Journal of Environmental Chemical Engineering

Journal of Environmental Chemical Engineering 11 (2023) 111384
Contents lists available at ScienceDirect
Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece
New insights on designing the next-generation materials for

electrochemical synthesis of reactive oxidative species towards efficient
and scalable water treatment: A review and perspectives
Amir Taqieddin a, 1, Stephanie Sarrouf b, 1, Muhammad Fahad Ehsan b, Akram N. Alshawabkeh b, *
a
Department of Mechanical & Industrial Engineering, Northeastern University, Boston, MA 02115, USA
b
Department of Civil & Environmental Engineering, Northeastern University, Boston, MA 02115, USA
A R T I C L E I N F O A B S T R A C T
Editor: Ana Loncaric Bozic Electrochemical water remediation technologies offer several advantages and flexibility for water treatment and
degradation of contaminants. These technologies generate reactive oxidative species (ROS) that degrade pol
Keywords: lutants. For the implementation of these technologies at an industrial scale, efficient, scalable, and cost-effective
Electrochemical cells in-situ ROS synthesis is necessary to degrade complex pollutant mixtures, treat large amount of contaminated
Water purification
water, and clean water in a reasonable amount of time and cost.These targets are directly dependent on the
Hydroxyl radicals
materials used to generate the ROS, such as electrodes and catalysts. Here, we review the key design aspects of
Electrocatalytic materials
Accelerated discovery of materials electrocatalytic materials for efficient in-situ ROS generation. We present a mechanistic understanding of ROS
generation, including their reaction pathways, and integrate this with the key design considerations of the
materials and the overall electrochemical reactor/cell. This involves tunning the interfacial interactions between
the electrolyte and electrode which can enhance the ROS generation rate up to ~ 40 % as discussed in this
review. We also summarized the current and emerging materials for water remediation cells and created a
structured dataset of about 500 electrodes and 130 catalysts used for ROS generation and water treatment. A
perspective on accelerating the discovery and designing of the next generation electrocatalytic materials is
discussed through the application of integrated experimental and computational workflows. Overall, this article
provides a comprehensive review and perspectives on designing and discovering materials for ROS synthesis,
which are critical not only for successful implementation of electrochemical water remediation technologies but
also for other electrochemical applications.
1. Introduction further decreasing the availability of fresh and safe drinking water. To
address this pressing concern, effective solutions for sustainable water
Water is essential for life and is a critical component for the survival management and safe water supply are necessary [4]. This can be ach
of ecosystem. However, vast majority of world population is unable to ieved through water treatment techniques including electrochemical
access clean and safe drinking water, which is a fundamental human processes [1,5–7]. Electrochemical water treatment, in particular, has
right. Studies show that approximately 1.42 billion people, including shown to be reliable and efficient in removing toxic heavy metals,
450 million children, are deprived of accessing safe water [1–3], oxidizing organic contaminants, reducing oxyanions, and disinfection
resulting in significant health outcomes. Specifically, approximately 700 [8].
children under the age of 5 die every day from diarrhea linked to unsafe Electrochemical technologies offer several advantages over other
water [3]. The limited accessibility to safe water is due to water scarcity, water treatment techniques, providing flexible and efficient treatment of
where demand surpasses the supply. Additionally, the fast development water from various sources [8]. Over the past decades, electrochemical
of industrial technologies and pharmaceutical companies has caused a technologies have gained increasing popularity for water treatment in
detrimental increase in the pollutants released into the environment, temperate regions, as they are considered ‘green’ that uses electrons as a
* Corresponding author.
E-mail address: [email protected] (A.N. Alshawabkeh).
1
Equally contributing authors.
https://doi.org/10.1016/j.jece.2023.111384
Received 13 June 2023; Received in revised form 20 September 2023; Accepted 30 October 2023
Available online 3 November 2023
2213-3437/© 2023 Elsevier Ltd. All rights reserved.
A. Taqieddin et al. Journal of Environmental Chemical Engineering 11 (2023) 111384
reagent [9]. One of the primary advantages of electrochemical water years, significant progress has been made in developing, testing, and
treatment is the ability to produce in-situ reagents for oxidation of utilizing efficient electrode materials for electrochemical synthesis of
contaminants. These on-site generated chemicals, such as hydroxyl H2O2 and other ROS. These materials include metal oxide-based [14],
radicals (•OH) and hydrogen peroxide (H2O2), are reactive oxygen graphite-based [15,16], activated carbon-based [17–19], polymers [20],
species (ROS) that can oxidize a wide range of contaminants in water [5, metallic nanoparticles [21], and low-dimensional [22] structures.
7,8]. For example, electrochemically synthesized H2O2 can oxidize Although numerous advanced oxidation processes (AOPs), such as
contaminants over the full range of pH with high oxidation potential, ozonation and UV irradiation, have been developed and are operating at
leaving only water and oxygen at the end of process, making it a safe and full-scale in drinking water treatment, there is still a large gap in
effective method for water treatment [5]. Addressing the global water achieving cost-effective industrial scale electrochemical water treat
management crisis will benefit from designing industrial and large-scale ment. The major goal is to develop promising next-generation electro
electrochemical water treatment units where the system scalability, catalyst material, optimize the electrochemical process, achieve
cost, and efficiency are directly correlated to high yields of ROS. Effi selectivity, efficiency, and stability toward 2-electron O2 reduction re
cient ROS synthesis is not only critical for water treatment applications action (2e-ORR) for H2O2 synthesis.
but also for various industrial and environmental applications. For In this article, we present an overview and outlook on the develop
instance, H2O2 is utilized in fuel cells [10,11], waste recycling of lithium ment of next generation materials for electrochemical synthesis of ROS.
batteries [12], and biomedical [13] applications. Identifying efficient Firstly, we emphasize on the significance of ROS in degrading contam
materials for the H2O2 synthesis is valuable for several industrial and inants, thereby improving water quality. We also discuss the funda
environmental applications. mental parameters that determine the design of electrochemical cells
Electrochemical production of ROS is primarily dependent on the used in water treatment, including the activity, stability, and selectivity
choice of electrode materials [5]. These electrodes are electrically con of electrodes that govern the ROS generation, summarized in Section 2.
ducting materials where electron transfer reactions through oxidization Following that, we review and summarize the current available mate
and reduction occur when current flows across the electrodes. Over the rials and emerging trends in the material research and development for
Fig. 1. Schematic of a) electrochemical water treatment reactor which consists of three material components: anode, cathode, and membranes, b) direct oxidation of
dissolved pollutants (i.e., R) into nontoxic forms (i.e., Rox), c) indirect oxidation of R using active electrode via ROS, d) indirect oxidation of R using inactive
electrode via ROS, and e) continuous flow-type electrochemical reactor for water treatment.
2
ROS synthesis as discussed in Section 3. Finally, we provide the the anode which is then transferred towards the cathode that converts
emerging trends and directions for discovering the next generation of O2 into H2 O2 (using Eq. 2) [19]. The activated carbon electrode surface
materials and designing electrochemical water treatment such as can then transform H2 O2 into •OH. Although this proposed design [19]
through the application of material informatics frameworks. Overall, shows efficient reactor configuration, its scalability and potential to
this article provides comprehensive both understanding of the current degrade contaminants require further investigation. The question is how
state-of-art and outlook for future direction to accelerate the discovery to maximize the distribution of •OH in the electrolyte, including its
and design of materials for effective in-situ electrochemical synthesis of diffusion and dispersion. Answering this question can maximize the
ROS for water treatment. potential for oxidizing large amounts of contaminants in a short span of
time (i.e., matching the flow rate of water) allowing instantaneous water
2. Mechanistic understanding and engineering of treatment. In the following subsections, we discuss design consider
electrochemical ROS generation ations of the electrode materials and the overall electrochemical reactors
for ROS synthesis. These discussions aim to help answer questions
An electrochemical water treatment system typically consists of two related to tunning and optimizing electrochemical water treatment
electrodes, an anode and a cathode, and an electrolyte. Typically, the processes.
electrochemical redox reactions including oxidation of at anode and
reduction at cathode are initiated by electron transfer at the electrode
[23]. Therefore, tunning the properties of the electrodes can be used for 2.1. ROS synthesis
controlling and optimizing the process and for targeting degradation of
specific pollutants. To develop and optimize the next generation of 2.1.1. Reactions & pathways
materials for electrochemical synthesis of ROS, it is necessary to review ROS are reactive chemicals typically formed from H2 O oxidation (i.
the fundamentals of electro-generation mechanisms of ROS [23]. Fig. 1 e., OER) or from the reduction of diatomic O2 (i.e., ORR) [31]. The
provides a schematic of an electrochemical treatment system where primary ROS utilized in water treatment include H2 O2 , •OH, hydroxyl
1
dissolved pollutants can undergo direct or indirect oxidation. In the anion (OH− ), superoxide radical (O•−2 ), singlet oxygen ( O2 ), and ozone
direct pathway, chemical pollutants are adsorbed onto the anode sur (O3 ). Several other secondary ROS are also generated, as summarized in
face, and electron transfer occurs directly from the anode to the pol Table 1 with their synthesis, reduction reactions, and redox potentials.
lutants [23]. The direct electrolysis requires applied potentials greater The generation of the primary ROS occurs via multi-step electron
than the water oxidation potential to prevent surface poisoning of the transfer reactions, such as 2e− and 4e− transfer, as illustrated in Fig. 2.
electrode and to ensure efficient oxidation. Alternatively, in the indirect Specifically, the reduction of O2 by the addition of one, two, three, or
pathway, highly oxidant species are generated in-situ at the electrodes, four electrons results in the formation of O•− 2 , H2 O2 , •OH and H2 O,
enabling indirect electrochemical oxidation of pollutants in the elec respectively [32]. Various redox reactions involving these ROS highly
trolyte [23–25]. ROS such as H2O2 can be generated at the cathode via depend on the electrode surface, and its interfacial and bonding in
2e-ORR for indirect electrochemical oxidation of organic pollutants [5]. teractions with ROS [31]. Understanding the electronic structure of ROS
While various oxidant and reductant species can be generated and uti is essential for engineering their energy and bonding transformation at
lized for water treatment, this review focusses on ROS due to their the electrode surface.O2 has two unpaired electrons, each on two anti
widespread use in electrochemical water treatment. bonding π orbitals of same energy with parallel spins (i.e., π∗x and π∗y ),
The rate and conditions of ROS generation are primarily determined which provides stability and paramagnetic properties in its ground state
by the electrode material properties. The electrodes used in electro configuration [32,33]. ROS are formed by successively filling the two π∗
chemical reactions can be classified into active, inactive, or a combi orbitals with an electron that could be followed by protonation to each
nation of both based on their enthalpy of adsorption of the ROS [23]. In orbital [34].
active electrodes (see Fig. 1e), their surface is chemically involved in the The electron configuration of the ROS is critical in controlling the
reactions, leading to the formation of strong chemisorbed species. In strength of the bonding between the oxygen and hydrogen atoms within
contrast, the surface of inactive electrode is not involved in the reaction, the specie. The strength of the bonding determines the needed activation
resulting in physiosorbed species [23]. Fig. 1 highlights the difference energy to oxidize/reduce the ROS, and eventually regulates the rate
between active and inactive electrode surfaces, which influences the determining step. The bonding and electronic interactions between the
activity of the ROS generation. The electro-generation of adsorbed hy ROS and the electrode surface are essential in determining the efficiency
droxyl radical (•OH) at the anode (M) is given as [23]: of redox reactions involving ROS. These interactions strongly influence
the interfacial binding strength and orientation which determine the
M + H2 O→M( • OH) + H+ + e− (1)
final ROS generation via redox reactions [31]. For instance, O2 can
where M(•OH) represents the adsorbed hydroxyl radicals, which can adsorb onto a metal surface in several different ways, such as side-on
lead to oxygen evolution in the subsequent reactions [23]. Generating binding to a single metal center according to Griffith model [35] or
greater amount of M(•OH) is dependent on the anode overpotential, bridging two metal sites according to the bridge model [36]. Both
which promotes the oxygen evolution reaction (OER) while minimizing models hinder any H2 O2 intermediates from leaving the electrode and
any other competitive reactions [23,26–29]. Additionally, the genera leading to 4e-ORR, which results in the H2 O formation [31]. However, if
tion of H2 O2 from oxygen reduction reaction (ORR) at the cathode is O2 binds to the metal surface following Pauli’s model where O-centered
given as: sp2 hybrid orbital donates electron to the d orbital of metal, it facilitates
the 2e-ORR and H2O2 will be the final product. These different binding
O2 + 2H+ + 2e− →H2 O2 . (2)
models rely on the orientation of electronic orbitals of electrode that
The rate of electrochemical H2 O2 generation using Eq. 2 is greatly bind with O2 , which determines the final ROS formation. Designing the
influenced by the selective adsorption of oxygen by the cathode [17,18, next-generation materials for ROS requires proper tuning of the binding
30]. Therefore, understanding the thermodynamic properties and the orientation to target specific ROS production through initiating selective
kinetics of the reactions enhances the electrode properties, such as high chemical processes. Besides binding orientation, the enthalpy of the
current densities and selectivity, for efficient ROS generation [31]. Be adsorption of O2 on the electrode surface should also be carefully
sides electrode materials, reactor configuration plays a critical role in designed to target selective ROS synthesis. For example, the binding
converting H2 O2 to •OH for oxidizing contaminants, as demonstrated in energy/enthalpy of adsorption should be weak for the final targeted
Fig. 1e [19]. For instance, a flow reactor can be used to generate O2 at product, such as H2 O2 , to allow the dissociation of the desired specie
before undergoing further OER or ORR [31]. The interfacial interaction
3
Table 1
Summary of various ROS, their synthesis, reduction reaction, and redox potential [37,38].
ROS Synthesis Reduction Reaction E /V vs SHE References
◦
Hydroxyl Radical ( OH) •

Production from Fenton’s reagent (H2O2) with addition of ferric ions; OH + H + e → H2O
• + −
2.8–2.87 [38]
Sulfate Radical Anion (SO−4 ⦁) Production by the electrochemical activation of SO2-4 attained by direct electron SO−4 ⦁ + e− → SO2−
4 2.6–2.8 [39]
transfer at the anodic surface;
Chlorine Radical (Cl• ) Electrochemically obtained via a single-electron-transfer reaction during the Cl• + e− → Cl− 2.47
[40,41]
chlorine evolution process at an applied potential higher than E0Cl.
Ferrate Ion (FeO24) Produced electrochemically by using a dissolving iron anode or an inert electrode FeO2-
4 + 8 H + 3e →
+ −
2.2–2.6 [42]
3+
in Fe (III) solution Fe + H2O
Ozone (O3) Produced electrocatalytically by the oxidation of water O3(g) + 2 H+ + 2e− → O2(g) 2.075–2.2 [43]
+ H2O
Peroxodisulfate Ion (S2O2-
8) Produced by electrochemical oxidation of cooled sulfuric acid, by using a Pt anode S2O2-
8 + 2e → 2SO4
− 2-
2.01 [44]
with ammonium thiocyanate (NH4SCN) with current densities higher than
500 mA/ cm2
Hydrogen Peroxide (H2O2) Electrogenerated by the two-electron oxygen reduction reaction (ORR) and water H2O2 + 2 H+ + 2e− → 1.763 [38]
oxidation reaction (WOR) 2 H2O
Permanganate Ion (I) (MnO−4 ) Conventionally synthesized in a two-stage process: 1) the oxidation of manganese MnO−4 + 4 H+ + 3e− → 1.67 [45]
dioxide to potassium manganate (Mn+6) by oxygen in highly concentrated MnO2(s) + 2 H2O
potassium hydroxide solutions; 2) electrochemical oxidation of potassium
manganate to potassium permanganate in a highly alkaline electrolyte
Hydroperoxyl Ion(I) (HO•2) Produced by the scavenging of H2O2 with HO. HO⦁2 + H+ + e− → H2O2 1.65 [46]
Permanganate Ion (II) (MnO−4 ) Potassium permanganate (KMnO4) decomposes to thereactive permanganate ion MnO−4 + 8 H+ + 5e− → 1.51 [45]
Mn2+ + 4 H2O
Manganese Dioxide (MnO2) Synthesized from the direct electrolysis of an aqueous bath of manganese sulfate MnO2 + 4 H+ + 2e− → 1.23 [47]
and sulfuric acid Mn2+ + 2 H2O
Oxygen (O2) Produced anodically through water electrolysis O2(g) + 4 H+ + 4e− → 1.229 [38]
2 H2O
Peroxomonosulfate Radical 5 is converted from SO3
SO•− •−
in the presence of dissolved oxygen SO•−
5 + e → SO5
− 2− 1.1
[41,48]
(SO•−
5 )
Superoxide Anion Radical (•O−2 ) Electrochemically generated from reduction of dissolved oxygen O−2
•
+ 2 H +e → H2O2
+ −
0.94
[49,50]
Sulfite Anion Radical (SO•−
3 ) Photolysis of sulfite anions under UV light or via sulfite anions reacting with SO•−
3 + e →
−
SO2− 0.63–0.84
3 [41,48,
transition metals and radicals like hydroxyl radicals
51]
Singlet Oxygen (1O2 ) Direct catalytic activation such as catalytic ozonation, or energy assisted 1
O 2 + e− → O•−
2 0.64 ± 0.01
[41,52]
activation like photocatalysis and electrochemical activation of hydrogen
peroxide (H2O2), persulfate (PS), periodate, and peracetic acid, etc.
Fig. 2. Schematic of a) ROS reduction reactions and their standard potential in red (adapted [34,59]), b) EF reactions, and c) migration distance and half lifetime of
main ROS [60].
4
and enthalpy of binding varies from one electrode material to another activity, selectivity, and stability must be optimized [61]. The activity of
depending on their physiochemical characteristics, as will be shown an electrode determines the electrochemical overpotential required for
later. At this stage, we highlighted the features that are critical in tuning the ROS synthesis [62]. This overpotential is the difference between the
the final ROS products. The structure-property relationship of these equilibrium potential of the reaction and the potential at which the
features as a function of various material will be discussed in Section 3. electrode/catalyst operates [63,64]. Typically, the overpotential repre
In addition, the interfacial binding energy can be controlled to sents the sum of various potential losses and energy costs that might
optimize the selectivity of the final ROS products. This can help ensure occur due to ohmic drop in the electrolyte [65], bubble coverage
that unwanted products are released from the electrode surface, pre [66–68], and temperature variation [69] etc., which must be overcome
venting them from accumulating and potentially poisoning the surface. to achieve the final electrochemical product (e.g., ROS). Fig. 3 depicts
By doing so, the density of active sites on the electrode can be main various components of overpotential losses. The total overpotential
tained or increased, which can promote the desired redox reactions. For represents the required thermodynamic energy to carry out the redox
example, if the target is to produce H2 O2 as the final product, any other reactions at the electrode. The goal is to find electrode materials with
products of ORR or OER, such as OH− , should have weak binding with low overpotential, high activity, and good durability [70]. Recent
the electrode surface. Furthermore, the surface of the electrode should studies have demonstrated that confining in-situ produced O2 gas via
be designed to generate OH− at an optimized rate, which can help avoid coating carbon catalyst with hydrophobic polymers can tune water
deprotonation of H2 O2 via OH− [31]. One effective approach to enhance oxidation reaction pathways, maximize the activity of generating H2O2,
ROS generation in the electrochemical cell is through electro-Fenton and lower the overpotential [71]. Additionally, optimizing the elec
(EF) process [53], which involves in-situ generation of ROS using tronic structure and hydrophilicity of medium-entropy alloy electro
reduction/oxidation of iron (Fe) species (i.e., Fe (III) or Fe (II)), as catalysts can enable extremely low overpotential of 187 mV during
illustrated in Fig. 2. Fe(II) can be generated in-situ using sacrificial oxygen evolution [72]. An efficient electrode design should target ma
anode which can be used in homogenous reactions to produce ROS [54]. terial selection with low overpotential to ensure less energy (i.e., applied
Additionally, Fe(II) can also be regenerated by reduction reaction of Fe current) is required to power the cell, thus enabling low-cost operation
(III) at the cathode [54]. Although the EF processes have attracted much [61]. Therefore, the electronic structure, thermal, and entropic charac
attention in water treatment due to their low cost, and other advanta teristic of the electrode are parameters to consider during the design
geous associated with their physiochemical characteristics [17,53, process. According to Butler-Volmer formula, the overpotential, η(V), is
55–58], designing the efficient electrodes and catalysts which can boost proportional to the applied current density, i(A/m2 ), as following:
their reaction efficiency with low cost is challenging [5,17,18,55]. ( ) ( )
i αa F αF
Therefore, developing efficient metal-free cathode, such as = exp η − exp c η (3)
activated-carbon, is important to avoid the drawbacks of dealing with io RT RT
the separation of the dissolved iron, and disposal of the iron sludge in the
where io (A/m2 )is the exchange current density, αa and αc are the anodic
water treatment cell during conventional EF processes [55]. Using
and cathodic transfer coefficients, respectively, F(96, 485C/mol) is
activated-carbon as cathode, the researchers successfully developed an
Faraday’s constant, R(8.314J/mol.K) is the ideal gas constant, and T(K)
iron-free EF process that demonstrated long term stability in the gen
is the temperature. Eq. 3 describes the electrochemical kinetics of a cell
eration of ROS. This serves as a prime example of the importance of
based on the applied current and the overpotential. As shown in Fig. 3,
discovering new materials that can enhance the efficacy of electro
the overpotential losses in the electrochemical cell are typically domi
chemical water treatment, while also facilitating its scaling and cost
nated by ohmic losses. One of the primary contributors to the ohmic
reduction.
losses is the interfacial physicochemical barriers at the electrode surface.
Studies revealed that the presence of O2 and H2 bubbles at the electrode-
2.1.2. Thermodynamic & interfacial challenges
electrolyte interface can also induce an overpotential fluctuation in the
To design electrode or catalyst materials for fuel cell operations, their
Fig. 3. Schematic of a) EDL structure which consists of two layers: stern and diffusion layers which can be described as two capacitors connected in series, and b)
overpotential in an electrochemical cell that is the sum of different energy losses.
5
order of 100 mV [66]. using CdS/ rGO as a photo-catalyst with the help of Fe2+ can achieve 100
Moreover, it is critical to understand and optimize the interfacial % degradation rate utilizing H2O2 [109,110]. However, the chemical
thermodynamic and electronic interactions between the electrode and complexity of water treatment, which involve various chemicals and
the reactants to elevate electrochemical kinetics for ROS production. require optimal conditions for the degradation of chemicals, makes
These electron-transfer reactions occur at solid–liquid and solid–liquid– materials selection and design challenging. In other words, the material
gaseous interfaces in water treatment cell. The interfacial structure at selection and design must be integrated with other design aspects that
the electrode surface plays a critical role in determining the reactivity can affect and control the pollutant degradation.
and selectivity of the electrodes to certain reaction pathways [73]. For
instance, introducing the defects in the electrode structure can help
2.3. Key design considerations
engineer solid-liquid interactions and adjust the electrode selectivity
[74]. The ionic and electronic solid-liquid interactions primarily take
Electrochemical processes can be initiated by applying either a
place within the electric double layer (EDL) [75], which ranges from
constant electrical potential (potentiostatic condition) or current (gal
several nanometers up to micrometer scale [75–78]. Additionally, EDL
vanostatic condition) [5]. Regardless of the operating conditions, these
forms at the charge surface of the electrode due to the potential differ
processes involve multi-physics and multiscale phenomena i.e., charge
ence between the solid electrode and the liquid electrolyte, caused by
transport, physicochemical kinetics, interfacial phenomena and ther
the presence of opposite charged molecules and atoms between the two
modynamics, etc [68]. Fig. 4 provides an overview of the design factors
phases [79]. The structure and properties of EDL play a major role in
that impact the ROS production and water treatment efficiency. To
determining the adsorption, enthalpy, and reaction kinetics between the
develop industrial scale electrochemical water treatment systems for
electrode and electrolyte [80]. EDL consists of two layers: stern and
ROS generation, various highlighted design aspects must be tuned and
diffusion layers (see Fig. 3). These two layers can be decoupled under
engineered. This process begins with the selection of efficient electrode
some conditions, such as large change in the ionic strength of electro
materials, which involves designing their structure properties, elec
lyte, or can be strongly coupled in low ionic strength aqueous solution
tronic behavior, reactivity, and stability. Effective integration of these
[81]. The properties of EDL can also determine the surface tension and
materials into the electrochemical reactor, aimed at achieving
wetting behavior between the two phases [82,83]. The wetting behavior
industrial-scale operational conditions (such as power consumption,
near the electrode is critical to determine the bubble generation condi
ROS generation rate, operating time, and contaminants removal rate), is
tions [67,68]. Increasing the ionic strength can compress the EDL
also necessary [137]. This integration depends not only on the electrode
thickness and lead to an increase in the solid surface hydrophilicity,
materials but also on the physicochemical properties of the electrolyte
altering the contact angle and wetting at the electrode-electrolyte
(such as pH and presence of additives), flow type (batch versus plug
interface [84]. Previously, we discussed the effect of tunning the ionic
flow), and several other factors as shown in Fig. 4. In the following
strength of electrolyte via adding additives to optimize the bubble for
sections, we discuss the various design considerations necessary for
mation and release at the electrode surface [67,68]. While generated gas
developing efficient and scalable materials for ROS synthesis.
bubbles, such as O2, can promote mass transfer near the electrode during
the electrochemical operations, adhesion of these bubbles to the elec
2.3.1. Activity, selectivity, and stability of the electrode material
trode surface can reduce its active sites leading to higher overpotential
The first step in screening electrocatalytic and electrode materials is
and less ROS generation [67]. Thus, tuning the interfacial properties of
to identify three key properties: activity, selectivity, and stability. As
the electrode material is to be considered for ROS synthesis.
previously discussed, the activity is a thermodynamic property which is
determined by the overpotential of the electrochemical reaction at a
2.2. Degradation of pollutants via ROS
given electric current. The activity of the electrode determines the
electrochemical reactivity and generation rate of ROS [62]. To design an
Various groups of chemicals, such as phenolic compounds [85],
electrode with optimal activity, it is necessary to integrate mechanistic
PFAS [86], synthetic dyes [87], pharmaceuticals [88–94], pesticides [5,
understanding of ROS generation with material properties i.e., electrode
56,95], and other refractory contaminants (e.g., EDTA, TNT, HA etc.)
potential as a function of the electrical current. Bridging these concepts
[57,96–98] are difficult to degrade due to their high stability. An effi
and linking them together will help in improving the design of the
cient electrochemical treatment system that generates ROS is inevitable
current electrode materials and discover new ones that can be used to
for the degradation of these recalcitrant organic pollutants. These in-situ
create large-scale and cost-effective electrochemical cells. Starting from
generated ROS can be used to degrade and mineralize a wide range of
a macroscopic level, the activity of the electrode can be related to the
contaminants during the water treatment process [5,8,99]. Table 2
electrochemical cell by aiming to minimize the electric energy con
summarizes various ROS and their potential applications, as well as their
sumption (P) of the cell as a function of time [137]:
associated advantages and disadvantages for degrading contaminants. A
∫t
high concentration of ROS is needed for complete degradation of con
P= U × I dt, (4)
taminants. In particular, H2O2 and •OH are two ROS that can be 0
simultaneously utilized in EF/EF-like processes for pollutant degrada
tion [92,100,101]. For example, H2O2 assisted degradation of phenolic where t is the final designed time of operation, U is the potential of the
compounds, such as p-nitrophenol, bisphenol A, chlorophenols and electrochemical cell, and I is the electrical current across the electrodes.
phenol has been comprehensively studied due to their extreme toxicity The overpotential is directly related to the cell potential as follows
to human health and aquatic life [5102–107]. An initial concentration of [137]:
50 mg/L of 3-chlophenol was completely degraded after 2.5 h at a pH of U = Eeq + ηanodic + ηcathodic + ϕIR (5)
5 using an EF process with a Pd/Fe alloy/carbon aerogel composite
cathode, and complete mineralization was achieved after 6 h [108]. The where Eeq is the equilibrium potential difference between the anodic
efficient degradation and mineralization in this example are attributed and cathodic reactions which can be described by Nernst equation
to the efficiency of electrode i.e., high Fenton catalytic performance of [137], ηanodic and ηcathodic are the respective total anodic and cathodic
the cathode, which reduces H2O2 into •OH. However, selecting and overpotentials, and ϕohmic drop is the potential ohmic drop by the elec
designing materials for the next generation of electrochemical water trolyte. Both Eq. 4 and Eq. 5 show the direct relation between the
treatment go beyond the electrodes. We must also explore physi electrode activity (i.e., overpotential) and the power consumption by the
ochemically effective, low-cost, and scalable materials for catalysts and designed cell. The electrode overpotential is also related to the current
membranes that can be used in the electrochemical cells. For instance, density at the electrode as given in Eq. 3. The latter is directly
6
Table 2
Summary of different ROS and their ability on degrading pollutants.
ROS Pollutant Advantages Disadvantages Ref
Hydroxyl Radical Chlorophenoxyacetic acid, Herbicides (2,4- Acts in non-selective oxidation towards Very oxidizing and unstable species; [111,112]
(•OH) D, 2,4-DP, CPMP, 2,4,5-T), Nitrophenols, organic compounds; Second strongest Mean lifetime is estimated as only a few
Amines, dyes, Pharmaceuticals, Pesticides, oxidizing agent after fluorine; Destroys most nanoseconds in water; pH dependence
Surfactants, Explosives. organics and organo-metallic pollutants until (pH=3); highly transient and confined to
complete mineralization the electrode surface
Sulfate Radical Anion Organic solvents containing chlorine, Enhances photoelectrochemical degradation; Significant risk of secondary exposure [113,114]
(SO−4 •) Polychlorinated biphenyls, Polycyclic Possesses higher selectivity for pollutants in
aromatic hydrocarbons aqueous medium than hydroxyl radicals or
super oxides
Chlorine Radical (Cl• ) Carboxylic and amino group-containing Compared to other ROS, e.g., •OH, it is less Cl• can be consumed in the system via
40,115
organic matter affected by the solution chemistry, and aids in recombination to generate Cl2,
efficient electrochemical decomplexation propagation with Cl− to form Cl•− 2 , and
reactions with other scavengers that can
limit its role in contaminant
transformation
Ferrate Ion (FeO24) Pharmaceutical pollutants Possesses higher selectivity for pollutants in The efficiency and chemistry of Fe (VI) [116]
aqueous medium than hydroxyl radicals or oxidation differs according to the
super oxides; Enhances degradation of reaction conditions and activation agent;
pollutants Green technology; Non-toxic
intermediates and quick treatment
Ozone (O3) Pharmaceuticals and personal care products Efficient in oxidation of pollutants; does not Produces additional toxic intermediates [117–119]
generate any hazardous waste; Cost efficient; compared to other parent compounds;
More selective Handling it with precautions; Highly
unstable; Shows limitations in water
treatment as corrosive pH is required;
low solubility in water is a bottleneck for
extended application
Peroxodisulfate Ion Aromatic Compound (Anisole, Benzene, Reacts as an oxidant to achieve a more stable Oxidation mechanism relies on pH [120,121]
(S2O2-
8) Benzoic Acid, Acetophenone, Nitrobenzene, oxidation degree; Ability to form more
Terephthalic acid oxidizing radicals by homolytic cleavage of the
O-O bond
Hydrogen Peroxide Beach pulp, Paper, textile, Clean electronic Greenest oxidizing agent: Eco-friendly as it Limited in type of organic species it can [122,123]
(H2O2) circuits, Agricultural waste, Disinfection in releases water as a by-product attack; Its slow reaction rate makes it
medical and industrial applications, Oxidant insignificant in the oxidation of organic
in organic synthesis and water treatment components
Permanganate Ion (I) Algae odorant in water, Phenolic Non-toxic reduction product; Green oxidant; Oxidation mechanism relies on pH; [45,124]
(MnO−4 ) compounds, Pesticide and Antibiotic organic Sufficiently stable to diffuse from the Oxidation of permanganate creates
micropollutants, Heavy metals electrodes surface into the bulk solution manganese oxide which contributes to
pore persevering and decreases the
effectiveness of treatment
Hydroperoxyl Ion(I) BTEX contaminants Ability to reduce Fe3+ ions and simultaneously Its role is usually neglected because this ]125]
(HO•2) generate hydroxyl radicals. radical is short lived (<seconds) and has
a moderate activity
Permanganate Ion (II) Organic constituents of microbial cells, Facilitate the abiotic oxidation of the May include toxicity to microorganisms [126]
(MnO−4 ) Phenolic compounds contaminants; Mineralization and oxidation of
organic contaminants to more biodegradable
products
Dichromate Ion Sulfamethoxazole Chemical treatment to convert metal surfaces It could affect the catalytic activity of [127,128]
(Cr2O2-
7) to improve the corrosion resistivities; catalyst by changing the mechanical
Dichromate ions can react with hydrogen property of passivated single crystal iron
peroxide to form high valence state of and surface property of composites
chromium which can also degrade pollutants
Manganese Dioxide Aqueous 1,4-Dioxane, Antibiotics, Anilines, α-MnO2 incorporated Fe3O4 could be an Low electrical conductivity; Bad cycle [129,130]
(MnO2) Phenol, Steroid, Estrogens excellent source as a photocatalyst owing to its performance
larger surface area and matching energy levels;
MnO2 can act as coagulant aid to improve the
performance of coagulation and filtration
process
Oxygen (O2) Bisulfite, phenol The sequential reduction of oxygen allows the Low redox potential, the reaction rate [131–133]
formation of other strong ROS such as H2O2 with organic compounds is slower than
and •OH that with radicals
Peroxomonosulfate Toxic and refractory organic compounds A conducive reactive specie that leads to an The degradation efficiency is limited by
[134,135]
Radical (SO•−
5 ) such as dyes and phenols, and iodinated improved degradation of iopamidol, a type of the pH of the solution; it can lead to the
contrast media (ICM), etc. contrast agent in medical imaging procedures generation of more toxic by-products
than other radicals
Superoxide Anion Halogenated hydrocarbons and heavy Initiator of radical reactions; powerful Cannot be maintained in a stable state for
[49]
Radical (•O−2 ) polychlorinated biphenyls (PCBs) nucleophile that can enable•O−2 to attack the a long time (stable only up to 348 K); not
positively charged components of any organic highly reactive despite being a free
species in the absence of protons; source to radical; its structure is susceptible to
generate HO•2; transported on sites where rotational disorder at sufficiently high
hazardous chemical waste is discharged temperatures
Sulfite Anion Radical Organics and inorganics: vinyl chloride, Triggers a chain of reactions to generate other Relatively weak oxidant; various
[48,136]
(SO•−
3 ) 2–4–6-trichlorophenol; acid orange 7 (AO7); active species in the presence of dissolved oxysulfur species generated from SO•− 3
oxygen play a major role in contaminant
(continued on next page)
7
Table 2 (continued )
ROS Pollutant Advantages Disadvantages Ref
methyl organe (MO); rhodamine B (RhB); removal, whereas SO•−3 plays a minor
phenols role
Singlet Oxygen (1O2 ) Phenols, sulfonamides Long lifetime (approximately Low redox potential; slower kinetic rates
[52]
2–4 μs)compared to •OH; high concentration than other radicals with organic
in water (e.g.,10− 14 − 10− 11 M); 60 % of total contaminants
organic carbon can be removed for
contaminants by1O2 ; good resistance of
inorganic anions in wastewater; outstanding
selectivity
Fig. 4. Schematic of a) Key design aspect of electrochemical water treatment, and b) architects of reactors and electrode.
8
proportional to the rate of generation of electrochemical species (e.g., performance as a function of cycling can be investigated, since industrial
ROS) at the electrode, r, by Faraday’s law as follows [67,68,137]: operations of water treatment via ROS generation require long-term
cycling in harsh environmental conditions [5]. Besides
i
r= (6) electro-chemo-mechanical stability of the electrode, possible tempera
zF
ture changes are considered, and their effects on disturbing the stability
where z is the number of electrons involved in the chemical reaction. of the electrode’s activity and selectivity [152,153]. Variations in the
The activity of an electrode is not only responsible for regulating the cell’s temperature can lead to changes in the transport phenomena (e.g.,
energy consumption of the electrochemical cell, but it also plays a role in diffusion rate), electrode overpotential, and wetting properties (e.g.,
determining the rate of ROS generation. Hence, tuning the electronic solid-liquid interactions). In conclusion, designing the electrode mate
properties (i.e., overpotential and current intensity) is the first step of rials requires bridging complex sciences to achieve optimized activity,
designing the next-generation electrode materials. It is important to selectivity, and stability characteristics. The coupling between these
emphasize that the term “tuning” is significant in this context. It is worth complex sciences is nonlinear and requires advanced phenomenological
noting that operating the cell at high currents may not necessarily lead models [137].
to the generation of large amounts of ROS, despite what Eq. 6 might
suggest. This is due to the limitations posed by kinetic and mass transfer 2.3.2. Architecture design
process that occur at the electrode surface [138], such as decomposition The design of efficient electrochemical cells and maximizing ROS
of H2O2, at high currents [19,139]. Therefore, screening an electrode generation can be categorized into two main aspects: electrode archi
material based on its activity requires proper understanding of the ki tecture and cell configuration. The electrode architecture focusses on the
netics and mass transfer of the targeted ROS. geometry of electrode, which has significant influence on the activity,
Furthermore, the reaction pathways in electrochemical processes are selectivity, and the stability of the electrode [5,61,73,92,154]. Porosity
determined by the activity of the electrode, which can lead to either 2e− is one of the features in designing the electrode geometry, as it controls
or 4e− pathways, depending on their respective equilibrium potential the effective transport rates (e.g., diffusion coefficient) in electro
(see Fig. 2). The ability of the electrode to preferentially promote one chemical systems by regulating the pore size [155,156]. The porosity
thermodynamic reaction pathway over the other is known as its selec and geometry of the electrode also need to be tuned to achieve the
tivity, a characteristic that should be carefully designed to optimize the desired wetting characteristics of the solid-gas interactions [157]. The
desired electrochemical reaction. The selectivity is usually quantified by size and distribution of pores have a direct impact on the in-situ bubble
Faradaic Efficiency (FE) [61,62,140], which can be determined using growth and departure at the electrode surface [67,157,158]. To maxi
the rotating ring electrode disk method [141]. FE represents the ratio of mize the ROS generation will require electrode geometry that minimizes
the utilized current to generate ROS to the total applied current [140], the time needed for the bubbles to depart from the electrode surface,
with 100 % selectivity indicating that a single reaction or species allowing fresh electrolyte to react and generate ROS [67,68]. A prefer
completely dominates the electrochemical processes by utilizing all the able electrode structure should have a high adsorptive area while
applied current. However, achieving 100 % selectivity is thermody allowing the desorption of ROS, such as H2O2, before it decomposes
namically unfeasible, and a realistic goal is to design materials with further. This occurs when the metal-ROS interactions are weak as in the
somewhat reduced selectivity (i.e., 95 %), accounting for the non-ideal case of fast mass transport [31].
conditions [5,31]. To avoid limitations associated with lower selectivity The cell/reactor configuration aspect in designing efficient electro
at higher current densities, lower current density can be applied to chemical cells focuses on several factors, including the inter-electrode
achieve higher selectivity [28], although this will result in lower gen distance, reactor dimensionality, electrode arrangements, flow condi
eration rates of ROS according to Eq. 6. An alternative approach is to use tions, and operation mode. Fig. 4 illustrates different possible configu
the pulsed current application to regulate the ROS generation and rations of electrochemical reactors/cells, which can be designed to have
overcome the mass transfer limitations, which can lead to higher either one-, two-, or three-dimensional configurations under divided or
selectivity [5]. In a recent report, the H2O2 production was significantly undivided conditions. Three-dimensional (3D) reactors are typically
enhanced by ~138 % under pulsed current in comparison to a constant used when the electrochemical reactions take place at a low current
current supply [142]. The design and development of materials and density in case of environmental or industrial applications [159], as
strategies for enhanced and selective ROS generation have received large currents in 3D electrodes can lead to considerable power losses due
considerable attention in the recent years [67,68,137,143–145]. More to difficulties in obtaining even distribution of the potential [160].
over, the selectivity of the electrode does not only depend on the applied Among the different studies performed to compare different reactors and
current and overpotential, but also on several other factors, including their effect on the ROS generation, three-electrode EF reactors have
the surface-active area of the electrode, additives within the electrolyte, shown a significant advantage [53,161,162]. These reactors include an
and the chemistry of the electrode, which will be briefly discussed in the additional cathode to act as a bridge between 4e− OER and 2e− ORR,
following subsections. avoiding air sparging while regulating the pH automatically [162]. The
The stability of the electrodes is another parameter for running large- proposed technique of three-electrode EF systems maximizes the utili
scale electrochemical water treatment operations. It refers to the dura zation of O2 by internally self-regulating the pH without adding any
bility of the electrode and its ability to maintain electrochemical effi external acidic solution. First, the protons (H+) are released via OER at
ciency during long-term operations. To design stable and robust the anode, which are later neutralized by the OH− produced at the
materials for water treatment, it is essential to understand the electro- cathode. This feature can be a promising technology for water
chemo-mechanical coupling of electrode properties and its interface purification.
[146–149]. As the electrical charges flow across the electrode during the The goal of designing an efficient electrochemical water treatment is
electrochemical processes, they induce mechanical stress and chemical to degrade the contaminants in a short period of time. However, this is
changes across the electrode surface [149]. First, the electrode surface challenging and lacks feasibility as the electrochemical degradation
evolves during the electrochemical processes, changing its active sites reaction requires time to generate adequate ROS concentration.
and porosity in response to the chemical transformations and adsorp Consequently, several reactor configurations, including batch and flow
tion. This change in the volume and the active surface of the electrode reactors, have been developed and tested to establish the correlation
can result in thermodynamic and chemical variations [150,151]. Sec between the contaminant degradation time and reactor configuration
ond, the induced surface charges on the electrode are directly correlated [19,163–165]. In batch reactors, water is placed inside a sealed control
to mechanical stresses that can lead to mechanical deformation or even volume where the electrochemical reactions take place. After sufficient
failure after long-term cycling [149]. Therefore, the electrode time, the contaminants are degraded, and the treated water is
9
subsequently removed and replaced by a new batch of water. This type by altering the kinetics at the electrode surface and enhance the H2O2
of reactors offers ease of control and monitoring, but they lack the production. For instance, addition of halide salts of N(alkyl)4 alters the
flexibility needed for rapid, large-scale applications. In contrast, flow EDL which adsorbs onto the electrode to increase the pH, making H2O2
reactors provide a more dynamic framework for large-scale water production more favorable [171]. Since H2O2 has multiple decomposi
treatment. In flow reactors, water is treated continuously, entering an tion pathways via heterogenous redox reactions at electrode or through
open control volume reactor from one side, interacting with the elec reactions in bulk solutions, it is recommended that the decomposition be
trodes, and exiting as treated water on the opposite side (see Fig. 1). As catalyzed by trace metal ions, such as Fe2+ [172–174].
degradation reactions need time, the flow rate of water should be The ionic conductivity and strength of the treated water are two
adjusted to ensure complete degradation before water exits the reactor. other physiochemical properties of the electrolyte that affect the effi
To upscale these reactors, electrodes with high activity and efficiency ciency of electrochemical process. According to Eq. 5, the cell potential
are necessary for generating ROS at a rate comparable to the water flow depends on the ohmic resistance of the electrolyte, which is inversely
rate. Additionally, increasing the surface area of interactions between proportional to the ionic conductivity. Therefore, increasing the ionic
the electrode and water enables the occurrence of highly selective re conductivity of the electrolyte can improve the efficiency of the process,
actions, allowing an increased degradation rate of contaminants. Elec which increases the applied current by reducing the charge and ion
trode geometry and flow regulation can be optimized to achieve this transport resistance between the electrode and the electrolyte [137].
goal (see Fig. 4). Perry et al. – 2020 [166] reviewed technologies with Accordingly, the cell potential and the reactor power also decrease as
various different reactor arrangements to maximize the interaction be the ohmic drop decreases (see Eq. 4 and 5). One way to increase the
tween the electrodes and electrolyte. The authors discussed the potential ionic conductivity is by adding additives to the water, such as sodium
of enhancing reactor designs by decorating their surface with nano chloride (NaCl) [5137]. However, adding such additives can alter the
structure electrocatalysts, incorporating porous electrodes, and select reaction medium, where some of these additives participate in the
ing proper reactor geometry. P é rez et al. – 2018 [167] proposed an electrochemical reactions [61]. For example, chloride anions could
electrochemical reactor design which combines low inter-electrode gap transform to chlorine gas or form an insulating layer on the electrode
and flow-through electrodes for water treatment. As the gap between the surface [137]. Therefore, the type and amount of these additives should
electrode decreases, the ohmic drop decreases and the required energy be carefully selected to ensure the maintenance of a high performance of
to operate the reactor becomes less. By realizing this, the authors the electrochemical cell operations. In addition to affecting the ionic
demonstrated a reduced required energy to power the proposed reactor. conductivity, adding electrolyte additives can also change the wetting
In addition, the flow-through electrodes maximize the surface area of and surface tension characteristics at the electrode surface [67,68], as
mass transfer/reactions, resulting in more efficient degradation and well as the physiochemical properties of the electrolyte. The solid-liquid
utilization of the electrochemical reactors. Overall, development of a and solid-liquid-gas interactions at the electrode interface depend on the
scalable electrochemical reactor for water treatment poses significant physiochemical properties of the electrolyte. Adding additives to the
challenges. Flow-through electrodes, such as porous and 3D geometry, electrolyte alters its thermodynamic phase structure (e.g., molecular
facilitate a large mass transfer surface area for degrading the contami radial distributions, adsorption energies…etc.) [175,176], which
nants. However, increasing the electrode size or distance between the directly impacts the EDL structure, and the bubble formation and de
electrodes can lead to additional overpotential losses as previously dis parture (i.e., surface tension between the electrode-electrolyte)
cussed (i.e., the voltage drop is proportional to the inter-electrode gap). [177–180]. Temperature is another factor that can affect the physi
ochemical properties of electrolyte and their interfacial characteristics
2.3.3. Physiochemical properties of the electrolyte [5]. For example, EDL thickness and adsorption between the electrolyte
In terms of physiochemical properties, the pH of the electrolyte so and the electrode are dependent on the temperature [181]. In addition,
lution plays a role in Fenton/Fenton-like processes for the production the diffusion coefficient of O2 in water increases with increasing the
and activation of H2O2 into •OH. Various studies have indicated that low temperature, which can enhance mass transfer and mixing during water
pH is initially beneficial for in-situ H2O2 production, as ORR requires treatment [68]. The effects of temperature optimization on electro
protons, which will eventually increase the pH of the solution. However, chemical water treatment are not considered as fully investigated topic
to produce •OH from catalytically decomposed H2O2, the pH needs to be as a design parameter and require further investigation [5]. Overall, the
in the lower range since alkaline pH can lead to the decomposition of physiochemical properties have a significant influence on the electro
H2O2 and the deterioration of Fenton/Fenton like processes catalysts. chemical processes, and there are many factors that need to be consid
Nevertheless, a very low pH might provoke undesired reactions, such as ered during the screening and design of materials for building
hydrogen evolution reaction (HER), and destabilize heterogenous cat electrochemical reactors.
alysts [168]. Therefore, 2–4 is the optimized pH in Fenton-like processes
for degradation of organic contaminants. To efficiently remove con 2.3.4. Systematic generation and regulation of ROS
taminants across a broad range of pH, particularly at neutral pH, it is The literature on electrochemical water treatment processes and
preferable to employ processes that facilitate in-situ H2O2 production. systems generally focuses on optimizing and improving the contaminant
This requires the utilization of O2 activators and H2O2 catalysts capable degradation and removal from water. The first step in designing efficient
of operating over a wide range of pH. Moreover, the effect of pH vari electrochemical water treatment processes requires the systematic
ations ranging from 3 to 9 is minimized in the electrochemical systems generation and quantification of ROS. This can be achieved by carefully
capable to self-regulate their pH levels [108]. optimizing control parameters and modeling the kinetics of ROS gen
In addition, the selectivity of EF reaction highly depends on the pH, eration. Kinetic models can provide significant information about the
as discussed previously, to the extent that the number of electrons/ key parameters in electrochemical processes for systematic ROS gener
protons accepted by O2 decreases when the pH increases. Consequently, ation [54]. These parameters directly affect the cathodic generation and
an increase in the OH− concentration can alter the electrode surface and activation of various ROS, homogenous/bulk reaction mechanisms, and
thus decreases the density of active sites, resulting in the deterioration of heterogeneous/surface reactions such as electro-sorption processes. The
H2O2 production [169,170]. Therefore, it would be advantageous to operational parameters of electrochemical processes include the current
alter an electrode surface with something other than OH− . In addition, density, initial chemical concentrations, pH value, and electrolyte
the partial poisoning of an electrode can result in reduced current composition [182]. The magnitude of the applied current density and
densities due to decreased electroactive area, leading to decreased ef their residence time are considered among the most important factors in
ficiency. This has led to the development of alternative electrolyte so designing the electrochemical processes for ROS generation since these
lutions that do not detriment current density but can enhance selectivity determine the reaction rates and energy consumption for the
10
electrochemical reactor. The production amount of a ROS, mROS , can be electrocatalytic materials on industrial scale since utilization of
determined using the integration of Faraday’s law over time as follows high-quality manufacturing processes at relatively low cost is chal
[183]: lenging. Besides, environmental conditions play a significant role in
∫t alternating the ROS regulation over time [190]. The environmental
i Aelectrode dt conditions include pH, chemical concentrations, and compositions as
mROS = 0 , (7)
n × F × MWROS uncontrolled parameters influencing the electrochemical performance
where Aelectrode is the active surface area of the electrode and MWROS is of ROS production. These uncontrolled challenges reduce the efficiency
the molecular weight of the formed ROS. Eq. 7 shows that the amount of and effectiveness of the electrochemical cells resulting in increased
generated ROS is directly proportional to the applied current density operational cost and energy performance, thus hindering their upscal
and the reaction time. Practically, the generation of electrochemical ing. Establishing comprehensive scale-up and life-assessment models
species (e.g., H2O2) over time shows a nonlinear behavior. At the helps in overcoming these challenges and bringing electrochemical
beginning of the electrochemical processes, when the concentration of water treatment systems closer to the communities at affordable costs
the targeted ROS is low, mROS increases with time up to a certain point at [191]. These models can translate the lab designs into pilot systems and
which the concentration of the generated ROS becomes high [16]. later into industrial scale levels by accounting for the common condi
Beyond this point in the electrochemical reaction, mROS reaches a tions and environmental profiles for the targeted water treatment re
plateau value due to saturation in the electrochemical and mass transfer gions. The scale-up processes should include scaling-up the chemicals (e.
processes. Moreover, mROS increases with increasing the value of i until g., electrolyte), mass transport conditions (e.g., pumps), energy usage,
a point where mROS becomes almost constant regardless of i, again due to environmental conditions (e.g., pH and temperature), and effective
the saturation in the electrochemical and mass transfer processes. costs. By studying the relative contribution of each parameter and its
Different in-situ current manipulation techniques, including pulsing impact on ROS generation, efficient electrocatalytic materials can be
current and polarity reversal, are effective in enhancing ROS generation designed by optimizing these conditions. Novel electrochemical tech
and selectivity [183]. For instance, pulsing current improves the selec niques such as electrochemical regeneration can be introduced to
tive H2O2 production and its activation into other chemical species overcome the scale-up costs. As the electrocatalytic materials have a
during the electrochemical water treatment processes [184,185]. It also limited lifetime, in-situ regeneration processes aim to restore the
increases the overall longevity and stability of the electrodes [185]. intrinsic adsorptive capacity of the material by removing the accumu
Similarly, polarity reversal has demonstrated its effectiveness in lated contaminations and functional groups at the surface of these ma
enhancing the electrochemical synthesis of ROS [183]. These techniques terials [192]. Self-cleaning electrochemical regeneration techniques
address the saturation of mass transfer during electrochemical processes have been utilized to extend the lifetime of carbon-based electrodes
via convective mechanisms, thereby regulating the ROS production where the regeneration processes did not require adding reagents to
[182,186]. The ratio of connective mass transfer to the diffusion rate can clean the electrode surfaces [190].
be expressed in terms of the dimensionless coefficient, the Sherwood Designing a large-scale electrochemical reactor can be challenging.
number (Sh), as follows [182]: The final design of a water treatment reactor should include several
( )0.333 general and essential considerations, including: moderate capital and
Sh =
kf d
= 3.3 ×
d
× Re × Sc , (8) running costs, convenience and reliability, appropriate facilities to
Dl L control and monitor the chemical changes, simplicity and versatility,
and provision for future developments [166]. In terms of performance
where kf is the mass transfer, d is the electrode spacing, Dl is the diffu optimization, reducing the energy consumption by the electrochemical
sion coefficient of the chemical species (e.g., ROS), L is the length of reactor and increasing the Columbic efficiency (CE) of the ROS gener
reactor, Re and Sc are Reynold and Schmidt numbers, respectively. It ation are important to reduce the running costs for industrial-scale
should be noted that the right-hand side correlation of Eq. 8 is valid for implementation. The energy consumption, EC (Wh/g), by the electro
reactors where L/d < 126 and Sh≫1. According to Eq. 8, increasing chemical reactor can be given as follows:
either the spacing between the electrodes or the flow velocity (i.e., Re),
or decreasing L can increase the convective mass transfer (Sh). This al EC =
P
, (9)
lows for better mixing and reduced ROS saturation within the reactor. In cROS × V
addition, fine-tuning of ROS generation can control the kinetics at the
where cROS (g/L) is the concentration of the generated ROS, and V (L) is
surface of the electrocatalytic materials and their selectivity, as dis
the volume of the electrolyte. CE can be expressed as follows:
cussed in Section 2.3.1. The electrocatalytic materials show different
efficiency and selectivity toward ROS generation depending on their cROS × V
CE = × 100. (10)
structure and chemical characteristics. The Supplementary Information mROS
(Tables S1 and S2) reports the main experimental results from the
Achieving high performance electrochemical processes requires
literature. The summarized results demonstrate the dependence of ROS
reducing the value of EC for enhanced CE. Selecting efficient electro
regulation on the operational conditions and the type of electrocatalytic
catalytic materials and designing effective operational conditions can
material.
increase the production rate of ROS, and their concentrations (cROS ).
Material selection has a direct influence on the value of P in Eq. 9 in
2.3.5. Uncontrolled conditions, scale-up challenges and performance
terms of determining the thermodynamic overpotentials and the cell
optimization
resistances as described in Eq. 5. Overall, Section 2 discusses the
Achieving systematic and regulated ROS generation requires over
fundamental design consideration and performance optimization. The
coming the uncontrolled conditions during the electrochemical water
following section provides detailed examples on material selection and
treatment processes and the inter-connected scale-up challenges. One of
performance.
these uncontrolled conditions includes structural defects of the elec
trocatalytic materials [187–189], which may arise from either the
3. Current & emerging materials for ROS synthesis in water
manufacturing quality or the dynamically lost stability of the material
treatment cells
surface. These defects alter the reactivity of the electrocatalytic mate
rials, which changes the effectiveness and selectivity of ROS generation
In this section, we discuss the current and emerging materials for
over time. Section 3 discusses this in more depth by providing examples
water treatment cells with a focus on efficient ROS synthesis. We have
of different materials. These defects can limit the scaling of
11
Fig. 5. a) Summary of publication trends for various material categories within electrochemical water treatment field, b-c) summary of publication subcategories in
2022 for carbon-based and metal oxide materials, respectively, and d) main features of next-generation material design for ROS synthesis.
developed and summarized a dataset of 500 electrodes and 130 catalysts classification. The published articles focus on several features to
(see Supplementary Information), which includes information on enhance the current materials and develop new designs for efficient ROS
degraded pollutants, used electrodes, removal efficiency, and reaction synthesis. Fig. 5d highlights the main features of material design for ROS
conditions. Fig. 5 summarizes current publication trends on the used synthesis, emphasizing the necessity for sustainable, cost-effective, and
materials within the water treatment applications for ROS synthesis for scalable materials. Gaining a deeper understanding of the current ma
the years 2012–2022, obtained from Scopus database. Additional data terials used for ROS synthesis is important for optimizing their proper
for various material types over the period 2000–2022 are summarized in ties and improving ROS generation. Table 3 summarizes the advantages
the Supplementary Information. The collected data shows that carbon- and disadvantages of various material classifications. In general, the
based and metal oxide materials are considered the top two material current materials summarized exhibit at least two limitations, which
categories for electrochemical water treatment over the years. New prevent relying on a specific material classification. The subsequent
trends of emerging materials are also observed, such as metal-organic subsections investigate the details of different material classifications
framework, gas-diffusion, and biochar electrodes [5,183,193]. Fig. 5b and the methods of enhancing their performance.
and c show the focus of 2022 publications on carbon-based and metal
oxide subcategories, respectively, where activated carbon and transition
3.1. Carbon-based & porous materials
metal oxides are the dominant subcategories in each material
In recent years, carbon-based materials have emerged as 2e− ORR
Table 3 catalysts for H2O2 synthesis due to their low cost, abundant availability,
Summary of material classifications and both their advantages and disadvan sustainability, and scalability. As illustrated in Fig. 5d, these are key
tages for ROS synthesis. features to design materials for ROS synthesis which make carbon-based
Material Advantages Disadvantages References materials of great interest. The carbon-based materials have several
Classification subcategories, including carbon nanotubes, aerogels, activated carbon,
Pure Metals • Stable over wide • Expensive [194,195] and graphite felt, as summarized in Fig. 5b. Due to the variety of their
range of conditions • Non-sustainable structures, these carbon materials can have dimensionality ranging from
• Robustness • Potential leaching (e. zero-dimensional (e.g., carbon spheres/fullerenes) to three-dimensional
• Re-producibility of g., toxic Pb)
(e.g., porous graphite) structures [205]. Fig. 6a summarizes these
the material
structure different structures of carbon-based materials (i.e., carbon allotropes),
Carbon-based • Cost-effective • Low current [5,17, which can either be sp2 or sp3 hybridized (see Fig. 6a).
• Abundant efficiency/ 196] Carbon-structures with sp2 hybridization have higher electronic con
availability conductivity ductivity and excess surface energy compared to sp3 hybridized struc
• Low activity and
selectivity compared
tures. For example, graphene is a semi metallic material with higher
to metals surface energy compared to the semiconductor hydrogenated or fluori
Metal-oxide • Acceptable cost • Scalability [197–199] nated graphene materials, and therefore, has a more hydrophilic surface
• High stability • High stability [206]. The variation in their dimensionality, structure, and bonding
• Relatively available • Relatively available
arrangements (sp2 or sp3) has allowed synthesizing various
• Lower selectivity
compared to metals carbon-based materials for electrochemical water treatment cells (see
Polymers • High surface area • Scalability [200,201] Fig. 6b). These materials can either have crystallized/ordered structures
and porosity • Performance depends (i.e., carbon felt) or porous/disordered structures (i.e., activated carbon
• Robust on the operating or aerogel) [205]. To optimize the electrocatalytic performance, these
• Cost-effective conditions
carbon-based materials require tunning of their pore structure (e.g., pore
12
Fig. 6. Schematics of a) carbon allotropes based on the structure dimensionality ranging from zero-dimensional (0D) up to three-dimensional (3D) which are
classified into two groups based on their electronic structure hybridization (i.e., sp2 and sp3), b) types of carbon-based materials used in water treatment cells, c) ROS
generation using granular activated carbon structure which utilizes advection and adsorption to generate ROS and degrade pollutants, d) H2O2 selectivity of carbon
and metal materials adapted from [202], e) equilibrium potential (vs. RHE) for 2e− and 4e− ORR to H2O2 and H2O using alloys and defected graphene adapted from
[203], and f) kinetic current density vs. potential for various catalysts adapted from [204].
size and distribution), graphitization degree (e.g., orbital hybridization acid) at high temperatures in an activation kiln [208], while physical
and structure ordering), and surface chemistry (e.g., functionalization) activation typically requires pyrolysis of carbon precursors at high
[205]. temperatures followed by gasification via oxidizing gas, such as CO2, O2,
Continuous efforts are being made to develop strategies for the air, or steam [205,209]. Activated carbon has been widely used for ROS
optimization of carbon-based materials to efficiently produce ROS, generation due to their rich pore structure, high surface area with 3D
specifically H2O2. In recent years, there has been extensive research on structures, and abundant oxygen containing functional groups [17–19,
activated carbon materials for ROS production [17–19,55,139,207]. 55,139,207–209]. Previous studies have shown that activated carbon
More than 50 % of the published articles in 2022 on electrochemical can generate up to 385.2 mg/L.hr H2O2 with large durability [210].
water treatment used activated carbon-based electrodes due to their However, the current efficiency is typically lower than 80 % [210] since
promising electrocyclic features (see Fig. 5b). Granular activated carbon these materials have poor electrical conductivity [205]. Therefore,
(GAC) based electrodes, for instance, have exhibited potential as a recent studies have been focused on increasing their conductivity to
promising electrode material for increasing the efficiency of ROS syn enhance their ROS synthesis capability. For example, even a moderate
thesis (see Fig. 6c) [19]. The porosity of activated carbon provides increase in the compaction of the packed GAC bed can increase its
higher surface area for reactions, enabling the enhancement of ROS conductivity by 17–28 times, while modifying the surface with
synthesis efficiency through coupling advection and adsorption at the oxygenated functional groups can also improve the conductivity [211,
electrode surface. In addition, these carbon-based materials can be 212]. Understanding and optimizing the carbon structure hybridization
chemically or physically activated, giving flexibility in their preparation can also help enhance the conductivity of the activated carbon-based
and production. The chemical activation process involves mixing carbon materials, as shown in Fig. 6a. Besides the challenge of enhancing the
precursors with activation and pore-forming agents (such as phosphoric conductivity of carbon-based materials, producing these materials
13
sustainably and implementing regeneration techniques have also been as bifunctional cathodes due to their favorable characteristics, including
recent focuses in the literature, as discussed later in section 3.5. high conductivity and commercial availability [228]. Recently, various
Moreover, optimizing the surface functionalities in carbon-based carbon-based materials have been tested for pollutant degradation and
materials can enhance their activity and selectivity for ROS genera water treatment. Carbon nanotubes (CNTs) co-doped with nitrogen and
tion. Studies revealed that controlling the surface chemistry of these boron with embedded nano-iron particles were used as bifunctional
materials via introducing functional groups such as ether, carboxyl and cathodes, serving as cost-effective material for pollutant degradation
quinone can be highly effective in their pre-activation, which alters their [229]. This bifunctional cathode exhibits high selectivity for generating
surface edges to create highly active ORR sites [213], as illustrated in H2O2 (~100 %) and the ability to activate H2O2 into •OH or 1O2.
Fig. 6d which summarizes the selectivity of H2O2 by different materials Bifunctional perovskite/carbon black/polytetrafluoroethylene elec
[202]. Modification of the surface edges after addition of various func trodes were used for the generation and activation of H2O2 into •OH
tional groups can increase the H2O2 selectivity from 60 %− 80 % in [227]. These electrodes demonstrated high activity and stability at
pristine carbon materials up to ~ 98 % (as depicted in Fig. 6d). For neutral pH, as well as significant removal rates of ANT and TOC at
example, electrochemical measurements revealed that using graphitic moderate electrochemical rates. Overall, designing and utilizing
nanosheets with abundant quinones enhanced H2O2 selectivity up to bifunctional carbon-based electrodes represents a promising trend for
97.8 % at 0.75 V [213]. Adding carbonyl and carboxyl functional groups cost-effective and scalable electrochemical water treatment processes.
to carbon black have also been reported to enhance the ORR selectivity One of the key challenges in designing these materials is their stability
by serving as active sites for H2O2 generation [214]. However, higher under various electrochemical and pH conditions. Earlier studies have
concentration of surface carbonyl groups might hinder the H2O2 shown that the stability of bifunctional electrodes can be enhanced
desorption due to its strong affinity with peroxide at higher potential. through the synthesis of proper chemical structure and binder to reduce
Therefore, interface engineering with appropriate functional groups is their susceptibility [230–232].
critical toward enhanced H2O2 generation [215]. Following the initial
reports on H2O2 generation over activated carbon [216], various
carbon-based catalysts, including nanotubes, fullerenes, hybrid mate 3.2. Metal-based materials
rials such as carbon doped with nitrogen, sulfur, fluorine, as well as
carbon sulfides have been studied [217–219]. Since pristine carbon Pure metals, such as gold (Au) and silver (Ag), are commonly used as
materials suffer from low selectivity [202], scientists have been studying the benchmark for producing ROS, especially H2O2, due to their high
to enhance H2O2 selectivity by doping different heteroatoms to the stability, selectivity and activity as indicated in Table 3. Furthermore, as
carbon structure [220]. For instance, nitrogen induced charge delocal depicted in Fig. 6f, these metal-based catalysts offer a wide range of
ization in nitrogen doped carbon nanotubes arrays alters the chemi stability in terms of kinetic current density over potential [204]. For
sorption mode of O2, which facilitates the ORR [221,222]. instance, Ag is considered one the best catalysts for H2O2 production due
Understanding the crystal structure and architecture of the functional to its higher kinetic current density as shown in Fig. 6f [233]. While Au
groups can help in designing and developing processes for cost-effective has high kinetic current density for a limited operating potential (up to
H2O2 electrosynthesis [223]. An alternative approach to improve ORR 0.5 V) and weak binding strength with O2, which result in higher H2O2
performance involved introducing impurity defects, as depicted in selectivity via 2e− ORR (see Fig. 6c), its potential toward activating O2
Fig. 6e. The inclusion of these defects can alter the electron symmetry to form intermediates species such as •OOH is also weak for the same
and electronic hybridization of the aromatic carbons, which leads to a reason [234], resulting in higher energetic cost of converting H2O2 at Au
non-homogeneous composition with variations in the binding energies surface. Additionally, metals including Pt, Pd, and Ag exhibit strong
between ROS and the carbon surface that can enhance 2e− ORR catalytic affinity toward •OH and •OOH, which eventually facilitate the 4e− ORR
activity thus improving the overall H2O2 selectivity to more than 80 % and make it difficult to accumulate H2O2 [234]. Alloys such as Au-Pt-Ni
[224]. Defects can be induced in carbon structures as lattice (e.g., single, can operate over larger potential range and higher kinetic current
or double atom vacancies), functionalization (e.g., adding functional density compared to pure metal such as Pt (see Fig. 6f). The alloy
defective groups at the edge of the materials), or doping (e.g., nitrogen) structure is made from single active elements for ORR, such as Pt, Pd,
defects [224]. and Ru, surrounded by an inert element such as Hg or Au. These isolated
While defects can significantly enhance the electrocatalytic perfor active sites in the alloys boost the activity of the metal-based materials
mance (i.e., selectivity and activity) of carbon-based materials, creating by enabling effective activation of the oxygen providing efficient routes
and tailoring these defects are challenging tasks especially for achieving to form H2O2 [234]. In addition to the higher stability range of alloys,
good scalability or making 3D electrode structures. 3D electrocatalytic they may have 100 % selectivity of H2O2 as shown in Fig. 6c (e.g.,
structures, such as GAC, offers the opportunity to overcome mass Ag-Hg). Overall, alloyed bimetallic nanoparticles often provide higher
transport limitation during contaminants degradation. These structures rates or selectivity than respective pure metal catalysts [235]. Nano
facilitate simultaneous adsorption of the targeted pollutant on to their particles made of Pt-Hg showed more than on order of magnitude
surface, and their electrochemical transformation into non-hazardous improvement than pure Ag metal for H2O2 production in terms of mass
compounds [225]. Therefore, increasing the adsorption of the targeted activity [233]. Further, Pd-modified Au nanoparticles (i.e., Pd1Aux) are
pollutants at the electrode surface can help reduce the mass transfer one of the most active catalysts for H2O2 synthesis as demonstrated in
limitations and minimize the side reactions due to the high selectivity fuel cell applications [236]. Pd1Aux structure allows-on site production
provided by the electrode. The electrochemical reaction can involve of H2O2 by offering preferential destabilization of transition states that
direct or in-direct degradation of pollutants and ROS generation, thus cleave the bond in O-O leading to increased H2O2 selectivity [236].
increasing the utilization and efficacy of these electrodes. Finding Mechanistic understanding of the reaction pathways at the surface of
mechanisms to engineer and scale such electrodes, includes tailoring pure metal and alloy particles can provide significant insights toward
defects within these 3D structures. increasing their selectivity and activity. However, the primary limitation
The overall cost of electrochemical water treatment processes can be of using these metal electrodes is their high cost, which prevents their
reduced through the design and utilization of bifunctional electrodes, use at large industrial scales. In addition, the toxicity of Pt- and Pd-Hg
which offer the ability to generate H2O2 and decompose it into other alloys prevents their widespread application [234]. Therefore, re
ROS without necessitating the transport or storage of H2O2 [226]. These searchers have investigated modification of metal electrodes using ma
electrodes are primarily based on the incorporating active catalytic terials such transition metal oxides (TMOs) and metal-organic
phases into various types of conductive support materials [227]. frameworks (MOFs). These alternative materials offer the opportunity to
Carbonaceous materials have shown promising effectiveness when used overcome the limitations of metal-based electrocatalytic materials.
14
3.2.1. Transition metal oxides (TMOs) structure and texture based on their multiple dimensionalities is an
Transition metals are a group of elements in the middle of the peri attractive feature for scaling them up, as well as to explore various
odic table between the main group elements that are known for their structures. This class of metal-based materials is relatively new which
unique electronic and chemical properties, which make them important has received significant attention over the last few years (see Fig. 5c).
for a wide range of applications, including catalysis [237]. In particular, The growing number of recent publications on the applications on water
some transition metals, including Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, treatment employing MOFs is an indicative of their great potential in
Pt, and Au play a role in the evolution and selectivity of H2O2 [238]. ROS generation for water treatment. The crystalline porous structure of
TMOs such as Ti2O, Fe3O4, and NiO have partially filled d-orbital which MOFs does not only offer high surface area, large variety in the pore size
provides these materials with unique physical and chemical properties and distribution, low mass density, and chemical tunability [250], but
for environmental treatment [238–241]. Due to a large variation in their also provides a diffusion pathway for the guest molecules through the
bandgaps, these TMOs can be categorized as good insulators, semi bulk solution. The fundamental characteristics of MOFs rely on the
conductors, metals, or even superconductors [237]. They also can show content of inorganic nodes, which affect the offering of active sites to
transition from metallic (V2O3) to a non-metallic state (VO2) depending initiate the catalytic performance [251,252]. These inorganic nodes
on the surrounding temperature and pressure [237]. While a wide range typically comprise of transition metals due to their high charge density
of TMOs offer several opportunities to utilizing them in ROS synthesis leading to highly active sites [253].
due to their flexible properties, their cost-effectiveness, good stability Fe-based MOFs are one of the most promising materials for
and lower toxicity make them superior catalysts than their metal-based contaminated water treatment due to their high chemical adsorption
counterparts [242]. Further, TMOs are easy to prepare with flexibility to capability, nontoxic nature, and low cost [254]. While vast majority of
modify their structure and properties for efficient ROS generation [242]. Fe-based MOFs have been developed, the use of bipyridine as organic
Fig. 5c illustrates the literature for main TMOs published in 2022, which ligand has received special attention due to their strong binding affinity
shows that iron and titanium related oxides are the two primary tran to ferrous Fe ions and oxidative resistance to •OH [254]. Binding ferrous
sition metals used for preparing TMOs for electrochemical water Fe with 2,2′-bipyridine-5,5′-dicarboxylate to build MOF catalyst has
treatment. shown high activity for H2O2 synthesis near neutral pH and superior
Titanium-oxide (i.e., TiO2) has been extensively used for the catalytic stability compared to other MOFs [255]. Several other MOFs beyond
H2O2 formation due to its low cost, abundant availability, stability, long- Fe-based structures, such as Cu-based MOFs, have also been investigated
term durability, and nontoxicity [242]. Notwithstanding the fact that as electrocatalysts for ROS generation via a 2e− ORR [256]. Addition
TiO2 exists in three polycrystalline phases (i.e., anatase, rutile, and ally, Ni-based MOF catalysts have also shown capability of having strong
brookite) which exhibit different band offsets and electrocatalytic ac stability in aqueous medium, and high faradic efficiency (i.e., above 60
tivity [243], the fast decomposition of H2O2 decreases its activity [244]. % and can reach up to 95 % at large voltage potential) for H2O2 for
On the other hand, iron-based oxides are attracting more attention due mation [257]. Low-dimensional and nanomaterial structures of MOFs
to their biocompatibility for environmental applications, nontoxicity, have also shown excellent features for efficient ROS generation. 2D
and antibacterial ability. Iron oxide (i.e., hematite, magnetite, and Co-MOF nanosheets were able to produce high rate of ROS, including
maghemite) and iron oxyhydroxides (such as goethite, ferrihydrite, and •OH and 1O2, since the reduced dimensionality in the MOFs structure
feroxyhyte) have also been used for potential H2O2 decomposition and facilitates higher mass transfer depending on the metal-cluster [258].
ROS production (e.g., •OH and •O−2 ) [245]. These investigations showed Nanocomposite MOF electrocatalyst (e.g., Mn-MOF@CuO) also shows
that iron-based oxides can have invalid consumption of oxygen during low overpotential (i.e., 247 mV) for OER [193].
the electrochemical reactions (i.e., the oxygen will be consumed during The efficiency of the MOFs can be enhanced by introducing addi
the electrochemical reactions resulting in the electrode depletion and tional active sites to its structure to boost the ROS generation. According
mass loss). To overcome the drawback of pristine TMO materials, to Jahan et. al, pyridine-functionalized graphene (i.e., reduced graphene
various optimization and modification strategies can be carried out to oxide) can serve as a building block for the formation of MOF [259]. It
enhance their performance for ROS generation such as optimizing re was found that reaction of pyridine-functionalized graphene with
action conditions, doping, and coupling it with other materials (e.g., iron-porphyrin to form a graphene metalloporphyrin MOF can result in
graphene, anion clusters, or metal nanoparticles) [245]. Optimizing the an enhanced catalytic activity for ORR. The graphene-MOF hybrid
reaction conditions (e.g., pH, temperature, and pressure) does not only catalyst exhibited similar current densities as the FePc/MWCNTs com
tune the reactivity of H2O2, but it has also influence on the physical and posite. However, it required a lower sample loading (159.2 μg/cm2) and
chemical properties of TMOs as previously discussed (e.g., VO2 shows provided a higher positive ORR onset potential at –0.087 V vs. SCE
transition from metallic to non-metallic depending on the temperature). compared to –0.094 vs. SCE in case of FePc/MWCNTs composite [259].
Doping TMOs can alter its electronic structure allowing higher activity This observation opens the door to investigate hybrid composite mate
of ROS production. For example, doping TiO2 by either nitrogen or rials comprising MOFs toward increasing their activity. In addition to
sulfur atoms boost the production of either H2O2 or •O−2 compared to enhancing the activity of MOFs, these materials are generally not stable
undoped TiO2 [246]. Finally, coupling TMOs with other materials such in water and, therefore, they decompose over time [253]. In other
as metal nanoparticle or carbon-based materials to make electrolytically words, it is difficult to separate MOF structures from the reaction solu
composite materials can improve their durability and performance for tion (e.g., water) for recycling due to their highly dispersive nature
ROS generation [247]. For example, surface modification of graphite felt which limits their sustainability and scalability. Finally, since MOF
with Fe3O4 nanoparticles is an attractive approach to fabricate development and implementation in field of water treatment is rela
self-standing composite materials for electrosynthesis of H2O2 and water tively considered at early stage, the understanding of complex MOFs in
treatment, which simultaneously provides iron source toward EF pro electrochemical synthesis of ROS is still at an early stage. Thus, the
cess for •OH production [248]. Overall, the development and integra researched MOFs materials still did not fulfil the requirements of
tion of TMOs for ROS generation and environmental applications have achieving a combination of high catalytic activity, vast linear range of
been an active research area for many years owing to their promising scalability, high selectivity, and sustainability features.
potential.
3.3. Conducting polymer
3.2.2. Metal-organic frameworks (MOFs)
MOFs are porous polymers assembled by the coordination of inor Polymers are macromolecules made of repeated subunits called
ganic nodes (i.e., metal ions or clusters) with the organic ligands offering monomers. Conducting polymers are polymers which conduct elec
excellent physiochemical characteristics [249]. The variety in their tricity due to the delocalization of π-electrons which can be either
15
metallic or semiconductor organic materials. These polymers have 3.4. Emerging materials
attractive properties including high electrical conductivity, robustness,
light weight, easy synthesis, and low cost [260,261]. Polypyrrole, pol Given the challenges and drawbacks in the existing materials as
yaniline, polyacetylene and polythiophene are examples of doped con thoroughly discussed in previous sections, there is a dire need to develop
ducting polymer materials [260,262]. These polymers can form 3D new materials for ROS generation in water treatment applications. The
network allowing both ion and electron transport where water and ions design and development of new materials should be focused on opti
can be swelled with the formed network [262]. Ideally, the formed mizing the design features highlighted in Fig. 5d. In this section, we have
matrix brings the reactant and electrons closer together allowing high explored the current trends in emerging materials for applications in
surface area of reaction. Like noble metals, the orbitals of the conducting water treatment.
polymers can directly interact with the reactants via chemisorption due
to the absence of passivation/insulating layer on their π-electronic sys 3.4.1. Biochar
tem [262]. This unique characteristic can boost the formation of acti Biochar represents a class of carbon-rich materials mainly derived
vated complex and lower the needed activation energy barrier for the from the organic waste [268]. Recently, there has been a significant
ROS reactions. Thus, conducting polymers can be promising increase in the number of reports on biochar-based electrocatalysts for
high-current density heterogenous electrodes for electrochemical water electrochemical water treatment (see number of publications in the
treatment systems. Liu et al. demonstrated that electro-conductive pol Supplementary Information) due to their promising properties, such as
yaniline/polyimide membranes are scalable materials to efficiently form low cost and sustainability. Fig. 6 depicts various sources of biomass,
•OH and OCl− species for degradation of organic pollutants [263]. These and thermochemical processes for their fabrication. Biochar can be
conducting polymer membranes allow combined effect of adsorption synthesized using various sources, including wood waste, animal res
and sieving during ROS generation pollutant degradation. In addition, idue, sewage, municipal solid waste, food/crops waste or industrial
they have high conductivity which significantly enhances their residues, etc. After obtaining and extracting the raw material, conver
self-cleaning ability [263]. The scalability and production of these spe sion processes take place to synthesis biochar structures from the raw
cific membranes are promising due to the excellent compatibility be supplied biomass. Pyrolysis is one of most practical approaches for their
tween polyaniline and polyimide structures which benefit their scale-up. synthesis where biochar is produced by heating the raw biomass at high
Poly(3,4-ethylenedioxythiophene), PEDOT, is another efficient and se temperatures (e.g., 400–900 oC) for given pyrolysis times [269]. Gasi
lective conducing polymer for H2O2 production [264]. PEDOT can show fication is another process used to produce biochar through supplying
a Faradic efficiency of 100 % during direct reduction of O2 to H2O2 oxidizing agent under high temperature (e.g., 700 oC) to convert the
[264]. However, their poor recycling stability is a primary limitation biomass into gaseous mixtures [269]. While these processes require high
that needs to be addressed [260]. temperatures, hydrothermal liquification/carbonization can alterna
The electrochemical and physical properties of conducting polymers tively produce high yields of biochar at lower temperatures (below 300
o
can be enhanced via improvement in their crystallinity, controlled C), which is a cost-effective approach for the production of biochar with
microstructure, and optimized surface morphology. These goals can be high moister content [269]. .
achieved either by optimizing the polymerization processes, inducing Various biochar-based materials were prepared and used for ROS
dopants with multiple oxidation levels [260]. Moreover, synthesis of generation within electrochemical water treatment [112,183,212,
conducting polymer-based composites with other active materials, such 270–272]. Recently, Ansari et al. prepared granular biochar-based
as carbon-based materials and metal oxides, has received attention as an cathode from banana peels for applications in water treatment [183].
approach to develop materials with unique properties [260,265]. The First, the banana peels were washed and dried, followed by pyrolysis
conjugate π-electronic characteristics of conducting polymers offer process at 350 oC to form granular banana-peel biochar. Finally, the
several advantages toward the formation of such composites. For formed biochar was packed in stainless steel mesh to fabricate the
instance, the morphology and porosity of carbon-based materials can be cathode. The fabricated biochar cathode was able to facilitate ORR
manipulated by the conducting polymers to increase the exposure of during water treatment offering a cost-effective solution for in-situ H2O2
active sites to the reactant species and, ultimately, improving the elec synthesis. However, the long-term performance and cycling stability of
trocatalytic performance for ROS synthesis [231]. In addition, the the banana-peel biochar decreased with increasing number of electro
ability of doping and adding functional groups to conducting polymers chemical cycles. The authors used polarity reversal technique to
make a great possibility to prepare uniform carbon-based nano improve the cyclability and durability of the biochar electrode. Pyrolysis
composites integrated with other materials such as metal oxides. For technique was also used to synthesize magnetic iron oxide doped
example, coordinating N-doped carbon-based materials derived from graphitic biochar composite for ROS generation [272]. The formed
N-rich conducting polymers with transition metal catalysts can sub composite functionalized over wide range of pH (2− 10) during degra
stantially reduce the energy barriers and optimize the reaction pathways dation of organic pollutants. Several ROS were generated during the
enhancing the electrocatalytic performance of OER processes [266,267]. electrochemical processes where •OH and 1O2 were found to be the
Li et al. reviewed and summarized conducting polymers based electro dominant active species. Luo et al. used hydrolysis (i.e., hydrothermal
catalysts for ORR and OER [265]. The authors provided detailed insights carbonization) to fabricate heteroatom-doped porous biochar catalyst
and examples of conducting polymer-derived structures and their elec [271]. This catalyst showed superior performance where H2O2 selec
trocatalytic performances for electrochemical reactions. Among various tivity reached almost 92 % with allowing efficient Fe2+ regeneration for
materials reviewed and summarized, bifunctional catalysts made from the EF process. Therefore, the degradation of the organic pollutants
conducting polymers which can carry out OER/ORR electrolysis is an achieved excellent efficiency of 98–100 % in first 15 min. Overall,
interesting candidate. Traditionally, two different catalysts are needed biochar-based materials are promising candidates for ROS synthesis,
to separately achieve ORR and •OH activation in EF-like processes. especially when it comes to the cost and sustainability. Given that bio
Encapsulating Fe or alloys nanoparticles in carbon-based conducting char is an emerging class of materials, comprehensive understanding
polymers can remarkably serve both these reaction steps as bifunctional and regulation of their quality, safety, and properties should be carried
electrocatalysts for ROS generation [226,265]. Development of bifunc out [273]. The stability (e.g., decomposition of their surface function
tional conducting polymer composites for OER/ORR processes can alities) as a function of the reaction conditions could be one of the main
improve the production rate and reduce the cost of ROS generation. issues that should be addressed.
However, these materials are still limited at bench-scale and require
further investigations to scale-up for practical applications within water 3.4.2. Transition metal-chalcogenides and -spinel oxides
treatment scope [234]. Transition metal chalcogenides (TMCs) represent another class of
16
Fig. 7. Schematic of biochar formation starting from biomass resources, followed by extraction via thermochemical processes (i.e., pyrolysis, gasification, or hy
drothermal liquidation) and ending with fabrication of biochar-based electrode for ROS synthesis.
promising materials where transition metals are bonded with chalco binder), gas diffusion layer (i.e., made of porous carbon-based materials
genides (i.e., S, Se, or Te). TMCs, specially low-dimensional structures, or a metal-mesh), and matrix. The gas-diffusion layer serves as current
recently witnessed significant attention on using these for water elec collector and provide gas flow channels from air to the catalyst. In
trocatalysis due to their outstanding physical and chemical properties addition, the gas-diffusion layer faces the air side sustaining the diffu
[274]. A recent study discovered that chalcogenides of binary earth sion of O2 whereas the catalyst layer faces the electrolyte side. Both
abundant metals, such as CoS2 [275], CoSe2 [276], and NiSe2 [277] can layers have significant influence on the electrochemical performance of
act as robust catalysts for 2e− ORR in both acidic and neutral solutions, the GDE [284]. Therefore, optimizing and tuning the characteristics of
providing new insights into catalytic activity, selectivity and stability these two layers can lead towards achieving efficient in-situ synthesis of
[278]. Specifically, NiSe2 electrocatalyst showed a selectivity of 90 % for ROS. Several approaches have been implemented to improve the elec
2e− ORR in acidic media. Similarly, transition metals-based spinel ox trochemical activity of GDEs in terms of increased •OH production at the
ides have unique characteristics which can allow efficient ROS genera cathode (especially at low voltage potentials), and extended activity
tion [279,280]. Spinel oxides are usually cubic closed-packed materials over a wide range of pH. Incorporating modifiers, such as metal oxide
with a general formula of AB2X4 (e.g., FeCr2O4) where A and B are the nanoparticles, into the carbon matrix can promote the selectivity and
transition metal cations and X is the oxygen anion. Previous studies reduce the overpotential of ORR [284]. Heteroatom-doping of GDE can
show that tunning the cation concentration and element type can help in create more active sites in carbon and alter the wetting characteristics of
improving the electrocatalytic properties of spinel oxides [280]. For the catalysts improving their properties [285]. Moderate doping is found
instance, substituting some cobalt with iron in ZnCo2O4 forming to produce GDE structures capable of achieving selectivity of H2O2
(ZnFexCo2–xO4) is found to promote the OER activity as the iron sub above 70 % and Faradic current efficiency up to 97 % [285]. GDE made
stitution promotes the electron transfer from oxygen [281]. Recently, of TMC/nanocarbon hybrids has been also proposed as efficient H2O2
Danyang et al. investigated high-entropy spinel oxide, (Fe0.2Zn0.2Co0.2 catalyst [286]. While GDEs have several unique characteristics, proper
Ni0.2Cu0.2)Fe2O4, as efficient electrocatalyst for H2O2 generation [279]. strategies are needed to mitigate the fouling on their surface and to
The fabricated high-entropy oxide exhibited H2O2 selectivity of up to ~ enhance their durability during water treatment. For example, carbon
85 % and effective long-term stability due to oxygen vacancies and black-polytetrafluoroethylene GDEs is found to have a decreasing cur
co-interaction of the multiple metal ions which facilitate the production rent efficiency of H2O2 from 95 % to 70 % over 46 days leading to the
of H2O2. Given their relative low cost, presence of metals serving as formation of precipitates within the contaminated water [287]. One
active sites and doping potential, these TMCs and spinel oxide materials approach to enhance their durability is by applying regeneration tech
are considered promising candidate for ROS synthesis. Since these ma niques [19]. As GDEs are still emerging, fundamental understanding of
terials are emerging, their properties and structure-property relationship their physical and chemical properties can be used to further improve
are still not fully understood for OER or ORR. Specifically, the toxicity these materials and scale them up at industrial level. The complexity in
and scalability of these emerging materials should be assessed [282]. In studying and developing GDEs arise from the coupling between the
addition, the durability of these materials should be investigated since three-phase environment which requires tunning the wetting, O2 flow
TMCs have shown the tendency of evolution/conversion as part of the rate and possibly other factors to enhance the GDEs properties. Recently,
electrochemical activities (e.g., after OER process) [283]. natural air diffusion electrodes have been developed as cost-efficient
electrodes in electrochemical water treatment [288–291]. These elec
3.4.3. Gas diffusion electrodes (GDEs) trodes do not require any pressurized system to externally supply air or
GDEs are porous electrodes made of carbonaceous materials where O2 hence reducing the electricity and power requirement and leading to
the solid catalyst is concurrently in contact with the liquid electrolyte (i. decreased operational costs. Instead, the air or O2 diffuses naturally
e., contaminated water) and a gas phase (e.g., atmospheric air) [284]. toward the reaction interface by adjusting the surface hydrophobicity of
They form excellent cathodes for high in-situ production of H2O2 due to the original GDE, thereby overcoming the natural resistance from the
their high electrocatalytic activity. This is achieved by the simultaneous gas diffusion layer, and resulting in higher utilization efficiency of O2 to
and active three phase interactions (see Fig. 4b), where the GDE is not generate H2O2 [292]. Designing superhydrophobic natural air diffusion
completely dry or wet allowing direct and steady contact with the re electrodes can enable higher current efficiency and larger diffusion co
actants. The GDE usually consists of catalyst layer (i.e., consists of efficient of O2 compared to normal GDE, offering great potential for
carbon-based materials with/without metal-doping, and a hydrophobic scalable electrochemical water treatment at industrial scales.
17

4. Outlook towards accelerated discovery of materials electrochemical processes. The proposed material informatics frame
work (see Fig. 8) aims to achieve fast, accurate, and robust acquisition,
Turning the current materials and discovery of new materials for management, analysis, and dissemination of materials data. Several new
designing cost-effective, efficient, and large-scale electrochemical re materials have been discovered using material informatics for various
actors requires bridging several interconnected fundamentals and applications [303–306]. The battery development has been significantly
complex sciences. In addition, electrochemical processes of ROS syn advanced using the recent material and battery informatics applications
thesis occur at multi-scale levels in terms of space and time [68]. [307–309]. The workflow of Fig. 8 begins with data acquisition stage in
Mechanistic understanding of these various complex phenomena re which the material properties (e.g., electrode characteristics, ROS ki
quires having large data (i.e., both experimental and computational), netics at the electrode, etc.) are determined. The data acquisition can be
phenomenological relations, and accurate models to predict the carried out via atomistics simulations (e.g., quantum chemistry or mo
behavior of the targeted materials under different conditions. The lecular dynamics), experiments, or by data mining from online database.
developed understanding allows designing, scaling, and implementing High-throughput atomistic simulations and experiments can signifi
these materials for electrochemical ROS synthesis. The currency of these cantly accelerate materials screening and data acquisition.
tasks is the available data. The recent significant advancement in robotic Even though battery and electrochemical water treatment cells have
and artificial intelligence fields [293–296] has opened the door for significant similarity, electrochemical water treatment development did
accelerating the discovery of materials for various applications. Specif not observe many applications of high-throughput data acquisition and
ically, autonomous labs where the experimental tasks are carried out by it is lacking in this research domain. Thus, the academic and industrial
robots have the ability of performing repetitive tasks in short time [296]. community should invest into borrowing and applying the existing
These labs can have the ability to examine various materials under material informatics tools from the battery and energy storage field into
different electrochemical conditions. Such testing will generate big data accelerating materials discovery for electrochemical water treatment. In
that can be useful to interpolate materials performance for upscaling. addition to generate big data using either high-throughput experiments
Over the past years, several autonomous syntheses of materials have or computations, the scientific community of electrochemical water
been successfully demonstrated including synthesis of polymers [297, technologies should invest in collecting and using the available data on
298], low dimensional [299], and thin-film materials [300]. Introducing materials in the literature. Data mining from the literature allows to
and implementing robotic labs within the electrochemical water treat build online database of existed and tested materials. Natural language
ment community can be a gamechanger to discover and design materials processing (NLP) and text-mining tools has received attention in mate
for ROS generation. The generated data from these high-throughput rial science and accelerated discovery communities due to their ability
experimentation can used into computation engines to not only accel in acquiring, sorting, and building database of materials [310–312].
erate the discovery of material via machine learning but also to scale up These databases can be used in the proposed workflow (see Fig. 8) to
the processes. accelerate discovery of materials. However, the main challenge of
Fig. 8 shows a schematic of integrated computational and experi deploying these artificial intelligence techniques is the nonunified data
mental material informatics framework which can be used to optimize structure in electrochemical water treatment literature. The discrepancy
electrochemical water treatment reactors using next-generation mate in reporting data and their unit in a unified protocol within the water
rial designs [301]. Screening electrochemical materials requires car treatment scientific field makes it hard to deploy generic text-mining
rying out computations from quantum scale using computational techniques. For example, we collected data from several electro
chemistry tools such as density functional theory up to macroscopic chemical water treatment literature (see Supplementary Information).
scale where computational fluid dynamics tools can be used to simulate We found there is inconsistency and missing information about the
full cells/reactors [68,302]. These computations can be integrated with electrochemical cells when comparing different papers together. This
machine learning tools and experimental analysis to scale up the highlights the importance of finding unified style of reporting data
Fig. 8. Schematic of workflow to accelerate material discovery and reactor design for large-scale water treatment application.
18
within the electrochemical water treatment community. to the development of current state of art and emerging electrocatalytic
Following the data acquisition stage, extraction of computed/ materials. Herein, we summarize the following challenges and oppor
measured/mined properties such reaction barriers and degradation ki tunities for developing the next generation of materials for ROS
netics can be sorted, stored, and investigated. This stage involves mak synthesis:
ing clean the data, understand it, extract structure-property relation, and
make structured datasets. Some of these datasets (e.g., reaction rates and • ROS have short lifetime with relatively limited spatial diffusion mean
diffusion coefficients) can be used in multiphase Multiphysics simula length. They can be used to develop materials that can combine
tions at the continuum scale to model full reactors. This allows to dispersion and adsorption mechanisms to enhance the pollutant
generate additional datasets and optimize the existing ones through degradation. For example, tri-functional catalysts eliminate the
investigating the reactor performance. Overall, the cell performance and desorption step of ROS since these enable strong binding between the
efficiency toward ROS synthesis are mainly controlled by the material organic pollutants and surface bonded •OH, enhancing overall
design and selection of the electrodes, catalysts, and membranes. efficiency.
Varying and optimizing the listed design conditions in Fig. 3 will mainly • Targeting fast-rate ROS generation requires a comprehensive un
depend on the potential and strength of the selected materials to operate derstanding of physiochemical processes between reactants and
the electrochemical reactions. For example, implementing moving electrocatalytic materials, especially in complex interfaces such as
electrode design or high flow rate conditions require selecting material GDEs.
with high mechanical strength to withstand the rotating force especially • Eco-economic features of the next generation materials are key
if the reactor is placed in hard environment such as soil. Further, design characteristics and are as important as the reactivity (i.e.,
operating the cell under pulse current or fluctuating pH requires stability, selectivity, and stability) properties of the electrocatalytic
emerging electrode with high stability and cyclicity. To be specific, the materials. While metal and alloy materials exhibit outstanding
electrode materials must have the following properties [313]: high physical and chemical properties, their high cost prevents from uti
physical and chemical stability, large electronic conductivity, lizing these materials at industrial scales. Therefore, carbon-based
wide-range of catalytic activity, chemical selectivity, optimized inter materials, metal oxides, and conducting polymers can overcome
facial properties (e.g., low adhesion for bubbles [67,68]), and low cost. cost-related challenges for ROS production, and their physical and
All these aspects can be included in the multiphase Multiphysics electro-chemical properties can be improved through doping and
framework through electro-chemo-thermal and fluidic transport composite formation.
coupling. • Biochar, TMCs, spinel oxides, and GDEs are emerging materials
After obtaining all datasets, material predication stage takes place which can effectively generate ROS. Their relatively easy and flexible
through the application of machine learning tools such as data-driven synthesis approaches, in addition to their outstanding properties,
techniques for material discovery [314,315]. Once the targeted mate make them attractive candidates for water treatment applications.
rial and reactor design candidates are predicted and optimized, we move While their activity can clearly be increased by introducing addi
the validation stage at which few experiments and simulations are tional active sites and enhancing the porosity, the comprehensive
needed to validate the predication and provide feedback for the dataset fundamental investigations allow the understanding of these mate
stage. By the end of validation, the final candidate which consists of the rials under various reaction environments. Specifically, their
electrode materials and reactor design can be moved to the research toxicity, scalability, and durability (i.e., long term cycling) should be
translation stage at which field implementation of the reactor occurs. At addressed.
this final stage, the final reactor can be built, implemented, verified, and • Regeneration processes of the electrocatalytic materials are critical
monitored towards large-scale water treatment operations. The overall to extend and enhance their durability. These processes should be
workflow of accelerate discovery and design of water treatment systems assessed and used to help in achieving robustness and sustainability
(see Fig. 8) can significantly boost the scaling-up of electrochemical for the next-generation materials.
reactors to the industrial demands, provide fundamental integration • Accelerating the discovery and design of the targeted materials,
between simulations and experiments to address knowledge gaps in ROS including their scalability and integration in full reactors under
synthesis field, and optimize the research time and cost through mini various conditions of electrochemical water treatment processes, can
mizing the number of needed experiments. The fundamental element in be achieved by deploying integrated workflow of experiments,
this workflow is “data”. Promoting data sharing and unifying data computations, and machine learning frameworks. High-throughput
reporting in the water treatment scientific community requires further experiments and computational simulations can help in screening
investigation [316,317]. various materials at relatively low-cost. Following, the promising
material candidates can be explored in detail. In addition, compu
5. Conclusions tational simulations can provide insights that is not easily accessible
by experiments such as reaction pathways. Machine learning tech
Large-scale synthesis of ROS requires a mechanistic understanding of niques can accelerate the experimental and computational efforts.
the reaction barriers, pathways, and the reactive environment, which The currency of these techniques is “data” which requires the sci
can provide fundamental insights toward designing the next generation entific community to adapt a systematic reporting style when
electrocatalytic materials to generate ROS for water treatment. The studying materials for ROS generation. Such reporting style can help
features of designing these materials include their stability, selectivity, generate and utilize unified database to predict and design the next
and activity. In addition, the integration of scalable and cost-effective generation materials for efficient ROS synthesis.
materials in electrochemical water treatment is essential. Interfacial
interactions between the electrolyte and the electrode is another Declaration of Competing Interest
parameter to consider in designing materials for ROS formation, as they
determine the formation and dynamics of the EDL in which charge The authors declare that they have no known competing financial
transfer and ion diffusion occur. Engineering the EDL can enhance ROS interests or personal relationships that could have appeared to influence
generation and the reduction of overpotential drop during the electro the work reported in this paper.
chemical reactions. We also explored other design parameters at the cell
level, including the reactor configuration, flow conditions, additive ef Data Availability
fects, and electrode configuration. These factors were integrated and
examined using experimental and computational techniques, which led The generated data are uploaded in the supplementary information.
19
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Journal of Environmental Chemical Engineering 11 (2023) 111384

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