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Research trends in the development of anodes for electrochemical oxidation

of wastewater

Article in Reviews in Chemical Engineering · March 2022

DOI: 10.1515/revce-2021-0067

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 Rev Chem Eng 2022; aop

Review

Devendra Rai and Shishir Sinha*

Research trends in the development of anodes for

electrochemical oxidation of wastewater
https://doi.org/10.1515/revce-2021-0067 1 Introduction
Received July 28, 2021; accepted December 27, 2021;
published online March 25, 2022
1.1 Background information to the
Abstract: The review focuses on the recent development in
electrochemical wastewater treatment
anode materials and their synthesis approach, focusing on
Over the last decades, several research efforts have been
their compatibility for treating actual industrial wastewater,
made for developing a broader domain, cost-effective, and
improving selectivity, electrocatalytic activity, stability at
higher concentration, and thereby reducing the mineraliza- sustainable technologies for the treatment of wastewater
tion cost for organic pollutant degradation. The advance- from industries containing persistent organic and inor-
ment in sol–gel technique, including the Pechini method, is ganic pollutants and heavy metals. Industries that have
discussed in the first section. A separate discussion related to massively invested in wastewater treatment technology
the selection of the electrodeposition method and its can find it challenging to adopt the technological changes
deciding parameters is also included. Furthermore, the effect in terms of cost, knowledge, and belief. The more adapt-
of using advanced heating approaches, including microwave able solution could be the technologies that can blend with
and laser deposition synthesis, is also discussed. Next, a their existing wastewater treatment plan, be cost-effective,
separate discussion is provided on using different types of and take smaller land and labor requirements to achieve
anode materials and their effect on active •OH radical gen- the required discharge wastewater standards. Advanced
eration, activity, and electrode stability in direct and indirect technologies should be compatible with the conventional
oxidation and future aspects. The effect of using different treatment for smoother adaptation by industries. The
synthesis approaches, additives, and doping is discussed emerging technologies include membrane distillation,
separately for each anode. Graphene, carbon nanotubes enzymatic treatment, and advanced oxidation processes
(CNTs), and metal doping enhance the number of active sites, like photocatalysis, H2O2/UV/O3 treatment, Fenton and
electrochemical activity, and mineralization current effi- Fenton-like, ultrasonication, supercritical water oxidation,
ciency (MCE) of the anode. While, microwave or laser heating and electrochemical oxidation (EO) (Buthiyappan et al.
approaches were proved to be an effective, cheaper, and fast 2016; Chaturvedi et al. 2021; Julian et al. 2021). EAOPs have
alternative to conventional heating. The electrodeposition been most extensively studied due to their ability to
and nonaqueous solvent synthesis were convenient and degrade pollutants in a broader domain and compatibility
environment-friendly techniques for conductive metallic and with any existing wastewater treatment technology to
polymeric film deposition. improve its performance (Naje et al. 2017).
Keywords: CO2 laser deposition; electrochemical oxida- EO is a widely studied treatment approach for waste-
tion; electrodeposition; microwave synthesis; photo elec- water treatment. EO treatment can degrade various
tro-Fenton. persistent organic compounds that cannot be treated using
conventionally accepted technologies like adsorption,
anaerobic and aerobic digestion. It has several advantages
related to operation, environment, and safety. The process
can be considered safe as it allows operation at normal
*Corresponding author: Shishir Sinha, Department of Chemical temperature and pressure. The process uses an electrical
Engineering, Indian Institute of Technology Roorkee, Roorkee, charge as fuel, generally does not require any external
Uttarakhand 247667, India, E-mail: [email protected]
Devendra Rai, Department of Chemical Engineering, Indian Institute of
chemicals, and produces no toxic waste. Moreover, this
Technology Roorkee, Roorkee, Uttarakhand 247667, India. process can be adapted with conventional treatment
https://orcid.org/0000-0001-5606-2364 technologies as a pre-/post-treatment approach. Designing
2 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

a suitable electrochemical reactor and selecting compat- stated in Eq. (6). The oxidation reaction competes with the
ible electrodes are significant challenges associated with oxygen evolution reaction (OER) due to the chemical
electrochemical treatment (Agrahari et al. 2014). The se- decomposition of higher oxide (Eq. (7)). Active anodes
lection of electrodes depends upon the nature of the include platinum (Guinea et al. 2008; Sopaj et al. 2016),
pollutant and the mechanism involved during their dimensionally stable anode (DSA®), graphite, and similar
mineralization. Very recently, the advances in methods to carbonaceous electrodes (Bu et al. 2019). Carbonaceous
develop compatible electrode materials for wastewater electrodes have a large surface area and are generally used
treatment was reviewed by (Salazar-Banda et al. 2021). as 3D-electrodes, e.g., in packed and fluidized bed reactors
However, there is a need to emphasize the effect of (Zhang et al. 2013) as porous electrodes.
selecting different electrode material and their compati-
M(•OH) → MO + H+ + e− (5)
bility with the type of wastewater to be treated. The selec-
tive or complete oxidation of contaminants is carried out at MO + R → M + RO (6)
the surface of anode (M) in three ways:
(i) The direct electron transfer reaction is shown in Eq. MO → M + ½ O2 (7)
(1), showing the oxidation of adsorbed pollutants at Non-active anodes, on the other hand, provide non-
the anode surface. This reaction is theoretically car- selective and complete demineralization of organic con-
ried out at low anodic potential before oxygen evo- taminants to CO2 and H2O at the intermediate layer of
lution reaction (OER), without the involvement of any M(•OH) formed between the anode and solution (Eq. (8)).
external oxidizing agent other than free electrons These electrodes do not effectively participate in the reac-
(Panizza and Cerisola 2009). tion but produce hydroxyl radicals in large amounts,
(ii) Using the physisorbed reactive hydroxyl radicals radially available to react with pollutants near the anode
(M(•OH)) produced during water discharge reaction surface. The decomposition of organic components can
(Eq. (2)), and partly with the help of relatively low also get affected with the competing side reactions to either
oxidation potential compounds like H2O2 and O3. generate lower oxidation potential compounds (Eq. (3)) or
These compounds are produced as parallel reaction direct conversion to oxygen (Eq. (9)). Nonactive anodes
by-products through dimerization of hydroxyl radi- include some TiO2 based mixed metal oxide(s) (MMO),
cals at the anode surface, as shown in Eqs. (3) and (4), PbO2, SnO2, SbO2, and boron-doped diamond (BDD) elec-
respectively. trodes. Comminellis and Nerini (Comninellis and Nerini
(iii) By interacting with the weaker oxidants, electro- 1995) performed the EO of phenol using Ti/IrO2 active and
generated from the ions present in bulk. Intermediates Ti/SnO2 nonactive anodes under NaCl electrolyte medium
produced by the water oxidation reaction can also at a current density of 100 mA cm−2. The electrodes were
oxidize the organic pollutants (Moreira et al. 2017). prepared by thermal decomposition technique using iso-
Rads − ze− → Pads (1) propanol solution for dissolving the chloride salts of the
metals. The nonactive SnO2 anode due to the •OH free
M + H2 O → M(•OH) + H+ + e− (2) radical generation converts phenol into a carboxylic acid,
which further showed stability towards ClO−. However,
2M(•OH) → 2MO + H2 O2 (3)
when Ti/IrO2 active anode was used, the phenol was
3H2 O → O3 + 6H+ + 6e− (4) initially degraded through the organochlorinated com-
pounds formed during electrolysis which finally oxidized
The decomposition of organic contaminants using
to volatile organic compounds like CHCl3. This study in-
M(•OH) can occur in two different mechanisms depending
dicates the different chemistry involved during the miner-
upon the type of anode used, defined by Comninellis as an
alization of pollutants using active or nonactive anodes.
active and nonactive anode (Comninellis 1994). Active
anodes (having O2 evolution potential less than 1.8 V/SHE) M(•OH) + R → M + mCO2 + nH2 O + H+ + e− (8)
(where SHE stands for standard hydrogen electrode) con-
M(oOH) → ½ O2 + H+ + e− + M (9)
tains strongly bonded chemisorbed hydroxyl radical,
formed through the interaction between the adsorbed hy- While selecting suitable electrodes for industrial
droxyl radical with the lattice oxygen already present at the wastewater treatment, the main hurdle is that the elec-
anode, transforms it to a higher oxide or superoxide (MO), trode must be compatible with a higher concentration of
Eq. (5). The MO/M redox couple favors the partial/selective organic compounds. It should also allow its use in a wide
oxidation of organic compounds at the anode surface, as pH range depending upon the influent wastewater’s pH.
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 3

The neutralization of the effluent stream poses additional efficiency, space-time yield, specific energy consumption, and
costs to the process, and further use of external chemicals limiting current density. Space-time yield can provide the
like acids or bases can again contaminate the wastewater oxidation capacity of a reactor with respect to the specific
stream. Other factors include the cost of an electrode, electrode area (area/volume). Limiting current density ( jlim),
surface poisoning, and, most importantly, compatibility on the other hand, provide information regarding the
with the existing treatment technology (Nidheesh et al. maximum reactor duty under a mass transfer control chemical
2020; Popat et al. 2019). From the past decade, it has been reaction. It can be determined using Eqs. (10) and (11).
observed that more and more emphasis is focused on
Generalized equation : jlim = 4FVCODt (10)
selecting novel methodologies to develop stable and
compatible electrodes (Figure 1). This paper comprehen- For complete mineralization of organics:
sively includes the advanced synthesis approaches used jlim = 4AFk m CODt (11)
in the last 10 years to produce novel electrode materials,
COD0 − CODt
particularly in EO processes. ICE = FV × 100% (12)
8jSt

where F is Faraday’s constant (96,485 C mol−1); V is the

1.2 Performance indicators volume of electrolyte (L); COD0 and CODt are the COD (g L−1)
at the time (t) equals to zero and t seconds, respectively; j is
Several performance indicators are used to define the progress the applied current density (A cm−2); S is the effective surface
in mineralization/degradation, reactor performance, and area of the electrode (cm2).
assessment of the efficiency of the working electrodes. Panizza Current efficiency and energy consumption can be
and Cerisola (2009) categorized them in four parts: current directly related to the electrode’s performance for the
mineralization of specific pollutants. The current efficiency
is a measure to calculate the actual number of electrical
charges utilized to the charge transferred for the mineral-
ization of organic compounds. Several research groups
determine the current efficiency in different ways, but the
most common were instantaneous current efficiency (ICE),
gross current efficiency, and mineralization current effi-
ciency (MCE).
ICE can be determined either through the oxygen flow
rate (OFR) method or the chemical oxygen demand (COD)
method (Panizza and Cerisola 2009). The COD method is
more convenient and widely used but can provide false
results when volatile components are present in a more
significant amount in the solution. It can be determined
using Eq. (12). The ICE will be theoretically 100% if the
applied current density ( j ) is less than jlim.
MCE of the electrode provides information related to the
net charge consumed for the complete mineralization of the
organic compound. It can be determined using Eq. (13).
TOC0 − TOCt
MCE = nFV × 100% (13)
4.32 × 107 xjSt

where x is the total number of C atoms in a pollutant; n is

the theoretical number of electrons required for complete
mineralization; TOC0 and TOCt are the TOC (g L−1) at the
time (t) equals zero and “t” seconds, respectively.
Figure 1: Schematic diagram representing new synthesis methods, Electron efficiency (EE) is an efficient way to evaluate
novel electrode materials, and technological modifications reported the total number of electrons that participated in the
recently. complete mineralization of organic compounds during the
4 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

EO process is using electron efficiency (EE) (Wang et al. 2 Selection of synthesis approach
2019b), Eq. (14).
32 n Δ(TOC) 2.1 Sol–gel technique and related
EE = (14)
12 4x Δ(COD) improvements
Finally, the cost of electrochemical treatment can be
The sol–gel method is considered adequate for producing
determined using specific energy consumption (EC), usu-
metal oxide nanoparticles and films as it provides ease in
ally expressed in kWh LCOD−1 or kWh LTOC−1, Eq. (15). It is the
size and morphological control of the desired product.
amount of energy consumed to degrade (or completely
The precursor solution prepared using this technique
mineralize) the pollutant from wastewater.
allows a controlled structure of metal/mixed metal ox-
UjSt UjSt ides, and hence it is used in several deposition techniques
EC = or (15)
VΔCOD VΔTOC such as electrospinning and dip coating. The “sol” can be
The current efficiency depends on temperature, elec- any homogeneous suspension of solids in a liquid me-
trolyte concentration, electrode gap, electrode’s active dium having a size ranging from 1 nm to 1 μm. Later, the
surface area, and applied potential/current density for polycondensation of the “sol” to a three-dimensional
wastewater treatment. It can vary for the type of electrode network transforms it into a “gel” (Figure 2) (Danks et al.
used, its material, and fabrication technique. The current 2016). The primary step is preparing precursor solution,
efficiency can be improved by reducing the oxygen evo- which is usually a mixture of organometallic compounds,
lution reaction at the anode. OEP of the electrode is one of such as metal alkoxides or any hydrated nitrate or chlo-
the deciding factors for improving the current efficiency. ride metal salts, mixed in a solvent. The reaction initiates
Higher the OEP of electrode lesser the chance of depleting with the hydrolysis and condensation of the precursor
oxygen evolution side reaction, and better the electrode’s solution to form a gel, followed by aging, dehydration,
performance. and densification.

Figure 2: Classification of gels formed during sol–gel synthesis. Adapted from Danks et al. (2016).
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 5

The gel’s structure and hence the product’s structural ethylene glycol to obtain a homogenous precursor solution.
properties depend upon the rate of hydrolysis and conden- The prepared metal-citrate chelate is heated to remove water
sation. The structure can be controlled by regulating the pH, and initiate the polyesterification reaction in the second step.
solvent, catalyst, mixing, time, and temperature. Base Finally, the obtained polymeric matrix is calcined, usually
catalyst can enhance hydrolysis and condensation rate, between 400 and 900 °C, to obtain the final metal oxides. This
while the acidic catalyst can slow down the process by approach allows the use of metals lacking its stable hydroxyl
influencing the electron-donating/withdrawing tendency species, allowing cheaper metal salts like chloride and ni-
of –OH versus –OR groups in the water–alkoxide mixture trates. Pechini’s process is widely used to obtain mixed metal
(Soumya and Xavier 2022). Neutral catalysts have nearly no oxides and thin-film electrodes.
effect on the rate of reaction. Another variable is the pres- Pechini’s method can be modified by replacing the
ence of a solvent, which can affect the process in two ways: citric acid with other di-, tri-, or tetra-carboxylic acids such
improving the mixing or directly interacting with the central as EDTA and other small molecule ligands, as discussed
metal. The solvent can be water or any organic solvent such above, or replacing the polyalcohol (or using water to
as ethanol, termed the hydrolytic or nonhydrolytic route. lower the number of organics used) to obtain the desired
While dealing with transition metals alkoxides, the structural properties. These modifications help to obtain
electronegativity difference between the alkoxides and the metal/mixed metal oxide, bulk materials, and thin film
water/hydroxyl group can trigger the hydrolysis rate to a of the desired crystallinity and morphology. The control-
violent state that most processes can require special ling parameters are the “metal salt: chelate: polyalcohol”
handling and storage (Velasco-Hernández et al. 2020). ratio and hydrolysis rate (Sunde et al. 2016). For example,
Moreover, while synthesizing mixed metal oxides, the the complexing of metal cations depends upon the pH and
variable hydrolysis rate can lead to the phase separation of concentration of the precursor solution. Acidic cations like
the metals during the condensation step. These in- transition metals easily form a stable complex, while basic
stabilities can be regulated by introducing bidentate or cations like alkaline earth metals form weak complexes,
multidentate ligands into the solution to substitute some and the stability of various cations can be obtained by the
alkoxide groups at the metal site. The use of small size standard database (The IUPAC Stability Constants Data-
molecules (mostly the chelating agents) allows the use of base, Academic Software). Hence, the introduction of
more stable and cheaper metal salts as a precursor, chelating agents like EDTA having multicarboxylic group
providing stable aqueous metal complexes whose struc- helps improve the stability.
ture be similar to the gels (Huang et al. 2019). A few ex- Sometimes, acids (e.g., nitric acid) and bases (e.g.,
amples of small molecule gelators include lactic acid, ammonium hydroxide) need to be added to control the
glucose, amino acids, glycolic acid, oxalic acid, ethyl- catalysis and precipitation, respectively. Adding urea into
enediaminetetraacetic acid (EDTA), epoxides, urea, and the precursor can help obtain a more controlled rise in pH
citric acid. Citric acid is one of the most widely used weak of the solution with desirable production of –OH, which
triprotic acids in sol–gel chemistry. However, optimizing can help to precipitate metal ions like Sn2+and Sb3+ to
the pH in citric acid-based precursors is essential for the the metal substrate during the hydrolysis step (Figure 3)
proper binding of carboxylates sites to the metals. (H. Yu et al. 2021). Moreover, ammoniated compounds like
urea, glycine, and hexamine can be added as a complexing
agent and fuel in the precursor solution (Rakočevic et al.
2.2 Pechini and modified Pechni method 2021; Saranya et al. 2019).
The synthesis approaches discussed above almost
Pechini method was developed on a similar principle where work on a similar procedure to obtain a polymeric medium
citric acid (as a hydroxycarboxylic acid) is used as a chelating (or gel) into which the metal ions are homogenously mixed
agent to prepare a homogenous metal/citrate complex to obtain the metal oxide nanoparticles. Some polymers
(Dimesso 2016). This complex solution is taken to the further that are solvent dissolvable and can interact with the metal
step of transesterification using polyalcohol such as ethylene ions (i.e., having some functional groups present to bind
glycol. The metal cations get entrapped in a transparent the metal ions) have also been used. A few examples
polymeric gel-like structure, allowing a more controlled and include synthetic polymers such as polyvinyl alcohol
homogenous crystalline product. The synthesis approach can (PVA), polyethylene glycol (PEG), polyvinylpyrrolidone
be divided into three steps; first, the metal salts (usually ni- (PVP), and some biopolymers like starch and chitosan.
trates or chlorides) are dissolved in water with citric acid and Recent research suggests that the –OH containing complex
6 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Figure 3: The XRD, X-ray photoelectron spectroscopy, and infrared spectroscopy data showing the effect of urea precipitation over con-
ventional electrodeposition approach on Ti/SnO2–Sb (TSSA) electrode fabrication, represented as TSSA-U and TSSA-E, respectively. Adapted
with permission from H. Yu et al. (2021).

agents like PEG and PVA were found suitable to promote salts are dissolved in the electrolyte, and by optimizing the
homogeneity in the final oxides (dos Anjos Bezerra et al. cell potential, the oxidized or reduced metal can be
2020; Li et al. 2016a). deposited at the working or counter electrode. At the same
The selection of the sol–gel approach depends upon time, the reference electrode monitors the working elec-
the desired morphology (porosity and homogeneity), trode potential. Parameters such as temperature, current/
synthesis temperature, and electrocatalytic properties potential, pH, and electrolyte composition can be tuned to
of the electrode. The effect of using sol–gel chemistry, obtain the desired morphological properties of the depos-
the Pechini method, polymeric solvents, and non-aqueous ited film (Yan et al. 2020). Pourbaix diagram detail the
routes like ionic liquid (IL) on the stability, morphology, stability for various redox states of an element as a function
and electrocatalytic properties of the anode is discussed in of pH and applied potential. These data can be utilized to
the succeeding sections. thermodynamically control the generated species by
altering the potential, cation concentration, and electrolyte
pH. Certain additives can also be added to the electrolyte
2.3 Electrodeposition and other solution to optimize the film’s grain size and other
morphological properties (Hossain et al. 2020). However,
electrochemical routes
the material to be deposited should have good conductiv-
ity, and the uniformity of deposit over the substrate is a
Electrodeposition is considered the most convenient
more significant challenge (Li et al. 2021). Herein, we
binder-free method to fabricate thin-film metal oxide
discuss the parameters affecting the electrodeposition and
coatings, especially for PbO2 electrodes. However, few
the ways to optimize them.
studies revealed promising performance for the electro-
deposited oxides of SnO2-Sb and TiO2NTs anodes (Duan
et al. 2014, 2016; Yang et al. 2017; Y. Sun et al. 2020). The 2.3.1 Electrical input
electrodes can be fabricated with adjustable shape, ge-
ometry, and thickness using this approach. A two or three- The electrodeposition can be classified with respect to the
electrode system is used for electrodeposition. The metal mode of electrical input as constant potentiostaic/
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 7

galvanostatic electrodeposition and pulse electrodeposi- performance (Wang et al. 2020). Moreover, it provides
tion. Depending upon the mode of the controllable vari- additional controlling variables such as pulse frequency ( f ),
ables and hence the properties of desired metal/metal average current density ( j), and duty ratio (γ), allowing
oxide films can be adjusted. more control over the deposit. Xu et al. (2018) highlight the
effect of Fe–Ce co-doping on TiO2NTs enhanced PbO2 anode
2.3.1.1 Galvanostatic and potentiostatic mode and the advantage of using pulse electrodeposition over the
Galvanostatic input is a dynamic approach that applies conventional electrodeposition method. It was evident from
constant charge input during deposition. The optimized the scanning electron microscope (SEM) and X-ray diffrac-
current input helps regulate the crystal growth, adhesion, tion spectroscopy (XRD) results that the pulse electrodepo-
and atomic ratio (in mixed metals) and thus the nucleation sition achieved uniform morphology with smaller grain size,
rate (Darabizad et al. 2015). Most of the electrodeposited providing higher available active surface area and improved
anodes discussed below opted for galvanostatic input, stability. Similar results were obtained when the Co-doped
allowing easy control over diffusion resistance limitations. PbO2 electrode was prepared using pulse electrodeposi-
For PbO2 anodes, the deposition at lower current density tion (Wang et al. 2015). Hua et al. (2020) prepared a porous
supports the β–PbO2 formation (Liu et al. 2021). Additionally, Ti/PbO2 electrode using this technique at the L9-orthogonal
Bian et al. (2019) reported the effect of pH during the gal- array experiment using f, j, γ, and time (t) as four operational
vanostatic deposition of α and β–PbO2 layers. The alkaline variables. The experiment was also normalized with the
pH supports the formation of α–PbO2, while acidic pH favors electrode prepared using the constant current electrodepo-
the β–PbO2 layer formation at the same current density. sition technique. The porous morphology is only obtained
While conducting the passivation studies on metal using a pulse supply with compact and uniform grains at the
surfaces, potentiostatic deposition allows recording the substrate. Figure 4 represents the effect of changing the
electrical current response before and at the diffusion- electrical input on the Bi2Te2.71Se0.15 thin film electrodepo-
limited potentials. The visible decrease in cell current can sition. The pulsating input provides sufficient time for
be alleviated by decreasing the interfacial mass transfer amorphous material deposition during “ON” time and
resistance through stirring or rotating the electrode. Usu-
ally, the set potential depends upon the type of coating
metal and substrate. This deposition potential can be
determined using broad-range linear voltammetry studies.
However, while doing co-deposition studies, the control
over applied potential is challenging due to the difference
in the redox potential of metals/nonmetals. Sasidharan
Pillai and Gupta (2015) performed the potentiostatic
deposition of PbO2 over a mild steel substrate at a potential
window between 1 and 2.5 V. Acidic pH favors the β–PbO2
formation, but due to the corrosion limitation for the mild
steel substrate, the deposition was carried out in an alka-
line environment. Crystal nucleation was favored at higher
potential up to 2 V. Beyond this voltage, the nonaligned
outgrowth of the coating was observed as the film exfoli-
ation initiated due to the increased potential.

2.3.1.2 Pulse input

During electrodeposition, nucleation and grain growth are
the two parameters that decide the compactness and
structure of the coating. Nucleation is favored at high
overpotential, while grain growth is usually favored at
higher interfacial diffusion and lower overpotential. More- Figure 4: Schematic representing the mechanism of film deposition
using constant-potentiometric electrodeposition (a) and pulse
over, the undesired reactions can also be controlled by using
electrodeposition (b). SEM images of the Bi2Te2.71Se0.15 thin film
synchronous input, i.e., applying the pulsed voltage/cur- electrode prepared using constant-potentiometric electrodeposi-
rent. The pulse electrodeposition provides a more compact tion (c) and pulse electrodeposition (d). Reprinted with permission
and engineered metal oxide coating with superior from Hong et al. (2021).
8 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

separately gives enough time for its crystallization during reusability. The apparent reason for improved stability was
“OFF” time (Hong et al. 2021). attributed to smaller, uniform, and compact grains ob-
It is clear from this discussion that the available tained using ILs.
additional variables in pulse electrodeposition help con- Deep eutectic solvents (DES) are another category of
trol the nucleation and grain growth in a more organized room temperature ILs and are generally termed green sol-
way than the constant current deposition. The pulse input vents. Smith et al. (2014) detail the insights on DES. This
can also help adjust the diffusion resistance, undesired complex compound is obtained by reacting the quaternary
chemical reactions, and obtain a compact mixed compo- ammonium salt with metal salt or any hydrogen bond
sition of metal oxides with better coverage (Duan et al. donor compound. Having better biodegradability, DES
2014). provides good dissolvability, higher mass transfer, and
conductivity. These properties attract DES as an emerging
2.3.2 Electrolyte non-aqueous solvent for thermal and electrodeposition of
metal/metal oxide electrodes (Gu et al. 2011). Figure 5
2.3.2.1 Solvent shows some commonly used hydrogen bond acceptor
The electrolyte consists of the solvent, solute, additives, (HBA), and hydrogen bond donor (HBD) used as a DES.
and salts (if required to improve the conductivity of the Various research groups prepared SnO2 based electrodes
solution). Aqueous electrolytes are generally used when using choline chloride and ethylene glycol complexed DES
the required operating potential is between the hydrogen as a solvent from the past decade (Ghosh and Roy 2014;
evolution reaction (HER) and OER regions. The electrolyte Vieira et al. 2017; Yavuz et al. 2020; Y. Sun et al. 2020). The
can be replaced with broader domain solvents such as DES-prepared electrode attained better electrocatalytic
dimethyl sulfoxide (DMSO), IL, deep eutectic solvents, or properties and improved morphology with higher phys-
any other suitable organic solvent when the required po- isorbed •OH generation, making the electrodes a suitable
tential is beyond this domain. nonactive anode with higher conductivity and improved
As a nonaqueous polar solvent, ILs are getting much oxygen evolution potential (OEP).
attention in this field due to their chemical and thermal
stability over a wide potential window and good electrical 2.3.2.2 Mixed metal salts and additives
conductivity. Additionally, it can be recycled hence The composition of metal salts during electrodeposition
providing a window for less chemical wastage and better also significantly affects the morphology of the deposited
environmental compatibility. Apart from a history of film, especially in the case of co-deposition. In a mixed
effectively depositing several metals, ILs are receiving metal salt electrolyte bath, the deposition is thermody-
more attention for electrodepositing the metal oxides such namically favored for comparatively less noble metal (Fan
as SnO2 and PbO2 (Jie et al. 2018; M. Chen et al. 2021; Shao and Piron 1996). The reason can be attributed to the
et al. 2019; Zhang et al. 2021). Ju et al. (2012) performed localized disbalance of ions near the substrate posed by
potentiostatic electrodeposition to obtain Ti/PbO2 elec- diffusion resistance. The co-deposition film’s nucleation,
trode having high •OH generation ability, stability, and crystal growth, and catalytically active area can be

Figure 5: Some commonly used hydrogen bond acceptors (HBA) and hydrogen bond donors (HBD), used as DES. Adapted with permission
from Singh et al. (2021).
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 9

improved by adjusting the lower solute concentration and polar nature. Organic solvents typically do not participate
introducing some nonmetallic mild reducing agents in the in microwave heating. Polar solvents with high dipole
electrolyte (Chen et al. 2010; Li et al. 2021; Tang et al. 2020). moments such as water, polyalcohols, and ILs are found to
Additives are added to the electrolyte to improvise the compensate the ammonia.
electrode characteristics. Floride additives such as NaF can Dielectric loss factor affects the microwave heating in
enhance the stability of the PbO2 electrode by occupying solvents, which is better compensated by polar solvents
some active oxygen vacancies on the crystal layer, reducing with high dipole moments (Hoogenboom et al. 2009). Some
the chances of Pb3+ oxidation to Pb4+ ion. It can also enhance examples include water, dimethylfuran (DMF), DMSO,
the OEP by substituting the OH− from F− ion at the gel layer N-Methylpyrrolidone (NMP), ethanol, and polyalcohols
of the electrode (Cao et al. 2007; Hossain et al. 2020). The (Castro Luna et al. 2014). Other factors that affect microwave
newly reported boron nitride was reported to improve the heating include temperature and vapor pressure. Some po-
morphological, hydrophilic/hydrophobic, charge transfer lar solvents like water lose their polarity at higher temper-
resistance, and electrocatalytic properties of the electro- atures. Low boiling solvents like methanol and ethanol pose
deposited electrodes (Hossain et al. 2020). Other additives high vapor pressure inside the reactor, increasing the safety
include surfactants like cetyl pyridinium chloride (CPC) and concern. Hence, alternative low vapor-pressure solvents are
triton X-100, sodium dodecyl sulfonate (SDS), Tween-80, suggested for high-temperature reactions. The ionic con-
and PVP (Bhattacharjee et al. 2014; Darabizad et al. 2015; ductivity in ILs makes them a suitable alternative to the
Han et al. 2020). However, certain additives like NaF can be dipolar aprotic solvents. Further, they have low vapor
toxic to the environment, and hence few research trends pressure and good dissolvability for metal salts.
suggest the inclination towards using biodegradable ILs for
the electrolyte preparation. Moreover, the selection of ad-
ditives depends on the type of metal oxide(s) deposited, 2.4.2 Laser deposition
which can be complicated during co-deposition.
In general, electrodeposition can be considered a Laser deposition is a widely accepted technology for metal
complex dynamic procedure, as multiple factors affect the oxide film fabrication used in sensing, photocatalysis,
deposition mechanism. While optimizing the interfacial communication, solar cells, thermistors, and material pro-
solute concentration, pulse input, nonaqueous solvents, cessing applications (de Santana Mota et al. 2021; Ganz et al.
and compatible additives are encouraged. 1997). This technology is also reported as an alternative
heating approach for improved metal oxide crystal nucle-
ation and grain growth (Jung et al. 2021). Laser heating pro-
2.4 Advanced heating approaches vides a large temperature gradient and enhanced diffusion
rates as compared to the conventional heating approaches.
2.4.1 Microwave synthesis Furthermore, advanced nanostructured materials such as
nanotubes (e.g., C, TiO2, ZnO), nanorods (e.g., Fe2O3), nano-
Compared to the conventional heating approaches used in sheets, and nanocrystals with the desired morphology can be
hydrothermal and sol–gel synthesis, microwave irradiated produced using laser heating approach. For an exhaustive
heating provides pure metal/metal oxides with a superior discussion on the laser heating approach, the reader is
synthesis rate, uniform heating, and reduced energy con- referred to the outstanding review by (Palneedi et al. 2018).
sumption (Divyapriya and Nidheesh 2020). The micro- Santos et al. (2019), for the first time, fabricated a
waves can penetrate the material and provide volumetric Ti/RuxIr1 − xO2 electrode using the CO2-laser heating
heating throughout the sample. The process can be scaled approach. The fabricated electrode presented enhanced
up industrially limited to the low penetration depth heat- stability (1.6 times) and higher electrochemically active
ing applications (Morschhäuser et al. 2012). It works on the surface area (1.9 times) than the electrode prepared using
principle of selective absorption of microwaves by mobile high-temperature furnace heating. Furthermore, the same
electrical charges or ions present in the electrolyte. The research group successfully prepared the Ti/RuO2–TiO2
heat is produced due to the microwave energy conveyed photo-anode and Ti/SnO2–Sb electrodes using a similar
uniformly around the surface. The uniform volumetric heating mechanism (de Oliveira Santiago Santos et al. 2020;
heating can help elevate the temperature rapidly, thus G.O.S. Santos et al. 2020). In all cases, the laser heating
improving the pace of reaction up to 1000 times (Mirzaei approach was a promising and speedy way to obtain elec-
and Neri 2016). However, the heating characteristics of trodes with enhanced morphology, stability, and electro-
microwaves depend on the reaction medium, mainly on its chemical activity. However, the optical and thermal
10 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

properties of the precursor should be considered carefully Qing et al. (2021) prepared a cost-effective PtRu/graphite
for the effective selection of laser parameters. anode using a simple pulsed electrodeposition technique to
remove ammonia from the aquaculture wastewater. The
combination of PtRu alloy catalysts helps achieve high
3 Advancement in electrode electrocatalytic activity and easy ammonia removal of real
wastewater in batch and flow modes. Graphite felt (GF)
materials for wastewater provides higher surface area, very high porosity, and stability
treatment compared to planar graphite electrodes (Nidheesh and
Gandhimathi 2014a). Recently, when GF/β–PbO2 was
3.1 Active anodes compared with planar graphitic G/β–PbO2 anode for herbi-
cide mineralization, the former provided higher degradation
3.1.1 Graphitic anode (100 vs. 65%), better mechanical stability (115 vs. 91 h),
higher OEP (1.89 vs. 1.84) and almost one a half surface area
Graphitic anode grabs attention among research groups due (1.2 vs. 0.85 m2 g−1) (Rahmani et al. 2021). However, in another
to its low cost and environmental affability, providing no research work, G/β–PbO2 anode was prepared using a similar
additional contamination into the solution. Table 1 summa- electrodeposition technique, and remarkable removal effi-
rizes the recent synthesis approaches used to produce active ciency (96.4%) was observed for methylene blue (MB) treated
graphitic anodes for electrochemical advanced oxidation of as a model pollutant. Further, the biodegradability of actual
synthetic and real wastewater (Nidheesh and Gandhimathi textile wastewater was enhanced to the BOD5/COD > 4, which
2014b). The porosity and high surface area of graphitic can be considered biodegradable (Samarghandi et al. 2020).
electrodes allow easy deposition of metals and metal oxides. However, the efficiency of these electrodes depends upon the
Hence, graphite-supported anodes having better conductiv- surface and chemical characteristics like the number of
ity, improved hydrophilicity, •OH generation rate, and other active sites, the functional group attached to the surface, type
electrocatalytic properties can be obtained. of graphite used, hydrophilicity, etc.

Table : Summary of recent synthesis approach used to produce active graphitic anodes for electrochemical advanced oxidation of synthetic
and real wastewater.

Anode Synthesis approach Contaminant Operating condition Removal (%) References


Hydrophilic GF Electrochemical and thermal Ciprofloxacin Anode area:  cm Hydrophobic GF: Chen et al.
Hydrophobic GF oxidation and NaOH modifica- Cathode: Pt electrode . ( min), ()
tion for increasing the Reactor: single compart- . ( min)
hydrophilicity ment cell ( ml) Hydrophilic GF:
Electrolyte: . M NaSO . ( min),
j: . mA cm− . ( min)
D GF/β–PbO and Anodic electrodeposition Diuron Anode area:  cm TOC:  ( min, Rahmani et al.
planar graphite/β-PbO herbicide Cathode: SS plate GF/β–PbO) ()
Reactor: batch electrolytic  ( min,
cell ( ml) graphite/β–PbO)
Electrolyte: . M NaSO
j: . mA cm−
PtRu/graphite Pulse electrodeposition Ammonia Anode area:  cm  ( min) Qing et al.
Cathode: graphite plate ()
Reactor: open round glass
cell (batch mode) and
custom flow reactor (flow
mode)
Electrolyte: ., ,
 mM NaCl
j: , ,  mA cm−
Graphite/β–PbO Electrodeposition Methylene Anode area:  cm Degradation: . Samarghandi
blue Cathode: SS plate ( min) et al. ()
Reactor: batch electrolytic
cell ( ml)
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 11

Table : (continued)

Anode Synthesis approach Contaminant Operating condition Removal (%) References

Electrolyte: . mg/L

NaSO
j:  mA cm−
RuO–TiO/nano- RuO–TiO/nano-graphite com- Methyl or- Anode area:  cm Degradation: . Li et al. ()
graphite composite posite: sol–gel method ange Cathode: Ti mesh ( min)
supported over Ti mesh Prepared composite then rolled Ceftriaxone Reactor: single compart- TOC: .
electrode over Ti mesh using hot press ment cell ( ml)
technology Electrolyte: . M NaSO
V:  V
TiO/activated carbon Sheep-in-a-bottle synthesis Phenol Anode area: . cm Degradation: . Wu et al. ()
fiber Cathode: graphite plate ( min)
Reactor: single compart-
ment cell ( ml)
Electrolyte: . M
NaSO
j: . mA cm−
TiO/nano-graphite Sol–gel followed by hot press- Ceftriaxone Anode area:  cm Degradation: . Guo et al. ()
composite ing on Ti mesh Cathode: Ti mesh ( min)
Reactor: single compart-
ment cell ( ml)
Electrolyte: . M NaSO
V:  V

Recently the effect of hydrophilicity of the GF anode diminished from TiO2 addition (Guo et al. 2015). However,
towards the degradation of antibiotic ciprofloxacin was further addition in higher amounts leads to forming a lump
investigated. It was observed that the presence of high of agglomerates, which decreases the number of active
sp3/sp2 and more significant nitrogen and oxygen-containing sites present at the electrode surface.
functional groups at the surface of hydrophilic GF improves
the performance of the electrode (Chen et al. 2021a). The 3.1.2 DSA® anodes
use of carbon-based anode is restricted to their operational
limitations like the lower ability for •OH generation and DSA® electrodes are a combination of metal oxides sup-
severe corrosion at higher electrical load, causing dimen- ported over the dimensionally stable Ti support. IrO2 based
sional and chemical instability (Recio et al. 2011). They are DSA® have excellent electrocatalytic properties and better
not robust enough against incineration reactions. Adding dimensional stability. It is a suitable electrocatalyst with
metal oxides over the carbon surface can enhance its high stability in an acidic medium for chlorine and oxygen
electrochemically active surface area, improve the inter- evolution reactions. The list of various synthesis ap-
connection structure in the carbon matrix to reduce the proaches used to produce active anodes for EO of synthetic
electrical capacitance, increase the wettability of the sur- and real wastewater is presented in Table 2. Fierro et al.
face, and improve the stability of the surface (Ntakir- (2007) investigated the OER on Ti/IrO2 electrodes using an
utimana et al. 2020). Metal oxides such as TiO2, RuO2, and 18
O isotope labeling technique and concluded that only the
IrO2 to the graphitic support can help to enhance the outer layer of IrO2 participated in the OER the evolved gases
electrocatalytic behavior and the •OH generation rate on the anode surface inhibit the inert part of the oxide
(Wu et al. 2016). Li et al. (2018) prepared a RuO2–TiO2/ coating. More interestingly, it was observed that the
nano-graphite composite using a one-step sol–gel process, participation of IrO2 up to several monolayers could be
and then the prepared composite was rolled over Ti mesh improved by conducting the electrolysis in acidic media.
using hot-press technology. Methyl orange and ceftriaxone Chatzisymeon et al. (2009) studied the EO of actual olive
were used as target pollutants, and the effect of loading mill wastewater (Initial COD 1300 ppm) using Ti/IrO2 anode
RuO2 was investigated. Incorporating RuO2 in a smaller prepared using thermal decomposition technique, taking
amount can help increase the electrode’s conductivity isopropanol as a precursor solution. EO was carried out at
12 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

an acidic pH of 4.6, and zirconium was used as a cathode in RuO2 has been widely used to produce active anodes
a batch reactor. The EO of model pollutants was carried because of its consistent metallic behavior, comparatively
out, and phenol degradation was found easier than cin- lesser cost than IrO2, and excellent electrocatalytic activity,
namic and caffeic acids, following zero-order rate kinetics. especially in chlorine medium. Ti/RuO2 electrode has been
Yaqub et al. (2018) prepared Ti/IrO2 anode through the used to treat actual wastewater from pharmaceutical,
thermal decomposition method using low Ir concentration textile, and distillery industries (Chauhan and Srivastava
(5 mg/ml) sol–gel solution. IrO2 was successfully sup- 2020; Johnson and Kumar 2020; Kaur et al. 2019a). Kaur
ported over the substrate, but the coating was nonuniform, et al. (2019a) studied the EO of Amoxicillin trihydrate
and the formation of TiO2 layers occurred at the exposed (AMT) using Ti/RuO2 electrodes in a series. The reactor
surface, leading to the substrate’s degraded conductivity. showed better mineralization efficiency and COD removal
The same pollutant was also treated using the previously at neutral pH, with 60% AMT and 48% TOC removal ob-
formed anode with a high Ir concentration solution (Yaqub tained at a current density of 5.88 mA cm−2. MCE of 7.67%
et al. 2014). The results indicated lower COD removal (50 vs. was observed which could be increased by reducing the
72%) and higher energy loss when low concentration current density at the cost of reduced removal efficiency.
Ti/IrO2 anode was used. The group also studied the same process in a continuous

Table : Summary of various synthesis approaches used to produce active anodes for electrochemical oxidation of synthetic and real
wastewater.

Anode Synthesis approach Contaminant Operating condition: anode Removal (%) References
area (A), cathode (C), reactor
(R), electrolyte (E ), current
density (j)/current (i)

Ti/IrO Thermal decomposition Olive mill wastewater A: . cm; C: Zr plate; R: COD:  Chatzisymeon
Precursor: isopropanol open round glass cell; E: ( min) et al. ()
. M HClO; j:  mA cm−
Ti/IrO Sol–gel method Polycyclic aromatic A:  cm; C: Ti plate; R: elec- COD:  ( h) Yaqub et al.
Precursor: ethylene glycol and hydrocarbons trochemical cell; E: . g/L (, )
acetic acid NaCl; j: ., .,  mA cm−
Ti/RuO – Tannery wastewater A:  cm; C: Pt wire; R: undi- COD: . Tien and Le Luu
Ti/IrO vided batch cell; j: , ( h, Ti/RuO); ()
 mA cm− . ( h, Ti/
IrO)
Ti/IrO–TaO Thermal decomposition Reverse osmosis A:  cm; C: SS plate; R: un- COD:  Zhou et al.
concentrate divided electrochemical cell; approx. ( h) ()
E: . g/L NaCl; j: .,
.,  mA cm−; ICE:
.
Ti/RuO – Chlorophenol A:  cm; C: Ti/RuO; R: COD: . Chauhan et al.
undivided batch cell; j: – ( min) ()
. mA cm−
Ti/RuO – Nitrate wastewater A:  cm; C: Fe plate; R: Nitrate:  Chauhan and
undivided batch cell; j: ( min) Srivastava
.–. mA cm− Total N:  ()
( min)
Ti/RuO – Distillery wastewater A: . cm; C: Ti sheet; R: COD:  ( h) Johnson and
undivided batch reactor; j: Color: . Kumar ()
. mA cm−
Ti/RuO Thermal decomposition Coke-oven A:  cm; C: Graphite sheet; COD: . Ken and Sinha
Precursor: ethanol wastewater R: undivided batch reactor; ( min) ()
E: .–. g/L NaCl; j: – Phenol: .
 mA cm− ( min)
Ti/RuO–IrO – Tetracycline A:  cm; C: CF; R: undi-  ( min) Wu et al. ()
vided cylindrical glass cell; COD: 
E: . M NaSO; i:  mA ( min)
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 13

Table : (continued)

Anode Synthesis approach Contaminant Operating condition: anode Removal (%) References
area (A), cathode (C), reactor
(R), electrolyte (E ), current
density (j)/current (i)

Ti/RuO–IrO Thermal decomposition Coking wastewater A: . cm; C: Ti plate; R: COD: . Zhi et al. ()
(CW) and coal gasifi- quartz glass batch reactor; (CW), .
cation wastewater E:  mM NaSO; j: (CGW) ( min)
(CGW)  mA cm− TOC: . (CW),
. (CGW)
( min)
Ti/(RuO).–(IrO). Microwave synthesis Methylene blue dye A:  cm; C: Pt plate; R:  TOC:  Gonzaga et al.
Sol–gel method electrode cell; E: . M ( min) ()
Precursor: ethylene glycol and NaSO +  mM NaCl; j: Color: 
acetic acid  mA cm−; service life: 
years
Ti/Ru.–Ti.O Thermal decomposition Alachlor A:  cm; C: Pt plate; R: un- Degradation: de Mello et al.
Precursor: divided batch reactor; E: . ( min) ()
-butylimidazolium hydrogen . M NaSO; j:
sulfate ((HBIM)HSO)  mA cm−
Ti/RuO–TiO Laser heating Clopyralid A:  cm; C: BDD; R: undi- TOC: Santos et al.
Sol–gel method vided batch reactor; E:  g/L (NaSO), ()
Precursor: ethylene glycol and NaSO, . g/L NaCl; j: . (NaCl)
acetic acid  mA cm− ( h)
Ti/RuO–IrO–TiO Laser heating Hexachlorobenzene A:  cm; C: Pt plate; R:  COD:  ( h) de Santana
Precursor: ethylene glycol and electrode cell; E: methyl- Mota et al.
acetic acid sulfonylmethane; j: ()
 mA cm−
La doped Ti/RuO– Thermal decomposition Methylene blue dye A:  cm; C: Pt plate; R:  Degradation: Zuo et al.
TiO Precursor: ethanol electrode cell; E: . M  ( min) ()
NaSO; j:  mA cm−
Ti/RuO–IrO–RhOx Thermal decomposition Phenol A:  cm; C: Same as anode; COD: ; Yu et al. ()
Precursor: isopropanol and R: undivided batch reactor; phenol: 
hydrochloric acid solution E:  mM NaSO; j:
 mA cm−; Service life:
 h
Pt modified DSA® Electrodeposition Tetracycline A:  cm; C: Two DSA®; R: one Degradation: Santos et al.
hydrochloride compartment cell; E: .; TOC: . ()
. M HSO; j:  mA cm− ( h)
DSA® containing Ru, Pechini’s method Tannery wastewater A:  cm; C: Pt wire; R: undi- TOC: . ( h) Costa et al.
Ir, Sn, and Ti Precursor: ethylene glycol and vided batch cell; j: , , ()
acetic acid  mA cm−
Ti/ Thermal decomposition Atrazine pesticide A:  cm; C: Pt plate; R: un- TOC: ; COD: Santos et al.
(RuO).–(SbO). Precursor: methylimidazolium divided batch reactor; E:  ( min) ()
hydrogensulfate ((Hmim) . M NaSO; j:  mA cm−
HSO)
Ti/ Thermal decomposition Reactive yellow  A:  cm; C: Pt plate; R: un- Degradation: Santos et al.
(RuO).–(SbO). Precursor: methyl- divided batch reactor; E:  (HEAA), ()
imidazolium hydrogen sulfate . M NaSO; j:  mA cm−; . ((Hmim)
((Hmim)HSO), service life:  h HSO)
-hydroxyethylammonium ac- ( min)
etate (HEAA)
Yb-doped Ti/RuO– Sol–gel method Coking wastewater A:  cm; C: Ti plate; R: un- COD: ; Wang et al.
SnO Precursor: citric acid and divided batch reactor; E: TOC:. ()
ethylene glycol . M NaSO; j:  mA cm− ( min)
SbO doped Ti/ Pechini’s method Indigo carmine A:  cm; C: Ti plate; R: COD: ; TOC: Palma-Goyes
RuO–ZrO Precursor: ethylene glycol and FM-LC reactor; E: . M  et al. ()
acetic acid NaCl; j:  mA cm−
14 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Table : (continued)

Anode Synthesis approach Contaminant Operating condition: anode Removal (%) References
area (A), cathode (C), reactor
(R), electrolyte (E ), current
density (j)/current (i)

FeO/Sb–SnO FeO/Sb–SnO magnetically Acid red G (ARG), A:  cm; C: Cu plate; R: Degradation: Shao et al.
attached on Ti/RuO– attached to Ti/RuO–TaO phenol -elecrode cell; E: . M  (ARG, ()
TaO NaSO; j:  mA cm−  min)
TOC: 
(phenol,
 min), 
(ARG,  h)

reactor, and the operational parameters were optimized incorporation of IrO2 decreases the activity of the electrode
using the response surface methodology technique. At an towards OER but increases the stability and effective sur-
optimum condition with pH 7.53, 0.7 A current, and resi- face area of the electrode. The best performance for OER
dence time of 175.6 min, 51.64%, and 37.82% of AMT and was found for Ti/Ru0.7Ir0.3O2 anode, while the longest life
TOC removal was obtained with the MCE of 9.81%, cycle was obtained from Ti/Ru0.1Ir0.9O2 anode. Introducing
respectively (Kaur et al. 2019b). The group also studied the IrO2 as a secondary oxide improves the performance of the
degradation of pharmaceutical ofloxacin and amoxicillin electrode for the oxygen evolution reaction under strongly
using Ti/RuO2 electrodes (P. Kaur et al. 2018; R. Kaur et al. acidic conditions while maintaining the activity and
2018). Nearly 80 and 60% of pollutant removal were ob- dimensional stability of the electrode (Chen et al. 2002).
tained during 30 and 60 min of electrolysis time with It is to be noted that these metal oxides can also affect
maximum mineralization efficiency of 7.87 and 1.77%, the stability and corrosion resistance in both ways. Kus-
respectively. mierek (2019), in his latest study, revealed the electro-
It has been reported that the high activity of RuO2 leads chemical and corrosion parameters of Ti/TiO2–RuO2
to low stability due to corrosion in an acidic medium dur- electrode modified with WO3 in a ferri-ferrocyanide and
ing electrolysis. Hence more chemically and electro- Na2SO4 solution. The introduction of WO3 increased the
catalytically stable metal oxides such as IrO2 (Chen et al. stability of the electrode but decreased the electrochemi-
2002; Zhi et al. 2020; Zhou et al. 2011), SnO2 (Costa et al. cally active surface area due to its insulating behavior.
2008; W. Wang et al. 2021), ZrO2(Palma-Goyes et al. 2015), However, corrosion tests revealed auspicious results with
Sb2Ox (J. Wang et al. 2021; Y. Yu et al. 2021), TiO2 (de Oli- an increase in 20% of corrosion resistance than unmodified
veira Santiago Santos et al. 2020; de Santana Mota et al. electrodes, which is associated with resistance provided by
2021; Zuo et al. 2020), or WO3 (Kusmierek 2019), etc., were WO3 active sites towards the RuO2 dissolution reactions.
mixed with RuO2 to obtain more stable MMO active anodes Ta, Sn, Ti, or Zr-based oxides are usually added as stabi-
(Rivera et al. 2018). Mattos-costa et al. (1998) synthesized lizing or dispersing agents to cut down the use of expensive
Ti/RuxIr1 − xO2 anode (x = 1, 0.9, 0.7, 0.5, 0.3, 0.1, 0) and Ir or Ru metals. However, the strong electrical resistance
studied the OER in acidic medium. The electrodes were provided by metal oxides like TiO2 limits its presence in a
prepared using the isopropanol/glacial acetic acid solution higher proportion. Adding components like Sb2Ox and
and dissolving the pre-prepared metal acetylacetonate into SnO2 as a mixed layer or as a dopant can improve the
the solution, followed by ultrasonication and thermal conductivity of these electrodes (Fernandes et al. 2014;
decomposition. The total voltammetric charge density of Santos et al. 2018). Moreover, the insulating TiO2 layer
electrodes increased with an increase in IrO2 content, with between the Ti substrate and metal oxides develops an
a maximum value corresponding to the 50% Ir loading. The Ohmic loss which can be considerably minimized either by
decrease in charge density at higher concentrations is due depositing the Pt layer of the surface of the substrate or by
to the hydrolysis of precursors forming metal hydroxides creating a hydride layer on the Ti surface (Fernandes et al.
into the solution. It results in the direct nucleation of some 2014; Shao et al. 2014b).
pure oxides at the surface of the substrate prior to the The synthesis approach affects the performance of the
thermal decomposition step. This nucleation leads towards electrode. Two Ti/RuO2 electrodes were prepared using the
the non-homogenous coating of the metal oxides. The isopropanol solution method (ISM) and polymer precursor
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 15

method (PPM) and were compared to understand the effect nanosheet, which in succession can behave as an electro-
of precursor solution during synthesis (Terezo and Pereira catalyst (Olu et al. 2018).
2002). It was observed that the presence of chloride ions Microwave synthesis is an advanced approach for the
during the thermal decomposition of RuCl3 in isopropanol synthesis of DSA®, being faster than thermal decomposi-
solution leads to distortion in cell parameters. The use of tion, providing uniform temperature distribution, ampli-
nitrate salt of ruthenium can help overcome this limitation. fied heating rate, and cost-effective approach. Applying
Moreover, the PPM method develops more wrinkles and microwave heating during calcination leads to an
morphological defects at the surface, enhancing the elec- improved homogeneity and increased crystallinity of the
trochemically active surface area for chemical reactions. particles over the surface of the electrode (Figure 7).
Another approach for MMO preparation uses IL as a Ti/(RuO2)0.5–(IrO2)0.5 electrode prepared recently using
solvent for electrode preparation. The use of highly viscous this approach contained better volumetric charge holding
and thermally stable IL provides better uniformity of metal capacity and improved accelerated service life (3.5 times
salts with easy applicability and a faster route. To prepare higher than the electrode prepared using thermal decom-
Ti/(RuO2)0.8–(Sb2O4)0.2 anode, two different IL’s viz. position technique) (Gonzaga et al. 2020). Due to its better
methyl-imidazolium hydrogen sulfate ((Hmim)HSO4) and electrocatalytic properties, the electrode showed full color
2-hydroxyethylammonium acetate (2HEAA) were used, and 60% TOC removal in 60 min of electrolysis of MB dye.
which showed better electrocatalytic properties owing to Another distinguished approach used recently is the
its 10 times greater viscosity and better crystallinity laser-heating technique, which utilizes high-energy CO2 laser
observed in SEM data (Figure 6). The prepared electrode during calcination. Ti/RuO2–IrO2–TiO2 electrode was pre-
was found to have a remarkable accelerated service life of pared using this approach, and the prepared electrode surface
20 h when tested at a current density of 500 mA cm−2, under was found to have a highly homogenous and rough coating.
0.5 M H2SO4 medium (Santos et al. 2018). In a similar way, Unlike the conventional thermal decomposition technique,
Ti/(RuO2)0.8–(Sb2O5)0.2 was prepared using methyl- no cracked-mud-like microstructure has appeared, while
imidazolium hydrogensulfate IL, and the degradation rapid heating and cooling of the sites leads to a low-relief
behavior of atrazine was compared with the electrode bubble-like structure that increases the active surface area of
synthesized by using the Pechini method and BDD elec- the electrode (Figure 8) (de Santana Mota et al. 2021). The
trode (Santos et al. 2016). The electrode prepared using IL prepared electrode showed improved electrocatalytic activity
was found superior and achieved similar degradation ef- and higher charge holding capacity.
ficiency compared to BDD electrode. de Mello et al. (2018) The laser deposition technique observed similar
prepared Ti/Ru0.3TiO0.7O2 anode using 1-butylimidazolium morphological and electrocatalytic improvements and a
hydrogen sulfate ((HBIM)HSO4) IL solution, which showed higher charge holding capacity for Ti/RuO2–TiO2 photo-
about 15% higher degradation for alachlor herbicide than electrode (G. O. S. Santos et al. 2020). This electrode, when
the commercially available electrode. These studies indi- compared with BDD anodes for the photo-electrochemical
cate that using IL as a precursor can unexpectedly enhance mineralization of herbicide clopyralid in chlorine medium,
the performance of prepared electrodes. showed better TOC removal due to the synergistic effect •OH
Apart from the acidic IL, sol-gel, and Pechini method, and •Cl radicals produced during the hemolysis of hypo-
another environment-friendly and effective approach was chlorous acid. On the other hand, BDD electrodes produced
used to prepare Ti/RuO2–IrO2 anode using PVA as a pre- more toxic and less active chlorate and perchlorate ions
cursor solvent (dos Anjos Bezerra et al. 2020). The prepared pertaining to its inherent scavenging effect.
electrode provided the highest removal efficiency for Zhou et al. (2011) studied the electrochemical treatment
model dye solution and a 2-fold fast pollutant degradation of high RO concentrate having high salinity using BDD,
rate as compared to the electrodes prepared using the Ti/IrO2–Ta2O5, and Ti/IrO2–RuO2 electrodes. Ti/IrO2–RuO2
Pechini method. showed reduced energy consumption due to superior elec-
Electrodeposition has several advantages over con- trical conductivity than other electrolytes used, while the
ventional approaches, including the monitored deposit highest COD removal and better free radical generation was
thickness, cost-effectiveness, and faster preparation. obtained through BDD anodes at the same current density.
Electrodeposition of Pt over commercial DSA® can increase However, Ti/IrO2–Ta2O5 anodes provided partial COD
the electrochemically active site over the electrode surface removal. Costa et al. (2008) compared the performance of
(Santos et al. 2021). In addition, deposition of metal ions DSA® containing oxides of Sn, Ir, Ru, and Ti in different
like Au and Pt can catalyze the partial reduction of RuO2 compositions, for the electrochemical treatment of tannery
16 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Figure 6: SEM (a, b), cyclic voltammogram (c, d), and accelerate service life tests (e, f ) for Ti/(RuO2)0.8–(Sb2O4)0.2 prepared using 2HEAA and
(Hmim)HSO4 ILs, respectively (Santos et al. 2018).
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 17

Figure 7: SEM and CV of Ti/(RuO2)0.5–(IrO2)0.5 anode prepared by microwave heating at 300 °C (a, b), 350 °C (c, d), and 400 °C (e, f) (Gonzaga
et al. 2020).
18 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Figure 8: XRD (a) and SEM with the magnification of 100× and 1000× (b) of laser prepared Ti/RuO2–IrO2–TiO2 anode. Adapted with permission
from de Santana Mota et al. (2021).

wastewater. Ti/Ru0.30Ti0.70O2 and Ti/Ir0.15Ru0.15Sn0.70O2 pro- towards simultaneous ammonia and phosphate removal.
vided better color and TOC removal at higher current density Traces of magnetic Fe3O4/Sb–SnO2, when attached with Ti/
(100 mA cm−2). Recently, DSA® Ti/RuO2 and Ti/IrO2 elec- RuO2–Ta2O5 in optimum amount, increased the removal
trodes’ performance for the electrochemical treatment of efficiency of acid red G dye to about 1100% (Shao et al.
tannery wastewater was compared with diamond electrodes 2020b). The electrode efficiency also improved for phenol
(Tien and Le Luu 2020). Ti/RuO2, due to its better electro- degradation, for which the unmodified electrode showed
catalytic activity in chloride media, performed better than the negligible performance.
Ti/IrO2 electrode. Doping of transition metal ions like Ni, Co, Zn, and Sb
Recent studies have proved that persistent organic in RuO2 can enhance the number of active sites by
compounds’ mineralization can be increased by combining providing a higher number of d-electrons, thereby
photocatalysis with conventional electrochemical treat- increasing the electrocatalytic activity of the electrode. In a
ment. The addition of components like TiO2 and WO3 into different study, Zuo et al. (2020) recently reported the effect
DSA® enhances the photocatalytic properties of these elec- of doping rare earth metal La over Ti/RuO2–TiO2 anode for
trodes. TiO2 can be a promising component for different the photo-electrochemical degradation of MB. Although
photo-electrocatalytic catalytic applications. The photo- the La-doped electrode, formed by using conventional
catalytic activity and efficiency of these nanomaterials can thermal decomposition technique, was found to have
be improved using new and improved synthesis methods. higher crack density and rugosity on the surface, but
N-doping on TiO2 improves photocatalytic behavior and negatively decreases the OEP, which decreases the effi-
reduces the energy bandgap towards the visible-light re- ciency of degradation. Conversely, W. Wang et al. (2021)
gion. Among various available methods, microwave syn- used Yb-doped Ti/RuO2–SnO2 electrode, prepared using
thesis and electrospinning are very effective and faster the sol-gel method, to degrade coking wastewater. The Yb
approaches that prove a broader bandgap and high elec- doping up to a specific limit helps to improve the crystal-
trocatalytic activity (Basavarajappa et al. 2019). The photo- linity of the SnO2 and RuO2. However, no comparative data
catalytic activity of the electrode depends upon the active on the effect of doping on degradation was shown. Thus,
sites present at the surface, which in turn is a factor of the more research is required to understand better the effect of
number of oxygen vacancies available under electric field doping rare earth metals.
and UV-photo illumination. In a different set of experiments, Yu et al. (2021)
D. Sun et al. (2020) used a creative technique of com- revealed the use of pseudocapacitive Ti/RuO2–IrO2–RhOx
bined electrooxidation (EO) and electrocoagulation (EC) by electrode for the electrochemical degradation of phenol.
assembling a composite anode consisting of zero-valent The electrode was prepared through thermal decomposi-
iron particles magnetically attached over Ti/RuO2–IrO2 tion using metal chloride salts, isopropanol, and HCl-
surface. The prepared electrode was found very efficient based precursor solution. The prepared electrodes were
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 19

analyzed in monopolar and bipolar mode, with 20 min anode. The cationic surfactant remarkably enhances the
polarity reversal time. The results indicate greater than 1.5 phenol removal with Ti mesh electrode to about 40%.
times better phenol degradation in both modes and 3.5 These surfactants support the chlorine evolution reaction
times higher service life than Ti/RuO2–IrO2 electrodes. It is and favor the oxidative polymerization of phenols by hin-
important to note that the prepared electrode produced dering the adsorption of cationic radicals over the cathode
comparatively less •OH radical, but due to the capability of surface. However, the presence of anionic and nonionic
Rh to oxidize to high valance RhOx metal oxide, under high surfactants was found to be insignificant.
potential, and due to the higher charge holding capacity of
the prepared electrode, RhOx worked as an electron scav-
enger and thereby oxidized the contaminants.
Minh et al. (2019) studied the EO of highly saline
3.2 Nonactive anodes
(5500 ppm chloride concentration) and nitrate-containing
3.2.1 Boron doped diamond (BDD) anodes
wastewater from the fish sauce manufacturing industry,
having COD of 187 ppm, at Ti/CeO2–Pt active anode and
The BDD electrode is proved to be the most promising
different metal cathodes (Cu, SS, and Cu–Zn). The role of
different cathode materials was also analyzed, and it was anode in several studies due to its inherent advantage of
observed that all cathodes were effective towards ammonia- having a very high potential for O2 evolution reaction
nitrogen and COD removal, while Zn/Cu performed better (Cornejo et al. 2020; He et al. 2019). When dealing with
against the reduction of by-product nitrate formed during wastewater containing a high amount of organic contam-
electrolysis. inants and in large amounts, the effect of substrate mate-
Sripriya et al. (2007) studied the electrochemical rial (over which the oxide or MMO is supported) plays a
destruction of p-chlorophenol and p-nitrophenol using fundamental role in deciding the practical implementation
H-type electrochemical cells having graphite/RuOx–IrOx– of the electrodes. Several intrinsic and extrinsic factors
TiOx or Ti/RuOx–IrOx–TiOx mesh anode and SS cathode. affect the performance of BDD electrodes, such as selection
The Effect of higher pollutant concentration and influence of substrate material (e.g., Si, Nb, Ta, and Ti substrates),
of cationic, anionic, and non-ionic surfactants on phenol amount of boron doping, sp3/sp2 ratio, diamond thickness,
disinfection was also studied with the help of CV and and type of electrolyte medium (Espinoza et al. 2019; Gar-
constant current electrolysis under NaCl and NaOH me- cia-Segura et al. 2015). The summary of various synthesis
dium. Better results were obtained under NaCl medium in approaches used to produce BDD anodes for electro-
all experiments. Adverse effects of all surfactants were chemical advanced oxidation of synthetic and real waste-
observed for pollutant removal while using graphitic water is presented in Table 3.

Table : Summary of various synthesis approaches used to produce BDD anodes for electrochemical advanced oxidation of synthetic and real
wastewater.

Substrate/ Synthesis Contaminant Operating condition: anode Removal (%) (time) References
film thick- approach area (A), cathode (C), reactor
ness (μm) (R), electrolyte (E ), current
density (j)/current (i)

p–Si/. Hot filament Chlorophenol A:  cm; C: BDD; R: DiaCell;  Gherardini

chemical vapor E:  M HSO; j: – et al. ()
deposition  mA cm−; ICE: %
technique
Ti/. Direct current – A:  cm; C: BDD; R: – Lu et al. ()
arc plasma CVD -parallel plate reactor; E:
 M HSO; j:  A cm−; ser-
vice life:  h
Porous Ta/ Electron assis- Methylene blue A:  cm; C: BDD; R: parallel  ( min by EO and Li et al. ()
. ted CVD plate reactor; E:  M NaSO;  min by EF)
j:  mA cm−
Plate and Hot filament Asprin A:  cm; C: BDD; R: parallel  He et al. ()
porous Ti/ CVD plate reactor; E: . M
.–. NaSO; j:  mA cm−; ICE:
20 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Table : (continued)

Substrate/ Synthesis Contaminant Operating condition: anode Removal (%) (time) References
film thick- approach area (A), cathode (C), reactor
ness (μm) (R), electrolyte (E ), current
density (j)/current (i)

–%; service life:  h

(plate) and  h (porous)
p–Si/. Hot filament Acetic acid A:  cm; C: BDD; R: DiaCell;  Gandini et al.
CVD Formic acid E: . M HSO; j: ()
Oxalic acid  mA cm−; ICE: –%
Stability of electrode:  h
(using anodic polarization)
Ti CVD p-cresol A:  cm; C: BDD; R: Mineralization: p-cresol: Nava et al. ()
o-cresol FM-LC; E: . M HSO; j:  ( min), o-cresol: 
 mA cm−; ICE: % ( min)
(p-cresol), % (o-cresol)
Ti Hot filament Tannery wastewater A:  cm; C: Ti/Pt; R: undi- COD: . ( h) Luu et al. (a, b)
CVD vided stirred batch reactor; E: and Luu et al.
. M HSO; j:  mA cm−; ()
ICE: % (p-cresol), %
(o-cresol)
p–Si/ Microwave Ketoprofen drug A: . cm; C: BDD; R: par- Mineralization:  ( h) Murugananthan
assisted allel plate reactor; E: . M et al. ()
plasma CVD NaSO, NaCl, NaNO; j: .–
. mA cm−; ICE: %
(. mA cm−)
p–Si/ Microwave Oxalic acid A: . cm; C: Pt wire; R: – Ivandini et al.
assisted single compartment cell; E: ()
plasma CVD . M phosphate buffer
solution
Ti/. Hot-filament Acid yellow  A: . cm; C: SS tube; R: Mineralization: ( h) Juang et al. ()
CVD tubular ceramic membrane;
E:  mL/L KCl; j:  mA cm−;
ICE: %
p–Si/. Hot-filament Pyrogallol A:  cm; C: SS plate; R: flow COD:  Nasr et al. ()
CVD cell; E: . mg/L
NaPO; j:  mA cm−; ICE:
almost %
p–Si/. Hot-filament Chloranilic acid A:  cm; C: SS plate; R: flow Mineralization:  Martínez-Huitle
CVD cell; j: . mA cm−; GCE: % et al. ()
p–Si/. Hot-filament ,,-trichlorophenoxiacetic A: . cm; C: Pt mesh; R: Degradation:  ( min at Santos et al.
CVD acid single compartment cell; E: pH .),  ( min at pH ()
. M NaSO; j:  mA cm− .)
Nb/.–. CVD Tannery wastewater A:  cm; C: BDD; R: Filter COD:  ( mA cm−),  Cruz-Rizo et al.
flow press cell; E: . mM ( mA cm−),  ()
NaCl or NaSO; j: , , ( mA cm−)
 mA cm−; MCE: %
Nb/.–. CVD Congo red A:  cm; C: SS plate; R: Degradation:  ( min) Jalife-Jacobo et al.
Filter flow press cell; E: (NaCl),  ( min) ()
 mM HClO, NaCl, HSO or (NaSO),  ( min)
NaSO; j:  mA cm−; MCE: (HClO, HSO)
% (using NaCl)
Nb/.–. CVD Tannery wastewater A: . cm; C: BDD; R: undi- TOC:  ( min, Isarain-Chávez et
vided stirred tank reactor; j:  mA cm−),  ( min, al. ()
,  mA cm−  mA cm−)
p–Si/. CVD High salinity RO concentrate A:  cm; C: SS plate; R: un- COD:  (. h) Zhou et al. ()
divided electrochemical cell;
j: ., .,  mA cm−;
ICE: .%
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 21

Table : (continued)

Substrate/ Synthesis Contaminant Operating condition: anode Removal (%) (time) References
film thick- approach area (A), cathode (C), reactor
ness (μm) (R), electrolyte (E ), current
density (j)/current (i)

p–Si/. Hot-filament Enrofloxacin A: . cm; C: SS plate; TOC: > ( h) Carneiro et al.
CVD R: filter press flow cell; E: ()
. M NaSO, NaCl, NaCO,
NaNO or NaPO; j:
 mA cm−; MCE: %
p–Si/. Hot-filament -napthol A:  cm; C: zirconium; R: COD:  Panizza et al.
CVD undivided flow cell; E: ()
. M HSO; j:  mA cm−;
CE: %
p–Si Hot-filament Acid red  A:  cm; C: carbon-PTFE air TOC:  ( min, Almeida et al.
CVD diffusion electrode; R: undi- . mA cm−),  ()
vided cylindrical cell; E: ( min,  mA cm−)
. M NaSO; j: .–
 mA cm−; CE: %
(. mA cm−)
Ni foam Ti coating: PVD RB- dye A:  cm; C: SS plate; R: un- TOC: . Mei et al. ()
coated with Diamond: hot divided batch cell; E: . M
Ti filament CVD NaSO; j: mA cm−; MCE:
% (>% till %
mineralization)
p–Si/. CVD Acid yellow  A:  cm; C: carbon-PTFE air TOC:  ( min) Espinoza et al.
diffusion electrode; R: undi- ()
vided filter press cell; E:
. M NaSO; j: , , ,
 mA cm−
Mineralization current effi-
ciency: % (>% till end)

Due to its ability to produce reactive oxygen species in ethanol industry) is treated electrochemically after bio-
large amounts on and near the surface of the electrode, logical treatment (Carneiro et al. 2018; Vilar et al. 2018).
BDD poses the most significant risk of producing toxic Detachment of the coating from the substrate was observed
byproducts like persulfates, perphosphate, percarbonates, for BDD electrodes in NaCl medium.
and perchlorates, in sulfate and especially in chloride The adhesion of diamond with the substrate material is
medium (Bergmann et al. 2009; Polcaro et al. 2009, 2007). a deciding factor for the stability of the electrode. Various
Nevertheless, on the other hand, these by-products could substrates have been used, such as Ta, Si, Nb, W, and Ti.
also work as an effective disinfectant if present in an op- The deciding factor for substrate selection is the closeness
timum amount. Hence, a careful and controlled applica- of the coefficient of thermal expansion (CoTE) between the
tion is needed to utilize an effective electrode for drinking substrate and diamond (1.18 × 10−6 °C−1) to maintain the
wastewater and environmentally oriented applications. film adhesion while cooling during the film deposition
Electrochemical reactor embedded with BDD anode step. Also, the CoTE value of the metal substrate should
and SS cathode has been used as post-treatment for the decline for its corresponding oxide to assure that the metal
complete mineralization of persistent napthalene1,5, oxide formed on the surface should not participate in the
disulfonate, and naphthalene trisulfonate, collected from diamond film’s delamination. Si and Ta are the most
the leachate of contaminated industrial sites, containing a compatible substrate material for the BDD electrode for-
mixture of naphthalene mono and disulfonates (Panizza mation (Chaplin et al. 2011).
et al. 2006). However, Ti/(RuO2)0.7(IrO2)0.1(Sb2O3)0.2 anode MMO electrodes show better compatibility in the
was found slightly more effective than BDD electrode in broader pH range than the diamond electrodes, especially
NaCl media when vinasse wastewater (which is a residue of in chlorine electrolyte media (Zhou et al. 2011). BDD has the
22 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

highest potential for chlorine evolution reaction (approx. pollutant Diuron® during 1 h of electrolysis (Figure 9). The
1.36 V/SHE), which is lesser than hydroxyl radical over- limitation related to the short service life of these electrodes
potential (approx. 2.8 V/SHE). Hence, it can generate can be improved by utilizing an advanced synthesis
several persistent organic compounds such as chlorates approach like CO2 laser heating during the calcination step.
and perchlorates along with Cl2 evolution (Polcaro et al. Recently, Ti/Sb–SnO2 electrode prepared using this
2009; Radjenovic and Sedlak 2015). However, DSA® elec- approach provided homogenous coating and a larger
trodes are found to produce these pollutants in a compar- electrochemical active surface area with an improved ser-
atively lesser amount and at a lower potential required for vice life of these electrodes up to 5 times compared to the
starting the chlorine evolution reaction (approx. 1.11V/ electrode prepared using thermal decomposition tech-
SCE). Hence, due to the availability of lower cost and nique (de Oliveira Santiago Santos et al. 2020).
reduced energy-consuming DSA® and similar electrodes, Qu et al. (2019) analyzed the effect of doping tin and
BDD electrodes are not found suitable for industrial antimony over Ti/SnO2 electrodes. Ti/SnO2 was prepared
wastewater having a large amount of chloride content. using electrodeposition techniques, while the tin and
Moreover, the formation of hypochlorites is superior in antimony were doped using dip coating and thermal
acidic pH; hence BDD works better at pH less than 4.0. decomposition technique, and the prepared electrode was
Conversely, it was observed in a study that chloride for- named Ti/NATO electrode. The electrochemical degrada-
mation can be avoided during electrolysis at BDD diamond tion of phenol was performed using the as-prepared anode
anode by operating in a very high pH (>14.2) region and gas diffusion cathode. The addition of tin enhances the
(Muddemann et al. 2018). However, BDD is an excellent direct anodic oxidation (2.1.V vs. SHE) and •OH production
non-active electrode in a non-chloride medium. up to 34% compared to the undoped Ti/Sb–SnO2 electrode.
Ti/NATO anode enhanced the electro-peroxone reaction
3.2.2 SnO2 electrodes and increased the O3 generation by 12.6%, which achieved
95% of TOC removal. The work focused on harnessing the
SnO2 and PbO2 electrodes are the two most promising reaction between the ozone generated at the anode with the
nonactive metal oxide anodes due to their high electro- H2O2 produced at the cathode to generate •OH free radicals
chemical performance and low cost. They can work as an in a more considerable amount.
effective anode if the service life and leaching character- Fe3O4/Sb–SnO2 magnetically attached to Ti/Sb–SnO2
istics (especially for hazardous Pb2+) of these electrodes can enhance the COD removal for up to 20% when EO of
can be improved. Sb doped SnO2 is a well-known semi- Acid Red G (ARG) and Guaiacol, a type of lignin (Jaiswal
conductor electrode, having low cost, high OEP, and et al. 2021; Shao et al. 2015). The improved performance may
greater •OH generation capacity. Table 4 presents various be endorsed due to the increased solid–liquid interface from
synthesis approaches used to produce different tin and the prepared 2.5D electrode, which has increased the mass
antimony-based mixed metal oxide nonactive anodes for transfer properties. Recently, the same research group
EO of synthetic and real wastewater. Recently, a study has prepared a polyaniline/Fe3O4 nanoparticles magnetically
been conducted to compare the degradation of herbicide attached Ti/Sb–SnO2 (2.5D Ti/Sb–SnO2/PANI) electrode for
2,4,5-trichlorophenoxiacetic acid at Sb-doped SnO2, PbO2, effective degradation of biorefractory wastewater (Shao
and BDD anodes. All three anodes degraded the contami- et al. 2020a). The prepared electrode also showed improved
nants in a similar mechanism. However, the Sb-doped SnO2 performance up to 60% for mineralization of these
anode provided the best results due to its high oxygen contaminants.
overpotential of 2.4 V and strong •OH holding capacity. Sb Waste SiC heating rod was used as a cost-effective
doping allows the structural modification of the SnO2 sur- substrate for Sb–SnO2 electrode (Zhang et al. 2019).
face, which could be attributed to the availability of Sb3+ Compared with the electrode supported over Ti, the pre-
and Sb5+ ions to substitute the Sn4+ ions and the active lone pared electrode provides better stability, low impedance,
pairs provided by the dopant (J.E.L. Santos et al. 2020). higher Sb–SnO2 loading, enhanced surface area, and
The latest study by (Moura de Salles Pupo et al. 2020) compact coating. These improvements jointly enhance the
examined the effect of doping different metals (M) like Ce, removal efficiency of actual paper-making wastewater by
Ta, Bi, and Gd with Sb doped SnO2 electrodes. Bi-based about 14%, reaching 55.48% removal of pollutants.
MMO presented the highest stability with a service life of Spray pyrolysis technique was used to synthesize
46.32 h among all the (SnO2)93Sb5M2 MMO anodes prepared Ti/SnO2–Sb2O5 and Ti/IrO2/SnO2–Sb2O5 anodes while the
using (Hmim)HSO4 IL precursor at different calcination service life study for the prepared electrodes at a current
temperatures. While Ce-based MMO best degraded the density of 100 mA cm−2 in 1M H2SO4 solution was
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 23

Table : Summary of various synthesis approaches used to produce different tin and antimony based mixed metal oxide nonactive anodes for
electrochemical oxidation of synthetic and real wastewater.

Anode (A) Synthesis approach Contaminant Operating Removal (%) Reference

condition

A: Ti/SnO–Sb Thermal Ceftazidime Anode area:  cm; . (A), . Duan et al.
A: Ti/PbO–Ce deposition + electrodeposition cathode: Ti plate; (A); COD: . ()
reactor: glass (A), . (A)
beaker ( ml);
electrolyte: NaCl,
NaNO; j: .,
., .,
 mA cm−
A: PbO Sol–gel (A); electro anodization ,,-trichlorophenoxiacetic Anode area: . cm EO: { (A,  min); Santos
A: Ti/Sb–SnO (A, A) acid (PbO),  cm  (A,  min);  et al. ()
A: BDD (SnO), . cm (A,  min)}; Photo-
A: Ti/TiO– (BDD), . cm (Ti/ EO:  (A,  min)
NTs/PbO TiO–NTs/PbO);  (A,  min)
cathode: Pt mesh;
reactor: single
compartment cell;
electrolyte: . M
NaSO; pH: , ; j:
 mA cm−
Ti/TiHx/Ni–Sb– Electrodeposition + spin Methylene blue Anode area:  cm;  ( min) Abbasi et al.
SnO coating + thermal decomposition cathode: Pt mesh; ()
reactor: single
compartment cell;
electrolyte:
. M HSO; pH:
.; j:  mA cm−
A: TiO–ENTA/ TiO-ENTA: twice anodization and Reverse osmosis concentrates Anode area:  cm COD:  (A, Chen et al.
SnO–Sb cathodization + sol– cathode: SS plate;  min);  (A, ()
A: TiO–ENTA/ gel + electrodeposition reactor: single )
SnO–Sb/PbO compartment cell
( ml); electro-
lyte: none; pH: .–
; j:  mA cm−
Oxide fine mesh Thermal decomposition Cibacron marine FG Anode area:  cm; Mineralization:  Da Silva
Sb–SnO cathode: SS plate; ( min) et al. ()
reactor: solid poly-
mer electrolyte filter
press; j: –
 mA cm−
Ti/TiHx/ Electrochemical reduction Acid red G, methylene blue, Anode area:  cm; COD:  (acid red G), Shao et al.
Sb−SnO sodium lignosulphonate cathode: graphite  (methylene blue), ()
sheet; reactor: sin-  (sodium ligno-
gle compartment sulphonate)
cell ( ml); elec- ( min)
trolyte:
. M HSO; pH: –
; j:  mA cm−
Ti/Sb–SnO Sol-gel Abacavir drug Anode area:  ( min); TOC: Zhou et al.
porous tube  cm; cathode: . ( h) (a)
SS tube; reactor:
penetrating reactor
( ml); inor-
ganic ions: NO−,
HCO−, and Cl−; pH:
–; j: .–
 mA cm−
24 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Table : (continued)

Anode (A) Synthesis approach Contaminant Operating Removal (%) Reference

condition

A: Ti/SnO–Sb Sol–gel (A); +electrodeposition Perfluorooctanoic acid Anode area: . (A), . (A), Lin et al.
A: Ti/SnO– (A, A)  cm; cathode: . (A) ( min) ()
Sb/PbO Pt wire; reactor:
A: Ti/SnO– single compartment
Sb/MnO cell ( ml); elec-
trolyte:  mM
NaClO; pH: , , ;
j:  mA cm−
Ti/SnO–Sb Electrodeposition solvent: Methylene blue Anode area:  cm; . ( h) Sun et al.
eutectic solvent cathode: Pt plate; ()
chlorine chloride: ethylene glycol reactor: single
(: M/M) compartment cell;
electrolyte: . M
NaSO; pH: ; j:
 mA cm−; service
life: . h
Ti/Sb–SnO– Electrodeposition solvent: . M Methylene blue Anode area:  cm;  ( min) Duan et al.
TiN citric acid +  mM tetramethyle- cathode: Pt plate; ()
nephosphonic acid reactor: -electrode
cell; electrolyte:
. M NaSO; pH:
; j:  mA cm−;
service life: . h
( mA cm−)
Ti/Sb–SnO Electrodeposition solvent: Methyl orange Anode area:  cm;  ( min) Duan et al.
dimethyl sulfoxide solution Rhodamine blue cathode: Ti plate; ()
reactor: single
compartment cell;
electrolyte: . M
NaSO; j:
 mA cm−; service
life: . h
( mA cm−)
Ce doped Ti/Sb– Electrodeposition solvent: Methylene blue Anode area:  cm;  ( min) Yang et al.
SnO glucose, citric acid, tartaric acid, cathode: Ti plate; ()
and oxalic acid reactor: single
compartment cell;
electrolyte:
. M HSO, . M
NaSO; j:
 mA cm−; service
life:  h
( mA cm−)
FeO/Sb–SnO FeO/Sb–SnO magnetically Acid Red G (ARG), guaiacol Anode area:  cm; COD:  (ARG,  h), Shao et al.
attached on Ti/ attached to Ti/Sb–SnO reactor: -elecrode  (guaiacol,  h) ()
Sb-SnO cell; electrolyte:
. M NaSO; i: .
A
Polyaniline/ polyaniline/FeO NPs magneti- Acid red G (ARG), Anode area:  cm; . (ARG,  h) Shao et al.
FeO NPs cally attached to Ti/Sb–SnO lignosulphonate reactor: -elecrode ()
attached on Ti/ cell; electrolyte:
Sb–SnO . M NaSO; i:
. A
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 25

Table : (continued)

Anode (A) Synthesis approach Contaminant Operating Removal (%) Reference

condition

Ti/SnO/PdO/ Sol-gel Tannery wastewater Anode area: COD: . ( min) Naumczyk
RuO  cm; cathode: and Kuchar-
SS plate; reactor: ska ()
single compartment
cell ( ml);
electrolyte:  g/L
NaSO; pH: .; j:
 mA cm−
Ti/SnO Thermal decomposition Tannery wastewater Anode area:  cm; COD:  ( min) Luu ()
cathode: Pt plate;
reactor: single
compartment cell
( ml); electro-
lyte: none; pH: ; j:
. mA cm−
SiC/Sb–SnO Thermal decomposition Azo dye Anode area:  cm; . (azo dye, Zhang et al.
Actual paper making cathode: Cu sheet;  min); . ()
wastewater reactor: single (wastewater,  h)
compartment cell;
electrolyte: . M
NaSO; pH: ; j:
 mA cm−
(SnO)SbM Thermal decomposition Diuron® Anode area:  cm;  ( min) Moura de
M: Ce, ta, Bi, Gd Precursor: (Hmim)HSO IL cathode: Pt sheet; Salles Pupo
reactor: -electrode et al. ()
cell; electrolyte:
. M NaSO;
pH: ; j:  mA cm−

performed (Correa-Lozano et al. 1997). Attaching the IrO2 an anodic electrodeposition technique (for hydride layer
interlayer due to its high anodic stability increases the formation) followed by thermal decomposition of the spin-
service life of the anode. More interestingly, copper doped coated metal chlorides solution (Abbasi et al. 2018). The
Ti/Cu–SnO2 electrode prepared using spray pyrolysis pro- stable TiHx layer was formed by cathodically reducing the
vided a very high potential for oxygen evolution reaction TiO2 layer coated over the substrate. The incorporation of
(2.7 V/NHE), equivalent to the potential observed in BDD TiO2 coating over Ti substrate and then reducing it to form
(Chen et al. 2016). The weak chemical adsorption of •OH on hydride ensures the protection of the Ti substrate (Shao
the (110) plane of Ti/Cu–SnO2 leads to such an increase in et al. 2014b) and reduced ohmic resistance between the
oxygen overpotential (Chen et al. 2019). metal oxides and substrates (Baronetto et al. 1994). The
The ohmic loss between the substrate and catalyst prepared Ti/TiHx/Ni–Sb–SnO2 anode showed better cur-
layers can be reduced by introducing a hydride layer. Shao rent efficiency (56%) for ozone generation, high reaction
et al. (2014b) prepared the Ti/TiHx/Sb–SnO2 anode using rate kinetics, complete degradation of the MB dye, and two
the electrodeposition technique and performed the life times better service life compared to Ti/Ni–Sb–SnO2 anode
cycle analysis to degrade various dyes. The prepared prepared without hydride layer. Hence, we can conclude
electrode’s accelerated life cycle was about six times that that inter Ohmic resistance between the substrate and
the Ti/Sb–SnO2 electrode and 1.5 times greater than the mixed metal oxides plays an essential role in the stability
Ti/TiO2–NTs/Sb–SnO2 electrode prepared using electro and activity of the electrode. Incorporating hydride instead
anodization followed by thermal decomposition of the of highly electrically resistive oxide could be a solution for
coated metal salts (Zhao et al. 2009). Another group syn- utilizing low-cost transition metal precursors and synthe-
thesized a three-layer Ti/TiHx/Ni–Sb–SnO2 electrode using sizing stable MMO electrodes.
26 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Figure 9: Cyclic voltammogram and Nyquist plot of (SnO2)93Sb5M2 (M: Ce, ta, Bi, Gd) electrode synthesized at 550 °C (Moura de Salles Pupo et al.
2020).

Pulse electrodeposition is another technique used to based electrodes. A compact and uniform (non-cracked)
prepare Ti/Sb–SnO2–TiN composite electrodes. The pres- electrode surface can be obtained using PbO2, which im-
ence of TiN nanoparticles facilitated Sb5+ formation and proves the substrate’s stability (Saadi et al. 2020). The list of
increased the number of active sites for EO (Duan et al. various synthesis approaches used to produce different PbO2
2014). The accelerated service life data showed about 15.7 based nonactive mixed metal oxide anodes for EO of syn-
times increased life of the prepared electrode compared to thetic and real wastewater is presented in Table 5.
Ti/Sb–SnO2 electrode. In another study, dimethyl sulfoxide The performance of Ti/PbO2 anode is compared with
solution (DMSO) was used as a solvent for electrodeposition. Ti/SnO2 and Ti/BDD electrodes for the degradation of
The synthesized Ti/Sb–SnO2 electrode presented low charge pharmaceutically active compound carbamazepine (CBZ)
transfer resistance and improved service life of 59.3 h, which in Na2SO4 electrolyte medium (García-Gómez et al. 2014).
was about 21 times higher than the conventionally prepared Ti/PbO2 and Ti/BDD electrode provided similar perfor-
electrode (Duan et al. 2016). Ce-doped Ti/Sb–SnO2 prepared mance, while Ti/SnO2 electrode was found ineffective for
by electrodeposition technique using glucose, citric acid, CBZ removal due to its ability to hold reactive oxygen
tartaric acid, and oxalic acid as solvent. Glucose performed species at the surface. Sequentially, membrane bioreactor
better due to comparatively lesser carboxylic groups’ pres- is combined with EO for CBZ removal using Ti/PbO2 anode
ence (Yang et al. 2017). The prepared electrode also showed and Ti mesh cathode (García-Gómez et al. 2016). The
better service life and improved electrocatalytic properties. combined system was found effective with nearly 99.9%
Recently, the eutectic solvent of chlorine chloride: ethylene CBZ removal. However, the effluent’s toxicity increased
glycol (1:2 M/M), was used to prepare Ti/Sb–SnO2 electrode due to toxic metabolite formation during EO treatment or
(Y. Sun et al. 2020). The prepared electrode showed the residual •OH in the solution.
highest MB degradation per coulomb charge among similar In-situ H2O2 generation is favored in basic pH, and
electrodeposited electrodes. It is clear from the above dis- hence the anode should be compatible in this region. BDD
cussion that the type of solvent used during the electrode- and DSA® electrodes generally perform better in acidic pH.
position of SnO2–Sb electrodes significantly affects the However, the favorable performance of Pb/PbO2 anode was
electrode’s electrocatalytic activity and service life. observed for the electrochemical disintegration of aniline
and 4-chloroaniline using carbon polytetrafluoroethylene
3.2.3 Lead oxide anode (PTFE) O2-fed cathode (Brillas et al. 1995). The reaction was
performed at a pH ranging from 10 to 13, and higher H2O2
Non-active anodes like BDD have high OEP, but a higher generation was observed for current greater than 100 mA
applied voltage is required due to its considerably significant with •OH and •O2H radicals found at the anode layer
surface resistance, leading to greater energy consumption. decomposing the pollutant. The one-electron reduction
An alternative and economical approach is the use of PbO2 reaction was observed at the cathode at a current below
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 27

Table : Summary of various synthesis approaches used to produce PbO based anodes for electrochemical oxidation of synthetic and real
wastewater.

Anode (A) Synthesis approach Contaminant Operating condition Removal (%) Reference

A: PbO Sol–gel (A) ,,-trichlorophenoxiacetic Anode area: . cm EO: { (A, Santos et al.
A: Ti/Sb– Electro anodization (A, A) acid (PbO),  cm  min);  (A, ()
SnO (SnO), . cm  min);  (A,
A: BDD (BDD), . cm (Ti/  min)}; Photo-
A: Ti/TiO– TiO–NTs/PbO); EO:  (A,
NTs/PbO cathode: Pt mesh;  min)
reactor: single  (A,  min)
compartment cell;
electrolyte: . M
NaSO; pH: , ; j:
 mA cm−; CE:
PbO/WO Composite electrodeposition Metribuzin Anode area:  cm; COD: . Yang et al.
composite cathode: Ti plate; ( min) (b)
reactor: single
compartment cell;
electrolyte: .M
NaSO; pH: .; j:
 mA cm−; A. Ser-
vice life:  h
( M HSO,  A
cm−); ICE (%): ∼
(% COD removal)
Ti/PbO–CeO Composite electrodeposition Malachite green (MG) Anode area:  cm; COD: . Yao et al.
cathode: SS plate; ( min) ()
reactor: single
compartment cell;
pollutant concentra-
tion: – ppm;
electrolyte: .M
NaSO; pH: .; j:
 mA cm−; A. Ser-
vice life:  h
( M HSO,  A
cm−); ICE (%): ∼.
(% COD removal)
Ti/PbO–CeO Composite electrodeposition Malachite green (MG) Anode area:  cm; COD: . Yang et al.
Herbicide metamitron (HM) cathode: SS plate; ( min) (a)
reactor: single
compartment cell;
pollutant concentra-
tion: – ppm;
electrolyte: .M
NaSO; pH: .; j:
 mA cm−; A. Ser-
vice life:  h
( M HSO,  A
cm−); ICE (%): ∼
(% COD removal)
Ti/calcined Electrodeposition Methylene blue Anode area:  cm; COD: . Jiao et al.
graphene/ cathode: SS plate; ( min) ()
PbO reactor: single
compartment cell;
electrolyte: . M
NaSO; pH: inde-
pendent; j:
28 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Table : (continued)

Anode (A) Synthesis approach Contaminant Operating condition Removal (%) Reference
−
 mA cm ; A. Ser-
vice life: . h
( M HSO,
. A cm−); ICE (%):
∼. (% COD
removal)
Ti/SnO–Sb/ Electrodeposition m-cresol Anode area:  cm TOC: (., Tan et al.
PPy/PbO (porous); cathode: Ti  mgL−) (., ()
mesh; reactor: sin-  mg L−)
gle compartment
cell; electrolyte:
. M NaSO; j:
 mA cm−; ICE (%):
∼. (% COD
removal)
-D ordered Polystyrene template through sedi- Flutriafol Anode area: TOC: ∼. Liu et al.
macroporous mentation . cm; cathode: ( min) ()
Ti/PbO film Electrodeposition perforated SS;
reactor: electro-
chemical filtration
reactor; electrolyte:
. M NaSO; j:
 mA cm−; MCE:
.%
Ti/SnO– Thermal Methylisothiazolinone Anode area: .; COD: .; Wang et al.
SbO/α, β– decomposition + electrodeposition biocide  ×  cm; cathode: TOC: . ()
PbO SS foil; reactor: sin- ( min)
gle compartment
cell; electrolyte:
.M NaSO, .M
NaNO, and .M
NaCl; pH: –; j:
.– mA cm−
Ti/SnO–Sb/ Thermal C.I. reactive red  azo dye Anode area: TOC:  ( h, Song et al.
PbO decomposition + electrodeposition  ×  cm; cathode: initial concentra- ()
nickel foam; reactor: tion  ppm), 
two compartment ( h, initial con-
cell; membrane: centration
Nafion- cation  ppm)
exchange mem-
brane; electrolyte:
.M NaSO; pH: ,
., ; j: , , ,
,  mA cm−
A: TiO– TiO-ENTA: twice anodization and Reverse osmosis Anode area:  cm COD:  (A, Chen et al.
ENTA/SnO– cathodization + sol– concentrates cathode: SS plate;  min);  (A, ()
Sb gel + electrodeposition reactor: single )
A: TiO– compartment cell
ENTA/ SnO– ( ml); electro-
Sb/PbO lyte: none; pH: .–
; j:  mA cm−; A.
Service life:  h
(. M HSO, .–
. A cm−); ICE (%):
∼. (A) .
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 29

Table : (continued)

Anode (A) Synthesis approach Contaminant Operating condition Removal (%) Reference
−
(A) (. A h L
charge)
Ti/SnO–Sb/ Sol–gel method Sulfamethoxazole Anode area:  cm; TOC: . ( h) Wang et al.
Er–PbO cathode: SS plate; ()
reactor: single
compartment cell
( ml); electro-
lyte: . M NaSO;
pH: –; j: –
 mA cm−
Ti/SnO–Sb/ Cathodic electrodeposition, +anodic p-dinitrobenzene Anode area:  cm;  ( min); Ansari and
β–PbO deposition cathode: SS plate; COD:  Nematollahi
reactor: single ()
compartment cell
( ml); electro-
lyte: . M NaSO;
pH: , , ; j: , ,
 mA cm−; A. Ser-
vice life:  h
(. M HSO,
. A cm−); ICE (%):
∼ (% COD
removal)
Ti/SnO– Thermal decomposition + anodic Hydrolyzed polyacrylamide Anode area:  cm;  ( min); Han et al.
SbO/β– electrodeposition cathode: SS plate; TOC: ; TN: ()
PbO reactor: single .
compartment cell
( ml); electrolyte:
–, ppm
NaCl; pH: –; j: –
 mA cm−
Ti/SnO– Sol–gel + electrodeposition Perfluorooctane sulphonate Anode area:  cm; Mineralization: Zhuo et al.
SbO/PbO– cathode: Pt plate; . ( min) ()
PTFE reactor: single
compartment cell
( ml); electro-
lyte:  ppm
NaClO; pH: , , ;
j:  mA cm−
A: Ti/Sb– Cathodic and anodic Aniline Anode area:  cm; Degradation & Li et al.
SnO electrodeposition cathode: graphite; COD: . & . (b)
A: Ti/Sb– reactor: single (A,  h), . &
SnO/PbO compartment cell . (A,  h),
A: Ti/Sb– ( ml); electro- . & . (A,
SnO/PbO lyte:  wt% NaSO  h)
and  wt% NaCl; pH:
, , ; j:  mA cm−
Ti/Sb–SnO Sol–gel Abacavir drug Anode area:  ( min); TOC: Zhou et al.
porous tube  cm; cathode: . ( h) (a)
SS tube; reactor:
penetrating reactor
( ml); inorganic
ions: NO−, HCO−,
and Cl−; pH: –; j:
.– mA cm−
30 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Table : (continued)

Anode (A) Synthesis approach Contaminant Operating condition Removal (%) Reference

A: Ti/SnO– Sol–gel (A); +electrodeposition Perfluorooctanoic acid Anode area: . (A), . Lin et al.
Sb (A, A)  cm; cathode: Pt (A), . (A) ()
A: Ti/SnO– wire; reactor: single ( min)
Sb/PbO compartment cell
A: Ti/SnO– ( ml); electro-
Sb/MnO lyte:  mM NaClO;
pH: , , ; j:
 mA cm−
Ti/SnO– Dip coating and thermal Methyl orange dye Anode area:  cm; . ( min); Pan et al.
SbO/α– deposition + electrodeposition cathode: Ti plate; COD:  ()
PbO/Ce– reactor: single ( min)
Nd–β–PbO compartment cell
( ml); electro-
lyte: . M NaSO;
pH: , ; j:
 mA cm−
Ti/SnO– Spray pyrolysis + electrodeposition Bisphenol A Anode area:  cm; COD:  ( min) Xue et al.
SbO/PbO cathode: SS plate; ()
reactor: single
compartment cell
( ml); electrolyte:
. M NaSO; pH:
; j:  mA cm−
Ti/SnO–Sb/ Dip coating and thermal Methyl orange Anode area:  cm;  ( min) Jin et al.
α–PbO/ deposition + electrodeposition cathode: Ni plate; ()
Fe–β–PbO– reactor: single
PTFE compartment cell
( ml); electro-
lyte: . M NaSO;
pH: ; j:  mA cm−
Ti/SnO–Sb/ Sol–gel + electrodeposition Benzophenone- Anode area:  ( min) Zhou et al.
Ce–PbO  cm; cathode: (b)
SS sheet; reactor:
single compartment
cell ( ml); elec-
trolyte:  mM
NaSO; pH: –; j:
 mA cm−
Ti/SnO– Dip coating and thermal Musk ketone Anode area:  cm;  ( min) Zhao et al.
SbO/PbO deposition + electrodeposition cathode: Cu foil; ()
reactor: single
compartment cell
( ml); electro-
lyte: . M NaSO;
pH: ; j:  mA cm−
Ti/SnO–Sb/ Sol–gel + electrodeposition Tricyclazole Anode area:  cm; .; COD: . Zhong et al.
PbO cathode: SS plate; ( min) ()
reactor: single
compartment cell
( ml); electro-
lyte:  g/L NaSO;
pH: ; j:  mA cm−
FeO/Sb– Ti/PbO magnetically assembled Acid red G, sodium Anode area:  cm; . ( min) Zhang et al.
SnO on Ti/ with FeO/Sb–SnO lignosulphonate cathode: Cu plate; ()
PbO reactor: single
compartment cell
( ml); electro-
lyte: . M NaSO;
j:  mA cm−
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 31

Table : (continued)

Anode (A) Synthesis approach Contaminant Operating condition Removal (%) Reference

Ti/Sb–SnO/ Sol–gel + electrodeposition Aniline Anode area: COD:  ( min) Shang et al.
PbO  cm; cathode: ()
Cu sheet; reactor:
single compartment
cell ( ml); elec-
trolyte:  g/L
NaSO; pH: ; j:
 mA cm−
Ti/SbO– Thermal Methylene blue Anode area:  cm; TOC: . Zhou et al.
SnO/Er-PbO decomposition + electrodeposition cathode: SS sheet; ( min) ()
reactor: single
compartment cell;
electrolyte: . M
NaSO; pH: ; j:
 mA cm−

100 mA, resulting in the formation of •O2H intermediate ions especially in basic medium. WO3 particles, due to their
and lesser H2O2 production at the cathode. The maximum stable morphology, were also used to develop a PbO2/WO3
current efficiency of 50% has been obtained for current composite electrode. The results provided extended service
ranging from 100 to 200 mA. life and high hydroxyl radical formation (Yang et al.
The degradation behavior for chloranilic acid using 2019b). However, contradictory results with the lowering of
Ti/IrO2, Pb/PbO2, and Si/BDD electrodes were analyzed in active sites were also reported due to the high resistivity of
terms of energy consumption. Being an active anode, WO3 particles (Kusmierek 2019).
Ti/IrO2 showed the least MCE and acid removal, while the β–PbO2 shows comparatively high conductivity, better
BDD electrode performed best in terms of mineralization oxygen overpotential, and stability against α–PbO2 being
and energy consumption (Martínez-Huitle et al. 2004). used for electrode preparation (Ansari and Nematollahi
However, Pb/PbO2 electrode also showed competent per- 2018; Zhou et al. 2005). The β–PbO2 was electrodeposited
formance in both parameters. Being a cheap and less over graphite, SS 316, Ti, and Pb foil substrates. The
engineered production approach, it attracts attention to- degradation and current efficiency were observed in a
wards its use. Ti/PbO2 and Ti/TiRuO2 based anodes were sequence of graphite > SS316 > Ti > Pb. The graphite- PbO2
compared to degrade high COD synthetic tannery waste- anode gave the highest color and COD removal for malachite
water. The Ti/PbO2 permits mineralization through both green (MG) of 100 and 94%. Additionally, the instantaneous
direct and indirect oxidation facilitated by chlorine, while current efficiency (ICE) was 17.5%, among the highest effi-
Ti/TiRuO2 based electrodes allow only indirect oxidation ciency reported.
(Panizza and Cerisola 2004). An evident higher oxidation The performance of Graphite-PbO2 anode has been
rate was found on Ti/PbO2 anode due to the additional analyzed recently for other pollutants. It was used for the EO
direct oxidation reaction at the anode surface. However, of ammonia nitrogen by chlorine-mediated oxidation. 96.4%
Ti/PbO2 anode’s stability was found lesser than Ti/TiRuO2 NH3–N was removed within 120 min, while its complete
anodes with the additional load of more toxic ion forma- mineralization to N2 was found to increase with an increase
tion. In terms of energy consumption for COD removal, in chloride concentration (Mandal et al. 2020). In another
both electrodes were found similar. case, when MB dye was mineralized using graphite-PbO2
The corrosion resistance can be promoted by sup- anode, complete mineralization with 96.4% removal effi-
porting certain stable metal oxides over the electrode. Zhao ciency was obtained in 60 min of electrolysis time, which
et al. (2014) studied the effect of Co3O4 support over was 2.6 times higher than the conventional graphite anode
Ti/PbO2 anode and observed that it increases the corrosion (Samarghandi et al. 2020). Due to its unique 2-D structure
resistance significantly. Additionally, the accelerated ser- and high specific surface area, CNT is used as an interlayer to
vice life of the modified Ti/PbO2/Co3O4 anode was found to obtain graphite/α–PbO2/CNT–Ce/β–PbO2–Ce electrode for
be 146 h, which can be a very promising improvement for the electrochemical degradation of antibiotic ceftazidime.
the lead oxide-based anodes labeled to generate the toxic CNT interlayer enhanced the accelerated service life of the
32 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

electrode from 12 to 21 h, while the service life of the proposed To obtain a homogenous PbO2 layer over the SS substrate,
electrode was found to be 25 h with additional stability the SiOx interlayer has been deposited through plasma-
ascended due to CeO2 doping at the surface (P. Duan et al. enhanced chemical vapor deposition technique (P-CVD). The
2020). morphology of the prepared electrode showed a four times
An interesting and different observation was reported higher β–PbO2/α–PbO2 deposition ratio compared to bare SS/
when Ti/PbO2 electrode was modified with a calcined gra- PbO2 electrode, which results in enhanced current transfer,
phene interlayer. The fabricated electrode was found inde- uniform layer, and better COD and color removal when
pendent of the initial pH concentration for the removal of pharmaceutical contaminants have been mineralized using
MB dye. The explanation was based on the fact that the H+ this electrode (Elaissaoui et al. 2019).
ions produced in an acid environment can react with the Recently, the thermal–electrochemical method has
central nitrogen atom of MB, developing a more persistent been used to prepare novel Pb/PbO2 electrodes using the
reduced compound. In the same way, under an alkaline thermal oxidation of Pb sheet, followed by electrochemical
environment, electrolyte consumption reduces degradation oxidation (Chen et al. 2021b). The concept is to provide a
(Jiao et al. 2021). However, no explanation regarding the PbO2 layer over the Pb substrate using thermal oxidation.
effect of the electrode was provided to better simulate the Then the prepared substrate is oxidized in a three-electrode
observation. cell at 1.5 V for a specific time interval to obtain the final
The graphitic substrate requires additional assembly to product. This approach was proved effective in refining the
support them due to their dimensional instability. Hence, crystal size and crystallinity of the anode. The accelerated
dimensionally stable Ti substrates always attract more service life of the anode was found to be 33.4 h
attention. However, Ti substrates form non-conductive TiO2 Porous electrodes are getting more attention among
over the surface when they come in contact with the elec- research groups due to their enhanced surface area and
trolyte. One way to improve the stability of the substrate better stability. Recently, a porous 3-dimensional graphene
without compromising its conductivity is to deposit a Pt (3DG) doped lead oxide electrode (Ti/SnO2–Sb2O3/3DG–α–
interlayer over it. Electrochemical degradation behavior PbO2/β–PbO2) was prepared (X. Duan et al. 2020). The
of actual textile wastewater using Ti–Pt/β–PbO2 and effect of doping over surface morphology and electro-
Ti/Ti0.7Ru0.3O2 DSA® anode was studied using a filter press catalytic activity of the anode has been studied during EO.
cell (Aquino et al. 2014). PbO2 based anode, due to its higher The OEP was found to be directly proportional to the
overpotential, generates oxidizing species like •OH and O3, amount of doping, obtaining the OEP of 2.03V/SCE for the
which enhances the indirect oxidation of pollutants excessive loading of 0.12 g L−1 3DG.
and performs better than the DSA® anodes. Also, when (Tan et al. 2020) prepared a 3-D hierarchically porous
Ti/β–PbO2, Ti–Pt/β–PbO2, and Ti/Ru0.3Ti0.7O2 DSA® anodes PbO2 anode using the electro-anodization technique by
were used to degrade acid green 28 dye in a filter press sandwiching conductive polymer polypyrrole (PPy) be-
reactor, the performance of DSA® anode provided compar- tween the Ti/SnO2–Sb and PbO2 layer. Coating conductive
atively less COD and color removal with high energy and hydrophobic PPy over the Ti/SnO2–Sb electrode sur-
consumption and no TOC removal. While Ti/β–PbO2 face using electrochemical polymerization reduces the
electrode provided comparative but best performance chance of TiO2 formation on the substrate. The polymer
than the Ti–Pt/β–PbO2 anode, with 100% COD and 32% also fills the cracks over the electrode surface incorporated
TOC removal, with an energy consumption of 19.7 kW h−1 during thermal decomposition and increases the available
(Irikura et al. 2016). It indicates that the Pt interlayer surface area by forming a cylindrical hollow tube-like
between the substrate and deposited PbO2 can enhance structure over the substrate (Figure 6 (a–c)).
the passivation of the substrate but does not contribute Hydrophobic and inert polymers like PTFE can be
to synergistically enhancing the electrochemical perfor- added to the surface to increase the hydrophobicity of the
mance of the electrode. An interesting observation was anode material. PTFE on the surface helps to disperse the
obtained when Ti/Pt/PbO2 and Si/BDD anodes were internal stress on the active sites and improves the hy-
compared during the electrochemical degradation of the drophobicity of the hydrophilic material like PbO2 (Zhuo
drug Ibuprofen. It was observed that Ti/Pt/PbO2 anode et al. 2020). (Sun and Chen 2016) prepared a CeO2/C–β–
showed better performance in case of low COD removal PbO2–PTFE composite electrode for the electrochemical
(<40%), which indicates that the reaction was initially degradation of dye and observed that the introduction of
kinetically controlled (Ciríaco et al. 2009). However, for cerium into the composite electrode produces more active
high COD removal, Si/BDD electrode performed well due material sites and increases the OEP but also helps in the
to enhanced indirect oxidation. adsorption of organic matter.
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 33

A polystyrene sphere template was deposited over the results directly indicate the mass transfer dominance dur-
Ti mesh substrate using the sedimentation and solvent ing the electrochemical reaction.
evaporation method to obtain a closely packed 3D macro- PbO2 is an effective electrode, but the shelf life of these
porous structure (Liu et al. 2017). The macroporous struc- electrodes is an essential factor in deciding its usability.
ture sustains even after the dissolution of polystyrene and S. Chen et al. (2021), in a new study, developed a stable
deposition of PbO2. These macropores improve the elec- graphitic carbon nitride (GCN) and multiwall carbon nano-
trode’s permeation flux and surface area, which allows the tube (MWCNT) codoped Ti/PbO2 electrode to degrade phar-
fluid to pass through it (Figure 10). The prepared electrode maceutical wastewater contaminants. GCN and CNT
was used to mineralize flutriafol fungicide in a flow- synergistically enhanced the accelerated service life of Ti/
through electrochemical reactor, and MCE of 24.4 was PbO2 (from 13 to 96 h). When combined with CNT, GCN can
observed. At the same time, the same electrode provides improve the •OH generation, resulting in the enhanced COD
the MCE of 8.96% when a batch reactor is used. These removal efficiency than introduced individually.

Figure 10: SEM images of PPy middle layer (a), Ti/SnO2–Sb/PbO2 surface (b), Ti/SnO2–Sb/PPy/PbO2 surface (c) (Tan et al. 2020),
3D-macroporous Ti/SnO2–Sb/PbO2 surface (d, e), the inset is a SEM image of cross sectional structure of electrode (Liu et al. 2017).
34 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

In a recent study, the stability and shelf life of PbO2 generation (Deng et al. 2020; Souza et al. 2014; Zhou et al.
electrodes have been significantly improved by incorpo- 2020). Indium doping effect over the PbO2 electrode has
rating black titanium oxide nanotube array (TiO2NTs) be- been studied to obtain a more oriented crystal and compact
tween the Ti substrate and β–PbO2 (Liu et al. 2020). This structure and enhanced service life. Higher oxygen evolu-
nanoarray showed excellent conductivity and mechanical tion potential, enhanced •OH radical generation, better
stability to hold the deposited PbO2. The accelerated lifetime accelerated lifetime, and up to 30% energy saving due to
of the electrode was improved to 96 h, which is compara- doping during pollutant mineralization have been observed
tively very high among previous studies (Li et al. 2020; Wang (Xia et al. 2020b). Similar results were obtained when Fe was
et al. 2018). doped over Ti/PbO2 (Xia et al. 2020a) and Ti/TiO2NTs/PbO2
Interestingly it has been observed that the oxygen electrodes (Jiang et al. 2014). However, a higher OEP of 2.7 V
evolution overpotential starts decreasing just after 5 s of the compared to 2.08 V for In doped electrode was seen. It
electrodeposition process. However, the least electro- can be due to the involvement of conductive interlayer of
catalytic enhanced “30-min-PbO2 anode” showed the TiO2NTs arrays on the electrode.
highest •OH and O3 electrogeneration due to the colloidal Cu doped PbO2 electrode was also used recently to
Pb(OH)2 hydrated crystal zone of PbO2. Another work degrade pharmaceutical drug amoxicillin, and about 16%
compared the synergistic effect of PbO2 and TiO2NTs by (Bian et al. 2019) and 5% (Hu et al. 2020) COD removal has
preparing three different electrodes for the electrochemical been improved compared to bare PbO2 electrode.
degradation of reverse osmosis concentrate (ROC) and The pulsating power supply technique has the potential
observed the COD removal efficiency in the order of of energy saving during mineralization reactions. Li et al.
Ti/TiO2NTs/PbO2 > Ti/PbO2 > Ti/TiO2NTs (Wei et al. 2021). (2015) demonstrated the effect of calcination temperature
This trend clears the significance of TiO2NTs that it enhance and the molar ratio of doping elements Sb and Mn over the
the electron transport between the material and substrate capacitance of Mn-doped Ti/SnO2–Sb–Mn/PbO2 electrode
and synergistically increases the reactive •OH radical during EO of phenol. The electrochemical capacitance is a
generation at the anode surface. unique phenomenon that can be used for storing energy over
From J.E.L. Santos et al. (2020) work on photo- the electrode surface for the degradation of organic matter.
electrochemical (PEC) degradation of herbicides, it has Co is another widely used dopant for PbO2 electrodes.
been shown that the synergy between PbO2 and TiO2NTs It is easy to deposit and improve the stability of the elec-
provide better electron transfer, high photoconversion effi- trode by providing structurally optimized pyramidal PbO2
ciency, high photocurrent density, and high pollutant grains at the substrate. ZnO/polyethylene glycol-Co(II)–
decomposition (99% removal as compared to 80% for PbO2 nanocomposite electrode was prepared using the
Pb/PbO2 anode). electrodeposition technique for phenol degradation (Gui
In another research, NiO@C nanosheets derived from et al. 2020). The incorporation of Co transformed the
2D Ni-metal-organic framework (MOF) were introduced morphology of PbO2 from the clustered to the spherical
over TiO2NTs supported over Ti substrate. The elec- structure by forming a Co–O nucleation structure, dis-
trode with final deposition of PbO2, collectively called placing the Pb–O nucleation site. At the same time, poly-
Ti/TiO2NTs/NiO@C/PbO2 anode, was used for the miner- ethylene glycol helped to increase wetting on the electrode
alization of persistent organic compound salicylic acid surface. These changes result in improving the degradation
wastewater (J. Wang et al. 2021). The introduction of efficiency of phenol. TiO2NTs/Co–PbO2 anode was pre-
TiO2NTs and NiO@C significantly increases the conduc- pared through pulse electrodeposition (P-EDP) and direct
tivity and durability of the electrode, mainly due to the electrodeposition (EDP) technique (Wang et al. 2015). The
NiO@C nanosheet array interlayer. Additionally, the Pb anode prepared using P-EDP observed higher oxygen
poisoning through leaching in the effluent stream was overpotential and excellent mineralization efficiency. The
also diminished through these supporting materials. reason can be attributed to the smaller crystal size, favored
The crystal size and morphology also affect the degra- orientation at low pulse frequency, allowing much compact
dation efficiency, and doping some elements (e.g., F, Bi, In, structure and larger active sites at the surface.
Er, Gd, La, Co, Ce, Sm, Pr) over the PbO2 surface can enhance Co and Sm were recently electrodeposited together over
the electrocatalytic performance of these electrodes (Kong Ti/PbO2 anode, and mechanical and electrocatalytic prop-
et al. 2007; Li et al. 2020; Yao et al. 2019). The presence of erties for the electrode towards atrazine herbicide degrada-
point defects on the surface induces the increase in electron tion have been performed (S. Chen et al. 2020a). These
transport tunnel and provides more oxygen active sites, metals aid in increasing the service life (78 h), conductivity,
which promotes the effective •OH and other similar radical and OER overpotential. The improved performance is
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 35

attributed to the synergistic effect of Co and Sm, providing a 0.5 mA cm−2 (Lin et al. 2013). These studies indicate that the
compact and smaller grain size pyramidal shape PbO2 energy consumption closely depends on the electrode’s
structure over the substrate. These structural changes can fabrication and pollutant load. However, higher CeO2 loading
prevent the substrate by limiting the impedance of electro- can be achieved using composite electrodeposition tech-
lytes. EIS studies of the prepared electrode display enhanced nique, providing enhanced electrode was stability, OEP, and
charge transfer on the modified electrode. This group also current efficiency (Yang et al. 2019a; Yao et al. 2015).
analyzed the synergistic effect of adding Pr and Co over the Y. Wang et al. (2019) prepared Ti/SnO2–Sb2O5/α, β–
PbO2 anodes. Similar observation with an enhanced service PbO2 electrode having OEP of 2.09 V/NHE, and investigated
life of 84 h is obtained for the modified electrode (S. Chen the degradation of biocide methylisothiazolinone. Only
et al. 2020b). 25.5% COD and 92.9% removal efficiency were observed,
suggesting more recalcitrant intermediates such as alde-
3.2.4 Sb–SnO2/PbO2 anodes hyde, ketone, and carboxylic acid. The incomplete miner-
alization may be favored by the presence of the PbO2 catalyst
Reports suggest that Ti-based PbO2 anodes, when coated layer at the cost of improved stability of the electrode.
with an intermediate Sb doped SnO2 layer, provide higher Apart from adding a new intermediate layer between
OEP and •OH evolution at the anode surface with the Ti substrate and active metal oxide or doping to
enhanced stability (Xue et al. 2011; Zhong et al. 2013). When enhance the electrical and catalytic properties, porous Ti
Ti/Sb–SnO2 and Ti/PbO2 anodes were compared during the substrate is also used to prepare a more stable electrode.
EO of lignin, it was observed that Ti/PbO2 anode favors the Porous Ti electrodes can provide a larger surface area,
incomplete mineralization, improving the biodegradability porosity, permeability, corrosion resistance, and biocom-
of the pollutant. In contrast, Ti/Sb–SnO2 anodes allow patibility (Zhao et al. 2015). A 3D-porous/macroporous Ti/
better COD removal due to its comparatively higher OEP, SnO2–Sb2O3/PbO2 electrode was prepared using a porous
allowing better nonselective oxidation of the contaminant titanium substrate (Zhao et al. 2016). Due to the larger
(Shao et al. 2014a). Various electrodes have been studied in specific surface area, smaller grain size and uniform crystal
different works of literature, and the efficiency of Ti/SnO2– growth were observed on the porous electrode. It helps in
Sb/PbO2 electrode can be considered dominant when uniform current distribution to the presence of larger active
compared with Ti/SnO2–Sb, and Ti/SnO2–Sb/MnO2 elec- sites and decreases the electrical potential, which supports
trodes (Lin et al. 2012, 2013). the crystal growth. The lead toxicity also gets decreased
Cerium (Ce) is a thermally stabile and diffusive rare-earth due to the improved accelerated service life, which was
element, considered a promising dopant for PbO2 electrodes. more than four times the planar PbO2 electrode. Improved
The Ce doping enhances the electrochemical activity and OEP, reduced Ohmic and charge transfer resistance, and
stability of PbO2 electrodes. Wang et al. (2016) compared the better double-layer capacitance can help in reducing the
EO of pharmaceutical Ibuprofen on Ti/Ce–PbO2, Ti/SnO2–Sb, operational cost for mineralization (Liu et al. 2018; Zhao
and Ti/SnO2–Sb/Ce–PbO2 anodes prepared through (EG: CA) et al. 2016). These electrodes’ morphological and structural
sol–gel process. The reaction rate constant for Ti/SnO2–Sb/ properties can also be enhanced by adopting technologies
Ce–PbO2 anode was 9.4 × 10−2 min−1 which was 2.0 and 1.7 like the pulse electrodeposition method. Recently, Hua
times then Ti/Ce–PbO2 and Ti/SnO2–Sb anodes, respectively. et al. (2020) prepared a porous PbO2 electrode with the
The reaction mechanism suggests that the hydroxylation of longest reported accelerated service life of 272 h, which
Ibuprofen through •OH free radicals results in its sequential portrays the stability and compactness that almost inhibits
conversion to carboxylic acid and successively complete the penetration of electrolyte into the substrate.
mineralization of this compound. The TOC removal at opti- Modern synthesis approaches are able to provide high
mum conditions was found to be 93.2% with 13.1 WhL−1 en- OEP at Ti/SnO2–Sb/β–PbO2 anodes. The performance of
ergy consumption. Another research reported the reduced these electrodes is compared with BDD anodes due to their
energy consumption at Ti/SnO2–Sb/Ce–PbO2 anode for the similar OEP. A recent study reported an overpotential of
degradation of chemical benzophenone-3 and its intermedi- 2.35 V for Ti/SnO2–Sb/β–PbO2 electrode when prepared
ate 4-hydroxy benzophenone as 3.3–62.1 and 3.6–79.5 WhL−1, using the electrodeposition technique. The complete COD
respectively (Zhou et al. 2019a). For the mineralization of removal for p-dinitrobenzene is observed, which is prac-
sulfamethoxazole using the Ti/SnO2–Sb/Ce–PbO2 anode, the tically immune to conventional chemical and biological
energy required for nearly complete mineralization was var- treatment (Ansari and Nematollahi 2020). In another
ied 19.6 times from 0.5 to 40 mA cm−2 with a change in current research, flat and porous Ti has been used as a substrate for
density, consuming 8.1 Wh L−1 at the current density of BDD electrode preparation, and the effect of a substrate
36 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

structure for the electrochemical degradation of the phar- indicate that Ti/Sb–SnO2/PbO2 worked as an active anode in
maceutical drug has been studied (He et al. 2015). The chloride and sulfate electrolyte medium. While Ti/Sb–SnO2/
mineralization characteristics were also compared with Pb3O4 showed the best performance in chloride medium due
PbO2 anode supported over Ti/SnO2–Sb2O5 substrate. to its high chlorine evolution capacity, similar favor towards
Porous Ti/BDD electrodes presented the highest current biodegradability was observed when Ti/Sb–SnO2/PbO2
and removal efficiency than flat Ti/BDD and PbO2 elec- anode was used to mineralize azo dye. The GC-MS results
trodes, owing to comparatively high OEP (2.45 vs. 1.95 V for revealed that multiple metabolites were formed during the
electrodeposited Ti/SnO2–Sb2O5/PbO2 electrode). Both EO of the dye, which further transformed into different small
research groups used similar electrolyte media of hydrocarbon compounds. At the end of the process, acetic
0.5M Pb(NO3)2 + 0.1M HNO3, but the former used NaF as an acid, formic acid, and oxalic acid show persistency and
additive to the solution. Additives like sodium dodecyl contribute to the most unremoved TOC (Song et al. 2010).
sulfate and NaF are used to obtain a smoother, smaller Recently the effect of incorporating Ti enhanced nano-
grain size and stabilize deposition of the PbO2 layer by tube array (Ti-ENTA) for improving the electrochemical
increasing the OEP (Hossain et al. 2020). Another reason properties of the traditional DSA® electrode was examined.
could be the synthesis approach and the amount of Sb used Secondly, Ti-ENTA was coated with Sb–SnO2 and with or
to obtain the SnO2–Sb with better morphology, lesser without the PbO2 layer (Figure 11). The introduction of ENTA
crack, homogeneity, and higher conductivity. increased the OEP (2.32V/NHE for Ti-ENTA/Sb–SnO2 and
In a different study, Ti/Sb–SnO2 anode was compared 2.10 V/NHE for Ti-ENTA/Sb–SnO2/PbO2) and •OH produc-
with the electrodes having different lead oxide support as a tion, while the PbO2 layer improved the service life at the
top layer viz. Ti/Sb–SnO2/Pb3O4 and Ti/Sb–SnO2/PbO2 for cost of reduced removal rate, making Ti-ENTA/Sb–SnO2
the electrochemical degradation of Aniline, a nonbiode- superior in terms of COD removal (M. Chen et al. 2020).
gradable and highly toxic compound in NaCl and Na2SO4
electrolyte medium (Li et al. 2016b). In the Na2SO4 medium, 3.2.5 Bifacial anodes
it was observed that Ti/Sb-SnO2 anode provided higher
Aniline and COD removal efficiency as compared to other Usually, one side of anode substrate remains unused
electrodes. However, Ti/Sb–SnO2/PbO2 anode increased the (primarily in two-electrode systems) or is utilized with an
biodegradability of the pollutant in both mediums after 2 h added cost of electricity. An exciting and effective
of electrolysis, which was sustained afterward. This was not approach has been identified using a bifacial electrode,
observed in the case of Ti/Sb–SnO2/Pb3O4 anode, where the containing one electrocatalytically active side while the
biodegradability reverses after some time. These results other can be used as a photoanode. The photoactive side

Figure 11: The schematic diagram for Ti/ENTA/SnO2–Sb/PbO2 electrode preparation. Adapted with permission from M. Chen et al. (2020).
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 37

can be used for COD determination and enhance the Zhang et al. (2020) proposed an attractive approach to
degradation of organic contaminants (Yao et al. 2014). preparing a magnetically assembled electrode by attaching
Photocatalysts have pretty low efficiency due to the rapid a magnet behind a 2D Ti/PbO2 anode, which helps bind the
recombination of the charge carriers, requiring sufficient auxiliary electrodes made up of magnetically attractive
potential for the separation of electron-hole charge. granules like Fe3O4/Sb–SnO2 and Fe3O4/PbO2. The com-
Recently praseodymium- PEG–PbO2//Ti//TiO2NTs bifacial bined 3D electrode can work in two ways; if the auxiliary
electrode has been prepared and used to degrade drug electrode can generate •OH free radicals like in the case of
acetaminophen (Figure 12) (Zhao et al. 2021). The involve- Fe3O4/Sb–SnO2, then complete mineralization of the or-
ment of photocatalysis helps increase the reactive oxygen ganics will occur. If no •OH formation is seen, then
species generation, which collectively increases the cur- incomplete mineralization of organics to lower chain hy-
rent efficiency and degradability. In a different set of ex- drocarbons will occur. Overall, the introduction of auxil-
periments, Ti/TiO2//Ti/SnO2–SbO3/PbO2 bifacial electrode iary materials reduces the charge transfer resistance by
was prepared, and the photo-electrocatalytic degradation incorporating more active sites and increased surface area,
of herbicide fenuron was carried out, and similar improved but at the cost of increased diffusion layer thickness which
results were obtained (Barbari et al. 2018). PbO2 pinned increases the zeta potential. Hence, no significant energy
Co3O4 NWs heterostructure was prepared over Ti foil to consumption change has been seen for such a system in
efficient photo-electrochemical degradation of dye used in terms of energy consumption.
textile wastewater (X. Wang et al. 2019). PbO2 was elec-
trodeposited over the hydrothermally synthesized Co3O4
NWs. The prepared anode showed a faster removal rate and 4 Discussion and future aspects
better reproducibility of results. The toxicity and leaching
of lead-based electrodes limit its use as an effective anode As discussed, it is evident that the synthesis approach
for wastewater treatment applications. strongly governs the electrocatalytic activity, stability,

Figure 12: Schemating representation of bifacial anode preparation. Adapted with permission from Zhao et al. (2021).
38 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

and compatibility of electrodes. In addition, the perfor- the metal oxides. Additionally, a larger quantity of low
mance of electrodes is affected by the type of pollutant, its crystalline oxide will form, increasing the total active sur-
initial concentration, and the type of electrochemical face area of the electrode (Gonzaga et al. 2020). CO2 laser-
process used. The wastewater with a high pollutant load based synthesis, on the other hand, produces electrodes
can affect the electrode’s performance and its service life. with different morphologies compared to conventional
Higher concentration leads to higher oxygen bubble for- treatment, providing fast and volumetric heating of the
mation at the working electrode’s surface and enhances materials. No cracked-mud-like structure was observed,
the passive layer formation at the interface between the which ensures the stability of the substrate. Instead, rapid
electrode and electrolyte. The integrated bubbles and heating and cooling lead to homogenous and rough
high pressure at the electrode surface accelerate the coating formation. Furthermore, forming a spherical
peeling of the active coating. It can also increase the low-relief bubble-like structure at the electrode surface
porosity of the surface, due to which the electrolyte can increases the available surface area and ensures no pene-
penetrate the electrode to more depth. tration of electrolyte to the substrate.
On the other hand, the increased thickness of the elec- Electrodeposition is another approach extensively
trode due to the generated passive layer increases its resis- used for the preparation of lead oxide electrodes. However,
tance and hence the current requirement. Working at a targeted modification in electrodes’ properties can be
higher current density is usually required to overcome this achieved using this approach. Formation of hydride layer
issue, which decreases the performance, and the deactiva- over the Ti substrate using this approach guarantees better
tion/depletion of coated metal oxide increases at a higher substrate stability (Abbasi et al. 2018). The OEP and elec-
current load (Moradi et al. 2020). Collectively, the rise in trocatalytic activity of the electrode can be increased using
improper surfaces due to piling, passive layer formation, this approach by depositing an additional layer of com-
increase in porosity of the anode surface, and hence the rise ponents like Pt, TIO2NTs, conductive polymers, graphene,
in the formation of nonconductive TiO2 layers at the elec- β–PbO2, and several metallic dopants. Additionally, this
trode surface highly affect the stability of the electrode. approach produces less quantity of waste components,
Preventively, the thickness of the active layer coating on the and utilization of clean energy enhances the environ-
electrode can be increased to compensate for the increased mental compatibility of this approach.
porosity. Table 6 reports the advantages and limitations of Novel solvents like ILs and PVA are proved to provide
using different materials as modifiers and discusses elec- attuned homogeneity and larger grain size of metal oxides.
trode performance. Improved crystallinity, better charge holding capacity,
As discussed above, the active anodes are prone to porous electrode formation, and additional protection of
passive layer formation and, therefore, can be deactivated the metallic support during dilation and contraction of
rapidly. Hence increasing the number of active metal ox- retrieving layer are the benefits associated with using ILs.
ides (e.g., a higher amount of IrO2) can enhance the service PVA is also reported to have near similar properties to ILs,
life. Nonactive anodes like PbO2 and SnO2 are prone to but being an environment-friendly and water-tolerant
depletion and more significant crack formation. It can be precursor can be a better alternative. Electrostatic trans-
due to the complete detachment of the active oxide coating formation of chloride salts of metal precursors to their
from the electrode surface or due to the formation of a hydroxide occurs while using PVA, which finally trans-
nonconductive TiO2 layer between the Ti substrate and the forms to oxide during calcination.
coating. It also leads to a decreased service life of the Apart from synthesis, the composition of metal ions
electrode. However, as discussed in the nonactive anode plays a crucial role in defining the electrocatalytic proper-
section, changing the composition of the electrode by ties, type of oxidation, reaction kinetics, and stability of the
providing an interlayer between the substrate and active electrodes. Modifications using new and improved materials
metal oxide (e.g., SnO2–Sb between Ti/PbO2, or TiHx layer) like TiO2NTs and nanoarrays, CNTs/NWs, doping with metal
can improve the stability of the electrode. and metal oxides, reduced graphene, calcined graphene,
Concerning the synthesis of an anode, microwave and aerogels, and conductive polymers, or using bifacial elec-
CO2 laser deposition are promising solutions during calci- trodes are reported. Calcined graphene sandwiched PbO2
nation steps. Microwave synthesis is a fast and economical electrode showed pH independence and promising OEP
approach and provides uniform heating throughout the (2.32 V). Similarly, CNTs as a dopant can help to improve the
substrate during decomposition. This leads to the shallow electrode morphology (especially for PbO2) by developing a
crack-mud morphology and broader grain size formation of compact fibrous structure with a smaller grain size.
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 39

Table : Advantages and challenges of using different materials and related electrode performance.

Advantages Challenges

Doping/ CNTs/NWs – Mesoporous tubular 2D network structure – Disorganized dispersion of CNTs due to
composite provides high surface area conglomeration
– Excellent conductivity – New technology, less testing can be done
– As an interlayer allows uniform catalyst grain – CVD and gaseous phase catalytic growth of
growth CNTs going on for scale-up.
– Increase number of reaction active sites, OEP, – Poor reproducibility
and stability of the film
Graphene – 2D material with high electrical conductivity – Poor reproducibility
– Good current carrier mobility, reduces the – Expensive technology and low scalability
charge transfer resistance of active (improvement using CVD and epitaxial
electrocatalyst growth techniques)
– Improve OEP, active surface area, •OH adsorp- – Larger defects when produced with
tion on the electrode cheaper technology
– Excellent mechanical properties, improve
stability
TiONTs – TiO2NTs interlayer relieve stress between – Poor electrical conductivity
substrate and active catalyst layer, improve – Do not perform as a better photocatalyst in
stability the visible light region
– Improve the number of available active sur-
face sites and OEP
– High oxidation efficiency and photocatalytic
capacity for pollutant degradation
– Low cost, nontoxic and chemical inertness
– Can improve •OH generation at the electrode
Conductive polymers – Reversible acid-base doping/de-doping – Degradation problem at higher potential
behavior – Low reproducibility of results
– Reduces electrode film resistance and – Lower conductivity
improve electron transfer – Electrochemical instability
– Hydrophobic interlayer reduces the chances
of TiO2 formation
– Uniformly cover the substrate and enhances
its stability in a harsh environment
– Promotes uniform active catalyst film
formation
– High adsorptivity, easy to prepare and stable
Synthesis Sol–gel/Pechini method – Most superficial, reliable, reproducible, and – Long deposition time required
approach controllable synthesis – High cost of fabrication
– The substrate with shape, size and geometry – Multiple repetitions are required to obtain
can be used uniform and thick layer of nanoparticles
– Homogeneous catalysts with high purity can – A typical cracked-mud-like structured
be obtained coating is obtained, low chance of
– Pechini method is more favorable for obtain- morphological enhancements.
ing homogenous thin films than the sol–gel – Residual porosity and hydroxyl groups are
route unavoidable
– Pechini method provides a chelating effect on
higher lattice parameters
Electrodeposition/elec- – Low-temperature process – Nonuniform thickness over the substrate
tro-polymerization – Fast processing and applicable to a wide va- – Nonconducting materials cannot be used
riety of metallic substrates, conducting poly- – Hydrogen embrittlement
mers, and metal salts
– A thick catalyst layer can be obtained
– Allows growth of functional 3D-NPs using an
NP template as a substrate
– High purity and porosity free films can be
obtained for enhanced stability
– Alloy composition can be easily controlled
40 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Table : (continued)

Advantages Challenges

Heating Microwave synthesis – Low energy required – Expensive equipment

techniques – Fast process, reaction time reduction (up to – Scale-up is complicated
1000 times) – Unfeasible reaction monitoring due to fast
– Uniform and selective heating reaction
– Excellent reproducibility – Generally incompatible with organic
solvents
– Low boiling solvents can elevate vapor
pressure, increasing safety concerns
Laser deposition – Suitable for complex materials – Particulate formation
– Fast and flexible process – Small area deposition
– High electrochemically active surface area – Loss of volatile elements
and stability
Electrode Carbon-based – Highly economical – Corrosion intolerance
– Good for laboratory-scale experiments – Low mineralization efficiency
– Low OEP
– Poor performance for industrial wastewater
Noble metals (Pt, Au) – Stable for wide potential range – Expensive
– Excellent reproducibility – Low mineralization efficiency
– Low OEP
– Poor performance for industrial wastewater
DSA® – Perform better as an active anodes – Low mineralization efficiency
– Improve biodegradability of pollutants – Cannot achieve the wastewater discharge
– Better reproducibility limits alone economically
– Thickness and composition can be altered – Passive layer formation
according to the wastewater
– Used as a compatible electrode in hybrid
wastewater treatment technologies
SnO–Sb, PbO, and – Nonactive electrode – SnO2-Sb and PbO2 toxic leaching
SnO–Sb/PbO – SnO2–Sb treated wastewater is comparatively – Not-suitable for industrial wastewater
less toxic than PbO2 treatment
– Better mineralization efficiency
– High OEP and improved stability
– Optimized electrochemical performance due
to interlayer
BDD – High OEP – Expensive
– Better mineralization efficiency – Reduced current efficiency at the low
– Excellent conductivity pollutant concentration
– High electrochemical stability – Works good in acidic pH and hence re-
quires an additional step of neutralization
after treatment
– Substrate (Si) can break during operation

Improved crystal growth and compactness were reported to 2020a). While the large surface area and strong mechanical
improve the overall performance of the electrodes (Duan strength of TiO2NTs help to hold PbO2 to the surface
et al. 2020; Xia et al. 2021; Xing et al. 2015). (J. Wang et al. 2021).
While incorporating PPy layer using electro- Yao et al. (2015) demonstrated the effectiveness of us-
polymerization technique can reduce the chance of ing CeO2–PbO2 composite electrode instead of Ce-doped
nonconducting TiO2 formation at the electrode’s surface, it PbO2 electrode for malachite green dye degradation. The
can help attain a more extended electrode’s service life by high amount of CeO2 loading was obtained using com-
reducing the chances of the SnO2–Sb layer peeling off. posite electrodeposition technique, which enhanced ICE
However, the conductive and high surface area TiO2NTs (4.2% for 45% COD removal), resulting in a reduced SEC (in
arrays having a large bandgap (3.2 eV) can significantly kWh m−3) of 2.91 versus 5.03 and 9.9 for Ce–PbO2 and PbO2
improve the electron transfer and hence the OEP and CE of electrodes, respectively. Enhanced performance was
semiconducting SnO2 based electrodes (S. Chen et al. observed for different herbicides removal and using
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 41

different composite material (WO3), demonstrating its Conflict of interest statement: The authors declare that
effectiveness for a broader domain of pollutants (Yang they have no conflicts of interest regarding this article.
et al. 2019a,b). These observations highlight the effect of
using an enhanced synthesis technique and doping over
the performance of the electrode. References
The current efficiency and energy consumption
directly depend upon the diffusion and mass transfer re- Abbasi, M., Backstrom, J., and Cornell, A. (2018). Fabrication of
sistances and hence on the type of reactor and its spin-coated Ti/TiHx /Ni–Sb–SnO2 electrode: stability and
geometrical parameters (Kaur et al. 2019b; Monteil et al. electrocatalytic activity. J. Electrochem. Soc. 165:
568–574.
2019). For example, Ti/SnO2–Sb/PbO2 better mineralize
Agrahari, G.K., Verma, N., and Bhattacharya, P.K. (2014). Removal of
flutriafol fungicide with improved MCE in a mass transfer benzoic acid from water by reactive extraction using hollow fiber
controlled flow-through reactor (24.4%) than the batch membrane contactor: experiment and modeling. CLEAN – Soil,
reactor (8.96%) (Liu et al. 2017). In terms of the diamond Air, Water 42: 901–908.
electrode, the type of substrate used, electrode thickness, Almeida, L.C., Garcia-Segura, S., Arias, C., Bocchi, N., and Brillas, E.
(2012). Electrochemical mineralization of the azo dye Acid Red 29
and the amount of boron doping are deciding parameters.
(Chromotrope 2R) by photoelectro-Fenton process.
Chemosphere 89: 751–758.
Ansari, A. and Nematollahi, D. (2018). A comprehensive study on the
5 Conclusions electrocatalytic degradation, electrochemical behavior and
degradation mechanism of malachite green using
electrodeposited nanostructured β–PbO2 electrodes. Water Res.
The selection of an efficient fabrication method leads to the
144: 462–473.
electrocatalytic properties and the stability of the elec-
Ansari, A. and Nematollahi, D. (2020). Convergent paired
trode. Recent studies reported that efficient, stable, and electrocatalytic degradation of p-dinitrobenzene by Ti/SnO2–
cost-effective electrodes could be prepared by using Sb/β–PbO2 anode. A new insight into the electrochemical
advanced heating methods, selection of appropriate pre- degradation mechanism. Appl. Catal. B Environ. 261: 118226.
cursor and solvents, material composition, and utilizing Aquino, J.M., Rocha-Filho, R.C., Ruotolo, L.A.M., Bocchi, N., and
Biaggio, S.R. (2014). Electrochemical degradation of a real textile
specific elements to trigger synergistic properties of the
wastewater using β-PbO2 and DSA® anodes. Chem. Eng. J. 251:
electrodes. Several environment-friendly yet effective sol- 138–145.
vents like ILs and DES were discussed in detail to synthe- Barbari, K., Delimi, R., Benredjem, Z., Saaidia, S., Djemel, A.,
size electrodes. Technologies like electrodeposition and Chouchane, T., Oturan, N., and Oturan, M.A. (2018).
modern heating approaches like microwave and laser Photocatalytically-assisted electrooxidation of herbicide
fenuron using a new bifunctional electrode PbO2/SnO2–Sb2O3/
synthesis were found to be more economical, faster, and
Ti//Ti/TiO2. Chemosphere 203: 1–10.
ecofriendly approaches than conventional approaches to
Baronetto, D., Kodintsev, I.M., and Trasatti, S. (1994). Origin of
produce effective electrodes. Modern advancement in ohmic losses at Co3O4/Ti electrodes. J. Appl. Electrochem. 24:
synthesis approaches created a competitive environment 189–194.
in fabricating novel active and non-active electrode mate- Basavarajappa, P.S., Patil, S.B., Ganganagappa, N., Raghava, K.,
rials. Diverse studies have been conducted for the elec- Raghu, A.V., and Reddy, C.V. (2019). Recent progress in metal-
doped TiO2, non-metal doped/codoped TiO2 and TiO2
trode’s optimization, yet the scale-up and use on a larger
nanostructured hybrids for enhanced photocatalysis. Int.
scale has been overlooked. Additionally, more research is J. Hydrogen Energy 45: 7764–7778.
required concerning actual wastewater and scale-up, using Bergmann, M.E.H., Rollin, J., and Iourtchouk, T. (2009). The occurrence
the prepared novel materials for better understanding and of perchlorate during drinking water electrolysis using BDD
optimizing the process. It can be concluded that advanced anodes. Electrochim. Acta 54: 2102–2107.
Bhattacharjee, A., Ahmaruzzaman, M., and Sinha, T. (2014).
technologies have great potential to create new footprints
Surfactant effects on the synthesis of durable tin-oxide
for electrode fabrication.
nanoparticles and its exploitation as a recyclable catalyst for the
elimination of toxic dye: a green and efficient approach for
Author contributions: All the authors have accepted wastewater treatment. RSC Adv. 4: 51418–51429.
responsibility for the entire content of this submitted Bian, X., Xia, Y., Zhan, T., Wang, L., Zhou, W., Dai, Q., and Chen, J.
manuscript and approved submission. (2019). Electrochemical removal of amoxicillin using a Cu doped
PbO2 electrode: electrode characterization, operational
Research funding: The authors acknowledge the help and
parameters optimization and degradation mechanism.
financial support from the Indian Institute of Technology Chemosphere 233: 762–770.
Roorkee and Ministry of Human Resources Department, Brillas, E., Bastida, R.M., Llosa, E., and Casado, J. (1995).
Government of India. Electrochemical destruction of aniline and 4-chloroaniline for
42 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

wastewater treatment using a vcarbon-PTFE 02-fed cathode. for atrazine degradation: effective electrocatalytic performance
J. Electrochem. Sci. Technol. 142: 1733–1741. and degradation mechanism. Chemosphere 268: 128799.
Bu, L., Ding, J., Zhu, N., Kong, M., Wu, Y., Shi, Z., Zhou, S., and Chen, S., He, P., Zhou, P., Wang, X., Xiao, F., He, Q., Li, J., Jia, L., Zhang,
Dionysiou, D.D. (2019). Unraveling different mechanisms of H., Jia, B., et al. (2021). Development of a novel graphitic carbon
persulfate activation by graphite felt anode and cathode to nitride and multiwall carbon nanotube co-doped Ti/PbO2 anode
destruct contaminants of emerging concern. Appl. Catal. B for electrocatalytic degradation of acetaminophen.
Environ. 253: 140–148. Chemosphere 271: 129830.
Buthiyappan, A., Abdul Aziz, A.R., and Wan Daud, W.M.A. (2016). Chen, S., Li, J., Liu, L., He, Q., Zhou, L., Yang, T., Wang, X., He, P.,
Recent advances and prospects of catalytic advanced oxidation Zhang, H., and Jia, B. (2020b). Fabrication of Co/Pr co-doped Ti/
process in treating textile effluents. Rev. Chem. Eng. 32: 1–47. PbO2 anode for efficiently electrocatalytic degradation of
Cao, J., Zhao, H., Cao, F., and Zhang, J. (2007). The influence of F− β-naphthoxyacetic acid. Chemosphere 256: 127139.
doping on the activity of PbO2 film electrodes in oxygen evolution Chen, X., Liang, J., Zhou, Z., Duan, H., Li, B., and Yang, Q. (2010). The
reaction. Electrochim. Acta 52: 7870–7876. preparation of SnO2 film by electrodeposition. Mater. Res. Bull.
Carneiro, J.F., Aquino, J.M., Silva, A.J., Barreiro, J.C., Cass, Q.B., and 45: 2006–2011.
Rocha-Filho, R.C. (2018). The effect of the supporting electrolyte Chen, Z., Lai, W., Xu, Y., Xie, G., Hou, W., Zhanchang, P., Kuang, C., and
on the electrooxidation of enrofloxacin using a flow cell with a Li, Y. (2021a). Anodic oxidation of ciprofloxacin using different
BDD anode: kinetics and follow-up of oxidation intermediates graphite felt anodes: kinetics and degradation pathways.
and antimicrobial activity. Chemosphere 206: 674–681. J. Hazard. Mater. 405: 124262.
Castro Luna, A.M., Bonesi, A.R., Moreno, M.S., Zampieri, G., Bengió, Chen, Z., Xie, G., Pan, Z., Zhou, X., Lai, W., Zheng, L., and Xu, Y.
S., and Triaca, W.E. (2014). Influence of metallic oxides on (2021b). A novel Pb/PbO2 electrodes prepared by the method of
ethanol oxidation. Int. J. Hydrogen Energy 39: 8690–8696. thermal oxidation-electrochemical oxidation: characteristic and
Chaplin, B.P., Wyle, I., Zeng, H., Carlisle, J.A., and Farrell, J. (2011). electrocatalytic oxidation performance. J. Alloys Compd. 851:
Characterization of the performance and failure mechanisms of 156834.
boron-doped ultrananocrystalline diamond electrodes. J. Appl. Ciríaco, L., Anjo, C., Correia, J., Pacheco, M.J., and Lopes, A. (2009).
Electrochem. 41: 1329–1340. Electrochemical degradation of Ibuprofen on Ti/Pt/PbO2 and Si/
Chaturvedi, A., Rai, B.N., Singh, R.S., and Jaiswal, R.P. (2021). A BDD electrodes. Electrochim. Acta 54: 1464–1472.
comprehensive review on the integration of advanced oxidation Comninellis, C. (1994). Electrocatalysis in the electrochemical
processes with biodegradation for the treatment of textile conversion/combustion of organic pollutants for waste water
wastewater containing azo dyes. Rev. Chem. Eng., https://doi. treatment. Electrochim. Acta 39: 1857–1862.
org/10.1515/revce-2020-0010 (Epub ahead of print). Comninellis, C. and Nerini, A. (1995). Anodic oxidation of phenol in the
Chatzisymeon, E., Dimou, A., Mantzavinos, D., and Katsaounis, A. presence of NaCI for wastewater treatment. J. Appl. Electrochem.
(2009). Electrochemical oxidation of model compounds and olive 25: 23–28.
mill wastewater over DSA electrodes: 1. The case of Ti/IrO2 Cornejo, O.M., Murrieta, M.F., Castañeda, L.F., and Nava, J.L. (2020).
anode. J. Hazard. Mater. 167: 268–274. Characterization of the reaction environment in flow reactors
Chauhan, R., Srivastava, V.C., and Hiwarkar, A.D. (2016). fitted with BDD electrodes for use in electrochemical advanced
Electrochemical mineralization of chlorophenol by ruthenium oxidation processes: a critical review. Electrochim. Acta 331:
oxide coated titanium electrode. J. Taiwan Inst. Chem. Eng. 69: 135373.
106–117. Correa-Lozano, B., Comninellis, C., and Battisti, A.D.E. (1997).
Chauhan, R. and Srivastava, V.C. (2020). Electrochemical Service life of Ti/SnO2–Sb2O5 anodes. J. Appl. Electrochem.
denitrification of highly contaminated actual nitrate wastewater 27: 970–974.
by Ti/RuO2 anode and iron cathode. Chem. Eng. J. 386: 122065. Costa, C.R., Botta, C.M.R., Espindola, E.L.G., and Olivi, P. (2008).
Chen, A., Xia, S., Ji, Z., and Lu, H. (2019). Insights into the origin of Electrochemical treatment of tannery wastewater using
super-high oxygen evolution potential of Cu doped SnO2 anodes: DSA®electrodes. J. Hazard. Mater. 153: 616–627.
a theoretical study. Appl. Surf. Sci. 471: 149–153. Cruz-Rizo, A., Gutiérrez-Granados, S., Salazar, R., and Peralta-
Chen, A., Zhu, X., Xi, J., Qin, H., and Ji, Z. (2016). Ultra-high oxidation Hernández, J.M. (2017). Application of electro-Fenton/BDD
potential of Ti/Cu–SnO2 anodes fabricated by spray pyrolysis for process for treating tannery wastewaters with industrial dyes.
wastewater treatment. J. Alloys Compd. 683: 501–505. Sep. Purif. Technol. 172: 296–302.
Chen, G., Chen, X., and Lock Yue, P. (2002). Electrochemical behavior Da Silva, L.M., Gonçalves, I.C., Teles, J.J.S., and Franco, D. V. (2014).
of novel Ti/IrOx–Sb2O5–SnO2 anodes. J. Phys. Chem. B 106: Application of oxide fine-mesh electrodes composed of Sb-
4364–4369. SnO2 for the electrochemical oxidation of Cibacron Marine FG
Chen, M., Li, S., Jin, C., Shao, M., and Huang, Z. (2021). Selective using an SPE filter-press reactor. Electrochim. Acta 146:
recovery of platinum by combining a novel reusable ionic liquid 714–732.
with electrodeposition. Separ. Purif. Technol. 259: 118204. Danks, A.E., Hall, S.R., and Schnepp, Z. (2016). The evolution of ‘sol–
Chen, M., Pan, S., Zhang, C., Wang, C., Zhang, W., Chen, Z., Zhao, X., gel’ chemistry as a technique for materials synthesis. Mater.
and Zhao, Y. (2020). Electrochemical oxidation of reverse Horiz. 3: 91–112.
osmosis concentrates using enhanced TiO2–NTA/SnO2–Sb Darabizad, G., Rahmanifar, M.S., Mousavi, M.F., and Pendashteh, A.
anodes with/without PbO2 layer. Chem. Eng. J. 399: 1–10. (2015). Electrodeposition of morphology- and size-tuned PbO2
Chen, S., He, P., Wang, X., Xiao, F., Zhou, P., He, Q., Jia, L., Dong, F., nanostructures in the presence of PVP and their electrochemical
Zhang, H., Jia, B., et al. (2020a). Co/Sm-modified Ti/PbO2 anode studies. Mater. Chem. Phys. 156: 121–128.
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 43

de Mello, R., Santos, L.H.E., Pupo, M.M.S., Eguiluz, K.I.B., Salazar- Fan, C. and Piron, D.L. (1996). Study of anomalous nickel-cobalt
Banda, G.R., and Motheo, A.J. (2018). Alachlor removal electrodeposition with different electrolytes and current
performance of Ti/Ru0.3Ti0.7O2 anodes prepared from ionic liquid densities. Electrochim. Acta 41: 1713–1719.
solution. J. Solid State Electrochem. 22: 1571–1580. Fernandes, A., Santos, D., Pacheco, M.J., Ciríaco, L., and Lopes, A.
de Oliveira Santiago Santos, G., Vasconcelos, V.M., da Silva, R.S., (2014). Nitrogen and organic load removal from sanitary landfill
Rodrigo, M.A., Eguiluz, K.I.B., and Salazar-Banda, G.R. (2020). leachates by anodic oxidation at Ti/Pt/PbO2, Ti/Pt/SnO2–Sb2O4
New laser-based method for the synthesis of stable and active Ti/ and Si/BDD. Appl. Catal. B Environ. 148–149: 288–294.
SnO2–Sb anodes. Electrochim. Acta 332: 135478. Fierro, S., Nagel, T., Baltruschat, H., and Comninellis, C. (2007).
de Santana Mota, W.J., de Oliveira Santiago Santos, G., Investigation of the oxygen evolution reaction on Ti/IrO2
Resende Dória, A., Rubens dos Reis Souza, M., Krause, L.C., electrodes using isotope labelling and on-line mass
Salazar-Banda, G.R., Barrios Eguiluz, K.I., López, J.A., and spectrometry. Electrochem. Commun. 9: 1969–1974.
Hernández-Macedo, M.L. (2021). Enhanced HCB removal using Gandini, D., Mahé, E., Michaud, P.A., Haenni, W., Perret, A.,
bacteria from mangrove as post-treatment after electrochemical Comninellis, C. (2000). Oxidation of carboxylic acids at boron-
oxidation using a laser-prepared Ti/RuO2–IrO2–TiO2 anode. doped diamond electrodes for wastewater treatment. J. Appl.
Chemosphere 279: 130875. Electrochem. 30, 1345–1350.
Deng, D., Wu, X., Li, M., Qian, S., Tang, B., Wei, S., and Zhang, J. Ganz, D., Reich, A., and Aegerter, M.A. (1997). Laser firing of
(2020). Electrochemical degradation of three phthalate esters in transparent conducting SnO2 sol—gel coatings. J. Non-Cryst.
synthetic wastewater by using a Ce-doped Ti/PbO2 electrode. Solids 218: 242–246.
Chemosphere 259: 127488. García-Gómez, C., Drogui, P., Seyhi, B., Gortáres-Moroyoqui, P.,
Dimesso, L. (2016). Pechini Processes: An Alternate Approach of the Buelna, G., Estrada-Alvgarado, M.I., and Álvarez, L.H. (2016).
Sol–Gel Method, Preparation, Properties, and Applications. In: Combined membrane bioreactor and electrochemical oxidation
Handbook of Sol-Gel Science and Technology. Springer using Ti/PbO2 anode for the removal of carbamazepine. J. Taiwan
International Publishing, Cham, pp. 1–22. Inst. Chem. Eng. 64: 211–219.
Divyapriya, G. and Nidheesh, P.V. (2020). Importance of graphene in García-Gómez, C., Drogui, P., Zaviska, F., Seyhi, B., Gortáres-
the electro-Fenton process. ACS Omega 5: 4725–4732. Moroyoqui, P., Buelna, G., Neira-Sáenz, C., Estrada-Alvarado, M.,
dos Anjos Bezerra, C.W., de Oliveira Santiago Santos, G., and Ulloa-Mercado, R.G. (2014). Experimental design
Moura de Salles Pupo, M., de Andrade Gomes, M., Santos da Silva, methodology applied to electrochemical oxidation of
R., Barrios Eguiluz, K.I., and Salazar-Banda, G.R. (2020). Novel eco- carbamazepine using Ti/PbO2 and Ti/BDD electrodes.
friendly method to prepare Ti/RuO2–IrO2 anodes by using polyvinyl J. Electroanal. Chem. 732: 1–10.
alcohol as the solvent. J. Electroanal. Chem. 859: 113822. Garcia-Segura, S., Vieira Dos Santos, E., and Martínez-Huitle, C.A.
Duan, P., Gao, S., Lei, J., Li, X., and Hu, X. (2020a). Electrochemical (2015). Role of sp3/sp2 ratio on the electrocatalytic properties of
oxidation of ceftazidime with graphite/CNT–Ce/PbO2–Ce anode: boron-doped diamond electrodes: a mini review. Electrochem.
parameter optimization, toxicity analysis and degradation Commun. 59: 52–55.
pathway. Environ. Pollut. 263: 114436. Gherardini, L., Michaud, P.A., Panizza, M., Comninellis, C., and
Duan, T., Chen, Y., Wen, Q., and Duan, Y. (2014). Enhanced Vatistas, N. (2001). Electrochemical Oxidation of 4-Chlorophenol
electrocatalytic activity of nano-TiN composited Ti/Sb–SnO2 for Wastewater Treatment: Definition of Normalized Current
electrode fabricated by pulse electrodeposition for methylene Efficiency (φ). J. Electrochem. Soc. 148: D78.
blue decolorization. RSC Adv. 4: 57463–57475. Ghosh, S. and Roy, S. (2014). Characterization of tin films synthesized
Duan, X., Wang, W., Wang, Q., Sui, X., Li, N., and Chang, L. (2020). from ethaline deep eutectic solvent. Mater. Sci. Eng. B 190:
Electrocatalytic degradation of perfluoroocatane sulfonate 104–110.
(PFOS) on a 3D graphene-lead dioxide (3DG–PbO2) composite Gonzaga, I.M.D., Dória, A.R., Vasconcelos, V.M., Souza, F.M.,
anode: electrode characterization, degradation mechanism and dos Santos, M.C., Hammer, P., Rodrigo, M.A., Eguiluz, K.I.B.,
toxicity. Chemosphere 260: 127587. and Salazar-Banda, G.R. (2020). Microwave synthesis of Ti/
Duan, Y., Chen, Y., Wen, Q., and Duan, T. (2016). Electrodeposition (RuO2)0.5(IrO2)0.5 anodes: improved electrochemical
preparation of a cauliflower-like Sb–SnO2 electrode from DMSO properties and stability. J. Electroanal. Chem. 874: 114460.
solution for electrochemical dye decolorization. RSC Adv. 6: Gu, C.D., Mai, Y.J., Zhou, J.P., and Tu, J.P. (2011). SnO2 nanocrystallite:
48043–48048. novel synthetic route from deep eutectic solvent and lithium
Elaissaoui, I., Akrout, H., Grassini, S., Fulginiti, D., and Bousselmi, L. storage performance. Funct. Mater. Lett. 4: 377–381.
(2019). Effect of coating method on the structure and properties Gui, L., Chen, Z., Chen, B., Song, Y., Yu, Q., Zhu, W., Hu, Q., Liu, Y.,
of a novel PbO2 anode for electrochemical oxidation of amaranth Zheng, Z., Lv, Z., et al. (2020). Preparation and characterization
dye. Chemosphere 217: 26–34. of ZnO/PEG–Co(II)–PbO2 nanocomposite electrode and an
Espinoza, L.C., Aranda, M., Contreras, D., Henríquez, A., and Salazar, investigation of the electrocatalytic degradation of phenol.
R. (2019). Effect of the sp3/sp2 ratio in boron-doped diamond J. Hazard. Mater. 399: 123018.
electrodes on the degradation pathway of aniline by anodic Guinea, E., Arias, C., Cabot, P.L., Garrido, J.A., Rodríguez, R.M.,
oxidation. ChemElectroChem 6: 4801–4810. Centellas, F., and Brillas, E. (2008). Mineralization of salicylic
Espinoza, C., Romero, J., Villegas, L., Cornejo-Ponce, L., and Salazar, acid in acidic aqueous medium by electrochemical advanced
R. (2016). Mineralization of the textile dye acid yellow 42 by solar oxidation processes using platinum and boron-doped diamond
photoelectro-Fenton in a lab-pilot plant. J. Hazard. Mater. 319: as anode and cathodically generated hydrogen peroxide. Water
24–33. Res. 42: 499–511.
44 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

Guo, X., Li, D., Wan, J., and Yu, X. (2015). Preparation and Jalife-Jacobo, H., Feria-Reyes, R., Serrano-Torres, O., Gutiérrez-
electrochemical property of TiO2/nano-graphite composite Granados, S., and Peralta-Hernández, J.M. (2016). Diazo dye
anode for electro-catalytic degradation of ceftriaxone sodium. Congo Red degradation using a Boron-doped diamond anode: An
Electrochim. Acta 180: 957–964. experimental study on the effect of supporting electrolytes. J.
Han, H., Lyu, J., Zhu, L., Wang, G., Ma, C., and Ma, H. (2020). Hazard. Mater. 319: 78–83.
Fabrication of BN modified Ti/PbO2 electrodes with tunable Jiang, Y., Hu, Z., Zhou, M., Zhou, L., and Xi, B. (2014). Efficient
hydrophobic characteristics and their electrocatalytic degradation of p-nitrophenol by electro-oxidation on Fe doped
performance. J. Alloys Compd. 828: 154049. Ti/TiO2 nanotube/PbO2 anode. Separ. Purif. Technol. 128:
He, Y., Huang, W., Chen, R., Zhang, W., Lin, H., and Li, H. (2015). Anodic 67–71.
oxidation of aspirin on PbO2, BDD and porous Ti/BDD electrodes: Jiao, M., Zhu, L., Xie, C., Zhao, H., Zhang, C., Li, Y., He, Y., Teng, H., and
mechanism, kinetics and utilization rate. Separ. Purif. Technol. Han, E. (2021). A novel electrodeposited sandwich electrode with
156: 124–131. an efficient performance in complex water treatment. Surf.
He, Y., Lin, H., Guo, Z., Zhang, W., Li, H., and Huang, W. (2019). Recent Coatings Technol. 406: 126645.
developments and advances in boron-doped diamond Jie, S., Ting-Yun, M., Hui-Xuan, Q., and Qi-Song, L. (2018).
electrodes for electrochemical oxidation of organic pollutants. Preparation of black Cu–Sn alloy with single phase
Separ. Purif. Technol. 212: 802–821. composition by electrodeposition method in 1-butyl-
Hong, M., Zou, J., and Chen, Z-G. (2021). Synthesis of thermoelectric 3-methylimidazolium chloride ionic liquids. Mater. Chem.
materials. In: Thermoelectricity and Advanced Thermoelectric Phys. 219: 421–424.
Materials. Elsevier, pp. 73–103. Jin, Y., Lv, Y., Yang, C., Cai, W., Zhang, Z., Tong, H., and Zhou, X. (2020).
Hoogenboom, R., Wilms, T.F.A., Erdmenger, T., Schubert, U.S., Fabrication of Superhydrophobic Ti/SnO2-Sb/α-PbO2/Fe-β-
Hoogenboom, R., Wilms, T.F.A., Erdmenger, T., and Schubert, PbO2-PTFE Electrode and Application in Wastewater Treatment. J.
U.S. (2009). Microwave-assisted chemistry: a closer look at Electron. Mater. 49: 2411–2418.
heating efficiency. Aust. J. Chem. 62: 236–243. Johnson, I. and Kumar, M. (2020). Electrochemical oxidation of
Hossain, M.D., Islam, M.M., Hossain, M.J., Yasmin, S., Shingho, S.R., distillery wastewater by dimensionally stable Ti–RuO2 anodes.
Ananna, N.A., and Mustafa, C.M. (2020). Effects of additives on Environ. Technol. Innovat. 20: 101181.
the morphology and stability of PbO2 films electrodeposited on Ju, P., Fan, H., Guo, D., Meng, X., Xu, M., and Ai, S. (2012).
nickel substrate for light weight lead-acid battery application. Electrocatalytic degradation of bisphenol A in water on a Ti-
J. Energy Storage 27: 101108. based PbO2–ionic liquids (ILs) electrode. Chem. Eng. J. 179:
Hu, J., Bian, X., Xia, Y., Weng, M., Zhou, W., and Dai, Q. (2020). 99–106.
Application of response surface methodology in electrochemical Juang, Y., Nurhayati, E., Huang, C., Pan, J.R., and Huang, S. (2013). A
degradation of amoxicillin with Cu–PbO2 electrode: optimization hybrid electrochemical advanced oxidation/microfiltration
and mechanism. Separ. Purif. Technol. 250: 117109. system using BDD/Ti anode for acid yellow 36 dye wastewater
Hua, G., Zhicheng, X., Dan, Q., Dan, W., Hao, X., Wei, Y., and Xiaoliang, treatment. Sep. Purif. Technol. 120: 289–295.
J. (2020). Fabrication and characterization of porous titanium- Julian, H., Nurgirisia, N., Sutrisna, P.D., and Wenten, I.G. (2021).
based PbO2 electrode through the pulse electrodeposition Advances in seawater membrane distillation (SWMD) towards
method: deposition condition optimization by orthogonal stand-alone zero liquid discharge (ZLD) desalination. Rev. Chem.
experiment. Chemosphere 261: 128157. Eng., https://doi.org/10.1515/revce-2020-0073 (Epub ahead of
Huang, J., Jing, H.X., Li, N., Li, L.X., and Jiao, W.Z. (2019). Fabrication of print).
magnetically recyclable SnO2–TiO2/CoFe2O4 hollow core-shell Jung, J., Shin, D., Lee, Y., and Pak, J.J. (2021). Fabrication of solution-
photocatalyst: improving photocatalytic efficiency under visible processed SnO2–based flexible ReRAM using laser-induced
light irradiation. J. Solid State Chem. 271: 103–109. graphene transferred onto PDMS. Curr. Appl. Phys. 25: 70–74.
Irikura, K., Bocchi, N., Rocha-Filho, R.C., Biaggio, S.R., Iniesta, J., and Kaur, P., Kushwaha, J.P., and Sangal, V.K. (2018). Electrocatalytic
Montiel, V. (2016). Electrodegradation of the acid green 28 dye oxidative treatment of real textile wastewater in continuous
using Ti/β–PbO2 and Ti–Pt/β–PbO2 anodes. J. Environ. Manag. reactor: degradation pathway and disposability study. J. Hazard.
183: 306–313. Mater. 346: 242–252.
Isarain-Chávez, E., De La Rosa, C., Godínez, L.A., Brillas, E., and Kaur, R., Kushwaha, J.P., and Singh, N. (2019a). Amoxicillin electro-
Peralta-Hernández, J.M. (2014). Comparative study of catalytic oxidation using Ti/RuO2 anode: mechanism, oxidation
electrochemical water treatment processes for a tannery products and degradation pathway. Electrochim. Acta 296:
wastewater effluent. J. Electroanal. Chem. 713: 62–69. 856–866.
Ivandini, T.A., Rao, T.N., Fujishima, A., and Einaga, Y. (2006). Kaur, R., Kushwaha, J.P., and Singh, N. (2019b). Electro-oxidation of
Electrochemical oxidation of oxalic acid at highly boron-doped amoxicillin trihydrate in continuous reactor by Ti/RuO2 anode.
diamond electrodes. Anal. Chem. 78: 3467–3471. Sci. Total Environ. 677: 84–97.
Jaiswal, Y., Pal, S.L., Jaiswal, H., Jain, A., Kush, L., Rai, D., and Tatar, D. Kaur, R., Kushwaha, J.P., and Singh, N. (2018). Electro-oxidation of
(2021). An investigation of changes in structural parameters and Ofloxacin antibiotic by dimensionally stable Ti/RuO2 anode:
organic functional groups of inertinite rich lignite during acid evaluation and mechanistic approach. Chemosphere 193:
treatment processes. Energy Sources, Part A Recover. Util. 685–694.
Environ. Eff.: 1–18, https://doi.org/10.1080/15567036.2021. Ken, D.S. and Sinha, A. (2021). Dimensionally stable anode (Ti/RuO2)
1923867. mediated electro-oxidation and multi-response optimization
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 45

study for remediation of coke-oven wastewater. J. Environ. Chem. Luu, T. Le. (2020). Tannery wastewater treatment after activated
Eng. 9: 105025. sludge pre-treatment using electro-oxidation on inactive anodes.
Kong, J., Shi, S., Kong, L., Zhu, X., and Ni, J. (2007). Preparation and Clean Technol. Environ. Policy 22, 1701–1713.
characterization of PbO2 electrodes doped with different rare Luu, T. Le, Stephane, D.D.F., Minh, N.H., Canh, N.D., Thanh, B.X.
earth oxides. Electrochim. Acta 53: 2048–2054. (2019a). Electrochemical oxidation as a post treatment for
Kusmierek, E. (2019). Electrochemical and corrosion characterization biologically tannery wastewater in batch reactor. Water Sci.
of TiO2–RuO2/Ti electrodes modified with WO3. Electrocatalysis Technol. 80, 1326–1337.
10: 499–515. Luu, T. Le, Tien, T.T., Duong, N.B., Phuong, N.T.T. (2019b). Study of the
Li, D., Guo, X., Song, H., Sun, T., and Wan, J. (2018). Preparation of treatment of tannery wastewater after biological pretreatment by
RuO2–TiO2/nano-graphite composite anode for electrochemical using electrochemical oxidation on BDD/Ti anode. Desalin.
degradation of ceftriaxone sodium. J. Hazard. Mater. 351: Water Treat. 137, 194–201.
250–259. Mandal, P., Yadav, M.K., Gupta, A.K., and Dubey, B.K. (2020). Chlorine
Li, J., Li, M., Li, D., Wen, Q., and Chen, Z. (2020). Electrochemical mediated indirect electro-oxidation of ammonia using non-active
pretreatment of coal gasification wastewater with Bi-doped PbO2 PbO2 anode: influencing parameters and mechanism
electrode: preparation of anode, efficiency and mechanism. identification. Separ. Purif. Technol. 247: 116910.
Chemosphere 248: 126021. Martínez-Huitle, C.A., Quiroz, M.A., Comninellis, C., Ferro, S., and
Li, P., Zhao, Y., Ding, B., and Wang, L. (2015). Effect of calcination De Battisti, A. (2004). Electrochemical incineration of chloranilic
temperature and molar ratio of tin and manganese on acid using Ti/IrO2, Pb/PbO2 and Si/BDD electrodes. Electrochim.
capacitance of Ti/SnO2–Sb–Mn/β–PbO2 electrode Acta 50: 949–956.
during phenol electro-oxidation. J. Electroanal. Chem. 747: Mattos-Costa, F.I., de Lima-Neto, P., Machado, S.A.S., and Avaca, L.A.
45–52. (1998). Characterisation of surfaces modified by sol-gel derived
Li, R., Li, Y., Yang, P., Wang, D., Xu, H., Wang, B., Meng, F., Zhang, J., RuxIr1-xO2 coatings for oxygen evolution in acid medium.
and An, M. (2021). Electrodeposition: synthesis of advanced Electrochem. Acta 44: 1515–1523.
transition metal-based catalyst for hydrogen production via Mei, R., Wei, Q., Zhu, C., Ye, W., Zhou, B., Ma, L., Yu, Z., and Zhou, K.
electrolysis of water. J. Energy Chem. 57: 547–566. (2019). 3D macroporous boron-doped diamond electrode with
Li, X., Xu, H., and Yan, W. (2016a). Preparation and characterization of interconnected liquid flow channels: A high-efficiency
PbO2 electrodes modified with polyvinyl alcohol (PVA). RSC Adv. electrochemical degradation of RB-19 dye wastewater under low
6: 82024–82032. current. Appl. Catal. B Environ. 245: 420–427.
Li, X., Xu, H., Yan, W., and Shao, D. (2016b). Electrocatalytic Minh, B.Q., Long, N.N., Van Hien, P., and Dung, N.T. (2019). Rapid and
degradation of aniline by Ti/Sb–SnO2, Ti/Sb–SnO2/Pb3O4 and efficient treatment of wastewater from fish sauce-manufacturing
Ti/Sb–SnO2/PbO2 anodes in different electrolytes. J. Electroanal. factories by using the electrochemical oxidation process.
Chem. 775: 43–51. Vietnam J. Chem. 57: 406–410.
Lin, H., Niu, J., Ding, S., and Zhang, L. (2012). Electrochemical Mirzaei, A. and Neri, G. (2016). Microwave-assisted synthesis of metal
degradation of perfluorooctanoic acid (PFOA) by Ti/SnO2–Sb, Ti/ oxide nanostructures for gas sensing application: a review.
SnO2–Sb/PbO2 and Ti/SnO2–Sb/MnO2 anodes. Water Res. 46: Sensor. Actuator. B Chem. 237: 749–775.
2281–2289. Monteil, H., Péchaud, Y., Oturan, N., and Oturan, M.A. (2019). A review
Lin, H., Niu, J., Xu, J., Li, Y., and Pan, Y. (2013). Electrochemical on efficiency and cost effectiveness of electro- and bio-electro-
mineralization of sulfamethoxazole by Ti/SnO2–Sb/Ce–PbO2 Fenton processes: application to the treatment of
anode: kinetics, reaction pathways, and energy cost evolution. pharmaceutical pollutants in water. Chem. Eng. J. 376: 119577.
Electrochim. Acta 97: 167–174. Moradi, M., Vasseghian, Y., Khataee, A., Kobya, M., Arabzade, H., and
Liu, S., Cui, T., Xu, A., Han, W., Li, J., Sun, X., Shen, J., and Wang, L. Dragoi, E.N. (2020). Service life and stability of electrodes
(2018). Electrochemical treatment of flutriafol wastewater using applied in electrochemical advanced oxidation processes: a
a novel 3D macroporous PbO2 filter: operating parameters, comprehensive review. J. Ind. Eng. Chem. 87: 18–39.
mechanism and toxicity assessment. J. Hazard. Mater. 358: Moreira, F.C., Boaventura, R.A.R., Brillas, E., and Vilar, V.J.P. (2017).
187–197. Electrochemical advanced oxidation processes: a review on their
Liu, S., Wang, Y., Zhou, X., Han, W., Li, J., Sun, X., Shen, J., and Wang, L. application to synthetic and real wastewaters. Appl. Catal. B
(2017). Improved degradation of the aqueous flutriafol using a Environ. 202: 217–261.
nanostructure macroporous PbO2 as reactive electrochemical Morschhäuser, R., Krull, M., Kayser, C., Boberski, C., Bierbaum, R.,
membrane. Electrochim. Acta 253: 357–367. Püschner, P.A., Glasnov, T.N., and Kappe, C.O. (2012).
Liu, X., Min, L., Yu, X., Zhou, Z., Sha, L., and Zhang, S. (2020). Changes Microwave-assisted continuous flow synthesis on industrial
of photoelectrocatalytic, electrocatalytic and pollutant scale. Green Process. Synth. 1: 281–290.
degradation properties during the growth of β–PbO2 into black Moura de Salles Pupo, M., da Silva, L.M., de Oliveira Santiago Santos,
titanium oxide nanoarrays. Chem. Eng. J. 417: 127996. G., Barrios Eguiluz, K.I., and Salazar-Banda, G.R. (2020).
Liu, Z., Luo, X., and Ji, D. (2021). Effect of phase composition of PbO2 on Synthesis and characterization of ternary metallic oxide
cycle stability of soluble lead flow batteries. J. Energy Storage 38: electrodes containing (SnO2)93Sb5M2 (M = Ce, ta, Bi, Gd) using an
102524. ionic liquid as the precursor solvent. Chem. Eng. Commun. 207:
Lu, X.R., Ding, M.H., Zhang, C., and Tang, W.Z. (2018). Investigation on 1736–1754.
microstructure evolution and failure mechanism of boron doped Muddemann, T., Bulan, A., Sievers, M., and Kunz, U. (2018). Avoidance
diamond coated titanium electrode during accelerated life test. of chlorine formation during electrolysis at boron-doped
Thin Solid Films 660: 306–313. diamond anodes in highly sodium chloride containing and
46 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

organic-polluted wastewater. J. Electrochem. Soc. 165: Panizza, M., Zolezzi, M., and Nicolella, C. (2006). Biological and
J3281–J3287. electrochemical oxidation of naphthalenesulfonates. J. Chem.
Murugananthan, M., Latha, S.S., Bhaskar Raju, G., and Yoshihara, S. Technol. Biotechnol. 81: 225–232.
(2010). Anodic oxidation of ketoprofen-An anti-inflammatory Polcaro, A.M., Vacca, A., Mascia, M., Palmas, S., Pompei, R., and
drug using boron doped diamond and platinum electrodes. J. Laconi, S. (2007). Characterization of a stirred tank
Hazard. Mater. 180: 753–758. electrochemical cell for water disinfection processes.
Naje, A.S., Chelliapan, S., Zakaria, Z., Ajeel, M.A., and Alaba, P.A. Electrochim. Acta 52: 2595–2602.
(2017). A review of electrocoagulation technology for the Polcaro, A.M., Vacca, A., Mascia, M., Palmas, S., and Rodiguez Ruiz, J.
treatment of textile wastewater. Rev. Chem. Eng. 33: 263–292. (2009). Electrochemical treatment of waters with BDD anodes:
Nasr, B., Hsen, T., and Abdellatif, G. (2009). Electrochemical treatment kinetics of the reactions involving chlorides. J. Appl.
of aqueous wastes containing pyrogallol by BDD-anodic Electrochem. 39: 2083–2092.
oxidation. J. Environ. Manage. 90: 523–530. Popat, A., Nidheesh, P.V., Anantha Singh, T.S., and Suresh Kumar, M.
Nidheesh, P.V. and Gandhimathi, R. (2014a). Removal of rhodamine B (2019). Mixed industrial wastewater treatment by combined
from aqueous solution using graphite–graphite electro-Fenton electrochemical advanced oxidation and biological processes.
system. Desalination Water Treat. 52: 1872–1877. Chemosphere 237: 124419.
Nidheesh, P.V. and Gandhimathi, R. (2014b). Effect of solution pH on Qing, G., Anari, Z., Abolhassani, M., Foster, S.L., Matlock, M., Thoma,
the performance of three electrolytic advanced oxidation G., and Greenlee, L.F. (2021). Electrochemical ammonia removal
processes for the treatment of textile wastewater and sludge and disinfection of aquaculture wastewater using batch and flow
characteristics. RSC Adv. 4: 27946–27954. reactors incorporating PtRu/graphite anode and graphite
Naumczyk, J.H. and Kucharska, M.A. (2017). Electrochemical cathode. Aquacult. Eng. 93: 102155.
treatment of tannery wastewater—Raw, coagulated, and Qu, C., Soomro, G.S., Ren, N., Liang, D.W., Lu, S.F., Xiang, Y., and
pretreated by AOPs. J. Environ. Sci. Heal. - Part A Toxic/ Zhang, S.J. (2019). Enhanced electro-oxidation/peroxone (in
Hazardous Subst. Environ. Eng. 52: 649–664. situ) process with a Ti-based nickel-antimony doped tin oxide
Nava, J.L., Núñez, F., and González, I. (2007). Electrochemical anode for phenol degradation. J. Hazard. Mater. 384: 121398.
incineration of p-cresol and o-cresol in the filter-press-type Radjenovic, J. and Sedlak, D.L. (2015). Challenges and opportunities
FM01-LC electrochemical cell using BDD electrodes in sulfate for electrochemical processes as next-generation technologies
media at pH 0. Electrochim. Acta 52: 3229–3235. for the treatment of contaminated water. Environ. Sci. Technol.
Nidheesh, P.V., Babu, D.S., Dasgupta, B., Behara, P., Ramasamy, B., 49: 11292–11302.
and Kumar, M.S. (2020). Treatment of arsenite-contaminated Rahmani, A., Seid-Mohammadi, A., Leili, M., Shabanloo, A., Ansari, A.,
water by electrochemical advanced oxidation processes. Alizadeh, S., and Nematollahi, D. (2021). Electrocatalytic
ChemElectroChem 7: 2418–2423. degradation of diuron herbicide using three-dimensional carbon
Ntakirutimana, S., Tan, W., Anderson, M.A., and Wang, Y. (2020). felt/β–PbO2 anode as a highly porous electrode: influencing
Activated carbon electrode design: engineering tradeoff with factors and degradation mechanisms. Chemosphere 276: 130141.
respect to capacitive deionization performance. J. Electrochem. Rakočevic, L., Strbac, S., Potočnik, J., Popovic, M., Jugovic, D., and
Soc. 167: 143501. Simatovic, I.S. (2021). The Nax MnO2 materials prepared by a
Olu, P.Y., Ohnishi, T., Mochizuki, D., and Sugimoto, W. (2018). glycine-nitrate method as advanced cathode materials for
Uncovering the real active sites of ruthenium oxide for the carbon aqueous sodium-ion rechargeable batteries. Ceram. Int. 47:
monoxide electro-oxidation reaction on platinum: the catalyst 4595–4603.
acts as a co-catalyst. J. Electroanal. Chem. 810: 109–118. Recio, F.J., Herrasti, P., Sirés, I., Kulak, A.N., Bavykin, D.V., Ponce-De-
Palma-Goyes, R.E., Vazquez-Arenas, J., Torres-Palma, R.A., Ostos, C., León, C., and Walsh, F.C. (2011). The preparation of PbO2 coatings
Ferraro, F., and González, I. (2015). The abatement of indigo on reticulated vitreous carbon for the electro-oxidation of organic
carmine using active chlorine electrogenerated on ternary pollutants. Electrochim. Acta 56: 5158–5165.
Sb2O5-doped Ti/RuO2–ZrO2 anodes in a filter-press FM01-LC Rivera, F.F., Rodríguez, F.A., Rivero, E.P., and Cruz-Díaz, M.R. (2018).
reactor. Electrochim. Acta 174: 735–744. Parametric mathematical modelling of cristal violet dye
Palneedi, H., Park, J.H., Maurya, D., Peddigari, M., Hwang, G.T., electrochemical oxidation using a flow electrochemical reactor
Annapureddy, V., Kim, J.W., Choi, J.J., Hahn, B.D., Priya, S., et al. with BDD and DSA anodes in sulfate media. Int. J. Chem. React.
(2018). Laser irradiation of metal oxide films and nanostructures: Eng. 16: 1–17.
applications and advances. Adv. Mater. 30: 1705148. Saadi, S., Moteshaker, P.M., Rokni, S.E., Ahmadidoust, G.,
Pan, Y., Luo, Y., Li, C., Wang, R., Yuan, Y., Li, M., and Na, P. (2020). Farnoodian, N., and Yousefi, A. (2020). The electrochemical
Preparation and characterization of Ti/SnO2-Sb2O3/α-PbO2/Ce- degradation of the metronidazole (MNZ) antibiotic using
Nd-β-PbO2 composite electrode for methyl orange degradation. electrochemical oxidation on a stainless steel316 coated with
J. Solid State Electrochem. 24: 545–555. beta lead oxide (SS316/β–PbO2) anode. Int. J. Chem. React. Eng.
Panizza, M. and Cerisola, G. (2004). Electrochemical oxidation as a 18: 20190226.
final treatment of synthetic tannery wastewater. Environ. Sci. Salazar-Banda, G.R., de Oliveira Santiago Santos, G.,
Technol. 38: 5470–5475. Duarte Gonzaga, I.M., Dória, A.R., and Barrios Eguiluz, K.I.
Panizza, M. and Cerisola, G. (2009). Direct and mediated anodic (2021). Developments in electrode materials for wastewater
oxidation of organic pollutants. Chem. Rev. 109: 6541–6569. treatment. Curr. Opin. Electrochem. 26: 100663.
Panizza, M., Michaud, P.A., Cerisola, G., and Comninellis, C.H. (2001). Samarghandi, M.R., Dargahi, A., Shabanloo, A., Nasab, H.Z., Vaziri, Y.,
Anodic oxidation of 2-naphthol at boron-doped diamond and Ansari, A. (2020). Electrochemical degradation of methylene
electrodes. J. Electroanal. Chem. 507: 206–214. blue dye using a graphite doped PbO2 anode: optimization of
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 47

operational parameters, degradation pathway and improving the Shang, H., Xia, Y., Zhou, Y., Liu, G., and Hu, X. (2020). Removal of
biodegradability of textile wastewater. Arab. J. Chem. 13: aniline from wastewater by electro-polymerization with superior
6847–6864. energy efficiency. Environ. Res. 190: 109931.
Santos, G.O.S., Eguiluz, K.I.B., Salazar-Banda, G.R., Saez, C., and Shao, Y.A., Chen, Y.T., and Chen, P.Y. (2019). Cu and CuPb electrodes
Rodrigo, M.A. (2020). Photoelectrolysis of clopyralid wastes with prepared via potentiostatic electrodeposition from metal oxides
a novel laser-prepared MMO–RuO2–TiO2 anode. Chemosphere in hydrophobic protic amide-type ionic liquid/water mixture
244: 125455. under ambient air for nonenzymatic nitrate reduction.
Santos, G.O.S., Silva, L.R.A., Alves, Y.G.S., Silva, R.S., Eguiluz, K.I.B., Electrochim. Acta 313: 488–496.
and Salazar-Banda, G.R. (2019). Enhanced stability and Singh, M.B., Kumar, V.S., Chaudhary, M., and Singh, P. (2021). A mini
electrocatalytic properties of Ti/RuxIr1-xO2 anodes produced by a review on synthesis, properties and applications of deep eutectic
new laser process. Chem. Eng. J. 355: 439–447. solvents. J. Indian Chem. Soc. 98: 100210.
Santos, J.E.L., de Moura, D.C., Cerro-López, M., Quiroz, M.A., and Smith, E.L., Abbott, A.P., and Ryder, K.S. (2014). Deep eutectic solvents
Martínez-Huitle, C.A. (2020). Electro- and photo- (DESs) and their applications. Chem. Rev. 114: 11060–11082.
electrooxidation of 2,4,5-trichlorophenoxiacetic acid (2,4,5-T) Song, S., Fan, J., He, Z., Zhan, L., Liu, Z., Chen, J., and Xu, X. (2010).
in aqueous media with PbO2, Sb-doped SnO2, BDD and Electrochemical degradation of azo dye C.I. reactive red 195 by
TiO2–NTs anodes: a comparative study. J. Electroanal. Chem. anodic oxidation on Ti/SnO2–Sb/PbO2 electrodes. Electrochim.
873: 114438. Acta 55: 3606–3613.
Santos, J.P.T.D.S., Tonholo, J., de Andrade, A.R., Del Colle, V., and Sopaj, F., Oturan, N., Pinson, J., Podvorica, F., and Oturan, M.A. (2016).
Zanta, C.L.D.P.E.S. (2021). The electro-oxidation of tetracycline Effect of the anode materials on the efficiency of the electro-
hydrochloride in commercial DSA® modified by electrodeposited Fenton process for the mineralization of the antibiotic
platinum. Environ. Sci. Pollut. Res. 28: 23595–23609. sulfamethazine. Appl. Catal. B Environ. 199: 331–341.
Santos, M.O., Santos, G.D.O.S., Mattedi, S., Griza, S., Eguiluz, Soumya, S.S. and Xavier, T.S. (2022). Effect of cobalt doping on the
K.I.B., and Salazar-Banda, G.R. (2018). Influence of the microstructural, optical and electrical properties of SnO2 thin
calcination temperature and ionic liquid used during synthesis films by sol-gel spin coating technique. Phys. B Condens. Matter
procedure on the physical and electrochemical properties of Ti/ 624: 413432.
(RuO2)0.8–(Sb2O4)0.2 anodes. J. Electroanal. Chem. 829: Souza, F.L., Aquino, J.M., Irikura, K., Miwa, D.W., Rodrigo, M.A., and
116–128. Motheo, A.J. (2014). Electrochemical degradation of the dimethyl
Santos, T.É.S., Silva, R.S., Meneses, C.T., Martínez-Huitle, C.A., phthalate ester on a fluoride-doped Ti/β–PbO2 anode.
Eguiluz, K.I.B., and Salazar-Banda, G.R. (2016). Unexpected Chemosphere 109: 187–194.
enhancement of electrocatalytic nature of Ti/(RuO2)x–(Sb2O5)y Sripriya, R., Chandrasekaran, M., Subramanian, K., Asokan, K., and
anodes prepared by the ionic liquid-thermal decomposition Noel, M. (2007). Electrochemical destruction of p-chlorophenol
method. Ind. Eng. Chem. Res. 55: 3182–3187. and p-nitrophenol – influence of surfactants and anode
Saranya, A., Devasena, T., Sivaram, H., and Jayavel, R. (2019). Role of materials. Chemosphere 69: 254–261.
hexamine in ZnO morphologies at different growth temperature Sun, D., Hong, X., Wu, K., Hui, K.S., Du, Y., and Hui, K.N. (2020).
with potential application in dye sensitized solar cell. Mater. Sci. Simultaneous removal of ammonia and phosphate by electro-
Semicond. Process. 92: 108–115. oxidation and electrocoagulation using RuO2–IrO2/Ti and
Sasidharan Pillai, I.M. and Gupta, A.K. (2015). Potentiostatic microscale zero-valent iron composite electrode. Water Res. 169:
electrodeposition of a novel cost effective PbO2 electrode: 115239.
degradation study with emphasis on current efficiency and Sun, P. and Chen, D. (2016). Electrochemical degradation of reactive
energy consumption. J. Electroanal. Chem. 749: 16–25. brilliant red X-3B with the (CeO2/C)–β–PbO2–PTFE composite
Shao, D., Liang, J., Cui, X., Xu, H., and Yan, W. (2014a). Electrochemical electrode. J. Rare Earths 34: 507–520.
oxidation of lignin by two typical electrodes: Ti/SbSnO2 and Ti/ Sun, Y., Cheng, S., Mao, Z., Lin, Z., Ren, X., and Yu, Z. (2020). High
PbO2. Chem. Eng. J. 244: 288–295. electrochemical activity of a Ti/SnO2–Sb electrode
Shao, D., Lyu, W., Cui, J., Zhang, X., Zhang, Y., Tan, G., and Yan, W. electrodeposited using deep eutectic solvent. Chemosphere
(2020a). Polyaniline nanoparticles magnetically coated Ti/Sb– 239: 124715.
SnO2 electrode as a flexible and efficient electrocatalyst for Tang, C.B., Lu, Y.X., Wang, F., Niu, H., Yu, L.H., and Xue, J.Q. (2020).
boosted electrooxidation of biorefractory wastewater. Influence of a MnO2-WC interlayer on the stability and
Chemosphere 241: 1–11. electrocatalytic activity of titanium-based PbO2 anodes.
Shao, D., Yan, W., Li, X., and Xu, H. (2015). Fe3O4/Sb–SnO2 granules Electrochim. Acta 331: 135381.
loaded on Ti/Sb–SnO2 electrode shell by magnetic force: good Sunde, T.O.L., Grande, T., and Einarsrud, M-A. (2016). Modified
recyclability and high electro-oxidation performance. ACS Pechini Synthesis of Oxide Powders and Thin Films. In: Handbook
Sustain. Chem. Eng. 3: 1777–1785. of Sol-Gel Science and Technology. Springer International
Shao, D., Yan, W., Li, X., Yang, H., and Xu, H. (2014b). A highly stable Publishing, Cham, pp. 1–30.
Ti/TiHx/Sb–SnO2 anode: preparation, characterization and Tan, X., Zhao, Y., Sun, W., Jin, C., Chen, L., Wei, H., and Sun, C. (2020).
application. Ind. Eng. Chem. Res. 53: 3898–3907. Three-dimensional hierarchically porous PbO2 electrode for
Shao, D., Zhang, Y., Lyu, W., Zhang, X., Tan, G., Xu, H., and Yan, W. electrochemical degradation of m-cresol. J. Electroanal. Chem.
(2020b). A modular functionalized anode for efficient 856: 113726.
electrochemical oxidation of wastewater: inseparable synergy Terezo, A.J. and Pereira, E.C. (2002). Preparation and characterisation
between OER anode and its magnetic auxiliary electrodes. of Ti/RuO2 anodes obtained by sol – gel and conventional routes.
J. Hazard. Mater. 390: 122174. Mater. Lett. 53: 339–345.
48 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment

The IUPAC Stability Constants Database. Academic Software. (n.d.). removal of the antibiotic tetracycline by electrochemical process
Tien, T.T. and Le Luu, T. (2020). Electrooxidation of tannery wastewater using carbon-felt cathode and DSA (Ti/RuO2–IrO2) anode.
with continuous flow system: role of electrode materials. Chemosphere 87: 614–620.
Environ. Eng. Res. 25: 324–334. Wu, M., Ouyang, Y., Zhao, K., Ma, Y., Wang, M., Liu, D., Su, Y., and Jin,
Velasco-Hernández, A., Esparza-Muñoz, R.A., de Moure-Flores, F.J., P. (2016). A novel fabrication method for titanium dioxide/
Santos-Cruz, J., and Mayén-Hernández, S.A. (2020). Synthesis activated carbon fiber electrodes and the effects of titanium
and characterization of graphene oxide – TiO2 thin films by sol- dioxide on phenol degradation. J. Environ. Chem. Eng. 4:
gel for photocatalytic applications. Mater. Sci. Semicond. 3646–3653.
Process. 114: 105082. Xia, Y., Bian, X., Xia, Y., Zhou, W., Wang, L., Fan, S., Xiong, P., Zhan, T.,
Vieira, L., Burt, J., Richardson, P.W., Schloffer, D., Fuchs, D., Moser, A., Dai, Q., and Chen, J. (2020b). Effect of indium doping on the PbO2
Bartlett, P.N., Reid, G., and Gollas, B. (2017). Tin, bismuth, and electrode for the enhanced electrochemical oxidation of aspirin:
tin–bismuth alloy electrodeposition from chlorometalate salts in an electrode comparative study. Separ. Purif. Technol. 237:
deep eutectic solvents. ChemistryOpen 6: 393–401. 116321.
Vilar, D.S., Carvalho, G.O., Pupo, M.M.S., Aguiar, M.M., Torres, N.H., Xia, Y., Feng, J., Fan, S., Zhou, W., and Dai, Q. (2021). Fabrication of a
Américo, J.H.P., Cavalcanti, E.B., Eguiluz, K.I.B., Salazar-Banda, multi-layer CNT–PbO2 anode for the degradation of isoniazid:
G.R., Leite, M.S., et al. (2018). Vinasse degradation using kinetics and mechanism. Chemosphere 263: 128069.
Pleurotus sajor-caju in a combined biological – electrochemical Xia, Y., Wang, G., Guo, L., Dai, Q., and Ma, X. (2020a). Electrochemical
oxidation treatment. Separ. Purif. Technol. 192: 287–296. oxidation of acid orange 7 azo dye using a PbO2 electrode:
Wang, C., Niu, J., Yin, L., Huang, J., and Hou, L. (2018). Electrochemical parameter optimization, reaction mechanism and toxicity
degradation of fluoxetine on nanotube array intercalated anode evaluation. Chemosphere 241: 125010.
with enhanced electronic transport and hydroxyl radical Xing, J., Chen, D., Zhao, W., Peng, X., Bai, Z., Zhanga, W., and Zhao, X.
production. Chem. Eng. J. 346: 662–671. (2015). Preparation and characterization of a novel porous Ti/
Wang, C., Wang, F., Xu, M., Zhu, C., Fang, W., and Wei, Y. (2015). SnO2–Sb2O3–CNT/PbO2 electrode for the anodic oxidation of
Electrocatalytic degradation of methylene blue on Co doped Ti/ phenol wastewater. RSC Adv. 5: 53504–53513.
TiO2 nanotube/PbO2 anodes prepared by pulse Xu, M., Mao, Y., Song, W., Ouyang, X., Hu, Y., Wei, Y., Zhu, C., Fanga,
electrodeposition. J. Electroanal. Chem. 759: 158–166. W., Shaoa, B., Lua, R., et al. (2018). Preparation and
Wang, C., Yu, Y., Yin, L., Niu, J., and Hou, L. (2016). Insights of characterization of Fe–Ce co-doped Ti/TiO2 NTs/PbO2
ibuprofen electro-oxidation on metal-oxide-coated Ti anodes: nanocomposite electrodes for efficient electrocatalytic
kinetics, energy consumption and reaction mechanisms. degradation of organic pollutants. J. Electroanal. Chem. J. 823:
Chemosphere 163: 584–591. 193–202.
Wang, J., Xu, M., Liang, X., Zhang, Y., Yang, D., Pan, L., Fang, W., Zhu, Xue, B., Zhang, Y., and Wang, J.Y. (2011). Electrochemical oxidation of
C.G., and Wang, F. (2021). Development of a novel 2D Ni-MOF bisphenol A on Ti/SnO2–Sb2O5/PbO2 anode for waste water
derived NiO@C nanosheet arrays modified Ti/TiO2NTs/PbO2 treatment. Procedia Environ. Sci. 10: 647–652.
electrode for efficient electrochemical degradation of salicylic Yan, Z., Liu, H., Hao, Z., Yu, M., Chen, X., and Chen, J. (2020).
acid wastewater. Separ. Purif. Technol. 263: 118368. Electrodeposition of (hydro)oxides for an oxygen evolution
Wang, J., Yao, J., Wang, L., Xue, Q., Hu, Z., and Pan, B. (2020). electrode. Chem. Sci. 11: 10614.
Multivariate optimization of the pulse electrochemical oxidation Yang, K., Liu, Y., and Qiao, J. (2017). Electrodeposition preparation of
for treating recalcitrant dye wastewater. Separ. Purif. Technol. Ce-doped Ti/SnO2–Sb electrodes by using selected addition
230: 115851. agents for efficient electrocatalytic oxidation of methylene blue
Wang, W., Wang, K., Hao, W., Zhang, T., Liu, Y., Yu, L., and Li, W. in water. Separ. Purif. Technol. 189: 459–466.
(in press). Preparation of Ti-based Yb-doped SnO2–RuO2 Yang, Y., Cui, L., Li, M., and Yao, Y. (2019a). Electrochemical removal of
electrode and electrochemical oxidation treatment of coking metribuzin in aqueous solution by a novel PbO2/WO3 composite
wastewater. J. Rare Earths, doi:https://doi.org/10.1016/j.jre. anode: characterization, influencing parameters and
2021.04.001. degradation pathways. J. Taiwan Inst. Chem. Eng. 102: 170–181.
Wang, X., Wu, Q., Ma, H., Ma, C., Yu, Z., Fu, Y., and Dong, X. (2019). Yang, Y., Cui, L., Li, M., Zhang, L., and Yao, Y. (2019b). Electrocatalytic
Fabrication of PbO2 tipped Co3O4 nanowires for efficient degradation of the herbicide metamitron using lead dioxide
photoelectrochemical decolorization of dye (reactive brilliant anode: influencing parameters, intermediates, and reaction
blue KN-R) wastewater. Sol. Energy Mater. Sol. Cells 191: pathways. Environ. Sci. Pollut. Res. 26: 27032–27042.
381–388. Yao, N., Wang, J., and Zhou, Y. (2014). Rapid determination of the
Wang, Y., Chen, M., Wang, C., Meng, X., Zhang, W., Chen, Z., and chemical oxygen demand of water using a thermal biosensor.
Crittenden, J. (2019). Electrochemical degradation of Sensors 14: 9949–9960.
methylisothiazolinone by using Ti/SnO2–Sb2O3/α, β–PbO2 Yao, Y., Jiao, L., Cui, L., Yu, N., Wei, F., and Lu, Z. (2015). Preparation
electrode: kinetics, energy efficiency, oxidation mechanism and and characterization of PbO2–CeO2 nanocomposite electrode
degradation pathway. Chem. Eng. J. 374: 626–636. with high cerium content and its application in the
Wei, F., Liao, D., Lin, Y., Hu, C., Ju, J., Chen, Y., and Feng, D. (2021). electrocatalytic degradation of malachite green. J. Electrochem.
Electrochemical degradation of reverse osmosis concentrate Soc. 162: H693–H698.
(ROC) using the electrodeposited Ti/TiO2–NTs/PbO2 electrode. Yao, Y., Li, M., Yang, Y., Cui, L., and Guo, L. (2019). Electrochemical
Separ. Purif. Technol. 258: 118056. degradation of insecticide hexazinone with Bi-doped PbO2
Wu, J., Zhang, H., Oturan, N., Wang, Y., Chen, L., and Oturan, M.A. electrode: influencing factors, intermediates and degradation
(2012). Application of response surface methodology to the mechanism. Chemosphere 216: 812–822.
 D. Rai and S. Sinha: Electrode fabrication for wastewater treatment 49

Yaqub, A., Isa, H.M., Kutty, S.R.M., and Ajab, H. (2014). Surface Zhao, J., Zhu, C., Lu, J., Hu, C., Peng, S., and Chen, T. (2014). Electro-
characteristics of Ti/IrO2 anode material and its electrocatalytic catalytic degradation of bisphenol A with modified Co3O4/β–
properties for polycyclic aromatic hydrocarbons (PAHs) PbO2/Ti electrode. Electrochim. Acta 118: 169–175.
degradation in aqueous solution. J. N. Mater. Electrochem. Syst. Zhao, W., Xing, J., Chen, D., Bai, Z., and Xia, Y. (2015). Study on the
17: 39–44. performance of an improved Ti/SnO2–Sb2O3/PbO2 based on
Yaqub, A., Isa, M.H., Ajab, H., Kutty, S.R.M., and Ezechi, E.H. (2018). porous titanium substrate compared with planar titanium
Preparation of Ti/IrO2 anode with low iridium content by thermal substrate. RSC Adv. 5: 26530–26539.
decomposition process: electrochemical removal of organic Zhao, W., Xing, J., Chen, D., Jin, D., and Shen, J. (2016).
pollutants in water. Electrochem. Energy Technol. 4: 1–5. Electrochemical degradation of musk ketone in aqueous
Yavuz, A., Kaplan, K., and Bedir, M. (2020). SnO–SnO2 film on carbon solutions using a novel porous Ti/SnO2–Sb2O3/PbO2 electrodes.
steel cycling in a choline chloride-based ionic liquid electrolyte J. Electroanal. Chem. 775: 179–188.
for energy storage devices. J. Electroanal. Chem. 877: 114635. Zhi, D., Zhang, J., Wang, J., Luo, L., Zhou, Y., and Zhou, Y. (2020).
Yu, H., Zhang, Z., Zhang, L., Dong, H., and Yu, H. (2021a). Improved Electrochemical treatments of coking wastewater and coal
norfloxacin degradation by urea precipitation Ti/SnO2–Sb anode gasification wastewater with Ti/Ti4O7 and Ti/RuO2–IrO2 anodes.
under photo-electro catalysis and kinetics investigation by J. Environ. Manag. 265: 110571.
BP-neural-network-physical modeling. J. Clean. Prod. 280: Zhong, C., Wei, K., Han, W., Wang, L., Sun, X., and Li, J. (2013).
124412. Electrochemical degradation of tricyclazole in aqueous solution
Yu, Y., Jin, H., Li, Q., Zhang, X., Zhang, Y., and Chen, X. (2021b). using Ti/SnO2–Sb/PbO2 anode. J. Electroanal. Chem. 705: 68–74.
Pseudocapacitive Ti/RuO2–IrO2–RhOx electrodes with high Zhou, C., Wang, Y., Chen, J., and Niu, J. (2019a). Electrochemical
bipolar stability for phenol degradation. Separ. Purif. Technol. degradation of sunscreen agent benzophenone-3 and its
263: 118395. metabolite by Ti/SnO2-Sb/Ce-PbO2 anode: Kinetics,
Zhang, C., Jiang, Y., Li, Y., Hu, Z., Zhou, L., and Zhou, M. (2013). Three- mechanism, toxicity and energy consumption. Sci. Total
dimensional electrochemical process for wastewater treatment: Environ. 688: 75–82.
a general review. Chem. Eng. J. 228: 455–467. Zhou, C., Wang, Y., Chen, J., Xu, L., Huang, H., and Niu, J. (2019b). High-
Zhang, X., Shao, D., Lyu, W., Tan, G., and Ren, H. (2019). Utilizing efficiency electrochemical degradation of antiviral drug abacavir
discarded SiC heating rod to fabricate SiC/Sb–SnO2 anode for using a penetration fl ux porous Ti/SnO2-Sb anode.
electrochemical oxidation of wastewater. Chem. Eng. J. 361: Chemosphere 225: 304–310.
862–873. Zhou, M., Dai, Q., Lei, L., Ma, C., and Wang, D. (2005). Long life
Zhang, X., Shao, D., Lyu, W., Xu, H., Yang, L., Zhang, Y., Wang, Z., Liu, modified lead dioxide anode for organic wastewater treatment:
P., Yan, W., and Tan, G. (2020). Design of magnetically electrochemical characteristics and degradation mechanism.
assembled electrode (MAE) with Ti/PbO2 and heterogeneous Environ. Sci. Technol. 39: 363–370.
auxiliary electrodes (AEs): the functionality of AEs for efficient Zhou, M., Liu, L., Jiao, Y., Wang, Q., and Tan, Q. (2011). Treatment of
electrochemical oxidation. Chem. Eng. J. 395: 125145. high-salinity reverse osmosis concentrate by electrochemical
Zhang, Z., Yi, G., Li, P., Wang, X., Wang, X., Zhang, C., and Zhang, Y. oxidation on BDD and DSA electrodes. Desalination 277: 201–206.
(2021). Recent progress in engineering approach towards the Zhou, Y., Li, Z., Hao, C., Zhang, Y., Chai, S., Han, G., Xu, H., Lu, J., Dang,
design of PbO2-based electrodes for the anodic oxidation of Y., Sun, X., et al. (2020). Electrocatalysis enhancement of α, β–
organic pollutants. J. Water Proc. Eng. 42: 102173. PbO2 nanocrystals induced via rare earth Er(III) doping strategy:
Zhao, B., Yu, H., Liu, Y., Lu, Y., Fan, W., Qin, W., and Huo, M. (2021). principle, degradation application and electrocatalytic
Enhanced photoelectrocatalytic degradation of acetaminophen mechanism. Electrochim. Acta 333: 135535.
using a bifacial electrode of praseodymium-polyethylene glycol- Zhuo, Q., Han, J., Niu, J., and Zhang, J. (2020). Degradation of a
PbO2//Ti//TiO2-nanotubes. Chem. Eng. J. 410: 128337. persistent organic pollutant perfluorooctane sulphonate with Ti/
Zhao, G., Cui, X., Liu, M., Li, P., Zhang, Y., Cao, T., Li, H., Lei, Y., Liu, L., SnO2–Sb2O5/PbO2-PTFE anode. Emerg. Contam. 6: 44–52.
and Li, D. (2009). Electrochemical degradation of refractory Zuo, J., Zhu, J., Zhang, M., Hong, Q., Han, J., and Liu, J. (2020).
pollutant using a novel microstructured TiO2 nanotubes/Sb- Synergistic photoelectrochemical performance of La-doped
doped SnO2 electrode. Environ. Sci. Technol. 43: 1480–1486. RuO2–TiO2/Ti electrodes. Appl. Surf. Sci. 502: 144288.

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