrode surface SnO2 and platinum anodes. They found that aliphatic acids
at high current densities and low substrate concentrations. were rapidly oxidized, with only very small amounts of aromatic
2.2.4 Tin dioxide electrodes. Pure SnO2 crystal is an n-type intermediates, using a SnO2 anode, but the Pt anode had low
semiconductor, which has a wide band-gap energy (Eg) value degradation rates and produced a large amount of intermedi-
(3.5–4.3 eV),95 and its conductivity is too poor to be used as ates. Comninellis measured a CE of 0.58 using an SnO2–Sb2O5
an electrode material. However, the conductivity of SnO2 can electrode, and obtained 71% degradation of phenol, compared
be enhanced by adding some doping elements. In most to lower CEs of 0.18 (PbO2), 0.17 (IrO2), 0.14 (RuO2) and 0.13
cases, antimony is used as a dopant, and new energy bands (Pt) at a current density of 500 A m−2 (pH = 12.5, initial phenol
can be induced. concentration = 10 mm, and reaction temperature of 70 °C).100

Table 2 Physicochemical characterization of FR-PbO2/TiO2-NTs/Ti, PbO2/TiO2-NTs/Ti, PbO2/Ti and BDD electrodes88

Electrode Loading capacity (g m−2) ROCP


ct (Ω) Extrapolated OEP0a (V vs. SCE) Service lifetime (h)
FR-PbO2/TiO2-NTs/Ti 971.6 12.2 2.50 335
PbO2/TiO2-NTs/Ti 950.1 34.8 1.90 170
PbO2/Ti 705.9 147 1.80 47
BDD — 34 500 2.40 —
a
The extrapolated OEP0 at zero current is obtained by using an extrapolation technique from the anodic polarization ( j–E) curve tested in 0.5
M H2SO4 aqueous solution, which is equivalent to the minimum decomposition potential for water.

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Electrochemical degradation of phenol was investigated by


Feng et al. using three different types of anodes: Ti/SnO2–Sb,
Ti/RuO2, and Pt. Although phenol was oxidised by all of the
anodes at a current density of 20 mA cm−2 or a cell voltage of
4.6 V, the intermediate products of phenol degradation, in-
cluding benzoquinone and organic acids, were subsequently
rapidly oxidized by the Ti/SnO2–Sb anode but accumulated in
solution using Ti/RuO2 and Pt. The degradation rates of the
Ti/RuO2 and Pt anodes were considerably slower, as the
SnO2–Sb coating improved the catalytic reaction and allowed
rapid organic oxidation driven by hydroxyl radicals generated
from anodic water electrolysis (Fig. 6).101
The great potential of SnO2 for electrochemical treatment of
many different organic chemicals has been shown, including:
phenol,96,102–108 aliphatic acids,106 dyes,109,110 drugs,111,112
Bisphenol A (BPA),113 nitrophenol,114 2,4-dichlorophenol,115
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4-chlorophenol,116 pentachlorophenol,117,118 perfluorooctanoic


acid,109,119 perfluorinated carboxylic acids (PFCAs),93 industrial
wastewater120 and naphthylamine.121 Nevertheless, the major
drawback that has prevented the practical applications of Ti/
SnO2–Sb electrodes is their relatively short service lifetime. The
short lifetime has been ascribed to the formation of a resistive
layer between the substrate and coating, a passivation layer
formed on the outer surface of the coating, and selective loss
of the catalyst into the electrolyte solution.
Many methods have been proposed to further improve
SnO2 electrodes. For example, doping SnO2 electrodes with
rare earth metals can improve the electro-catalytic decompo-
sition of organics such as phenol, as shown in several exam-
ples summarized in Table 3.122
The addition of Gd can improve the morphology and per-
formance of Ti/SnO2–Sb electrodes. Both phenol and interme-
diate products (e.g., benzoquinone) were shown to decom-
pose more rapidly at 2% doping of Gd for the electrodes,
over a doping range of 0–10% (Fig. 7).103
The enhanced performance of Gd-doped Ti/Sb–SnO2
electrodes is due to the increased adsorption capacity for hy-
droxyl radicals on the electrode surface, and the lower mobil-
ity of oxygen atoms in the SnO2 lattice.
Other new methods to improve the lifetime of SnO2
electrodes include using TiO2 NTs or CNTs serving as carriers
for further loading of the nanocrystal catalyst both to enhance
the performance of the Ti/SnO2 electrode and to improve its
service lifetime, without reducing its O2 evolution potential.
Another approach to improve the stability based on chang-
ing the electrode microstructure was proposed by Zhao et al.,
in which a TiO2-NTs/SnO2 electrode that had high oxygen evo-
lution potential, excellent electrocatalytic performance, and
relatively long-term stability was constructed by implanting Fig. 6 Electrochemical degradation of phenol (490 mg L−1) on Ti/
Sb-doped SnO2 into highly ordered TiO2 nanotubes (TiO2- SnO2–Sb, Ti/RuO2 and Pt anodes at a current density of 20 mA cm−2:
NTs) grown in situ on a Ti substrate under controlled condi- (A) phenol degradation, (B) TOC removal, and (C) pH variation.101
tions. The service lifetime of this electrode (TiO2-NTs/SnO2)
was 2.4 times higher than that of a traditional Sb-doped
SnO2 (SnO2) electrode. Based on TOC removal rates, the TiO2- The substrate architecture is a main factor in the im-
NTs/SnO2 electrode also completely mineralized benzoic acid proved performance of TiO2-NTs/SnO2–Sb anodes for organic
(BA).123 pollutant degradation. The pore diameter and length of the

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Table 3 Parameter values of different rare earth metal-doped Ti-based SnO2 electrodes122

The optimum molar The time of degradation Oxygen evolution The sequence of
ratio of rare earth of phenol from 100 mg L−1 potential (V (vs. ˙OH-producing Oxidation
Electrode metals to Sn to below 10 mg L−1 (h) Ag/AgCl)) capacity mechanisms
Ti–Ce–Sb–SnO2 1 : 50 3.0 2.16 The redox couple of
Ce4+/Ce3+
Ti–Eu–Sb–SnO2 1 : 50 2.5 2.21 Adsorbed˙OH species
Ti–Gd–Sb–SnO2 1 : 50 2.5 2.23
Ti–Dy–Sb–SnO2 1 : 200 1.6 2.24
Ti–Nd–Sb–SnO2 1 : 200 <1.5 2.28
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Fig. 7 (a) UV scan curves of electrolytes for phenol and some possible intermediates; (b) UV scan of electrolytes of the 2% Gd-doped Ti/SnO2–Sb
anode; (c) UV absorbance at 269 nm and (d) at 290 nm of electrolytes as a function of time for different compositions of Gd-doped Ti/SnO2–Sb
electrodes, i = mA cm−2.103

TiO2-NTs substrates of the TiO2-NTs/SnO2–Sb electrode were is 2.23 V, which is 0.07 V higher than that of an electrode
shown to be critical factors in enhanced pollutant degrada- lacking CNTs. As a result, the competitive reaction was weak-
tion, with TiO2-NTs electrodes that had an 85 nm pore diam- ened, the current efficiency was improved, and an accelerated
eter and a 51 m length having the best performance.107 lifetime test indicated that the service life would be 1816 h at
A SnO2–Sb2O4-based anode modified with Cr3C2 and CNTs a current density of 50 mA cm−2, which is 4.8 times longer
was examined for phenol oxidation.102 The service lifetimes than that of the Ti/SnO2–Sb electrode without CNTs. Ti/SnO2–
of the Ti/SnO2–Sb2O4–Cr3C2 and Ti/SnO2–Sb2O4–CNT–Cr3C2 Sb–CNT electrodes have been demonstrated to have a supe-
electrodes were 7.4 times and 5.6 times longer than that of rior electrochemical oxidation and degradation ability using
the Ti/SnO2–Sb2O4 electrode, respectively. The Ti/SnO2–Sb2O4– Acid Red 73 as a model organic pollutant. The CNT-modified
CNT–Cr3C2 electrode showed the highest oxygen evolution po- electrode had a 1.9× higher kinetic rate constant, 1.3× greater
tential, COD removal and current efficiency (CE). chemical oxygen demand (COD) and total organic carbon
Carbon nanotubes (CNTs) can be incorporated into Ti/ (TOC) removal efficiencies, 1.4× improved mineralization cur-
SnO2–Sb electrodes using a pulse electrodeposition method rent efficiency, and a similar (0.98×) specific energy con-
to improve performance.124 An electrode modified with CNTs sumption compared to Ti/SnO2–Sb electrodes (Fig. 8).
had a higher specific surface area and smaller lattice size, Among the several materials which have been proposed as
which provided more active sites for hydroxyl radical genera- anodes, synthetic BDD exhibits several technologically impor-
tion and contaminant oxidation compared to electrodes with- tant properties that distinguish it from conventional
out CNTs. The oxygen evolution potential of Ti/SnO2–Sb–CNT electrodes, such as an inert surface with low adsorption

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carboxylic acids on BDD anodes, Cañizares et al. found that


the organic compounds were completely mineralized regard-
less of the characteristics of the wastewater (initial concentra-
tion, pH, and supporting media) and operating conditions
(temperature and current density) used. They also found that
the phenolic compounds could be oxidized by the hydroxyl
radicals on the electrode surface, and also by inorganic oxi-
dants electrogenerated on the BDD anodes in the bulk of the
solution, depending on the electrolyte composition, such as
peroxodisulfuric acid from sulfuric acid oxidation.132
The rate of oxidation of azo dyes at BDD/Si electrodes can
be tuned indirectly by changing the boron doping level.
Bogdanowicz et al. first investigated the influence of the level
of [B]/[C] ratio on the degradation and mineralization of aro-
matic pollutants like azo-dyes.144 They found that the me-
chanical and chemical stability of the electrodes resulted
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from a microcrystalline layer with a relatively high sp3/sp2


band ratio. The influence of commonly used electrolytes,
NaCl and Na2SO4, on the dye removal efficiency was also in-
vestigated. They found that the efficiency of the BDD process
depended on the electrode's doping level. Higher amounts of
Fig. 8 (a) TOC removal efficiency and (b) mineralization current
dopant on the surface of the BDD electrode resulted in the
efficiency (MCE) in 1.0 g L−1 Acid Red 73 and 0.1 M Na2SO4 solution at
a current density of 50 mA cm−2.124 higher efficiency of dye removal in both electrolytes (Fig. 9).
BDD electrodes show good performance for the electro-
chemical oxidation of pesticides and drugs. The degradation
properties and a strong tendency to resist deactivation, re- of 2,4-D herbicide in a recirculation flow plant has been stud-
markable corrosion stability even in strongly acidic media, ied with Pt/air-diffusion and BDD/BDD electrodes by electro-
and an extremely high O2 evolution overvoltage.125,126 There- chemical oxidation and electro-Fenton processes. In both
fore, it has received great attention in the past decades as a treatments, the use of a single BDD/BDD cell always achieved
new electrode material. a higher degree of degradation, with 59% mineralization and
2.2.5 Boron-doped diamond (BDD) electrodes. The use of 0.42 kW h g−1 TOC specific energy after 300 min of electroly-
BDD electrodes has received great attention in recent years for sis for the electro-Fenton process at 25 mA cm−2.151
chemical pollutant destruction. The first BDD patent by Carey The use of BDD anodes has also been widely investigated
et al.127 20 years ago claimed that BDD could be used as an an- for the removal of surfactants from wastewater. The degrada-
ode for the oxidation of organics in wastewater. Since then, a tion rates of seven perfluorinated compounds (PFCs) with
very large number of papers and patents have shown that BDD
can be effective in the destruction of organic pollutants, such as
phenolic compounds,128–139 synthetic dyes,140–146 pesticides
and drugs,147–153 surfactants154–155 and wastewaters.156–159
The behavior of BDD anodes for the electrochemical oxida-
tion of different organic compounds has been investigated in
depth by Comninellis and co-workers160–168 and Cañizares and
co-workers.128,130–133,141 In a research study on Si/BDD anodes
for a wide range of pollutants by Comninellis et al.,168 it was
found that independent of the organic pollutant nature, the cur-
rent efficiency and the amount of intermediates were affected
by local concentrations of ˙OH relative to organics concentration
on the anode surface. Based on this observation, they proposed
a comprehensive kinetic model to relate COD concentrations
and current efficiencies for the electrochemical oxidation of a
wide range of pollutants with BDD electrodes. The energy
consumption during the process was predicted based on ex-
perimental conditions including the applied current inten-
Fig. 9 Rubin F-2B concentration as a function of charge passed Q at
sity, organic concentration, and mass-transfer coefficient. BDD2 ([B]/[C] = 2000) and BDD10 ([B]/[C] = 10 000) in NaCl and Na2SO4
Based on the studies of oxidation of different phenolic electrolytes. Experimental conditions: [Rubin F-2B]initial = 20 mg L−1,
compounds (phenol, chlorophenols, and nitrophenols) and pHinitial = 6.2, [NaCl] = 0.12 M, [Na2SO4] = 0.05 M, T = 20 ± 2 °C.144

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different carbon chain lengths and head groups were com- tials for BPA electrolysis at the same current densities. In
pared by Zhuo et al. using BDD electrodes.155 Intermediates comparison to the Ti/Sb–SnO2 anode, the Ti/BDD anode with
of PFCs were detected, with degradation rates showing high durability and good reactivity for organic oxidation
pseudo-first-order kinetics of perfluoroalkyl carboxylates and appeared to be the most promising for the effective EC treat-
sulfonates that increased with carbon chain length. They also ment of BPA and similar endocrine disrupting chemical
proposed electrochemical oxidation mechanisms of PFCs on (EDC) pollutants.113
a BDD anode, where PFC decomposition began with a direct, Electrochemical oxidation of ibuprofen (Ibu) was exam-
one-electron transfer from a carboxyl or sulfonate group to ined using Ti/Pt/PbO2 and BDD electrodes in a batch cell at
the BDD, with the formed PFC radicals decarboxylated or de- different current densities (10, 20 and 30 mA cm−2) in a
sulfonated to yield a perfluoroalkyl radical which permitted a Na2SO4 electrolyte. Very good degradation of Ibu was
defluorination reaction between a perfluoroalkyl radical and achieved, with COD removal between 60 and 95%, and TOC
a hydroxyl radical (Fig. 10). removal from 48 to 92%, in 6 h experiments, with higher
Electrochemical oxidation of a pesticide residue 2,6- rates obtained with the BDD electrode. The combustion effi-
dichlorobenzamide (BAM) with Si/BDD and Ti/Pt–Ir anodes ciency (ηC), which can be estimated from the rate of decrease
was studied to compare non-active with active anodes.149 The of TOC compared to that of COD, indicated slightly higher re-
results showed that BDD, as a non-active anode, was more ef- moval with the BDD at lower current densities, with 100% re-
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ficient than the Pt–Ir electrode, and it produced a lower moval for both types of anodes at 30 mA cm−2.90
amount of degradation intermediates due to the non- BDD and Ti/IrO2–RuO2 electrodes were compared to test
selective nature of the hydroxyl radicals formed on the anode. their effectiveness for electrochemical oxidation of an azo dye
The initial degradation pathway was found to be different for (Reactive Red 120) in acidic media (1 M HClO4).150 Ti/IrO2–
the two cells, where the BDD electrode gave rise to both a ca- RuO2 exhibited a low oxidation power with high selectivity to
thodic and an anodic pathway, compared to the Pt–Ir cell organic intermediates and low TOC removal (10% at 25 °C
which only had an anodic pathway. and 40% at 80 °C), while the use of the BDD electrodes in-
Electrochemical degradation of bisphenol A (BPA) was ex- duced total mineralization to CO2. In both cases, the
amined on four different anode materials: Ti/BDD, Ti/Sb– decoloration of the solution was rapid, but very rapid, nearly
SnO2, Ti/RuO2 and Pt. BPA was readily destroyed on the Ti/ 100% removal was achieved with the BDD (2 A h L−1) com-
Sb–SnO2 and Ti/BDD anodes, while the Pt anode had a mod- pared to a slower rate with Ti/IrO2–RuO2 (25 A h L−1). The ef-
erate ability to remove BPA and the Ti/RuO2 anode did not ef- fectiveness of these materials was examined based on the in-
fectively oxidise BPA. Compared to the Pt and Ti/RuO2 an- stantaneous current efficiency (ICE) (%), which was
odes, the Ti/Sb–SnO2 and Ti/BDD anodes were found to have determined from COD measurements using the following
higher oxygen evolution potentials and higher anodic poten- equation:

Fig. 10 Pseudo-first-order kinetic reactions for (a) PFXA and (b) PFXS decomposition; the defluorination ratios for (c) PFXA and (d) PFXS on a BDD
electrode (reaction conditions: [PFXA]0 = [PFXS]0 = 0.114 mM; i = 23.24 mA cm−2; T = 32 °C; electrolyte = 1.4 g L−1 NaClO4).155

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ICE = (CODt − CODt+Δt)FV/8IΔt (1) and the high cost of Ta, Nb and W. Considering the tradeoffs
in performance and cost, BDD films synthesized on a tita-
where (COD)t and (COD)t+Δt are the chemical oxygen de- nium substrate are preferable due to their good conductivity,
mands at times t and t + Δt (in gO2 dm−3), respectively, I is high strength, low price, high anticorrosion, and quick
the current (A), F is Faraday's constant (96 485 C mol−1), V is repassivation behavior. However, the poor adhesion strength
the electrolyte volume (dm3), and 8 is the oxygen equivalent of diamond with Ti has been a problem in realizing high-
mass (geq.−1). The ICE was up to 0.13 in the case of Ti/IrO2– performance BDD/Ti electrodes. For example, it was observed
RuO2, and up to 0.45 for the BDD. that an extreme difference in temperature during substrate
The electrochemical mineralization of environmentally per- cooling (from 850 °C to ambient temperatures) resulted in a
sistent long-chain perfluorinated carboxylic acids (PFCAs), large thermal residual stress on the formation of a TiC inter-
perfluorononanoic acid (C8F17COOH, PFNA) and layer, reducing diamond film adhesion to the substrate, and
perfluorodecanoic acid (C9F19COOH, PFDA). was investigated a short service life of the Ti/BDD electrode.171 For this rea-
over Ti/SnO2–Sb–Ce (SnO2), Ti/SnO2–Sb/Ce–PbO2 (PbO2), and son, various methods have been developed to improve adhe-
Ti/BDD (BDD) anodes. The energy consumption was calculated sion, such as fabrication by the microwave plasma-enhanced
based on the electrical efficiency per log order reduction (EE/O) chemical vapor deposition (MPCVD) method. A sand-blasted
in the electrochemical oxidation process, as follows: treaded substrate and the introduced buffer layer were favor-
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able for producing electrodes with improved adhesion and


(2) good electrochemical properties.172
2.2.6 Carbonaceous electrodes. Building on the idea of
where P is the power (W), t is the reaction time (h), V is the using three-dimensional electrodes, several types of carbona-
treated wastewater volume at time t (L), and Ci and Cf are the ceous anode materials are now being investigated that have
initial and final concentrations, respectively (mg L−1). high specific surface area, good conductivity, excellent ad-
For PFNA, EE/O was 54 W h L−1 for SnO2 and 72 W h L−1 sorption capability and better catalytic and electric capabili-
for the PbO2 electrodes. The lowest EE/O value of 42 W h L−1 ties such as activated carbon fibers,173–178 carbon felt179,181
was achieved with the BDD electrode. The EE/O values for and carbon nanotubes.182–185
PFDA were EE/OIJSnO2) = 1.4 × EE/O(PbO2) and 1.9 × EE/ The electrochemical degradation of amaranth, a type of azo
O(BDD).93 dye, using an activated carbon fiber (ACF) electrode was investi-
The anodic oxidation of methamidophos (MMD), a highly gated under potentiostatic or galvanostatic conditions.173,174
toxic pesticide used worldwide, was studied in a sodium sul- With either approach, three different decolorization processes
fate aqueous solution using Pb/PbO2, Ti/SnO2, or Si/BDD occurred: adsorption, electroreduction, and electrooxidation.
electrodes at 30 °C. Under galvanostatic conditions, it was ob- The adsorption was insignificant for the removal of color, COD
served that the performance of the electrode material was and TOC. The electrooxidation and electroreduction benefitted
influenced by pH and current density, and the MMD degra- color, COD and TOC removal, and electroreduction was more
dation using Pb/PbO2 in acidic media (pH 2.0 and 5.6) gener- effective than electrooxidation.
ated formaldehyde as the main product. Under the same con- Another azo dye, alizarin red S (ARS), was electro-
ditions, Ti/SnO2 had low formaldehyde production compared chemically oxidized using activated carbon fiber (ACF) felt as
to the Pb/PbO2 electrode, while the Si/BDD electrodes did not an anode. The initial pH, current density and the type of
show any formaldehyde production. The ATR-FTIR character- supporting electrolyte all played an important role in ARS
istics of MMD in crystalline form and in aqueous solution degradation. The large specific surface area and higher meso-
were established, which showed the formation of phosphate pore percentage of ACF anodes provided effective electro-
as the reaction progressed, suggesting complete MMD miner- chemical degradation of the dye, as shown by an increase in
alization using the Si/BDD electrode.169 color removal efficiency from 54 to 84% as the specific sur-
Diamond films are usually deposited on a titanium or sili- face area of the ACF anodes was increased from 894 to 1682
con substrate. A diamond layer was deposited onto a 3-D po- m2 g−1.175
rous Pt nano-sheet perpendicular to the BDD hybrid film ACF electrodes have been tested with other materials. For
using a simple and facile double template method. Physical example, they were used with TiO2 (TiO2/ACF), with the
and electrochemical results indicated that the 3-D porous Pt/ electrode prepared using a simple and inexpensive sol–gel-
BDD/Si electrode had a high catalytic ability and was resis- adsorption method.176 Tests using phenol and other organic
tant to poisoning for methanol electro-oxidation, because of pollutants showed that intermediates were always produced,
the larger electrochemically active area and porous structure demonstrating that the adsorbed ˙OH generated on the TiO2/
and the activity of the BDD substrate.170 ACF–graphite anode was the most active species in the
BDD electrodes have been fabricated using numerous electrochemical oxidation system.
other materials. Although high-quality BDD films can be de- The use of an electrospun ACF electrode modified with
posited on silicon, tantalum, niobium and tungsten, they are CNTs (e-CNT/ACF) was examined for the electrochemical deg-
unsuitable for application in wastewater treatment because radation of the dye, methyl orange (MO).178 Results showed
of their poor mechanical strength, the low conductivity of Si, that the CNTs in the web-like e-CNT/ACF composites helped

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to improve the pore distribution and conductivity of the com- generation of polymers rather than trying to regenerate the
posite electrode, resulting in ∼90% degradation of MO in 60 electrodes after passivation.
min, which was much higher than that obtained using only In all cases with these sp2-hybridized carbonaceous anode
the commercial woven ACF under similar conditions. materials, however, electro-oxidation is generally accompa-
Two pieces of ACF with CNT packed evenly between them nied by surface corrosion. Thus, the application of three-
were used as the anode and cathode to treat wastewater con- dimensional electrodes will require further investigation into
taminated with a dye (X-3B) in a system called a seepage car- the electrode passivation mechanisms, electrode regeneration
bon nanotube (SCNT) reactor.179 This reactor was designed techniques, and passivation prevention methods.185
to facilitate contaminant mass transfer from bulk solution to
the electrode surface, in order to improve electrochemical 2.3 Indirect electro-oxidation via in situ generated chemical
wastewater treatment rates. Comparison of color and COD re- oxidants
movals showed that the SCNT electrode reactor removed total To avoid the deactivation of the anode during direct oxida-
color by 94.4% and COD by 57.6% in 90 min levels of treat- tion of chemicals, an alternative approach is indirect oxida-
ment were much higher than 32.8% (color) and 28.0% (COD) tion by destroying pollutants through the electrochemical
obtained using conventional electrochemical reactors (with generation of chemical reactants such as active chlorine, oz-
ACF-CNT electrodes positioned vertically at the center of the one, persulphate, and hydrogen peroxide.
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same reactor). The research also showed that the current effi- 2.3.1 Electrogeneration of active chlorine. Due to the natu-
ciency of the SCNT reactor was 340% higher than that of con- ral abundance of chloride ions in most waters, and the fact
ventional reactors, and the energy consumption to mineralize that oxide electrodes are very active for Cl2 evolution, chemi-
the same amount of organics was only 16.5% of that for con- cal species such as Cl2, HOCl, and OCl−, collectively called ac-
ventional reactors. tive chlorine, can be electrochemically generated and used
A novel polyIJaniline-co-o-aminophenol) (PAOA)-modified for electrochemical oxidation of pollutants. Active chlorine
carbon felt electrode reactor was designed and investigated species are well known to be strong chemical oxidants and
for fluoride removal from aqueous solutions. This reactor de- are commonly used for organics oxidation, both in model so-
sign was innovative because it operated under a wider pH lutions and in actual wastewaters.186–193 The production of
range due to the coating of the electrode with a copolymer active chlorine in electrolytic cells can be described by the
PAOA ion exchange film. Contaminant mass transfer from following reaction mechanisms:
bulk solution to the electrode surface was enhanced by the
use of porous carbon felt as an electron-conducting carrier 2Cl → Cl2 + 2e− (3)
material compared to other reactors.180 The electro-oxidation
of CeIJIII) on a carbon felt anode that proceeded with a high Cl2 + H2O → HClO + H+ + Cl− (4)
current efficiency was studied which showed that at a current
of 2 A, oxidation of cerium had a current efficiency of 92% HClO ↔ ClO− + H+ (5)
with the majority of Ce (>80%) oxidized to CeIJIV) within 40
min.181 In the presence of active chlorine, oxygen transfer can be
Carbon nanotubes (CNTs) have been used as carbon- carried out by the adsorbed oxychloro species, which are con-
based electrodes for chemical degradation or pollutant re- sidered intermediates of the chlorine evolution reaction as
moval. The use of a carbon nanotube filter for electro- shown in Fig. 11.188
chemical water treatment was investigated by Vecitis and co- The predominance of different chemical species in active
workers.182–185 They found enhanced performance of the chlorine is well known to be a function of pH. Cl2 is the pre-
three-dimensional electrodes due to the high electrode sur- dominant stable species at pH <3; when the pH is between 5
face area and porosity, and therefore an increased number of and 6, active chlorine exists as hypochlorous acid (HClO) and
electrochemically active surface sites. hypochlorous anions (OCl−) are present at pH ≥6; at higher
The primary passivation mechanisms and electrode regen- pH values (>7.5), hypochlorous anions (OCl−) are the pre-
eration methodologies of electrochemical filtration with dominant species. HClO is the most powerful oxidant among
three-dimensional carbon nanotube (CNT) networks were in- the active chlorine species for oxidation of organics, and thus
vestigated using phenol. Polymerization of phenol on the reactions are best conducted in acidic rather than alkaline
CNT surface resulted in a reduction of current and electro- media.
chemical performance. Polymerization therefore needs to be The choice of the anode material utilized is important for
prevented to stabilize the performance of these electrodes, or in situ generation of active chlorine, and DSA-type anodes
the electrodes must be cleaned. Calcination and redispersion coated with a layer of RuO2 or IrO2 are particularly effective
in HCl (pH = 1.7), toluene, and hexanes are effective for re- due to their good electrocatalytic properties for chlorine evo-
moval (>97%) of the passivating electropolymer coating. lution, as well as their long-term mechanical and chemical
However, prevention is better than post-treatment for dealing stability.194–197
with passivation of CNT, and conducting electrochemical fil- Other non-active electrodes, including BDD, SnO2 and
tration at a higher potential could be useful in avoiding the PbO2, are not useful for this approach under some conditions

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hanced production of organochlorinated compounds resulted


in a solution with high ecotoxicity.229 Future work using sa-
line solutions must therefore focus on developing both effec-
tive electrodes and experimental conditions which do not re-
sult in the formation of organochlorinated intermediates that
will limit the overall reduction in toxic chemical species in
water.
2.3.2 Electro-Fenton method. Indirect electro-oxidation
methods based on the cathodic electrogeneration of hydro-
gen peroxide are being developed for the treatment of certain
wastewaters, such as acidic wastewaters containing toxic and
refractory organic pollutants.231–236 The direct remediation of
wastewaters using this approach is limited by the low oxida-
Fig. 11 Reaction scheme of chlorine-mediated electrochemical oxida- tion potential of H2O2. The electro-Fenton process is a more
tion of organics. effective method of wastewater treatment, which is based on
using H2O2 in acidic effluents with Fe2+ ions as catalysts
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(Fenton's reagent) to give homogeneous ˙OH as a strong oxi-


because the high anodic potential typical of these electrodes dant of organics according to the reaction:237–239
can lead to oxidation of Cl− to form chlorate (ClO3−) and
perchlorate (ClO4−), which do not have any oxidizing capac- Fe2+ + H2O2 → Fe3+ + ˙OH + OH− (6)
ity.198 For example, Palmas et al. showed that chlorates and
perchlorates could easily be formed from further oxidation of Electro-Fenton methods have become very attractive be-
hypochlorite on BDD anodes.199 Similar results were reported cause of the much higher degradation rates of organic pollut-
by Lacasa et al. who also showed that the anode material sig- ants than those using traditional Fenton approaches due to
nificantly influenced the speciation of chlorine, with the for- the continuous regeneration of Fe2+ at the cathode via:
mation of perchlorate obtained using BDD electrodes.200
Thus, these electrodes are not useful for treatment of drink- Fe3+ + e− → Fe2+ (7)
ing water due to the hazardous risks associated with the for-
mation of these chemical species. Chlorate and perchlorate This electrochemical approach thus avoids Fe3+ accumula-
formation is minimal on DSA-type and Pt electrodes.201,202 tion in the medium, thereby eliminating the production of
Active chlorine production is suitable for the treatment of iron sludge. The electro-Fenton process has been successfully
some types of wastewaters, such as olive oil, textile, and tan- used to treat non-biodegradable or refractory organic com-
nery effluents.203–229 Due to an abundance of chloride in pounds such as phenolic compounds,240–246 dyes,247–249 pesti-
these wastewaters, there is usually no need for addition of cides and herbicides,250–254 leachates,255–257 drugs,258–260 and
chloride salts for effective treatment. For example, Turro reverse osmosis concentrates.261
et al. investigated the behavior of a Ti/IrO2–RuO2 anode for BDD electrodes are particularly effective for the electro-
the electrochemical oxidation of landfill leachate under dif- Fenton process. The mineralization process and decay kinet-
ferent concentrations of the supporting electrolyte. They ics of atrazine and cyanuric acid were examined by means of
found that the addition of 20 mM NaCl gave results similar an electro-Fenton process with Pt or BDD anodes using an
to those with no salt addition. In this case, the leachate undivided cell with a carbon-felt cathode under galvanostatic
contained 175 mM chlorides, and therefore increasing the conditions. The electro-Fenton process was more effective
Cl− concentration by ∼10% had a marginal effect on indirect with the BDD for the degradation of both compounds. There
oxidation.230 was nearly total mineralization of atrazine based on 97% to-
Under active chlorine mediation, the risk of formation of tal organic carbon (TOC) removal. Efficient removal was due
chlorinated organic compounds during electrolysis results to rapid oxidation by ˙OH formed at the BDD compared to
has increased wastewater toxicity, which ultimately could those in the bulk solution in a conventional Fenton reaction.
limit the wide application of this approach to wastewater Cyanuric acid was more slowly mineralized, mainly via ˙OH
treatment. For example, analysis of the reaction products produced at the BDD surface, but it was not degraded using
during the oxidation of phenol in the presence of NaCl with a Pt anode. These results highlight that electrochemical pro-
DSA-type Ti/SnO2 and Ti/IrO2 anodes showed that cesses using a BDD anode are more powerful than the classi-
organochlorinated intermediates were formed. Although cal electro-Fenton process with Pt or PbO2 anodes.262
these compounds were then mineralized to CO2 or oxidized The main limitation of Fenton-based approaches is the re-
to volatile chlorinated compounds (i.e., chloroform), the tox- quirement of low pH conditions. Fe3+ precipitation from so-
icity of the solution remained above desirable limits.187 In lution at pH ≥3.5 can lead to the termination of this reac-
another study, increasing the concentration of NaCl from 20 tion. The electro-Fenton system also requires a low solution
mM to 100 mM resulted in higher COD removal, but the en- pH, typically within the pH range 2–4, and consequently, it is

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impractical if large amounts of chemicals are needed to acid- The mineralization of the antibiotic chloramphenicol in a
ify the water prior to treatment. Therefore, the inherent draw- synthetic sulfate solution at pH = 3 was studied by anodic ox-
back of the need for a low pH limits the wide application of idation with electrogenerated H2O2 (AO-H2O2), electro-Fenton,
Fenton-based approaches, although they are useful when the UVA photoelectro-Fenton, and SPEF processes. The results
solutions are initially quite acidic. demonstrated that SPEF with a BDD anode was the best
One approach proposed to overcome this low pH require- method among these approaches examined for chemical
ment was an electro-Fenton-like (EFL) system that used a mineralization.267
Keggin-type iron-substituted heteropolytungstate anion Another integrated process is the sonoelectro-Fenton ap-
PW11O39Fe(III)(H2O)4− to substitute for Fe3+ in the conven- proach, where the solution in the electrochemical reactor is
tional electro-Fenton system. Experimental results using 0.1 simultaneously irradiated with ultrasound.268 Compared to
M dimethyl phthalate (DMP) showed complete degradation the conventional electro-Fenton approach, a significant syner-
in <80 min at pH = 6.86 at a potential of −0.5 V, with aera- getic effect was obtained by this coupled reaction due to the
tion using an O2 flow rate of 60 mL min−1. A TOC removal of additional effect of enhancement of the mass transfer rate to
56% was achieved within 120 min. A comparison with a con- the electrode. For example, during the sonoelectrolytic pro-
ventional electro-Fenton oxidation treatment of DMB showed cess, despite the existence of some degassing, the high yield
that this approach had a higher efficiency of chemical degra- of hydrogen peroxide produced at the anode significantly en-
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dation, suggesting its potential use in treatment of water and hanced the rate of mass transfer of oxygen toward the cath-
wastewater with a more neutral pH.263 ode due to the sonication.268
Further development of electro-Fenton methods is pro- Another electro-Fenton-based approach, called the peroxi-
ceeding based on coupling of the process with other AOPs electrocoagulation method, was successfully used to degrade
with the aim of obtaining a synergetic effect for water and chlorophenoxy and chlorobenzoic herbicides, and 2,4,5-
wastewater treatment. The most developed integrated process trichlorophenoxyacetic acid. In this process, the soluble Fe2+
is the photoelectro-Fenton approach, where the contaminated ions that react with cathodically generated H2O2 are continu-
solution treated under electro-Fenton conditions is exposed ously supplied to the solution from the sacrificial oxidation
to UV illumination favouring the generation of homogeneous of an iron anode. Fenton's reaction occurs with this iron and
˙OH and the photodegradation of complexes of FeIJIII) with produces Fe3+ ions, inducing coagulation. Thus, the pollut-
organics:238 ants are removed by the combined action of degradation by
˙OH generated by Fenton's reaction and their coagulation
Fe(OH)2 + Fe2+ + ˙OH (8) with Fe(OH)3 precipitates formed from the anodic corro-
sion.269 Treatment of sodium dodecyl sulfate (SDS) surfactant
The mineralization of flumequine, an antimicrobial agent wastewater by the peroxi-electrocoagulation process showed
belonging to the first generation of synthetic fluoro- that SDS in the aqueous phase was effectively removed with a
quinolones which is detected in natural waters, was studied mean energy consumption of 1.63 kW h kgSDS−1, with the SDS
by using the electro-Fenton and photoelectro-Fenton ap- removal efficiency reaching 82%.270 The removal of phenol
proaches with UVA light. The photoelectro-Fenton process from water using this peroxi-electrocoagulation method was
was more powerful, resulting in almost total mineralization examined using a mild steel anode and a graphite cathode in
with 94–96% total organic carbon removal.264 a pilot-scale reactor. Ferric hydroxide and hydroxyl radicals
Solar photoelectro-Fenton processes (SPEF) are also being generated in the cell removed phenol from the water, making
investigated, where the electrical energy needed by the it drinkable, demonstrating the feasibility of the process.271
electro-Fenton reactor is produced from solar energy.
The degradation of the industrial textile dye Disperse Blue 3. Electrochemical reduction
3, examined using the solar photoelectro-Fenton process,
showed a positive effect of sunlight and Fe2+, with complete 3.1 Electrodeposition
decolorization and mineralization of solutions in relatively Aqueous effluents containing metal contaminants from some
short time periods.265 Decolorization and mineralization of electrochemical industries, such as the metallurgical and
another dye, Sunset Yellow FCF (SY) azo dye, were examined electroplating industries, printed circuit boards, and battery
by using several processes: anodic oxidation coupled with manufacturing require special treatment to remove toxic
electrogenerated H2O2 (AO-H2O2), electro-Fenton, UVA- metal ions or recycling of valuable materials. The electro-
illuminated photoelectro-Fenton, and SPEF.266 The results chemical recovery of metals from water has been practiced in
showed that the most powerful method was solar photo- the form of electrometallurgy for a long time.272 The first
electro-Fenton, achieving almost total mineralization and recorded example was in the mid-17th century in Europe
higher degradation compared to UVA-illuminated photo- which involved the electrochemical recovery of copper from
electro-Fenton due to the higher UV intensity of sunlight, cupriferous mine waters.273
which quickly photolyzed Fe(III)–carboxylate complexes that The electrochemical mechanism for metal recovery is
could not be destroyed by ˙OH in traditional electro-Fenton based on cathodic deposition, which provides an efficient
processes. way to remove heavy/toxic metals or recover precious metals

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Table 4 Current efficiency (CE) for gold-rich alloys and for gold recovery tion on the removal of cadmium and lead ions from an aque-
on VC and on Ti for the potentials shown275
ous synthetic wastewater (Fig. 12).278
Cathode VC Ti An electrochemical reactor with a rotating cylinder
E vs. SCE (V) Alloy/% Au/% Alloy/% Au/% electrode (RCE) and a pH controller were utilized to optimize
the electrochemical recovery of nickel from a synthetic nickel
−1.0 — — 23 15
−1.1 11 5 19 11 plating wastewater. Control of the pH to ∼4 was crucial for
−1.2 11 5 17 8 recovering high-purity nickel, while preventing the precipita-
−1.4 18 9 — — tion of hydroxides and oxides (Fig. 13).279
−1.5 21 7 — —
−1.6 16 5 — —

from water and wastewater without leaving any residues dur-


ing metal separation.274
One example of the selective electrochemical removal of
metals is the recovery of gold-rich alloys using a filter-press-
type electrochemical flow reactor with highly polished vitre-
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ous carbon (VC) and titanium (Ti) flat cathodes.275 Vitreous


carbon and titanium were determined to be outstanding
cathode materials for gold recovery from gold plating waste-
water. Both materials are easy to polish and chemically resis-
tant to a wide range of chemicals. Cathodic efficiencies were
higher on the Ti cathode in which 23% was observed for a
gold-rich alloy recovered at 1.0 V, and 15% when only gold
was considered (Table 4).
Metals can also be recovered from aqueous solutions
containing chelating agents such as EDTA, nitrilotriacetic
acid and citrate. Using a two-chamber cell containing a com-
mercial cation exchange membrane, a minimum of 40% of
the metal was recovered with the greatest amount of 90%
obtained for copper.276 Electrodeposition can be integrated
with ultrasound to increase metal recovery. It was found that
copper removal increased to 95.6%, and EDTA was also re-
moved (84% COD removal) from the wastewater.277
The fluid mechanical environment is also important in re-
actor efficiency. A hydrodynamic study of a bench-scale Fig. 13 Sketch of the electrochemical reactor with a rotating cylinder
electrochemical reactor using parallel plates with an inert flu- electrode utilized to perform the electrochemical recovery of nickel: (a)
idized bed (glass beads) showed the importance of fluid mo- rotating cylinder electrode, (b) rotating motor, (c) pH control system.279

Fig. 12 Schematic representation of the complete apparatus developed and employed in the experimental procedure: (1) electrochemical reactor;
(2) hydraulic system; (3) centrifuge pump; (4) Łrecirculating batch flow system; (5) pressure gauge; (6) a dispositive to facilitate the injection of a
tracer substance.278

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3.2 Cathodic electrochemical dechlorination dichloroethylene (1,2-DCE), tetrachloroethylene (TCE) and


chloroethylene (CE)). The electrocatalytic activity of PCE was
Chlorinated organic compounds (COCs) are prevalent in found to be affected by the specific structure, with the effi-
many wastewaters, particularly those from industries that use ciency of the electrocatalytic degradation increasing with the
solvents, as well as chemical industries that produce herbi- number of Cl atoms bound to the same carbon center. The
cides, fungicides, and pesticides. The presence of these COCs number of Cl atoms bound to a second C atom had different
in the environment poses threats to human health due to effects: there was an activation enhancement due to polar ef-
their toxicity and high stability. Many methods have been fects. For the most active electrodes examined, the order of in-
used for cleaning wastewaters containing COCs. Compared to creasing electrocatalytic reactivity was: 1,1-DCA < 1,1,1-TCA <
conventional physico-chemical, biological and chemical 1,2-DCA < HCA < 1,1,2,2-TeCA < 1,1,2-TCA < 1,1,1,2-TeCA.
dehalogenation techniques, electrochemical reductive dechlo- Two distinct reduction mechanisms for the reductive cleavage
rination has emerged as an attractive technique to destroy of PCEs were observed. Geminal PCEs showed sequential
COCs due to its mild reaction conditions and the avoidance hydrodechlorination where one chlorine atom was lost in each
of possible secondary pollutants.280–285 reduction step, until completely dechlorinated ethane was
3.2.1 Electrode materials. The choice of cathode materials obtained. Alternatively, reduction of vicinal PCEs involved re-
can have a major impact on the efficiency of electrochemical moval of two chlorine atoms in an overall 2e− process resulting
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dechlorination processes, as the material can govern the reac- in the formation of the corresponding (chloro)ethylene, which
tion pathway and the selectivity for pollutant destruction.286 could be further reduced by using more negative potentials.301
During the past few years, silver-based cathodes287–296 have The size of the metal particles on the electrode is impor-
been shown to have extraordinary electrocatalytic activity to- tant. Electrospun polyacrylic acid (PAA)/polyvinyl alcohol
wards the reduction of COCs, showing dechlorination reduc- (PVA) polymer nanofibers were used to immobilize Fe/Pd bi-
tion peaks at less negative potentials than those needed by metallic nanoparticles to treat trichloroethylene (TCE)-con-
glassy carbon, leading to up to 1 V gains in energy effi- taminated groundwater. This bi-metal nanostructure that was
ciency.286 Studies suggest that the reason for the excellent ac- immobilized within the polymer nanofibers was much more
tivity of Ag is the formation of a bridge-like R⋯X⋯Ag effective in remediation of TCE, especially at high initial con-
adsorbed intermediate.297,298 centrations, than colloidal-sized Fe/Pd nanoparticles.313
Another electrode widely used for the dechlorination of Other materials have been used for successful electro-
COCs is a palladium-based electrode.289–304 The use of a Pd chemical dechlorination of chemicals. TCE degradation was
cathode leads to the preferential production of totally satu- investigated in a recirculated solution of an electrolysis sys-
rated products, as a consequence of their catalytic activity for tem containing a cast iron anode and a copper foam cathode.
hydrogen evolution and hydrogenation reactions. The ability The cast iron anode generated a reducing electrolyte that
of palladium to adsorb hydrogen helps to promote indirect prevented the electron and proton combination with
hydrodehalogenation.305 dissolved oxygen, thus the reduction of TCE on the copper
3.2.2 Electroreduction of chlorinated organic compounds. foam cathode was enhanced. The conductivity of the electro-
Over the years, electroreduction methods have been proven lyte was an important factor for both the final elimination ef-
to be highly effective for the dechlorination of a wide range ficiency (FEE) of TCE and specific energy consumption. Un-
of COCs such as chlorinated volatile organic compounds der optimal conditions, FEE reached up to 98%, at an energy
(VOCs),306–315 polychlorophenols,316–323 and polychlorinated consumption of 6.49 kW h kg−1. This electrolysis system was
hydrocarbons.324,325 The efficiency and extent of chemical de- proposed to remediate groundwater contaminated by chlori-
struction vary for different chemicals and anodes. nated organic solvents or wastewater contaminated with chlo-
Nanostructured Pd thin films prepared by a cyclic rinated compounds.314
voltammetric deposition method were shown to be effective Several types of electrodes have been examined for degrada-
in the electrochemical reductive dechlorination of carbon tet- tion of 2,4-dichlorophenoxyacetic acid (2,4-D). Palladium/nickel
rachloride (CT). Electrochemical characterization and CT re- foam (Pd/Ni foam) electrodes resulted in 87% removal of 2,4-D
moval using gas chromatography showed that adsorbed hy- within 4 h, with generation of phenoxyacetic acid (PA),
drogen was important for removing CT from acidic solutions o-chlorophenoxyacetic acid (o-CPA) and p-chlorophenoxyacetic
through a surface reaction with chemisorbed CT molecules, acid (p-CPA) as intermediates. The palladium loading and the
providing a good mechanistic reason for the efficiency of NaCl concentration impacted the dechlorination kinetics of
electrochemical dechlorination.312 2,4-D.300 With Pd/PPy–SLS/foam–Ni electrodes, 2,4-D was
Electrochemical reduction of several polychloroethanes has completely dechlorinated. The stability of the electrode was good
been investigated using electrodes containing different transi- as the dechlorination efficiency was maintained at 100% even af-
tion metals, including PCEs (1,1-dichloroethane (1,1-DCA), 1,2- ter being reused 8 times.321
dichloroethane (1,2-DCA), 1,1,1-trichloroethane (1,1,1-TCA), Roughened silver–palladium cathodes (Pd/Ag(r)) have also
1,1,2-trichloroethane (1,1,2-TCA), 1,1,1,2-tetrachloroethane been tested for electrocatalytic hydrogenolysis (ECH) dechlo-
(1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), hexa- rination of 2,4-D in an aqueous solution.321 The mechanism
chloroethane (HCA), 1,1-dichloroethylene (1,1-DCE), 1,2- of ECH dechlorination of 2,4-D on the Pd/Ag(r) cathode can

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be described as occurring in several steps. First, 2,4-D is pyrene.324 As the amount of naphthalene was reduced to 0.01
adsorbed to Ag followed by the generation of chemisorbed equivalents, there was complete dechlorination of mono-
hydrogen on Pd. Hydrogenolysis of 2,4-D then proceeds as in chlorobenzene with 77 × 104 C mol−2 of electric quantity. This
catalytic hydrogenation by the reaction of the adsorbed 2,4-D same amount of total charge was then used in the presence of
with chemisorbed hydrogen, followed by desorption of the four different types of arene mediators: biphenyl, phenan-
product. The effects of OH−, Cl−, and ethanol were discussed, threne, anthracene, and pyrene. Complete dechlorination was
and the results showed that Cl− was detrimental to ECH de- achieved with all mediators except anthracene. Similar results
chlorination, whereas OH− was able to promote the dechlori- were also obtained when this reaction was applied to 1,3-di-
nation of 2,4-D. Ethanol deactivated the Pd/Ag(r) cathode if and 1,2,4-trichlorobenzene, with phenanthrene appearing to
an aqueous alkaline solution was used for the reaction. Un- be the most effective mediator among those examined.
der optimal conditions, 25 mM 2,4-D was selectively
dechlorinated to phenoxyacetic acid with 85% removal at a 3.3 Cathodic electrochemical denitrification
CE of 66% at 298 K after 6 h. The only products generated be- Electrochemical reduction of nitrate and nitrite ions has
sides phenoxyacetic acid were 2-chlorophenoxyacetic acid and gained more attention in the past several years,325–329 particu-
4-chlorophenoxyacetic acid. larly for the treatment of nitrate-containing ground waters. As
A multifunctional Pd/C gas-diffusion cathode was examined for many other chemicals, nitrate reduction products depend
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for phenol degradation in successive environments of hydrogen on the nature of the electrode surface,330–334 making this reac-
gas and then air. Hydrogen gas was initially fed for 5 min at a tion very interesting from a mechanistic point of view.
rate of 25 mL s−1 to reach saturation. Hydrogen gas was then Electrochemical nitrate reduction was investigated on
fed into the gas compartment for the first 60 min (electrolysis coinage (copper, silver and gold) and transition-metal
time) of the experiment, followed by air. The electrochemical re- electrodes (platinum, palladium, rhodium, ruthenium, irid-
duction and oxidation was examined using three different chlo- ium) at 0.1 M nitrate ions in acid solutions.333 The conclu-
rinated phenols [4-chlorophenol (4-CP), 2,4-dichlorophenol sion was that the rate-determining step on most of these
(2,4-DCP) and pentachlorophenol (PCP)].322 The Pd/C gas- electrodes was the reduction of nitrate to nitrite, based on
diffusion cathode reductively dechlorinated the phenols when the values of the Tafel slope, the kinetic order, and the effect
hydrogen gas was present, and then it accelerated the two- of co-adsorbing anions. Cyclic voltammetry showed that cur-
electron reduction of O2 to H2O2 by feeding air for oxidation rent densities at given applied voltages for nitrate reduction
of the chemicals. The combined process of reduction and oxi- depended strongly on the nature of the electrode. The activi-
dation improved the chlorinated phenol degradation effi- ties for the electroreduction of nitrate decreased in the order
ciency with the removal efficiency of chlorinated phenols Rh > Ru > Ir > Pd and Pt for the transition-metal electrodes,
reaching nearly 100%. The degradation sequence was the and in the order Cu > Ag > Au for the coinage metals. On-
best for 4-CP, followed by 2,4-DCP, and then PCP. line mass spectrometry measurements for Pt and Rh showed
1,2,3-Trichlorobenzene (1,2,3-TCB) was used as a model for no formation of gaseous products such as nitric oxide (NO),
the degradation of a persistent organic pollutant (POP) under nitrous oxide (N2O) or nitrogen (N2), suggesting that ammo-
an inert gas atmosphere, as summarized in Table 5.323 Trace nia and hydroxylamine were the main products using
amounts of dichlorobenzene were observed with different transition-metal electrodes. This conclusion was in agree-
amounts depending on the electrode material. Electrodes ment with the known mechanism for NO reduction, which
with Ru and Pd were selective mainly for meta-position de- forms N2O or N2 only if NO is in solution. For Cu, measure-
chlorination, while those with Pt groups were selective ments showed the production of gaseous NO, which could be
mainly for ortho-position (o-position) dechlorination. A PdO explained by the weaker binding of NO to Cu as compared to
sintered electrode had an especially high selectivity for transition metals.
meta-position (m-position) dechlorination. Different cathode materials were examined for nitrate re-
The electrochemical dechlorination of chlorobenzenes was duction in an electrocatalytic reactor consisting of a solid
studied in the presence of various arene mediators such as polymer electrolyte/Pt electrode assembly. The reactivity and
naphthalene, biphenyl, phenanthrene, anthracene, and selectivity of electrocatalytic reduction of NO3−/NO2− in the
membrane electrode assembly (MEA) reactors were largely de-
pendent on the metallic composition of the cathode. Pt alone
Table 5 The dechlorination rates with different noble metals323 was relatively inactive, but rates were significantly improved
Cathode electrode Dechlorination rate (%) by the deposition of Ni, Cu, Ag and/or Rh onto the Pt
electrode. Although the activity was enhanced mostly by Cu
Sintered RuO2 (major)/Pt/PdO 91
Pt (major)/IrO2/RuO2 81 or Ag, their reaction mechanisms were quite different. Cata-
Sintered RuO2 59 lytic hydrogenation of nitrate (H2–NO3− reaction) occurred on
Sintered PdO 96 the Cu–Pt cathode, compared to electrochemical nitrate re-
Sintered Pt 53
duction using a Ag–Pt cathode.334
Sintered PdO/Pt 97
Sintered Pd/Pt 82 These results suggest that synergistic positive electro-
Plain Pd plate 70 chemical impacts can be obtained when using two or more

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metallic species on the surface of the working with a decrease from 25 to 11%. Faradaic efficiency (% FE)
electrodes.335–338 Anastasopoulos et al. synthesized composi- increased with the increase of nitrate concentration from
tional gradient thin films of PdCu alloys and found that a 25% at 0.1 M to 78% at 1 M, with 95% of the nitrate reduced
low concentration of Pd in copper resulted in the normally ir- in both cases. At high concentrations of nitrate, hyponitrite
reversible copper surface redox becoming reversible. This and hydroxylamine were detected as intermediates of the
change led to a sharp increase in the rate of both nitrate and reduction.350
nitrite reduction. In both cases, these effects were thought to To develop a theoretical model of the electrochemical re-
be associated with the ability of Pd to activate water.339 duction of nitrate ions, a powerful analytical method, called
Sn modification of polycrystalline palladium or platinum the Homotopy Analysis Method (HAM), was used. This ap-
films on gold electrodes enhanced nitrate reduction. Modifica- proach, which provides a convenient way to control and ad-
tion with Sn was the key to these rates as pure Pd did not have just the convergence region and rate of approximation series
a measurable impact on nitrate reduction. The dominant vol- when necessary, was used to obtain approximate analytical
atile products identified were N2O and smaller amounts of solutions to a nonlinear ordinary differential equation. The
N2, while NH2OH was the dominant non-volatile product.340 obtained analytical expressions of concentrations and current
The activity for electrocatalytic reduction of nitrate on the were found to provide satisfactory agreement with numerical
amorphous Pd33Ni60P7 electrode was tested with cyclic solutions.351
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voltammetric in a neutral 0.1 mol L−1 KClO4 solution with or


without KNO3. The Pd33Ni60P7 alloy enhanced nitrate reduc-
tion in comparison with the electrodeposited films of Pd, Ni
4. Electrocoagulation/
and Pd–Ni, likely attributed to its amorphous structure. The electrocoagulation–flotation
reduction reaction of NO3− on the electrode was found to be
Electrocoagulation (EC) is a process which causes the in situ
a totally irreversible process.341
electrochemical production of coagulated species and metal
The use of carbon as a substrate material for the prepara-
hydroxides that destabilize and aggregate particles or precipi-
tion of the working electrode has major advantages over other
tate and adsorb the dissolved contaminants.352–354
materials, due to its good conductivity, high surface area, good
Compared to the conventional coagulation process, the
fluid permeability, relatively high overpotential for hydrogen
electrocoagulation process has been proven to be very effec-
evolution, and high chemical stability over a wide range of pH
tive for contaminant removal from water with two outstand-
values. Hybrid electrode materials, with metals dispersed on
ing characteristics. On the one hand, it provides better re-
activated carbon fiber (ACF) and surface-functionalized carbon
moval capabilities for the same species than chemical
nanotubes (CNTs), have therefore been pursued for nitrate re-
coagulation without addition of chemicals. On the other
duction. Pd/Sn-modified activated carbon fiber (ACF)
hand, it produces less sludge, thus lowering the sludge dis-
electrodes were fabricated by the impregnation of Pd2+ and
posal cost.355–359
Sn2+ ions onto ACF by Wang et al. Electrocatalytic reduction
In practice, an electrocoagulation (EC) process will be often
of nitrate was shown, by this Pd/Sn–ACF electrode, with the
followed by an electroflotation (EF) process that is a simple
Pd/SnIJ4/1)-modified ACF electrode producing the highest
process where pollutants can float to the surface of a water
rates of nitrate reduction over a pH range of 5.3–7.6.342
body via tiny bubbles of hydrogen and oxygen gases generated
Other approaches to enhance nitrate reduction include de-
from water electrolysis. This combined system can be consid-
position onto traditional glassy carbon electrodes to study the
ered as an electrocoagulation–flotation (ECF) process.360,361
reaction kinetics. A GC/MWCNT–Rh electrode was prepared by
electrodepositing multi-walled carbon nanotubes modified
with rhodium particles on a glassy carbon electrode. It is inter- 4.1 Effects of various operating parameters on EC
esting to observe that during prolonged electrochemical reduc- It can be noticed from the literature that the efficiency of EC
tion of nitrite, the catalytic activity of this hybrid electrode processes significantly depends on the operating parameters.
remained almost unchanged demonstrating good temporal Solution pH and current density are the variables that have
stability. This suggests the substantial absence of poisoning been studied widely.362–365
due to irreversible and strong adsorption of reactants, interme- 4.1.1 Effect of solution pH on performance. The influent
diates, and/or reaction products on the active catalytic sites.343 pH has been established to be an important operating factor
Nitrate concentrations can also impact rates, showing that influencing the performance of electrochemical processes.
they do not proceed according to zero-order kinetics.344–349 For the EC process, the maximum pollutant removal effi-
Katsounaros et al. showed that the impact of nitrate con- ciency is obtained at an optimum solution pH depending on
centration on the rate of nitrate reduction could be ade- the nature of the pollutants. The pollutant removal efficiency
quately described by a simple Langmuir–Hinshelwood kinetic decreases by either increasing or decreasing the pH of the so-
model. The selectivity to nitrogen increased from 70 to 83% lution from the optimum pH. It should be noted that one of
as the concentration of nitrate increased from 100 to 1500 the advantages of this process is that the effluent pH after
mg L−1, and then it remained almost constant at higher ni- electrocoagulation treatment would increase for acidic influ-
trate concentrations. Ammonia exhibited the opposite trend, ents but decrease for alkaline influents.

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A study of the influence of the pH of waste in the coagula- It is a known fact that the operating current density in
tion with aluminum by conventional and electrochemical dos- ECF processes directly determines the coagulant dosage and
ing showed that a simple change in the pH of the waste could the rate of bubble generation, which influence both mixing
result in a significant change in the efficiency of the coagula- and mass transfer in the reactor.
tion process, and that if the same pH conditions were found at For example, the work by Holt et al. has reported that at
the end of the treatment, the efficiencies of the solution dosing low operating currents in which settling dominates, the pol-
and electrochemical dosing technologies were very similar.366 lutant fraction that is removed by flotation increases as the
The effect of initial pH on the batch removal of syntheti- current increases because at higher operating current densi-
cally prepared wastewater having high concentration of hu- ties, bubble densities increase, resulting in a greater upward
mic substances has been investigated by the electro- momentum flux and thus faster removal of pollutants and
coagulation method using plate electrodes. The effects of coagulants by flotation from the active reactor volume to the
initial pH on an electrocoagulation system may be twofold. surface.371
These are distribution of the aluminum hydrolysis product, On the contrary, the obtained results from the studies by
transformation of the humic substance related to the initial Mohora show that the increase in operating current density
pH and finally the effects of the gel layer especially at high caused a decrease in reactor DOC removal efficiency. They
humic substance concentrations and high initial pH formed concluded that for higher operating current densities, more
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on the anode surface. They observed that the initial humic aluminum was available per unit of time in the ECF reactor
substance concentration and initial pH have great effects on volume but its residence time in the active reactor volume
the removal rate and efficiency. For example, in the range of was shorter, which caused the decline in NOM removal
200–500 mg L−1, a decrease in the removal efficiency was ob- efficiency.372
served due to gel layer formation on the surface of the anode.
In order to prevent this gel formation, the initial pH of the 4.2 Application of EC and ECF processes
wastewater was adjusted to 5.0 and high removal efficiencies Electrocoagulation was first proposed in the nineteenth cen-
were observed.367 tury and the first treatment plant was erected in 1889 in Lon-
The removal of hexavalent chromium from synthetic solu- don for the treatment of sewage wastewater. EC or ECF pro-
tions with different pH values using the electrocoagulation cesses are now used widely in the treatment of many types of
method was studied. The results showed that the pH of the wastewaters including dye and textile wastewater,373–377 re-
solution has a significant effect on the CrIJVI) removal effi- fractory oily wastewater,378–380 municipal wastewater,381–385
ciency and the maximum chromium removal efficiency was manufacturing wastewater,386–388 and wastewaters with phe-
obtained at pH = 4. They further reported that the pH of the nol,389 toxic metals390–393 and inorganic metals.394–398 Bench
synthetic solution after the EC process increased with an in- and pilot-scale research studies on using EC and ECF tech-
crease in the electrolysis time due to the generation of OH˙ in nologies to remove pollutants from many types of water and
the EC process.368 wastewaters were recently reviewed by Emamjomeha et al.,399
4.1.2 Effect of applied current density on EC. The current while Khandegar et al. provided a more focused review on re-
density is an important experimental parameter for control- moval of dyes from textile effluents.400
ling the electrochemical reaction rate. In the case of the The performance of EC/ECF technologies can be enhanced
electrocoagulation process, the current density determines by integrating the process into a process train with other
the amount of Al3+ or Fe2+ ions released from the respective technologies. For example, Farhadi et al. compared electro-
electrodes and thus affects the electrocoagulant dosage rate coagulation with photoelectrocoagulation, peroxi-electro-
in the electrochemical cell.369 coagulation, and peroxi-photoelectrocoagulation for the re-
It should be noted that the selection should be fixed with moval of COD from pharmaceutical wastewater. Under
respect to other operating parameters like solution pH, tem- optimum operating conditions for each process, the COD re-
perature and flow rate. moval efficiency was in the order of peroxi-electrocoagulation
The effect of the current density and flow rate of a > peroxi-photoelectrocoagulation > photoelectrocoagulation
continuous-flow electrocoagulation–flotation reactor on the > electrocoagulation.401 Cotillas et al. looked into coupling of
removal efficiency for direct red 81 dye was investigated by electrocoagulation with iron electrodes and UV irradiation
Salim Zodi et al. The results indicated that the current effi- (photoelectrocoagulation) for the simultaneous removal of
ciency (Faradaic yield) was strongly dependent on flow rates turbidity and bacteria (Escherichia coli) from treated munici-
and current densities. For example, the efficiency of this spe- pal wastewaters. Coupling UV irradiation to electro-
cific reactor produced a considerable DR 81 removal from coagulation was shown to improve the process performance
71.5% at 100 A m−2 to 90.2% at 200 A m−2 for the same flow compared to electrocoagulation alone. An examination of the
rate of 10 l h−1. When the flow rate was increased to 28 l h−1, effect of current density on process performance showed that
the dye removal efficiency increased from 61.5% at 100 A m−2 there was a synergistic interaction of both technologies at
to 76.8% at 200 A m−2. Hence, to achieve higher DR 81 re- low current densities (1.44 A m−2), but an antagonistic effect
moval efficiency, the current density needs to be higher when at high current densities (7.20 A m−2). This antagonistic effect
the flow rate is increased.370 was caused by the less efficient transmission of UV

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irradiation to the bulk solution due to the increase in the


concentration of solids.402
Grey water treatment using electrocoagulation (EC) was ex-
amined in an integrated process with a submerged mem-
brane bioreactor (SMBR). The combined EC–SMBR process
resulted in a 13% reduction in membrane fouling. COD and
color removal increased from 86% and 91.2%, respectively,
using only the submersed membrane bioreactor, to 88.6% Fig. 14 Schematic of BMED (BP, bipolar membrane; A: anionic
and 93.7% with EC–SMBR.403 membrane; C: cationic membrane; M+: cation; X−: anion; H+: hydrogen
Treatment using EC was enhanced when combined with ion; OH−: hydroxide ion; CH3O−: methoxide ion).407
ozone treatment or hydrogen peroxide treatment. Song et al.
showed that the color removal efficiencies of the azo dye (C.I.
Reactive Black 5), reached 10% by treatment with only ozone mixture using an organic extractant HR (a complexing agent,
and 83% with only EC, but the combined process achieved where R = OH− or CH3O−) at a slightly alkaline pH, which was
94% color removal.404 A combined electrocoagulation process maintained by the OH− ions supplied by a bipolar mem-
followed by electrogenerated hydrogen peroxide treatment brane; second, movement of the bound Cu2+ ions across the
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was evaluated for copper ion removal from an industrial cation-exchange resins to decrease the ohmic resistance of
wastewater.405 The maximum COD removal was 80%, which the compartment filled with HR to the other compartment
was about 20% greater in terms of COD removal than that of along with the organic solution; third, release of the bound
copper electrocoagulation alone. This additional organics re- Cu2+ ions by substitution with the H+ ions from water split-
duction was due to a Fenton-like reaction between CuIJII) ions ting, which regenerates the HR. Tests showed that this ap-
that remained in solution and the peroxide, generating OH˙ proach, along with the use of ion exchange resins as a cham-
which oxidized the organics that were not adsorbed by the ber spacer, improved current densities and substantially
electrocoagulation treatment. increased performance. An average current efficiency of 90%
was achieved at a current density below 5 mA cm−2 with a gel
5. Electrodialysis ion-exchange resin, compared to a porous cation resin.409
A BMED process as a tool for the reclamation of NaOH
An electrodialysis (ED) process is an electrochemical separa- from glyphosate neutralization liquor was investigated as well
tion process where ions are moved across polymeric anion- as its subsequent use as an absorbent for CO2 capture.410 A
and cation-exchange membranes in a potential field (voltage). bench-scale BMED process was also used to examine the in-
When an electrical potential difference is applied across an fluence of operating conditions on the recovery of HCl and
alternating series of cation- and anion-exchange membranes NaOH from seawater RO concentrates. The results showed
between two electrodes, positive ions migrate to the cathode that this technology was a technically feasible option for the
(negative electrode) and negative ions migrate towards the production of 1.0 M or higher acid and base solutions that
anode. The presence of the ion exchange membranes traps could potentially be used within the treatment plant, with
them in alternating compartments, resulting in streams of di- current efficiencies in the 60–90% range (Fig. 16).411
lute and concentrated ions.406 ED has also been integrated with processes used in water
Development of ED processes was initiated in the 1950s treatment and reuse, including pressure-driven membrane
for production of table salt, when polymeric IEMs were processes, such as microfiltration (MF), ultrafiltration (UF),
manufactured on a commercial scale. Since then, ED has nanofiltration (NF), and reverse osmosis (RO). A pilot-scale
been a useful process for separation of ions and salts using wastewater treatment and reuse system was developed using
IEMs. The development of a bipolar membrane, which is a ED and MF, which indicated that the treated water using
composite membrane consisting of a cation-exchange layer such integration could meet the standards of water reuse and
and an anion-exchange layer pressed together, realized the its quality remained stable for more than 6 months.412
splitting of solvents into H+ and OH−/CH3O− at the interface UF was used as a pre-treatment process prior to ED (UF–
under a reverse potential bias. The use of this bipolar mem- ED) to treat river water and use it to add to surface waters to
brane has resulted in new technologies categorized as bipolar balance the depletion of surface water caused by excessive ex-
membrane electrodialysis (BMED).407 This solvent splitting ploitation.413 The results showed acceptable reductions in
technique has been used in more applications than other concentrations for the following ions: Cl−, SO42−, NO3−,
conventional ED techniques (CED) in chemical or bio- HCO3−, Na+, Mg2+, K+ and Ca2+. The use of NF, rather than
chemical synthesis, food processing, and pollution control UF, resulted in insufficient removal of these ions, especially
(Fig. 14). the monovalent ions.
BMED was combined with an organic extraction process ED was also tested in conjunction with a membrane biore-
and an ion exchange process to develop an improved method actor (MBR).414,415 A CED process was used to concentrate
for Cu2+ recovery (Fig. 15).408 This integrated process re- the feed before it was pumped into MBRs to increase the so-
quired three steps: first, extraction of copper ions from the lution conductivity, and thus provide a more stable voltage in

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Fig. 15 Concentration of copper from mixture solutions.408


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Fig. 16 Bipolar membrane electrodialysis scheme to obtain acid and base (BP: bipolar membrane; C: cationic membrane; A: anionic
membrane).411

the ED stack. Water with high nitrate content was purified by ment of toxic and/or recalcitrant organic compounds. Conse-
using this integrated process. Denitrification by the MBR of quently, a number of studies have shown that DSA-type oxide
the concentrate produced by CED resulted in the treated wa- electrodes can be utilized in photo-assisted electrochemical
ter with a nitrate concentration below the acceptable value of degradation processes in which the limitation of generation
50 mg L−1. of highly reactive oxidants can be overcome through UV light
irradiation. In addition, these anodes can generate chloro ox-
6. Photoelectrochemical and idant species (Cl2, HOCl, and OCl−), when electrolysis is car-
sonoelectrochemical approaches ried out using a solution with a high chloride concentration
under certain pH conditions. Thus, the combination of the
In recent years, the integration of electrochemistry with photo-
chloro oxidant species generation and UV irradiation can re-
catalysis and sonochemistry methods has led to a new and inter-
sult in the formation of highly reactive species.416–424
esting possibility for treatment of pollutants from wastewater.
The photo-assisted electrochemical (PAE) removal of di-
methyl phthalate ester (DMP) was examined using a one-
6.1 Photo-assisted electrochemical methods compartment filter press flow cell and a commercial DSA an-
In the recent years, there has been growing interest in the ode.424 Removal rates were similar to those reported using
integration of photocatalysis and electrocatalysis for the treat- electrooxidation and a BDD anode. The highest rates of DMP

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and TOC removal were attained at high NaCl concentrations vice. A theoretical analysis showed that converting hydrogen
and current densities, due to the generation of high concen- energy to electricity and utilizing waste heat recovery for ad-
trations of reactive oxidants, such as ˙OH radicals, as well as sorption chiller or heat pump applications resulted in good
other oxidants (h+, O2˙−, and Cl˙), in the PAE method. Thus, energy savings.434
the PAE method improved the production of these chemicals Hydrogen gas production with simultaneous COD removal
and the rate of pollutant transport and degradation. was achieved by electrochemical treatment of landfill leach-
ate. The rates and yields of hydrogen gas were investigated
6.2 Sonoelectrolysis (SECT) using different applied voltages with aluminum electrodes
and a DC power supply. Hydrogen gas was concluded to be
In an electrochemical oxidation process for the treatment of
mainly produced by ED of the leachate organics based on
pollutants, the current efficiency usually gradually decreases
negligible H2 gas production using water in control experi-
during treatment. Thus, the pollutants and their intermedi-
ments. The highest COD removal (77%) was obtained with
ates are often adsorbed onto the electrode surface during oxi-
an applied voltage of 4 V.435
dation and reduce the active sites on the electrode surface,
The recovery of heavy metals from industrial aqueous so-
resulting in partial or complete poisoning of the electrode.
lutions has received great attention in recent years, mainly
Treatment efficiency requires that consistently higher oxida-
due to more stringent laws for the protection of the environ-
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tion efficiency be maintained. In addition, an electrochemical


ment. Conventional techniques for metal ion abatement,
process is often limited by the mass transport in the system,
such as hydroxide precipitation or direct electroreduction, do
which also decreases the current efficiency.
not result in sufficient removal. One alternative technique is
Recently, sonochemical technologies have been proposed
electrodialysis with the advantage that the low concentration
in order to activate the electrode surface and enhance mass
of heavy metals can be concentrated, and the remaining ef-
transfer efficiency. This hybrid process has been applied to
fluent water can be diluted for reuse. However, the disadvan-
degradation of several organic pollutants, including textile
tage of this approach is that it does not work well at high
dyes,425,426 aromatics,427,428 nitro compounds,429 and chlori-
metal concentrations due to membrane fouling. Therefore, a
nated compounds.430,431 The efficient conductive diamond
future research direction could be some hybrid method to en-
electrochemical oxidation (CDEO) coupled with ultrasound
hance electrodialysis processes through methods that reduce
(US) was recently used for the degradation of progesterone in
membrane fouling. For example, for copper recovery and wa-
wastewater. Synergistic effects were clearly observed on the
ter reuse from copper electroplating wastewater, a laboratory-
oxidation rates due to the improvement of mass transfer to
scale process was developed that combined electrolysis (EI)
the conductive-diamond surface of the electrode.432
and ED. The results showed that this combined process
could achieve high recovery of both copper and water using
7. Combination of electrochemical wastewater with high or low concentrations of copper. Almost
processes for resource reclamation 99.5% of copper and 100% of water could be recovered.436
from wastewaters Compared to copper, the recovery of nickel is more chal-
lenging because the electrodeposition of nickel on the cath-
In recent years, various electrochemical approaches have ode is difficult due to the hydrogen evolution reaction, and
been used to degrade organic matter in aqueous solutions, therefore the recovery efficiency is low.437 The feasibility of
but wastewater treatment facilities consume a large amount nickel recovery and water reuse was investigated using three
of energy. Therefore, it is useful to develop novel hybrid tech- electrochemical processes (EI, ED and electrodeionization
nologies that can purify water and save or even generate elec- (EDI)) for both high and low nickel concentrations in waste-
trical power. water. Almost 99.8% of nickel could be recovered, with a pu-
The possibility for both electrochemical degradation of rity of 93.9%, and nearly 100% of water could be reused.438
wastewater organics and simultaneous production of hydro- ED has been combined with membrane processes, such as
gen fuel has been recently explored. The electrochemical oxi- membrane filtration (MF), nanofiltration (NF), and reverse os-
dation process with an option of microfiltration for real mu- mosis (RO) processes along with precipitation–neutralization
nicipal wastewater treatment was investigated in terms of processes to treat recycled water and sulfuric acid rinses from
organic matter removal and hydrogen generation.433 Hydro- lead battery production lines.439 On average, 88 wt% sulfuric
gen production was enhanced with municipal wastewater acid and 25 wt% rinse water were recovered. This treatment
due to the presence of specific organics and by adding NaCl resulted in savings due to both water and acid recovery, along
to increase conductivity. The average current efficiency and with additional savings due to a reduction in the chemicals
the energy efficiency increased by approximately 10% when needed for neutralization and the costs of sludge disposal.
wastewater organics were present, whereas they increased by An integrated ED–electrochlorination process was also
>20% when 50 mM NaCl was added to wastewater. used to treat wastewater. The process reduced the wastewater
Other research studies have shown that it is possible to conductivity and TOC concentrations, and produced a valu-
carry out wastewater treatment, hydrogen production, and able hypochlorite solution in the electrode rinse compart-
waste heat recovery in a single electrochemical processing de- ment (Fig. 17).440

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Fig. 17 Experimental set-up.440

8. Conclusions Fenton process seems to be towards integrated processes, such


as photoelectro-Fenton, sonoelectro-Fenton and peroxi-
Environmental electrochemistry can be used to achieve a electrocoagulation methods, with the aim of obtaining a syner-
cleaner environment, as evidenced by the increasing number getic effect for water and wastewater treatment.
of new technologies and successes in treatment of polluted Although laboratory and pilot tests have been successful,
waters that were provided here in this review. Some of the industrial applications of these electrochemical oxidation
most promising aspects are based on the use of different oxi- methods are still limited, due to the relatively high energy
dation strategies and combinations of different technologies. consumption needed to treat low concentrations of chemicals
Electrochemical oxidation is considered to be a very pow- in wastewater.
erful tool able to mineralize completely non-biodegradable Future development of electrochemical oxidation tech-
organic matter. Anodic oxidation of organic contaminants niques will require development of anode materials with spe-
can be performed in several different ways including direct cific characteristics that can make the process economically
and indirect oxidation. Compared with direct anodic oxida- competitive with other conventional technologies. Energy
tion that leads to very poor decontamination, indirect anodic consumption could be reduced using so-called “advanced
oxidation via intermediates of oxygen evolution can avoid electrochemical oxidation processes”, based on the combina-
electrode fouling, in which the nature of the electrode mate- tion of anodic and cathodic electrogeneration of highly oxi-
rial strongly affects both process selectivity and efficiency. dizing hydroxyl radicals.
Other strategies of indirect oxidation pathways for organic Three electrochemical reduction processes, electrodeposi-
oxidation, such as active chlorine mediation and E-Fenton pro- tion, cathodic electrochemical dechlorination, and electro-
cesses, are powerful and effective approaches for wastewater chemical denitrification, were presented as the proposed
treatment. For the interaction of active chlorine with organics, technologies for the removal and reclamation of pollutants
further research directions should focus on developing novel from wastewater.
electrode materials that can suppress the side formation of For electrodeposition, the main advantage is that the de-
organochlorinated intermediates. Results from the literature posited metals can be easily recycled by electrometallurgical
cited here show that the electro-Fenton process with a BDD processes. However, the surface of the cathode is modified
anode was the more powerful treatment for organic pollutants during electrodeposition and it may need additional treat-
with a higher amount of reactive ˙OH than is expected to be ment. The electrodeposition of some heavy metals, like
formed on a BDD alone. Further development of the electro- nickel, on the cathode is difficult due to the hydrogen

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evolution reaction which can greatly reduce the recovery effi- The integration of electrochemistry with photocatalysis
ciency of the metal. and sonochemistry methods has led to a new and interesting
For cathodic electrochemical dechlorination, the choice of possibility for the treatment of pollutants in wastewater.
the cathode materials has been found to have a major effect Using a photo-assisted process, it is possible to promote the
on the efficiency of this process, as it governs the reaction direct generation of highly reactive species, such as ˙OH radi-
pathway and the selectivity. One of the main issues in the cals, and also a series of other oxidants (h+, O2˙−, and Cl˙) in
electrochemical reductive dechlorination of organic chlorides the bulk solution that would be absent in a purely electro-
is the energy consumption associated with the process. The chemical approach. Sonochemical technology shows promise
cost of the electricity needed for driving the electrolysis is too as a method to improve the electrochemical process by acti-
high to enable commercial success of this approach, and vating the electrode surface and enhancing mass transfer effi-
therefore suitable electrocatalysts are needed to lower the cell ciency. Presently, greater effort is needed to fully understand
potential and thus reduce energy demands. the degradation process that occurs with hybrid electro-
Electrochemical denitrification is receiving increased at- chemical technologies.
tention because of its advantages as an environmentally The electrochemical processing of wastewaters can have high
friendly, safe, selective, and cost-effective technique. From an energy demands, and therefore developing novel hybrid technol-
environmental viewpoint, it is advantageous in that no ogies that can purify water and generate or save energy is ur-
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chemicals are needed for the process, and nitrogen com- gently needed to advance the applications of these technologies.
pounds formed by the electrocatalytic reduction of nitrate The possibility for both electrochemical degradation of wastewa-
can have value. The efficiency of electrode reactions depends ter organics and simultaneous resource reclamation of materials
strictly upon the chemical and physical nature of the working in wastewater during treatment could make many of these pro-
electrodes. Synergistic electrochemical effects, in terms of cesses useful compared to existing technologies.
catalytic activities, can be obtained when two or more metal-
lic species are mixed together on the surface of the working
electrodes. Although the reaction mechanisms on binary or Acknowledgements
ternary electrodes have been extensively examined, many sub-
This work was supported by the National Natural Science Fund
jects including the specific role of the foreign metal, the opti-
for Distinguished Young Scholars (Grant No. 51125033) and
mal surface composition, the surface morphology, and other
the State Key Laboratory of Urban Water Resource and Envi-
factors are still under investigation and evaluation.
ronment (Harbin Institute of Technology) (No. 2015DX05).
Electrocoagulation (EC) and electrocoagulation/flotation
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