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org/estengg Review

Electrified Membranes for Water Treatment Applications

Meng Sun,# Xiaoxiong Wang,# Lea R. Winter, Yumeng Zhao, Wen Ma, Tayler Hedtke, Jae-Hong Kim,
and Menachem Elimelech*
Cite This: https://dx.doi.org/10.1021/acsestengg.1c00015 Read Online

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sı Supporting Information

ABSTRACT: Electrified membranes (EMs) have the potential to address

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inherent limitations of conventional membrane technologies. Recent studies

have demonstrated that EMs exhibit enhanced functions beyond separation.
Electrification could enhance the performance and sustainability of membrane
technologies and stimulate new applications in water and wastewater
treatment. Herein, we first describe EM materials, synthesis methods,
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electrofiltration modules, and operating modes. Next, we highlight applications

of EMs in water decontamination, purification, and disinfection. Additionally,
we discuss state-of-the-art electrification methods for controlling membrane
organic fouling, biofouling, and inorganic scaling. We also evaluate the energy
consumption of EMs for water treatment and fouling control. We conclude by
discussing the challenges for improving the stability and practicality of EMs
and by proposing pathways for future research and development. On the basis
of our discussion, we suggest that EMs may be viable for ultrafiltration and
microfiltration but not for salt-rejecting reverse osmosis and nanofiltration applications. Further, we find that EMs are promising for
decontamination and organic fouling control, and these systems could be deployed for fit-for-purpose distributed treatment
applications.
KEYWORDS: electrified membranes, reactive membranes, water and wastewater treatment, water decontamination and purification,
membrane fouling control

■ INTRODUCTION
Addressing the outstanding challenges in global water scarcity
and water pollution requires water treatment technologies that
are multifunctional, modular, scalable, resilient, chemical-free,
and energy-efficient. Mature membrane technologies for
drinking water purification, wastewater treatment and reuse,
and saline water desalination play a key role in providing clean
and safe water, reducing adverse environmental impacts, and
augmenting water supply.1 These membrane-based separation
processes, including microfiltration (MF), ultrafiltration (UF),
nanofiltration (NF), and reverse osmosis (RO), separate
solutes and contaminants from water by physicochemical
mechanisms that are highly dependent on the properties of the
membrane materials.2 For example, the removal of emerging
toxic contaminants with low molecular weight and neutral
charge is very challenging using most membrane materials, due
to the limitations of conventional size- and charge-exclusion
separation mechanisms.3 In addition, interactions of organic
molecules, inorganic salts, and microorganisms with membrane
surfaces inevitably lead to membrane fouling, which deterio-
rates process performance and shortens membrane lifetime.4−6
These challenges have spurred the development of novel
membranes with additional properties and functionalities
beyond those of conventional membranes.
Electrified membranes (EMs) have the potential to address
these challenges by introducing electroactivity as an additional
membrane function.7,8 Specifically, in addition to the tradi-
tional membrane functions of solute separation via steric
hindrance and charge exclusion, EMs extend the role of
membranes beyond pure separation by exploiting a variety of
electro-based phenomena, including electrochemical oxidation
and reduction, electrostatic adsorption and rejection, electro-
phoresis, and electroporation. 9−12 Therefore, EMs can
effectively degrade and/or transform contaminants and
enhance rejection of charged species during filtration
processes.
To achieve these functions, EMs have been employed as
porous flow-through electrodes in a two-electrode setup
(working and counter electrodes) by applying an electric
potential difference across the electrodes. Compared to
traditional flow-by electrochemical systems,13−16 the electro-
Received: January 10, 2021
Revised: February 22, 2021
Accepted: February 23, 2021

© XXXX American Chemical Society https://dx.doi.org/10.1021/acsestengg.1c00015

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chemical flow-through filtration configuration can improve
reaction kinetics,17 electrode stability,18 and mass transport of
contaminants to electrode active sites.19,20 The enhanced
performance of EMs with porous flow-through electrodes has
been attributed to co-occurring field effects (e.g., thermal, fluid,
and electric fields) under spatial confinement within nanoscale
intraporous structures,19,21−23 contributing to rapid contami-
nant removal. EMs can target diverse contaminants, including
heavy metals,24 emerging organic pollutants,25 pharmaceuticals
and personal care products,26 pathogenic microorganisms,27,28
and uncharged molecules.29
In addition to contaminant removal, EMs can mitigate
membrane fouling and scaling through various electrochemical
strategies.30−32 For instance, organic and biological foulants
can be degraded by electrochemical self-cleaning based on in
situ generation of strong oxidizing species (e.g., reactive oxygen
and reactive chlorine species).18 Furthermore, the chemical
and hydrodynamic environments near the membrane surface
can be tuned by controlling pH and bubbling with electrolysis
to mitigate inorganic scaling.9,33 Beyond using electrochemical
reactions for fouling control, tailoring membrane surface
properties such as charge,9 hydrophilicity,34 and interfacial
nanostructure35 by applied voltage may provide an additional
means to reduce membrane fouling by natural organic matter
(NOM), microorganisms, and inorganic scalants.
To date, considerable research efforts have demonstrated the
potential of EMs to tackle practical problems in water
treatment. However, most studies on EMs remain at the
laboratory scale under well-controlled conditions, while
neglecting to explore their effectiveness in real aqueous
environments. Furthermore, the implementation of contami-
nant removal and fouling control in scalable and modular EMs
is challenging, as these processes are heavily influenced by the
electrofiltration mode, module geometry, and filtration
residence time. Therefore, translating EM processes to real-
world applications will require considerable improvement in
contaminant removal efficiency and selectivity, material
stability, and process sustainability as well as optimization of
module design. Given the gap between experimental studies
and practical applications, evaluating EMs, from membrane
materials synthesis and working principles to process-limiting
factors and energy consumption, is essential for guiding the
development of EMs for environmental applications.
Herein, we critically review recent advances in EMs, focusing
on water and wastewater treatment applications. We start by
introducing materials categories, synthesis procedures, and
electrified filtration operating modes. We then discuss
applications of EMs, including water decontamination and
purification through electrooxidation and reduction, strategies
to control membrane fouling and scaling, and water
disinfection via bacterial and viral inactivation (Figure 1).
Limitations to EM performance such as membrane material
longevity, system compatibility, and process sustainability are
also discussed. Further, we evaluate the energy consumption of
EMs for contaminant removal and fouling mitigation. We
conclude by highlighting future challenges and promising
applications for EMs.
■
PREPARATION AND OPERATION MODES OF
ELECTRIFIED MEMBRANES
Materials for Electrified Membranes. EM preparation
entails fabricating membrane active layers with high electrical
conductivity and porosity. We evaluated the literature from the
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Figure 1. Potential environmental applications of electrified
membranes (EMs): water decontamination and purification, water
disinfection, and membrane fouling control.
past 10 years on conductive materials used for EM preparation,
including carbonaceous materials, metals, metal oxides, and
polymers. Details are provided in Table S1, Supporting
Information.
Approximately 60% of the EMs reported are prepared using
carbonaceous materials, as shown in Figure 2A. The carbon
atoms in these materials are mostly sp2 hybridized with
delocalized π−π electrons, imparting high conductivity.36
Carbonaceous materials can serve as either the anode or the
cathode. Most carbonaceous anodes are considered as “active”
anodes with an overpotential for oxygen evolution reaction
(OER) generally lower than 0.4 V.37 The “active” anode
surface (M) interacts strongly with electrogenerated hydroxyl
radicals (•OH) to form a higher anodic oxide, M(•OH) →
MO + H+ + e−, which is only capable of partially oxidizing
organic compounds. Hence, a voltage below the oxygen
evolution potential (OEP) of carbonaceous electrodes is
generally applied for applications involving physicochemical-
based mechanisms, such as electrostatic repulsion, electro-
phoresis, and direct oxidation/reduction.38−40
Carbon nanotubes (CNTs) are the most common
conductive materials for EM fabrication due to their
applicability for facile formation of an interwoven and compact
structure with high electrical conductivity and porosity.41,42
This structure enables CNTs to bond with each other through
van der Waals interactions, thereby maintaining their stability
during EM operation. Graphene-based materials, including
graphene oxide and reduced graphene oxide, also exhibit
beneficial electrical properties. The conductive layer can be
synthesized through deposition, resulting in a high specific
surface area and controllable pore size distribution.43,44
Functionalization with oxygen-containing groups enables
CNT- and graphene-based materials to bind with other
metal catalysts, such as Fe and Pd.45,46 We note that boron-
doped diamond (BDD), one of the most promising flat plate
“nonactive” anodes for •OH production (i.e., anodes with high
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Figure 2. Electrified membrane (EM) materials, preparation, and electrified modules. (A) Summary of publications on conductive materials for
electrified membrane preparation for environmental applications, based on a total number of 150 papers published in the past 10 years (2011−
2020). Details are provided in Table S1, Supporting Information. The conductive materials are divided into three categories: carbon, metals
(including metals and metal oxides), and polymers. These materials include carbon nanotubes (CNTs), graphene, and boron-doped diamond
(BDD); substoichiometric titanium oxide (Ti4O7) and porous titanium (Ti); and polyaniline (PANI) and polypyrrole (PPy). Schematic illustration
of EM preparation through (B1) free-standing membrane casting, (B2) membrane modification, and (B3) composite membrane assembly.
Schematic illustration of electrified membrane modules and cross-flow filtration mode for (C1) flat-sheet and (C2) hollow-fiber and tubular
membranes. Thick blue arrows represent feedwater flow, and thin blue arrows represent water permeation through the membrane surface.
Schematic illustrating the effect of water convection on diffusion in (D1) flow-by and (D2) flow-through operation modes. Thick black arrows
represent the direction of convective transport, and thin blue arrows and lines indicate the direction and changes of the diffusive transport,
respectively.

OEPs),47 is rarely reported for EM fabrication, because the
methods for fabricating the BDD layer with high specific
surface area and porosity are complicated and expensive.48 In
addition, mesh electrodes such as carbon fiber cloth and
carbon paper can be used as conductive substrates for the
modification of membrane structures.49−51 The use of high
specific surface area coal and graphite has also been
reported.52−54
Metals and metal oxides are another category of conductive
materials that are promising for EM preparation. Among these
materials, numerous investigations have focused on the use of
Magnéli phase Ti4O7,55−57 the most conductive phase of the
substoichiometric titanium oxides (TinO2n−1, 4 ≤ n ≤ 10).58
When employed as a “nonactive” anode, the OEPs of Ti4O7
(2.2−2.7 V vs SHE) are comparable to those of BDD
electrodes (2.3 V vs SHE),59 demonstrating its superior
performance for •OH production via water oxidization.
Further, Ti4O7, possessing a porous, stable monolithic
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structure, can be synthesized by anodic polarization.60
Among metal materials, Ti mesh is one of the most promising
metal substrates used for functionalization with electro-
catalysts, such as IrO2, RuO2, and doped SnO2.61−63 In
addition, steel mesh substrates can serve as cathodes for
electrochemical reduction or for catalyzing electro-Fenton
reactions.64,65
Conductive polymers possess a conjugated backbone that
forms a series of alternating single and double carbon
bonds.66,67 The overlap of p-orbitals in the π-bonds allows
the electrons to delocalize and move between atoms.
Polypyrrole (PPy) and polyaniline (PANI) have been applied
extensively for EM fabrication because of their stability under
harsh conditions, such as high pressure and chemical
exposure.12,68 However, many polymer-based EMs suffer
from low conductivity and water flux.67,69 The combination
of conductive polymers with carbonaceous materials, such as
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Figure 3. Electrified membrane (EM) filtration for water decontamination and purification. (A) Schematic diagram illustrating decontamination by
EM filtration. (B) When voltage is applied, EM interacts with contaminants via electrooxidation, electrostatic adsorption, and electrostatic
repulsion, among which electrooxidation is predominantly responsible for water decontamination. The indirect electrooxidation process is
categorized according to the main oxidation mechanisms: (C) •OH-mediated anodic oxidation, (D) active-chlorine-mediated oxidation, and (E)
electro-Fenton process.
CNTs and graphene, can enhance the electrical performance of
EMs.70,71
Electrified Membrane Preparation. EMs are generally
prepared using free-standing membrane casting, membrane
modification, or composite membrane assembly. Free-standing
Ti4O7 and carbonaceous EMs, possessing both separation and
electrical properties within a porous monolithic structure, can
be prepared through the membrane casting method,72−75 as
shown in Figure 2B1. Generally, a mixture of the conductive
materials and binders, such as paraffin oil and polymers,60,76 is
first prepared. The free-standing EMs are fabricated by
mechanical pressing, gel casting, or wet-spinning methods to
shape the mixture, followed by thermal treatment to remove
the binder.
The most common method for EM preparation consists of
modifying a porous substrate with conductive materials
(Figure 2B2). Conductive substrates such as carbon filter
cloth,77,78 Ti mesh,79,80 stainless steel,81,82 and PANI70,83 are
widely used. Functionalization of electrocatalytic materials,
such as CNTs,84−86 graphene,87−89 and doped SnO2,62,90,91 on
the substrates improves their electrochemical performance
and/or controls the membrane pore size. Cross-linked
polymers with conductive materials such as CNTs can enable
accurate control of the EM pore sizes.28,92,93 Additionally, the
application of nonconductive substrates, including ceramic
(Al2O394,95 and TiO218) and polymeric (polyvinylidene
difluoride (PVDF)35,96 and polytetrafluoroethylene (PTFE))
membranes,97,98 is also common.
A straightforward method to prepare EMs consists of
assembling mesh electrodes on commercial membranes
(Figure 2B3). In this case, flat plate electrodes with large
pore sizes may be used as the active layer. A mesh electrode
can be pasted onto the membrane substrate or assembled into
an electrofiltration module with a membrane.25,63,99,100 We
note that the current efficiency of such EMs containing
conductive layers with large pore sizes is much lower than that
of EMs prepared by the other two methods, although their
specific surface areas can be comparable, as discussed later.
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Electrified Membrane Modules and Filtration Modes.
Different types of flat-sheet, hollow-fiber, and tubular EMs can
be used for water treatment.101−103 Electrified membrane
modules and filtration modes are illustrated in Figure 2C1,C2.
In practical use, the EM generally serves as one of the
electrodes, while the counter electrode is placed either on the
feed or on the permeate side. The conductive layer of the EM
generally faces the feed side.
Cross-flow filtration is the most common mode for practical
water treatment applications. In this filtration mode, the feed
flow passes along the membrane surface and the electric field is
perpendicular to feed flow (Figure 2C1,C2). Dead-end
filtration, in which feed flow is perpendicular to the membrane,
suffers from rapid formation of a cake layer, which hinders EM
performance.
Benefiting from the flow-through configuration, EMs are
able to achieve sufficient removal of contaminants through
convection-enhanced mass transport.72,104,105 Conventional
nonmembrane electrified processes, operated in batch or
flow-by modes using flat plate electrodes, result in the
formation of thick diffusion boundary layers (∼100 μm).
Therefore, these processes suffer from mass transport
limitations, because the overall reaction rate is governed by
the diffusion rate of the contaminants to the electrode surface
(Figure 2D1).106 By contrast, in flow-through mode, the
application of porous electrodes such as EMs decreases the
thickness of the diffusion boundary layer to a length scale that
is comparable to the membrane pore radius (Figure 2D2), thus
significantly enhancing the mass transport rate. Generally, the
smaller the EM pore size and the higher the water flux, the
lower is the mass transport limitation.
When the membrane pore size is on the scale of nanometers,
i.e., UF scale, the contaminant removal can be further
enhanced through nanoconfinement.107 The primary mecha-
nisms induced by nanoconfinement include the enrichment of
reactant species, such as •OH, in nanoconfined spaces, as well
as the reduction of activation energy barrier or change of
reaction pathways and kinetics.22,23,108 Carbonaceous materials
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such as CNTs, which are commonly used to form porous
structures with nanoconfinement, are also effective for the
adsorption of target contaminants within the membrane pores,
increasing the residence time and removal efficiency.29,41 The
adsorption rate and capacity can be improved significantly by
electrochemical assistance.109,110 Nanoconfinement also en-
riches the local concentration of contaminant molecules,
promoting adsorption and facilitating the subsequent reac-
tions.107,111
The mechanisms discussed above can enable EMs with
superior properties to achieve a single-pass removal of
contaminants within seconds. Notably, the removal rates are
several orders of magnitude higher than those achieved by
conventional batch and flow-by modes using flat plate
electrodes.112,113
■ ELECTROCHEMICAL OXIDATION FOR WATER
DECONTAMINATION AND PURIFICATION
Emerging micropollutants are frequently detected in drinking
water sources, wastewater effluents, and natural water bodies.
These micropollutants, including pesticides, antibiotics, and
personal care products, pose risks to human health and the
environment.114 Although conventional RO and NF mem-
branes can achieve effective rejection, these filtration processes
can only physically separate the micropollutants from the
influent, thereby producing toxic waste streams.
To overcome limitations of conventional membranes, recent
studies have focused on the application of EMs for micro-
pollutant removal (Figure 3A).7,115 EMs are able to degrade
and transform micropollutants into nontoxic substances,
thereby minimizing the need for post-treating the waste
streams. Notably, EMs demonstrate decontamination rates that
are orders of magnitude higher than those of conventional flat
plate electrodes.112,113 Such fast kinetics are primarily ascribed
to the convection-enhanced mass transport in EM under flow-
through configuration, which is the rate-limiting step of most
electrochemical reactions.104,116
Decontamination mechanisms of EMs mainly involve
electrochemical oxidation, while electroadsorption and electro-
repulsion also contribute to micropollutant removal (Figure
3B).29,110 Direct electrooxidation, i.e., electrons transferring
directly from the micropollutant to the anode surface, is
effective for selectively degrading organics that readily donate
electrons. By contrast, indirect electrooxidation via in situ
electrical generation of strongly oxidizing free radicals enables
nonselective micropollutant degradation.
Anodic Membrane Filtration: Hydroxyl-Radical-Medi-
ated Decontamination. Hydroxyl-radical-mediated oxida-
tion is the most widely explored pathway for water
decontamination by EM filtration. Anodic membrane filtration
directly oxidizes water molecules for •OH production without
the addition of chemicals (Figure 3C). •OH, the most potent
reactive oxygen species (ROS), has a high standard potential
(2.80 V vs SHE),117 which enables the nonselective and
complete oxidation of most organic contaminants. The water
decontamination efficiency of such EM filtration depends on
the type of anodic membrane material and the applied voltage.
Electrically generated •OH undergoes different electro-
chemical pathways, depending on the type of anode. For an
“active” anode, •OH can further react with the anodic material
to form a higher oxide, which enables selective, incomplete
oxidation of organic contaminants. In contrast, for a “non-
active” anode, •OH interacts weakly with the anode,
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preventing the further transformation of •OH into a higher
oxide.13,118 Hence, “nonactive” anode materials are adopted in
EM fabrication for high •OH yield, among which Ti4O7 and
BDD are the most efficient anode materials.11,119,120 In
addition, the •OH production efficiency is influenced by the
applied voltage due to the occurrence of the side OER.
Anodic Membrane Filtration: Active-Chlorine-Medi-
ated Decontamination. Due to the ubiquity of chloride ions
(Cl−) in natural waters and wastewater effluents, anodic
membrane filtration can oxidize chloride into active chlorine,
thus enabling water decontamination. Active chlorine includes
the potent reactive chlorine species (RCS), such as Cl• (2.40 V
vs SHE), and free chlorine, namely Cl2 (1.36 V vs SHE),
HClO (1.49 V vs SHE), and ClO− (0.89 V vs SHE).41,121 The
formation of active chlorine can occur both with and without
the involvement of •OH. Specifically, Cl− first undergoes
oxidation at the anodic membrane surface to form Cl•,
followed by Cl2 ; subsequent disproportionation of Cl 2
generates HClO and ClO− (Figure 3D, left pathway).
Alternatively, anodically generated •OH can react with Cl−
to form HClO, ClO−, and RCS (Figure 3D, right path-
way).118,122
While both “active” and “nonactive” anodes can be applied
for active-chlorine-mediated decontamination, their underlying
mechanisms and efficiency for active-chlorine generation are
different. Specifically, “active” anodes mostly perform the left
pathway in Figure 3D due to the absence of •OH, while both
pathways take place at “nonactive” anodes. Additionally,
previous studies have shown that “active” anodes (e.g., IrO2
and RuO2) often yield higher current efficiency for active-
chlorine generation than “nonactive” anodes (e.g.,
BDD).123,124
In addition to anode material, other factors such as side
reactions, solution pH, and water flux influence active-chlorine
formation in EMs. Water oxidation is the main side reaction
competing with chloride oxidation. Additionally, the formation
of weak oxidants, i.e., oxychlorides in higher oxidation states
(e.g., ClO3− and ClO4−), reduces the amount of effective active
chlorine.125,126 Active-chlorine formation by chloride oxidation
is favored at lower solution pH, because the OER side reaction
is hampered at low pH and its occurrence further lowers the
local pH.127,128 Stronger oxidation of the organic contaminants
also takes place at low pH, because of the more facile
generation of RCS and free chlorine (e.g., HClO).121,129
Additionally, decreasing the EM permeate water flux can favor
active-chlorine generation.130−132
Cathodic Membrane Filtration: Electro-Fenton Driv-
en Decontamination. Under cathodic potential, EM can
generate •OH indirectly through electro-Fenton reaction,
featuring in situ electrogeneration of Fenton reagents,
hydrogen peroxide (H2O2) and ferrous ion (Fe2+), for water
purification. In the electro-Fenton process, EM serves as an
electron donor to electrically generate •OH precursor, H2O2
(0.695 V vs SHE),133 by reducing dissolved O2 through a two-
electron oxygen reduction reaction (ORR), i.e., O2 + 2H+ +
2e− → H2O2 (Figure 3E). The Fenton catalyst, Fe2+, is
concurrently regenerated on the EM by electroreduction of
Fe3+. In this way, cathodic EM filtration produces •OH
continually in the bulk stream via Fenton reaction and
oxidatively removes organic pollutants.
The water purification efficiency of the electro-Fenton
filtration depends on the •OH generation rate, governed by the
supply of H2O2 and Fe2+. Efficient H2O2 production
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necessitates the selection of electrode materials with optimal
adsorption energy above the threshold for adsorbing dissolved
O2 and under the level of releasing intermediate species.134
Among potential candidates, carbonaceous materials (e.g.,
graphite,135 CNTs,44 carbon cloth136) are favorable for
cathodic EM fabrication because of their low cost and tunable
morphology. EM operation conditions likewise influence H2O2
production. For example, increasing the electric potential
enhances H2O2 generation through accelerating O2 reduction;
however, excessive voltage leads to H2O formation through
H2O2 decomposition or four-electron ORR (O2 + 4H+ + 4e−
→ 2H2O), thereby reducing ROS generation and increasing
energy consumption in EM operation. In general, EM filtration
operating at a 0.5−2 V (vs SHE) cathodic potential produces
10−40 μM H2O2, which is sufficient for initiating Fenton
reaction.44,137 Furthermore, H2O2 generation is promoted in
O2-rich feed streams, which can be realized by adjusting
transmembrane pressure and flow rate of EM filtration.135,136
In cathodic filtration, the Fenton catalyst, Fe2+, is generated
through three potential pathways: (i) directly adding Fe2+ to
the feed solution,53,138 (ii) electroreduction of Fe3+ in the feed
by EM,44,136 and (iii) using stainless steel as a sacrificial anode
to generate Fe3+/Fe2+ in the feed.65 Cathodic EM maintains
the Fenton catalyst sustainability through electroadsorption of
the oxidized catalyst, Fe3+, on the membrane, and sequentially
in situ regeneration of Fe2+ by electroreduction. Fe2+ could also
be regenerated in the bulk solution through redox interaction
between Fe3+ and pollutants or H2O2, although the reaction
rate of such a pathway is negligible compared with Fe2+
consumption for H2O2 activation. In general, water decon-
tamination efficacy in electro-Fenton filtration increases
proportionally with Fe2+ concentration; however, excessive
Fe2+ consumes •OH and hinders pollutant oxidation.
Compared with traditional water purification by Fenton/
Fenton-like oxidation, in situ electrogeneration of the Fenton
reagent in EM filtration requires fewer chemical additives,
produces less iron sludge, and consumes less energy. However,
electro-Fenton filtration is still favorable under acidic environ-
ments, due to the predominance of the Fenton reaction,
absence of iron precipitation, and reduced decomposition of
H2O2.53,138 Notably, preliminary studies have demonstrated
the feasibility of driving electro-Fenton reaction at a near
neutral pH via in situ regeneration of Fe2+, when the iron
catalyst is bound to a carbon-based structure.44,45,139
Challenges and Limitations. RCS and •OH are the
primary free radicals contributing to water decontamination
and purification in EM processes. RCS are more selective in
oxidizing contaminants with electron-rich moieties.140 The
partial oxidation inevitably results in the formation of
organochlorinated disinfection byproducts (DBPs) in RCS-
based EM filtration processes. In contrast, •OH can lead to
complete oxidation of a large category of organic contaminants
without DBP generation. However, the ubiquitous Cl− in
feedwaters can scavenge the •OH (eq 1) and trigger RCS
oxidation concomitantly (eq 2),141,142 thereby inducing
chlorinated DBP generation:
• However, the implementation of light-activated catalysts is
OH + Cl− → ClOH•− k = 4.3 × 109 M−1 s−1 (1)
ClOH•− + H+ → Cl• + H 2O
k = 2.1 × 1010 M−1 s−1 (2)
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Notably, these DBPs along with the electrogenerated oxy-
chlorides may exhibit higher toxicity than the original
contaminants143,144 and therefore should be carefully moni-
tored for all oxidation-based EM filtration processes in
practical applications.
Anodic EM filtration enables in situ generation of •OH
directly through water oxidation. However, OER is inevitable
under this filtration mode due to the close anodic potentials for
•
OH generation (thermodynamic potential of 2.38 V vs SHE)
and OER using “nonactive” anodes (2.2−2.7 V vs SHE).59
This side reaction can reduce the current efficiency and may
lead to partial blockage of the electroactive sites by the
generated oxygen bubbles.13,118 For cathodic EM filtration,
H2O2 generation is imperative for electro-Fenton reactions.
However, H2O2 generation capability can vary greatly in
different scenarios, depending on the electrode materials, water
quality, and operational conditions.134 Fine-tuning the applied
voltage is thus prerequisite to ensure H2O2 generation in
parallel with Fe2+ regeneration in cathodic EM filtration,
whereas the selection of voltage for anodic filtration is less
restricted. Further, electro-Fenton reactions can only be
applied under acidic or near neutral environments. The
addition of Fe2+ or the use of sacrificial anodes of stainless
steel are also not sustainable due to the loss of iron catalysts.
Therefore, broadening the application of electro-Fenton
filtration in water decontamination and purification neces-
sitates Fenton-like reagents that are active and stable over a
wider pH range.
■
ELECTROCHEMICAL REDUCTION OF NITRATE
Nitrate ions in water can damage the environment and pose
human health hazards. Treated wastewater and agricultural
runoff contain relatively high concentrations of nitrate, which is
difficult to remediate using conventional methods.145 These
wastewaters often are discharged to the environment,
contributing to groundwater contamination, harmful algal
blooms, and disruption of biogeochemical nitrogen
flows.146,147 In the U.S., nitrate contamination is the most
commonly reported water quality violation, and over 40
million people rely primarily on private groundwater wells.148
Current technologies for treating nitrate include ion
exchange, membrane separations, and biological denitrifica-
tion/uptake.148−151 However, processes based on physico-
chemical separations using ion exchange and membranes
produce a concentrated nitrate waste stream that must be
remediated prior to disposal. While biological denitrification
transforms nitrate into more benign forms of nitrogen, this
process has limited applicability due to the long hydraulic
retention times as well as sensitivity to pH. A promising
approach to nitrate removal involves catalytic transformation,
which can achieve high activity and selectivity toward
environmentally benign dinitrogen.152 However, the imple-
mentation of catalytic nitrate remediation is limited by
difficulties related to the recovery of catalytic nanoparticles
suspended in treated water and the requirement of adding
reductant chemicals. Photocatalytic nitrate reduction has been
investigated increasingly in recent years for water treatment.153
limited by geometrical and light absorption capacity
challenges,154,155 and the addition of a hole scavenger such
as formic acid is required.156
Nitrate conversion via the electrochemical nitrate reduction
reaction (NO3RR) represents an approach that avoids the
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Figure 4. Nitrate reduction in wastewater using catalyst-functionalized electrified membranes (EMs). (A) Radar chart of trade-offs among common
electrocatalytic materials employed for the NO3RR. (B) Illustration of nitrate reduction in treated wastewater, agricultural runoff, or well water
sources using an electrocatalyst-functionalized EM cathode into N2 and NH3 products, including possible mechanisms for enhancement in nitrate
reduction performance using EMs. (i) Intensification of intraporous mass transport within small pore sizes and under nanoconfinement may affect
reaction kinetics and energetics, improving activity. (ii) Improvements in reaction selectivity may be achieved using a flow-through configuration
with an upstream anode in order to prevent reoxidation of partially reduced products. (iii) Rejection of foulants by the membrane may protect
active sites and improve electrocatalyst stability. (iv) Electrocatalytic conversion involves the rate-determining step of nitrate conversion to nitrite
(NO2−) followed by the selectivity-determining reduction to desirable N2 or NH3 products. (C) Enhancements in nitrate conversion, selectivity
toward N2, and reaction rate using flow-through catalytic membranes and electrocatalytic membranes. Data are obtained from the literature, with
the corresponding references indicated, for Pd−Cu catalysts either as powders or immobilized on membranes used in stirred tank/diffusion
operation (solid bars), and used in flow-through mode with catalytic membranes (hatched bars). Data from Gayen et al.17 compare the nitrate
conversion and observed NO3RR rate constants (kobs) for catalytic membranes and EMs at −2.5 V vs SHE and water flux of 1440 L m−2 h−1. The
results represent catalytic nitrate reduction with initial nitrate concentrations of 30−200 mg L−1 with acidic conditions.

addition of reductant or hole scavenger chemicals, and
electrochemical reduction technologies have been applied to
treat ion-exchange brines, groundwater, municipal wastewaters,
and urine.157−159 The integration of electrocatalytic processes
with water treatment membranes may provide opportunities to
address some of the challenges associated with conventional
NO3RR.
Mechanisms and Catalysts for Electrochemical
Nitrate Reduction. The NO3RR converts nitrate into either
N2 or NH3/NH4+ as the primary final reaction products, where
innocuous N2 is more desirable. The initial reaction step
involves adsorption of nitrate onto the cathode surface. The
subsequent reduction of nitrate to nitrite is the rate-
determining step and controls the overall nitrate reduction
kinetics:160
NO3− + 2H+ + 2e− → NO2− + H 2O
E 0 = 0.01 V vs SHE
Adsorbed nitrite is rapidly converted to NO(ad), which is
considered to be the key intermediate controlling selectivity
toward final N2 or NH3 production.145 The overall reactions
proceed through complex mechanisms involving many
intermediate species with nitrogen oxidation states spanning
from +V to −III:145,161−163
2NO3− + 12H+ + 10e− → N2 + 6H 2
E 0 = 1.17 V vs SHE (4)
NO3− + 9H+ + 8e− → NH3 + 3H 2
E 0 = −0.12 V vs SHE (5)
Metal catalysts may be used to stabilize different transition
states and reaction intermediates in order to control reaction
selectivity. The solution conditions, including pH, dissolved
oxygen, and the presence of other ionic species, as well as the
reactor geometry and overpotential, also may influence the
(3) reaction pathway.158 The primary challenges for efficient
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nitrate remediation by electrochemical methods consist of
improving the reaction rate, including increasing mass
transport of reactants to active sites, controlling reaction
selectivity toward N2, and enhancing catalyst stability.
Many studies have targeted the development of NO3RR
electrocatalysts with improved properties, although advance-
ments are limited by trade-offs among catalyst activity,
selectivity, and stability (Figure 4A). Coinage metals including
Cu, Ag, and Au, as well as Fe, enhance the reaction kinetics for
nitrate reduction to nitrite, with Cu catalysts demonstrating the
highest activity.164−166 However, these metals also show high
selectivity toward NH3 and are prone to corrosion and
leaching.167−171 Platinum group metals (PGMs), especially Pd,
offer high N2 selectivity and corrosion resistance, with NO3RR
activity decreasing in the order Rh > Ru > Ir > Pd − Pt.166
However, PGMs also are active for the hydrogen evolution
reaction, which competes with the NO3RR. Ir, Ru, and Rh also
suffer from poisoning due to strong and irreversible NO
binding.166,172,173 In addition, PGMs are much more expensive
than nonprecious metals. Bimetallic catalysts can achieve
synergy between the high N2 selectivity of Pt and Pd and the
rapid nitrate reduction kinetics of nonprecious metals, as
observed for Pt−Cu and Pd−Cu catalysts.165,174−177 Cu−Ni
bimetallic combinations can improve corrosion resistance,
stability, and Faradaic efficiencies compared to monometallic
Cu electrodes, especially for treatment of water with high Cl−
concentration.168,176,178 Advances in developing more active,
selective, and stable NO3RR catalysts using lower amounts of
precious PGMs have been successful, although many
challenges related to activity/selectivity trade-offs and mass
transport limitations remain.145,179 Therefore, the integration
of NO3RR electrocatalysts into water treatment membranes
may provide opportunities for improvements beyond those
attainable using catalyst optimization alone.
Nitrate Reduction Using Electrified Membranes.
Major challenges for nitrate removal from water via electro-
chemical conversion involve improving the reaction kinetics,
selectivity to N2, catalyst stability, and mass transport of nitrate
to electrocatalyst active sites, as well as optimizing electrode
and reactor geometry for both scalable and modular
applications. As illustrated in Figure 4B, the combination of
electrochemical nitrate conversion with membrane processes
may be able to address these challenges to improve NO3−
removal processes.
While few examples of NO3RR using EMs have been
reported, several examples of catalytic membranes for
heterogeneous reduction of NO3− with H2 have been
described in the literature, with most studies employing
supported Pd-based bimetallic catalysts on ceramic mem-
branes.180−187 As with the NO3RR, the reaction kinetics of
catalytic NO3− reduction by H2 typically are controlled by
mass transport limitations. Significant enhancements in nitrate
conversion rate as well as selectivity to N2 have been achieved
using flow-through catalytic membranes compared to stirred-
tank/diffusion operating modes or fluidized bed reactors, with
80−100% nitrate conversion reported (Figure 4C).180−182,188
Catalytic activity also was found to increase with trans-
membrane flow rate and reduction of the pore size.186 These
enhancements have been attributed to intensification of
intraporous mass transport with increased flow
rate,182,188−190 concentration polarization effects, and increase
in solvent viscosity related to low ionic and hydrogen
diffusivities under nanoconfinement.187
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In contrast to investigations of catalytic membranes for
nitrate reduction, EMs have only begun to be explored for the
NO3RR. Unlike catalytic nitrate reduction, electrocatalytic
reduction does not require a supply of H2 or other reducing
agents.161,179 Instead, the NO3RR uses electricity to obtain
protons in the aqueous phase and reduce nitrate. Furthermore,
the electricity-driven processes enable voltage settings to
function as an additional parameter for controlling reaction
activity and selectivity. Gayen et al.17 were the first to report
the use of an EM for the NO3RR, employing Pd−Cu and Pd−
In electrocatalysts deposited on TiO2 MF membranes with an
upstream counter electrode. The EM achieved nitrate
reduction from 1.0 mM to below the EPA regulatory standard
(700 μM) with high N2 selectivity (<2% toward NO2− and
NH3) in a single pass (∼2 s residence time). The electro-
catalytic reduction kinetics were an order of magnitude higher
than catalytic NO3− reduction kinetics, as shown in Figure 4C,
resulting in residence times that are >40 times shorter than
those required for catalytic NO3− reduction in flow-through
reactors. The success reported in this study demonstrates the
promising opportunities for improving the activity, selectivity,
and stability of the NO3RR using REMs.
Opportunities for Improving Nitrate Reduction Using
Electrified Membranes. As discussed above, the NO3RR in
conventional electrochemical cells suffers from mass transport
limitations.59,145,191 While improvements in catalytic materials
are required to enhance the kinetics of nitrate reduction to
nitrite, the overall observed reaction kinetics can be augmented
via mass transport enhancements using EMs. As observed with
catalytic membranes, nanoconfinement and improved catalyst
dispersion on high-surface-area supports can enhance transport
of reactants to active sites (Figure 4B,C).180−182,188 EMs
serving as porous flow-through electrodes can enhance mass
transport rates by over an order of magnitude relative to
traditional parallel-plate electrochemical cells, achieving
reactant conversion with residence times on the order of
seconds.59
In addition to improving NO3RR activity, EMs also may
provide an additional knob for controlling the reaction
selectivity. Since the interactions among adsorbates and their
corresponding effects on reaction mechanisms are highly
dependent upon solution conditions, it is probable that the
high flux conditions and modified local solution conditions in
EMs influence the selectivity. For example, higher densities of
surface-adsorbed hydrogen can promote NH3 produc-
tion,192,193 and voltametric analysis suggests that adsorption
of molecular H2 can inhibit the NO3RR.194 Flow-through
catalytic membranes have been shown to improve N 2
selectivity compared to diffusion-operated catalytic reactors
(Figure 4C);182,184,185 therefore, the flow-through conditions
of EMs may facilitate the removal of evolved H2 and retard
ammonia production. Furthermore, nitrate reduction on a
downstream EM cathode under continuous flow conditions
avoids the reoxidation of NO3RR products on the anode
without requiring the use of a separator, which can improve the
overall faradaic efficiency (Figure 4B).17,145
EMs may improve NO3RR catalyst stability. When electro-
catalysts are located within membrane pores, the membrane
may block foulants from reaching active sites and prevent
catalyst poisoning and corrosion (Figure 4B). Depending on
the EM fabrication and electrocatalyst immobilization
methods, leaching of electrocatalysts may be minimized
through stabilization on the membrane material. For example,
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Figure 5. Electrochemical reduction of toxic contaminants using an electrified membrane (EM). (A) Schematic diagram of a typical electrified
flow-through filtration system composed of a DC power supply, a downstream cathodic EM serving as the working electrode, and an anodic metal
ring as the counter electrode (CE). The contaminated feedwater flows through the system from the CE to the EM. Note that an upstream EM is
also used for the system. Schematics (dotted circles) and reaction mechanisms (dashed line boxes) of EM-mediated reduction of (B) nitro-organic
compound (e.g., 4-nitrophenol and NDMA) and (C) heavy metals (e.g., Cr6+).

N-doped graphitic carbon-encapsulated Fe nanoparticles used
for nitrate electroreduction demonstrated high stability, even
under testing with real industrial wastewater, since the
graphitic shells protected the catalysts from the electrolyte
and prevented dissolution and oxidation.195
Opportunities exist for utilizing graphitic and other carbona-
ceous materials to facilitate membrane functionalization with
electrocatalysts, since many examples of nanoparticle electro-
catalysts supported on carbonaceous substrates have been
reported.162,195−198 The addition of metal particles to
membrane materials may increase the water permeability of
the membrane199 due to hydrophilization by hydrophilic
particles200 and modification of the skin of asymmetric
membranes due to the incorporation of particles.180 The
enhanced permeability in turn may promote mass transport to
active sites and improve membrane flux.
Challenges and Limitations. According to a recent
analysis, electrocatalytic nitrate reduction may be able to
compete economically with conventional ion-exchange remov-
al of nitrate,201 where electrochemical transformation can
provide a more environmentally friendly approach. However, it
is not clear whether employing a flow-through EM electrode
offers sufficient advantages over a flow-through electrode. An
EM that combines membrane and electrochemical properties
into one system may offer advantages related to simplification
of use, but real advantages related to synergy and overall
process improvement compared to using separate membrane
and electrochemical processes currently remain uncertain. The
major challenges to improving the competitiveness of NO3RR
technologies hinge on reducing the PGM requirements while
maintaining high reaction activity and selectivity to N2, as well
as enhancing stability and catalyst lifetime. Scalable reactors
with low mass transfer limitations and high electrode surface
areas such as EMs could potentially reduce the PGM
requirements, lowering the costs of electrochemical nitrate
reduction. The influence of using EM materials and
configurations on overall stability will need to be determined,
since the system lifetime will significantly influence the overall
treatment costs. EMs may improve stability, as discussed
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above, but the generation of reactive species from electro-
chemical reactions also may degrade susceptible membrane
materials and impair system reliability.
In addition, applications of nitrate removal from drinking
water (e.g., well water) and treated wastewater involve
relatively low nitrate concentrations, generally below those
employed in bench-scale studies, suggesting that the removal
efficiency may be too low when those methods are applied to
these more dilute water sources. The overall low salt content of
these water sources also limits the conductivity of the solution,
lowering the efficiency of the electrochemical process and
potentially necessitating a preconcentration step or the
addition of salts. Further research is required to assess the
extent to which EMs can advance the viability of using NO3RR
technologies to treat a variety of source waters, including RO
concentrate, ion-exchange brine, and water with low nitrate
concentrations (e.g., contaminated groundwater).
■ ELECTROCHEMICAL REDUCTION OF TOXIC
CONTAMINANTS
Cathodic EMs enable reductive transformation of recalcitrant
toxic contaminants into benign forms. As shown in Figure 5A,
a typical flow-through electrofiltration system is composed of a
direct current (DC) power supply, a cathodic EM as the
working electrode, and an anodic metal ring as the counter
electrode (CE). Both upstream and downstream EM cathodes
are used in the electrofiltration system. The contaminants are
reduced continuously as the contaminated stream flows
through the EM electrode. This section reviews the application
of EMs for reducing nitro-organic compounds and heavy
metals from feedwaters. The reductive destruction and/or
transformation mechanisms of these contaminants by cathodic
EMs are introduced, and the key challenges for improving EM
removal efficiency are discussed.
Nitro-Organic Compound Reduction. EMs have been
exploited for the electrochemical reduction of some refractory,
toxic nitro-organic compounds, such as 4-nitrophenol and N-
nitrosodimethylamine (NDMA), during a flow-through
electrofiltration (Figure 5B).29,202,203 Compared with conven-
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Figure 6. Membrane fouling and scaling control by the implementation of electrified membranes. (A) Representative water constituents and
foulants relevant to membrane separation and their estimated sizes. (B) Schematic diagrams illustrating fouling on a conductive layer (i.e., the
interwoven framework) deposited on a porous membrane substrate: (i) without application of voltage (left panel), (ii) membrane antifouling
process with continuous application of voltage (middle panel), and (iii) membrane self-cleaning process with intermittent application of voltage
(right panel). The electrified antifouling and self-cleaning processes are implemented before and after the formation of the foulant layer,
respectively. (C) Schematic representing the change in the normalized water flux and applied current as a function of time with a continuous
antifouling operating mode. The horizontal red line indicates a constant applied current during the fouling process. The solid and dashed blue lines
indicate the trends of water flux as a function of operating time with and without applied current, respectively. (D) Schematic representing the
change in the normalized water flux as a function of time with an intermittent self-cleaning operating mode. The short dashed (current-off) and
solid (current-on) red lines indicate an intermittent applied current over operating time. The solid and dashed blue lines depict the trends of water
flux with and without current, respectively.

tional catalytic reduction of these organic compounds, EM-
enabled electrochemical removal minimizes the use of
reductants (e.g., NaBH4 and H2) and can be achieved in a
single-pass electrofiltration process. For instance, an EM
functionalized with Co−Pt alloy catalysts demonstrated fast
conversion of 4-nitrophenol to 4-aminophenol at a cathodic
potential of −0.35 V, rendering the 4-nitrophenol industrial
effluent biodegradable.29 The reductive transformation of 4-
nitrophenol by the EM is faster than that using heterogeneous
suspension systems or parallel-plate electrochemical
cells.204−210 The mechanism responsible for the electro-
chemical-reduction of 4-nitrophenol by EMs with metal
catalysts likely involves the electrochemical generation of
atomic hydrogen, which is particularly capable of hydro-
genating N−O bonds to form N−H bonds and H2O.16,211
In addition to metal nanoparticles, metal oxides have also
been deposited on EMs for reducing nitro-organic com-
pounds.29,212 A Ti4O7−CNTs composite EM was developed
for simultaneous adsorption and electrochemical reduction of
NDMA, a carcinogenic DBP.29 The EM achieved 99.99%
removal of 10 μmol L−1 NDMA in a single-pass electro-
filtration (residence time of 22 s) at −1.1 V (vs SHE), equal to
a removal rate of 2.0 mmol m−2 h−1 for NDMA. The near-
complete removal of NDMA in such a short time suggests fast
kinetics of NDMA reduction in the EM. Both experimental
and theoretical studies confirmed that a direct electron transfer
from the EM to the nitro-group of NDMA is the dominant
mechanism, whereas a hydrogen atom transfer mechanism is
negligible. In sum, electrochemical reduction using cathodic
EM flow-through electrofiltration systems represents an
effective means of remediating nitro-organic compounds.
Further improvements in lowering electrical energy con-
sumption and enhancing selective transformation of contam-
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inants should be pursued to enable practical implementation of
these systems.
In sum, electrochemical reduction using cathodic EMs may
provide an alternative approach to conventional electro-
chemical methods for remediation of wastewaters contami-
nated by nitro-organic compounds. Since hydrogen evolution
is ubiquitous in electrochemical reduction processes, lowering
electrical energy consumption of EMs by suppressing hydrogen
evolution from cathodes is challenging. Viable means include
enhancing adsorption of nitro-organic compounds on EMs
through the functionalization of conducting polymers with
benzene rings.137 Enhanced adsorption of these contaminants
enables the electrochemical reduction reaction to occur at
lower potentials, thereby saving more energy. Also, a complete
removal of nitro-organic compounds requires additional
biological processes for denitrification and degradation.
Therefore, enabling denitrification of nitro-organic compounds
by enhancing selective electrochemical reduction with EMs,
beyond merely transforming these toxic organics, is of
paramount importance. When a sequential electrochemical
reduction and oxidation process is implemented, a Janus EM is
expected to decompose thoroughly nitro-organic pollutants in
seconds,115 minimizing adverse environmental impacts.
Heavy Metal Detoxication. Heavy metal ions represent
another category of hazardous pollutants that readily permeate
conventional UF membranes in water and wastewater
treatment. Transforming high-valence heavy metal ions into
low-valence-state metal species such as metal oxides, ions, and
elemental metals by means of electrochemical reduction is an
effective strategy for heavy metal detoxication (Figure 5C).19,21
A CNT-poly(vinyl alcohol) (PVA) composite EM was
fabricated to remove low-concentration hexavalent chromium,
Cr(VI), from drinking water sources by low-pressure electro-
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filtration.93 Results demonstrated that the membrane surface
electrical potential governed overall Cr(VI) removal efficiency.
Due to surface passivation, the voltages applied to the EM for
Cr(VI) reduction were higher than the theoretical value (Cr3+/
Cr6+, 1.33 V vs NHE);213 hence, 45% and 99% of Cr(VI) was
removed by applying 3 and 7 V, respectively,93 suggesting that
a thorough Cr(VI) removal by EM is accomplished with
increased overpotentials.
Theoretically, ORR will be triggered by a cathodic EM at a
low overpotential, leading to the in situ production of H2O2,
unless the electrofiltration system is deaerated. Therefore,
Cr(VI) detoxication through an indirect H2O2-mediated
reduction is potentially viable and energy-efficient.214 To
date, studies for Cr(VI) detoxication by EMs with an
application of low voltage (i.e., <2 V) are lacking. Additionally,
the removal of Cu2+ and Ni2+ by a cathodic EM has not been
discussed herein.81,119
Heavy metal detoxication using cathodic EMs is not effective
for coinage metals, including Cu, Pb, Au, Ag, and Hg. The
reduction of coinage metals generally results in the formation
of elemental metals, which tend to deposit on the membrane
surface or in the membrane pores, thereby severely
compromising membrane permeability. For metals that are
less toxic at their high-valence states (e.g., As and Sb),
electrochemical oxidative transformation using EMs can
potentially detoxify these metals. However, studies on metal
detoxication using anodic EMs are lacking. Lastly, techno-
economic analyses should be carried out to assess whether
heavy metal detoxication via EMs is viable compared to
conventional technologies.
Beyond metals, electrochemical reduction using EMs is a
potentially effective strategy for removing chlorinated organic
compounds, perchlorate, bromate, and perfluoroalkyl and
polyfluoroalkyl substances.56,72,112,215 The possibilities for
removing a variety of toxic contaminants using cathodic EMs
remain to be explored. Notably, the impacts of competing ions
on electrochemical detoxication of contaminants should be
minimized to achieve sustainable and energy-efficient EM
processes during long-term operation, especially in complex
water matrices.
■
MEMBRANE FOULING AND SCALING CONTROL
The performance of traditional membrane processes is largely
constrained by membrane fouling and scaling. Major foulants
that are ubiquitous in natural water sources and wastewaters
include bacterial cells, organic molecules, and inorganic scales
formed by sparingly soluble salts (Figure 6A). These foulants
accumulate on the membrane surface or within the membrane
pores, adversely impacting water productivity and reducing
membrane lifespan. To date, membrane fouling and scaling as
well as corresponding control strategies have been studied
extensively for conventional membrane processes. Recent
studies demonstrated that rendering conventional membranes
electroactive through the implementation of EMs can be
effective for mitigating fouling and scaling.103 The introduction
of a conductive layer on the membrane substrate plays a key
role in improving membrane robustness by controlling fouling
and scaling.
Organic Fouling Control. NOM in drinking water sources
and effluent organic matter (EfOM) in municipal wastewater
are the predominant organic foulants for conventional
membranes.216,217 The accumulation of these organic macro-
molecules on the membrane surface forms a thick cake or gel
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layer, thus blocking membrane pores.218 Compared with
conventional means of membrane fouling control, the
implementation of EMs results in exceptional antifouling
performance by enabling several electrochemical processes.5,219
The efficacy of using EMs to control organic fouling depends
on a variety of factors, such as membrane polarity, applied
voltage, and feedwater chemistry.94,220,221
Electrokinetic phenomena, including electrostatic repulsion
and electrophoresis, are important mechanisms that hinder
accumulation of foulants on the membrane surface. As NOM
and EfOM are negatively charged, the conductive layer
deposited on the membrane substrate is typically used as a
cathode to repel the negatively charged organic foulants. In this
way, the cathodic EM increases the electrostatic energy barrier
to the attachment of foulants.103 Studies have demonstrated
that EMs with negatively charged surfaces mitigate membrane
fouling by humic acid and alginate through a continuous
application of a voltage of 2 V.110,222 Similarly, the electro-
phoretic effect enabled by a relatively low voltage can also drive
the charged foulants to migrate away from the membrane
surface, thus inhibiting organic fouling. Modeling studies
suggest that the electrophoretic effect is less pronounced for
organic fouling reduction than the electrostatic repulsion effect
due to the smaller electric driving force.103,220 The ionic
strength of the feed solution is critical for influencing the
efficacy of electromediated fouling mitigation. Notably, an
excessive solution ionic strength negates the overall antifouling
performance due to charge screening and electrical double-
layer compression.103
Changes in membrane morphology and structure tuned by
the change of an external electric field is another approach to
retard organic fouling of EMs.223,224 This electroresponsive
antifouling performance is dependent on the featured
membrane materials.222,223 For example, an electroresponsive
polymer with cross-linked ferrocene (Fc) and β-cyclodextrin
(β-CD) groups on a PTFE membrane support was fabricated
to prevent membrane fouling by proteins.225 Specifically, this
study demonstrated that by decross-linking the Fc/β-CD
complexes via charging of the fouled membrane, the attached
proteins could detach from the membrane surface, achieving
organic fouling control. In another work, a polypyrrole-
dodecylbenzenesulfonate (PPy-DBS) EM with electrically
tunable pores was developed to alleviate pore blocking by
humic acid.35 Specifically, the pore size of the PPy-DBS
membrane can be enlarged to enhance membrane backwashing
under positive (i.e., oxidation) voltage and recovered to ensure
salts rejection under negative (i.e., reduction) voltage.
Foulant degradation by electrochemical oxidation is an
alternative and perhaps more practical pathway for organic
fouling mitigation in EMs. ROS such as H2O2, superoxide
(O2•−), and •OH have been confirmed to be responsible for
degrading and decomposing refractory organic fou-
lants.115,116,222,226 Generally, these active species are generated
in situ by either electrochemical ORR or electro-Fenton
reactions in cathodic EMs.227,228 In addition, microbubbles
generated from the cathodic EM surface via water electrolysis
facilitate mixing and shear forces for the detachment of organic
foulants from the membrane surface.32,229 Further, anodic EMs
are employed to tackle irreversible organic fouling via the
implementation of electrochemical oxidation reactions, mini-
mizing adverse impacts of organic fouling by in situ membrane
self-cleaning.221,230
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Figure 7. Biofouling control in electrified membrane (EM) filtration by inactivating bacteria and preventing biofilm formation. (A) Under anodic
filtration, bacteria are inactivated by EMs through direct oxidation and indirect free radical-mediated oxidation. (B) Under cathodic filtration, EMs
reduce attachment of bacteria via (i) electromigration of bacterial cells away from the membrane surface and (ii) NP regeneration in metal
nanoparticle enabled antibiofouling. (C) Altering the direction of direct current can increase the energy efficiency of biofouling control in EMs.
Initially, EMs work under low voltage cathodic filtration to reduce bacterial attachment (①). When water flux decline reaches a predetermined
value, a reverse current is applied, and EMs operating at moderate voltage anodic filtration oxidize the attached microorganisms (②). After bacteria
inactivation, EMs are switched to low voltage cathodic filtration to detach cell debris (③).

Inorganic Scaling Control. Inorganic scaling, induced by
species like Ca2+, SO42−, and silica, is particularly problematic
in brackish water desalination.231 Scaling occurs in RO and NF
processes when the concentration of these inorganic ions
exceeds their solubility threshold at the membrane/water
interface, causing severe water flux decline. To date, strategies
that implement electrochemical means to control scaling have
focused mainly on changing membrane local pH and
disrupting crystal nucleation.9,10,34
Altering localized pH on the membrane surface through
electrochemical water splitting reactions can be used to control
scaling of pH-sensitive scale.10 A polyamide RO membrane
functionalized with CNTs served as an anode to mitigate
calcium carbonate (CaCO3) scaling by applying an inter-
mittent voltage of 2.5 V.34 Specifically, anodic water oxidation
on the membrane surface created a local low-pH environment,
which prevented the formation of CaCO3 crystals. In another
study, cathodic water electrolysis was employed by a
polypropylene membrane coated with a CNT/poly(vinyl
alcohol) layer for silica scaling control in membrane distillation
(MD).9 In this approach, a local high-pH environment is
formed by the application of an intermittent DC of 20 mA,
thereby preventing the formation of scale due to the increase of
silica solubility.
Another approach for scaling control, suitable for sulfate-
based crystalline scale which is not affected by pH, is through
an anodic membrane surface.34 Specifically, to prevent gypsum
(CaSO4·2H2O)scaling on RO membranes, a continuous
application of 1.5 V DC to a conductive layer deposited on
the membrane has been suggested. Due to the positively
charged anodic membrane surface, a sulfate ion (SO42−) layer
was formed close to the membrane surface, thereby retarding
gypsum development. Although gypsum crystals still formed
outside the SO42− counterion layer, a high cross-flow velocity
can be employed to carry away the formed crystals.
We note, however, that scaling mitigation is only relevant to
desalination membranes, such as RO and NF, where inorganic
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scaling is a major hurdle for high water recovery. These
mature, state-of-the-art membrane technologies employ low-
cost spiral wound membrane modules that enable compact and
reliable operation of membrane systems. Application of EMs to
mitigate scaling would be quite challenging, as it requires the
development of entirely new module designs which will
significantly increase the cost of desalination. Electroactive
coatings could also compromise water flux and salt rejection,
impairing product water quality and increasing energy
consumption. Hence, more viable approaches to prevent
membrane scaling should be considered, including pretreat-
ment of feed waters to remove scale-forming species,
innovations in process design to reduce residence time in
membrane modules below the induction time for scale
formation, or effective addition of antiscalants.
Importance of Electrofiltration Mode in Fouling and
Scaling Control. Electrofiltration operating mode plays an
important role in membrane fouling and scaling control. As
shown in Figure 6B (left panel), without applied voltage,
organic fouling and inorganic scaling of a membrane with a
conductive carbonaceous material (e.g., CNTs) layer are
inevitable, since CNTs have functional groups favoring organic
foulant adhesion and heterogeneous nucleation of inorganic
scale.103 To prevent membrane fouling, it is imperative to
apply a continuous voltage to the electrically conducting
surface (Figure 6B, middle panel). Continuous electrification
of the membrane surface creates a potential-induced energetic
barrier to foulant attachment, achieving membrane antifouling
and adequate water production, as illustrated in Figure 6C.
However, despite the potential for membrane fouling control,
the continuous electrofiltration operating mode is energy-
intensive.
Given the high energy consumption of continuous voltage
application, an intermittent application of voltage is more
sustainable for practical applications (Figure 6B, right panel).
As shown in Figure 6D, applying voltage when the water flux
starts to decline is essential to prevent the membrane surface
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from forming an irreversible fouling layer. Studies have shown
that short-term (1−10 min) in situ electrified membrane self-
cleaning is able to remove irreversible organic foulants.31,32
Combined with a short backwashing procedure for removing
reversible foulants, a CNT-functionalized ceramic membrane
achieved a near-complete water flux recovery under repeated
fouling, backwashing, and self-cleaning cycles.18 This com-
bined, chemical-free cleaning strategy is viable for reducing
system operation and maintenance costs. Additionally, the
intermittent, short-duration electrofiltration operation mode is
conducive to minimizing the impacts of electrochemical side-
reactions, achieving low-cost, sustainable fouling control.
■ BIOFOULING CONTROL
Biofouling originates from the deposition and growth of
microorganisms, mainly bacteria, and their subsequently
produced extracellular polymeric substances on the membrane
surface.232 Biofouling deteriorates membrane performance and
increases energy consumption. Numerous strategies have been
proposed for designing antibiofouling membranes, by altering
surface physicochemical properties to prevent the initial
attachment of bacterial cells or inhibit bacterial growth on
the membranes. However, most of these strategies only delay
the biofilm formation or minimize the impacts of biofilms on
membrane performance.233 EMs provide several chemical-free
approaches that are able to achieve simultaneous bacteria
inactivation and biofilm removal (Figure 7). Herein, we
address biofouling control strategies in EMs that prevent or
hinder the development of biofilms on the membrane surface
through bacteria inactivation.
Electrooxidation via Anodic Filtration. Anodic EMs
serve as electron acceptors under an applied electric field while
also adsorbing negatively charged bacterial cells on the
membrane. Bacteria on EMs or in solution are inactivated
during anodic filtration by either direct or indirect electro-
oxidation pathways (Figure 7A). The direct oxidation pathway
transfers electrons from the bacteria to anodic EMs, leading to
cell inactivation by triggering cellular oxidative stress.234,235
Direct oxidation is a contact-mediated bacteria inactivation
process with a required anodic potential below that of water
electrolysis, thereby minimizing side reactions and toxic
byproduct formation.2−5 However, bacteria inactivation by
direct oxidation is limited (60−90%),28,234−236 indicating that
a direct oxidation pathway alone is not adequate for biofouling
control in long-term membrane operation.
Indirect oxidation depends on electrogeneration of highly
reactive species (e.g., •OH and Cl•) on anodic membranes
through electrooxidation of water molecules or chloride ions.
Compared to direct oxidation, indirect oxidation exhibits
superior bacteria inactivation, which is likely ascribed to one or
more of these pathways: (i) reactive species oxidize proteins
and lipids in the cell membrane leading to leakage of
intracellular substances (e.g., electrolytes, enzymes);237 (ii)
reactive species damage key metabolism enzymes (e.g., catalase
and superoxide dismutase) and inhibit cell growth;238−240 (iii)
the electric field adversely impacts cell membrane potential,
which hinders synthesis of adenosine triphosphate and
interferes with cell activity.237,241 In general, biofouling control
in anodic EMs primarily depends on ROS/RCS generation,
which increases as the applied electric potential is increased.242
However, increasing electric field strength increases side
reactions, such as the OER and the formation of chlorinated
DBPs, thereby drastically decreasing EM current efficiency.
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Therefore, the applied voltage for ROS/RCS generation
should be fine-tuned to achieve effective biofouling control
in EM operation with optimal current efficiency.
Metal Nanomaterial Assisted Cathodic Filtration.
Cathodic membranes suppress bacterial deposition by electro-
migration of negatively charged microbes away from the
membrane surface. Moreover, the cathodically generated H2O2
influences gene expressions related to cell respiration and
energy metabolism,28,243 thus decreasing the density and
viability of bacteria on the EM. Compared to •OH, H2O2 has a
much lower oxidation potential, which is insufficient to achieve
the desired level of bacterial inactivation.28 To address this
problem, functionalization of cathodic membranes with metal
nanoparticles (NPs) (e.g., AgNPs,244 CuNPs,245 AuNPs246,247)
has been proposed as an alternative strategy for biofouling
control in cathodic EM filtration (Figure 7B).
The mechanism of bacteria inactivation by metals is complex
and not yet fully understood. Several potential pathways for
cell death have been proposed: (i) the oxidation of metal NPs
releases electrons and stimulates ROS generation, thus
inhibiting the proliferation of attached bacteria;248 (ii) the
contact between metal ions and bacteria depolarizes the cell
membrane and causes abnormal bacterial growth;249 (iii) the
binding of metal ions to sulfur- or phosphorus-containing
biomolecules (e.g., proteins and DNA) distorts the cell
structure and disrupts metabolic processes.250 However,
metal-NP-functionalized membranes have short lifespans as
biocidal particles dissolve over time. This problem can be
alleviated by tethering metal NPs to a cathodic membrane
which serves as an electron donor. Cathodic EMs maintain the
activity of tethered AgNPs/CuNPs through electroadsorption
of dissolved metal ions, Ag+/Cu2+, to the membrane and in situ
regenerating the biocidal NPs by electroreduction.222,251 Such
electrochemical- assisted metal NP regeneration prevents
massive metal leakage and prolongs the lifespan of the
antimicrobial cathodic EMs. Functionalization of EMs with
AgNPs and CuNPs can significantly mitigate water flux decline
associated with biofilm development during cathodic filtra-
tion,222,251 and Ag+ concentration in the effluent is reduced by
2 orders of magnitude by applying a voltage of 2.0 V. However,
the long-term biofouling-resistance in metal nanomaterial-
assisted cathodic filtration requires further evaluation.
Energy-Efficient Operation Mode for Biofouling
Control. Compared to DC anodic and cathodic filtration,
alternating current (AC) with periodic changes in direction
and voltage may be advantageous for preventing biofouling. In
AC mode, bacteria inactivation and cell detachment occur
concomitantly on the electrode.252,253 Moreover, the net
charge in a complete symmetrical AC cycle is zero, minimizing
chemical reactions and reducing the risk of electrode
corrosion.254 However, most studies highlighting the merits
of AC mode are based on flow-by electrolysis, which is
different from the flow-through mode of EMs.255,256 The
feasibility of incorporating AC in EM biofouling control has
yet to be explored. Hence, there is a need for a systematic
comparison of biofouling control in AC- and DC-driven EMs
for biofouling control.
Considering the different electric potentials required for
biofouling mitigation in DC-controlled cathodic (1−2 V)
versus anodic (near 3 V) filtration, EM operation with
alternating direct current is proposed here as a potentially
energy-efficient strategy (Figure 7C). A complete operation
cycle consists of three stages. Initially, the EM works under
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Figure 8. Virus removal and inactivation in electrified membrane (EM) filtration. (A) Schematic depicting viruses passing through a conventional,
nonconductive membrane and inactivation by anodic EM filtration via direct oxidation and reactive-oxygen or -chlorine-species (ROS/RCS)-
mediated indirect oxidation. (B) Schematic showing the influence of solution chemistry on virus inactivation in EM filtration. Natural organic
matter (NOM) competes with viruses for ROS/RCS consumption, which reduces inactivation efficacy. Solutions having a high NaCl concentration
facilitate RCS production in anodic filtration and promote virus inactivation. Divalent ions (e.g., Ca2+) cause virus aggregation, which enhances
virus removal via physical retention and then electrooxidation by EMs. (C) Comparison of applied voltage, water flux, and corresponding virus
removal efficiency in different categories of flow-through filtration membranes. The water flux of membranes during virus inactivation is presented
as liters per square meter per hour (LMH). Solid and dashed ovals indicate log virus (triangle) and bacteria (circle) inactivation under identical
conditions. EM electrooxidation potentially achieves desired virus inactivation with relatively low voltage and moderate water flux. Data are
obtained from selected literature. The model bacteria mainly used are Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis). Data shown are
mainly for MS2 and UZ1 viruses.269−278 (D) Enhancing virus removal in anodic EM filtration with optimized membrane electrode geometry.
Engineered nanowire, nanorod, or nanodot additions to membrane geometries potentially increase nanoscale mass transport by locally amplifying
the electric field,278 concentrating reactants, increasing temperature,21 and enhancing flow convection.19

cathodic filtration with low electric potential (below the value
required for ORR) to reduce bacterial deposition by
electromigration. When water flux decline reaches a
predetermined value (e.g., 15%), the direction of applied
current is reversed, and the electric potential is increased in
order to electrically generate ROS/RCS in situ. Electrically
generated reactive species inactivate the attached bacteria and
disperse bacterial colonies. After such electrically driven self-
cleaning, the EM works under low voltage cathodic filtration to
electrically detach cell debris, which are flushed away from the
membrane surface by crossflow.
In addition to the anodic and cathodic antibiofouling
pathways discussed above, other strategies can also impart
biofouling resistance in EM operation. Examples include
operating EMs under resistive mode to inactivate or detach
bacteria by increasing membrane surface temperature;253
generating H2 microbubbles through electrolysis to detach
bacteria or loosen biofilms developed on EMs;257 and
significantly enhancing the local electric field to inactivate
bacteria by electroporation (discussed in the following Virus
Inactivation section).258 Although some positive results were
demonstrated, such studies were based on experiments with
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simplified conditions, such as synthetic water solutions and
model bacteria. Moreover, the scale-up of these technologies
still faces critical challenges, considering their unique working
conditions (e.g., utilizing noble metal electrodes) and
potentially high energy consumption (e.g., resistive heating).
Therefore, a comprehensive evaluation of antibiofouling
performance under different operation modes with realistic
water chemistries is required. Furthermore, there is a need for
a comprehensive techno-economic analysis to evaluate the
economic viability of these strategies for biofouling control.
Challenges and Limitations. Biofouling control is
particularly important for RO membranes used in seawater
desalination and wastewater reuse. This mature membrane
technology employs low-cost, high-surface-area spiral wound
membrane modules that enable modular and highly efficient
operation of membrane systems. Modifying the membrane to
function as an anodic or cathodic EM would be impractical as
it requires the development of new module designs which will
significantly increase the cost of desalination. Furthermore,
such surface modifications could significantly impact the water
permeability and salt rejection of the membranes. Hence, a
more viable approach to preventing biofouling in RO
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membranes would be effective pretreatment of feedwater or
the development of chlorine-resistant membranes.259 This
discussion therefore suggests that EMs for biofouling control
would be more suitable for UF and MF membranes. Further,
EMs should be designed to meet multiple objectives, such as
fouling and biofouling control as well as degradation of water
contaminants.
■ VIRUS INACTIVATION
The outbreak of the global COVID-19 pandemic has directed
universal concern toward the threat of pathogens to public
health. As one of the most common media for microorganism
transmission, natural water bodies and wastewater are at high
risk of pathogen contamination, motivating exploration of
technologies for pathogen removal and inactivation.260,261
Traditional MF/UF membrane filtration is an effective
approach for removing most waterborne pathogens (i.e.,
protozoa and bacteria); however, MF/UF fails to completely
reject viruses, which are much smaller than bacteria.234
Therefore, the demand for enhancing membrane performance
in virus inactivation, in addition to water production, is
growing. Since they feature simultaneous membrane filtration
and in situ electrochemical reactivity, EMs possess potential
advantages in virus disinfection.
Virus Inactivation by Anodic EMs. EMs remove viruses
by integrating physical retention with electric field induced
electroadsorption and electrooxidation (Figure 8A). Applying
EMs as the anode electrically adsorbs negatively charged
viruses onto the membrane surface during filtration,262 while
simultaneously inactivating viruses through generating oxida-
tive stress via direct and indirect electrooxidation.234,236
Additionally, reactive oxidants such as ROS and RCS are
widespread in the permeate, preventing viral propagation and
securing water safety. Oxidant generation rates are critical to
virus inactivation in EM filtration, which is greatly influenced
by membrane materials, applied voltage, and feedwater
chemistry.
CNTs are favored for fabricating anodic EMs over a variety
of conductive materials, such as titanium suboxide and silver
nanowires.263−265 Without applying an external voltage, a
CNT-EM has achieved 4 log virus removal (with an initial
virus concentration of 107 PFU/mL) through aromatic π-band
induced adsorption. When an external potential (2 and 3 V)
was applied to the EMs, no culturable viruses (>6 log removal)
could be detected in the permeate.234−236 Viruses are
inactivated in electrofiltration with a residence time (in CNT
reactor) of only 30 s,234,236 likely because of (i) the damage of
viral morphology under electric field236 and (ii) the induced
oxidative stress on viral envelope, capsid protein, and nucleic
acids caused by ROS/RCS.266,267 Compared with conventional
electrochemical approaches for point-of-use virus inactiva-
tion,268 the energy consumption of the CNT-EM is lower: only
8.3 Wh m−3 of permeate (with applied voltage of 2 V as an
example).234
Realistic solution chemistries of feed waters affect not only
electrochemical reactions (e.g., oxidant generation) but also
viral migration and aggregation behavior, thereby influencing
the viral inactivation effectiveness of EMs. Three well-studied
solution components affecting viral inactivation are NOM,
chloride ions, and divalent cations (Figure 8B).236,279 Co-
occurring NOM in feedwater likely impacts disinfection
efficacy of EMs through (i) competing with viruses for oxidant
consumption, (ii) preventing the aggregation of viral particles
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by electrosteric stabilization, and (iii) preventing virus−
membrane contact by blocking EM reactive sites or binding
with viruses to create a shielding layer.236 Chloride ions
remarkably improve virus inactivation efficacy of a CNT filter
at an applied voltage over 2.3 V, as such potential is capable of
initiating the one-electron oxidation of chloride ion to
RCS.18,236 Although the RCS generation is favorable for viral
removal in EM operation, the risk of DBP formation is a
problem. Therefore, DBP concentration should be continu-
ously monitored when high-concentration chloride ions coexist
with viruses in the feedwater. Divalent cations, most notably
Ca2+ ions, lead to virus aggregation by charge neutralization or
through bridging between viral particles and NOM (or CNTs),
and subsequently enhance virus removal by EMs through
physicochemical filtration.264
Efficacy of Viral Removal. Besides EMs, other types of
membranes, such as nanocomposite membranes and flow-
through electroporation, have been explored for viral
disinfection. Nanocomposite membranes functionalized with
metal NPs (e.g., AgNPs,272,273 Cu2O,274 TiO2NPs,269 Ag-/Cu-
TiO2 hybrid NPs270,271) show appreciable viral removal (3−5
log) through synergy between physical retention by the
membrane and the biocidal property of metal NPs (Figure
8C).269−274 As the activity of nanocomposite membranes
mainly relies on contact between viruses and anchored NPs,
low permeate flow rate (permeate flow rates of 101−102 L m−2
h−1) are required for viral disinfection.
Electroporation employs sharp tip structures (e.g., metal
nanowires, NWs) on a membrane electrode to locally enhance
the electric field;6,13−15 this induces a transmembrane potential
that results in pore formation in the lipid bilayer of enveloped
viruses and subsequent viral inactivation.280,281 Although
electroporation exhibits superior bacteria disinfection (>6 log
bacterial removal under a flow rate of 103−104 L m−2 h−1)
(Figure 8C),258,276,278,282 its virus removal (1−2 log) is
significantly lower under similar conditions. Moreover,
disinfection via electroporation of nonenveloped viruses has
not yet been investigated. Among all categories of membrane,
EM filtration achieves comparable performances for both virus
and bacteria disinfection under a flow rate of near 100 L m−2
h−1 with moderate applied potential (2−3 V).234,236 The
relatively long retention times needed is a major drawback, as
these cannot be achieved in practical membrane filtration
without recirculation.
Altering membrane−electrode geometry can enhance viral
disinfection efficacy. Narrowing membrane channels induce
nano/micro-scale spatial confinement in EM filtration,
promoting electrochemical reactions by increasing the
frequency of collisions between viral particles and electrically
generated oxidants.23 Experimental and computational studies
have demonstrated that patterned nanostructures enhance
mass transport in the electrode−solution interfacial region,
likely through the following pathways (Figure 8D): (i)
nanostructures locally amplify the electric field, which increases
oxidant generation on electrodes;263,283 (ii) patterned nano-
geometry results in nano/microscale turbulence, increasing
convection and local mixing of reactants;19 (iii) the geometric
morphology leads to spatially confined redox reactions at
electrode/solution interfaces that generate temperature gra-
dients along the nanostructures, which then accelerate local
convection and enhance reactant mobility.21 However, the
practical application of this strategy faces challenges concern-
ing the stability of patterned nanostructures under complex
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water matrices and the fabrication of the sophisticated
nanostructures inside porous EMs. New materials and
technologies to fabricate nanostructure engineered EMs,
which can provide a large surface area, high conductivity,
and high corrosion resistance, merit further exploration.
Furthermore, detailed techno-economic analyses should be
carried out to assess the economic viability of these
technologies compared to conventional desalination methods.
Challenges and Limitations. While several studies exist
on EMs for virus inactivation, EMs designed solely for this
purpose are unlikely to reach economic viability as
technologies involving chemical disinfection or membranes
with smaller pore sizes (e.g., “tight” UF, NF, and low-pressure
RO) can already achieve virus disinfection/removal. In MF/
UF processes, virus inactivation may be concomitantly
achieved when designing EMs for water decontamination
and purification via electrochemical oxidation. Hence, many of
the outlined challenges for electrochemical oxidation are also
relevant to challenges specific to virus inactivation. For
example, testing conditions of EMs for virus inactivation
must extend beyond a single model virus and ideal water
matrices due to the impacts of species variations and the
presence of NOM combined with low virus concentrations.
Additionally, nanostructure-enabled EM processes for virus
inactivation generally lack practicality, because of the
sophisticated methods for material fabrication and the
unpredictable operational stability under an electric field and
harsh water flow conditions.
■ PERFORMANCE LIMITING AND ENABLING
FACTORS
Stability of Electrode Materials. The stability of
electrode materials is of vital importance for long-term EM
operation. Materials are usually less susceptible to deactivation
when serving as the cathode, but often are not anodically
stable.48 Electrode passivation, which involves the formation of
an inhibiting layer of polymers or byproducts, usually occurs in
“active” anodes, leading to a significant decrease of electro-
activity.284,285 Carbonaceous materials such as CNTs are the
most common conductive materials used for EM fabrication.
These materials favor the electropolymerization of phenols,
especially under low anodic potentials, due to the generation of
intermediate phenolic radicals that are polymerized on the
anode surface by radical chain reactions.20,286 In addition, the
adsorption of intermediates during electrooxidation, such as
carboxylic acids, can also passivate the electrode.144 Although
operating EMs at a potential over that for water oxidation can
prevent electropolymerization, corrosion of carbonaceous
materials is inevitable at high anodic potentials.90,287 The
formation of oxygen-containing functional groups interferes
with electron transfer and disrupts the carbonaceous structure.
Several studies have focused on increasing the stability of
CNTs by anchoring metal nanoparticles or mixing with
polymers such as poly(vinyl alcohol).220,288 EM stability also
may be compromised due to the oxidation of the membrane
substrate by active chlorine species, which are easily generated
from chloride ions at the anode.289
In “nonactive” anodes, the in situ generation of •OH on the
EM surface minimizes the impact of electropolymerization
through oxidization.37 Among these “nonactive” anodes, doped
SnO2, BDD, and Ti4O7 demonstrate good chemical resistance
during water treatment. Doped SnO2 has a short service life,
although it shows good activity for •OH generation.290 The
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lack of porosity for BDD limits its applicability for EM
fabrication, as discussed in the section Preparation and
Operation Modes of Electrified Membranes. Ti4O7 EMs are
relatively stable during operation due to their resistance to
corrosion under both alkaline and acidic conditions.59
Nevertheless, characterization results suggest the formation
of TiO2 on the Ti4O7 surface due to passivation.291
The possibility of metal dissolution and leaching of electrode
materials may pose risks to the environment and human
health. Several nanomaterials show cytotoxicity to aquatic
organisms, causing cellular metabolic disturbances.292 The
application of single-atom catalysts might be a solution to
avoid this problem.293 In addition, EMs should avoid the use
of toxic heavy metals, such as lead and antimony, in order to
prevent contamination of the treated water. More work is
needed to develop EMs with high stability and low toxicity for
long-term operation.
Background Electrolyte Solution. Electrolyte solution
affects the performance and stability of EM processes primarily
based on the solution conductivity, composition, and pH.
Generally, EM electrical performance is enhanced with
increasing solution conductivity.289 Lab-scale studies com-
monly use synthetic solutions with salt concentrations around
100 mM in order to increase conductivity. Although such high
concentrations can be found in brackish waters or in
concentrates from advanced membrane-based wastewater
reuse, salt contents are much lower in many other feedwater
sources that are treated by membrane technologies, such as
municipal wastewater and drinking water. Thus, the feasibility
of operating EMs with solutions of low conductivity requires
further investigation.
Sulfate and chloride are common ions in water and
wastewater sources. During anodic oxidation, the formation
of sulfate radicals and persulfates from sulfate ions at the
surface of “nonactive” anodes enhances oxidation reactions.294
The generation of RCS in the presence of chloride ions
increases the selectivity of •OH-mediated oxidation toward
contaminant degradation.295 However, other ions in the
feedwater may affect the treatment through radical scavenging
(eqs 6 and 7 below).296,297 Competing reactions of •OH with
NOM also lower the removal efficiency during •OH-mediated
electrooxidation (eq 8):298
•
OH + CO32 − → CO3•− + OH−
k = 3.9 × 108 M−1 s−1 (6)
•
OH + HCO3− → CO3•− + H 2O
k = 8.6 × 106 M−1 s−1 (7)
•
OH + NOM → Products k = 2.2 × 108 L
(mol C)−1 s−1 (8)
Additionally, some electrolyte ions can competitively adsorb to
the active sites of the EM, which decreases the electrocatalytic
activity and affects the kinetics of specific reactions, as is the
case for nitrate reduction.145,166
The influence of pH is an important consideration in EM
operation. Notably, water electrolysis results in either proton
or hydroxide ion production in the porous structure when the
EM is used as the anode or cathode, respectively, leading to a
gradient of pH between the membrane surface and the bulk
solution:12,130
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Figure 9. Electrical energy consumption during electrified membrane operation. (A) Energy consumption per order (ECEO) of different direct
electrooxidation, electro-Fenton, and hydroxyl-radical (•OH)-mediated anodic oxidation processes for organic contaminant degradation. The
median ECEO for all these EM-based oxidation processes is 0.4 kWh m−3. (B1) Specific energy consumption (SEC) of different membrane
antifouling and self-cleaning processes and (B2) energy consumption per effective membrane area (ECA, left boxplot) and electricity application
time required for sufficient water flux recovery (right boxplot) of the membrane self-cleaning processes. Median values of the energy consumption
are shown next to the median lines. Data used for the analysis are collected from papers published in the past 10 years (2011−2020).

2H 2O → O2 (g) + 4H+ + 4e−
2H 2O + 2e− → H 2(g) + 2OH−
The modification of local pH at the EM anode can prevent
scaling on the membrane. In contrast, the deposition of salts
within the porous structure should be taken into consideration
when the EM serves as the cathode. As for contaminant
degradation, the low pH that arises in the porous structure
facilitates RCS-mediated oxidation, whereas neutral and
(9) The formation of toxic DBPs, especially chlorinated organic
compounds and ClO4−, pose environmental concerns. These
byproducts are formed in the presence of active chlorine
(10) species and are usually more recalcitrant than the parent
molecules.143,304 Chlorinated organic compounds can be
adsorbed by carbonaceous structures and then converted by
•
OH, suggesting a possible strategy for minimizing their
release.48 However, ClO4−, the least reactive oxidant of the
chloro-oxyanions, is extremely stable under reductive and
oxidative conditions and therefore must be controlled
separately.

alkaline conditions are favorable for •OH generation through
water oxidation.37 The optimal pH for the electro-Fenton
process is generally close to 3 in order to promote •OH
generation from H2O2 and prevent iron precipitation.53,135,299
When steel mesh is used as the EM substrate, the performance
of the electro-Fenton process drops sharply with the increase
of pH.82 However, when iron is bound to a carbon-based
structure, the in situ regeneration of Fe2+ enables the electro-
Fenton process to operate near neutral pH.45,139,300
Operational Challenges. Potential drop across the EM
reduces the available electrochemical surface area and
interferes with the contaminant removal reactions.12,59
Simulations show that the potential drops significantly in a
porous structure with the distance from the counter electrode,
influenced by pore radius, specific solution resistance, exchange
current density, and overpotential.301 In •OH-mediated anodic
oxidation, the anodic potential is able to drive •OH production
only in the top portion of the EM active layer.33 Deeper in the
pores, only direct electrooxidation occurs; therefore, the overall
oxidation efficiency decreases and electropolymerization is
induced. Applying higher potential and/or increasing the
residence time by reducing the water flux could achieve
sufficient contaminant removal when reactions are under
charge transfer control, whereas increasing the thickness of the
conductive layer would be ineffective.
Microbubbles are generated through eqs 9 and 10 when the
potential exceeds the OEP. These bubbles induce a pressure
drop across the EM and affect the electrochemical activity by
blocking surface sites.33,72 However, microbubbles generated at
the membrane surface also can act as a physical barrier to
prevent fouling or increase the scouring of deposited foulants
for membrane self-cleaning.67,302,303
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■
ELECTRICAL ENERGY CONSUMPTION
Electrical energy consumption represents a chief barrier to
achieving sustainable and economically viable EM processes.
Specific energy consumption (SEC) during EM operation can
be calculated as228,289
UcellIt
SEC =
V (11)
where Ucell is the applied cell potential, I is the current, t is the
operation time, and V is the filtration volume.
Energy consumption increases exponentially with the
current since Ucell is proportional to I. Current, or the more
commonly used term current density, determines the overall
performance of the EMs.37 The efficiency of EM processes can
be evaluated as the ratio of the theoretical equivalent current
density for a specific reaction to the actually applied current
density, i.e., current efficiency (also known as faradaic
efficiency).11,305 In general, an increase in current density
enhances contaminant removal for charge transfer-controlled
reactions.59 Conversely, when reactions are mass transport
limited, an increase in current density leads to decreased
current efficiency and unchanged or even lower removal rate
due to the intensification of competitive reactions such as
water electrolysis. Additionally, the energy consumption in a
membrane process is also affected by the filtration volume per
operation time, i.e., permeate flow rate. An increase in
permeate flow rate is expected to lower the energy
consumption and improve the current efficiency due to the
convection-enhanced mass transport. However, when the
process is limited by charge transfer, the removal efficiency
might be reduced because of the decrease in residence time.
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ACS ES&T Engineering
We calculated the electrical energy consumed by different
EM processes for contaminant oxidation and fouling mitigation
using data from papers published in the past 10 years (details
in Tables S2 and S3, Supporting Information). Water
disinfection processes to inactivate microorganisms by EMs
are not included because, in addition to the electrochemical
inactivation, the membrane provides a physical barrier for
separating microorganisms. The energy consumption for
electrical water disinfection using a flow-through configuration
without a membrane structure is low (0.002 kWh m−3)
because of the high mass transport efficiency.263 Therefore, the
energy required for water disinfection using an EM would be
similarly low.
Energy Consumption of Contaminant Oxidation. The
electrical energy consumption of contaminant oxidation is
evaluated as the energy consumption per order (ECEO):112
ÄÅ ÉÑ
ÅC Ñ
Q logÅÅÅÅ C f ÑÑÑÑ
UcellI
ECEO =
ÅÇ p ÑÖ
(12)
where Q is the permeate flow rate and Cf and Cp are the
contaminant concentrations in the feed and permeate,
respectively. ECEO represents the electrical energy needed to
degrade a contaminant by 1 order of magnitude, equivalent to
90% removal efficiency. Considering the various initial
concentrations and removal efficiencies among different EM
processes, ECEO is considered to be the most representative
figure-of-merit for EM energy consumption.48 The median
ECEO for EM-based oxidation is 0.4 kWh m−3 (Figure 9A),
which is lower than the energy consumption of conventional
wastewater treatment (∼0.6 kWh m−3)306 and comparable to
advanced oxidation processes for organics removal.307,308
These comparisons of energy consumption suggest that EM-
based oxidation is competitive with mature water treatment
technologies.
We classify the ECEO of different EM processes based on the
oxidation mechanisms of direct electrooxidation, electro-
Fenton, and •OH-mediated anodic oxidation (Figure 9A).
Direct oxidation, in which electrons transfer directly from the
contaminant to the anode surface, is energy-efficient with a
median ECEO of 0.06 kWh m−3; this efficiency is attributed to
the low applied cell potential, ranging from 1 to 3 V. Only a
few competitive reactions occur under these potentials,
resulting in high current efficiency for contaminant degrada-
tion. However, direct oxidation is only effective for degrading
organics that readily lose electrons, limiting its application to
specific conditions.
In electro-Fenton processes, cell potentials are usually set
from 2 to 4 V in order to ensure the regeneration of Fe2+ in
parallel with H2O2 electrogeneration, resulting in a median
ECEO of 0.37 kWh m−3. The generation of •OH from H2O2 on
the cathode enables nonselective oxidation of contaminants,
making this process suitable for treating wastewaters
containing multiple recalcitrant organics. However, electro-
Fenton processes are feasible only under acidic or near-neutral
conditions. Further, the current density during operation
should be carefully controlled in order to prevent loss of the
iron catalysts and to minimize side reactions.
A relatively high ECEO (1.73 kWh m−3) is inevitable for
•
OH-mediated anodic oxidation processes due to the high
thermodynamic anodic potential required for generating •OH
through water oxidation (2.38 V vs SHE).59 Parasitic reactions
pubs.acs.org/estengg Review
such as water electrolysis further increase the energy
consumption and lower the current efficiency. Nevertheless,
•
OH-mediated anodic oxidation represents the most promising
EM-based oxidation method because of its efficient and stable
performance for contaminant degradation under a broad range
of pH. Furthermore, the generation of other radical species,
such as chlorine and sulfate radicals, through anodic oxidation
improves the overall oxidation performance.
In sum, a relatively high electrical energy consumption is
necessary for treating wastewaters with complex components
and recalcitrant contaminants using EM processes. Notably,
effluent residual concentration (i.e., Cp), not removal
efficiency, is the decisive factor for wastewater treatment.
Many EM-based oxidization processes are not able to achieve
near-complete removal of the contaminants due to the short
residence time and the limited current efficiency under low
residual concentrations. Energy consumption would increase
dramatically with the higher current densities needed to
achieve lower residual concentration, considering the ex-
ponential relationship between energy and current.72 There-
fore, future work should focus on the optimization of EM
processes for near-complete contaminant removal with high
overall current efficiency and low energy consumption, for
example, by enhancing mass transport under low residual
concentrations.
Energy Consumption for Membrane Fouling Control.
The specific energy consumption of EM processes for fouling
mitigation is provided by eq 11. EMs consume 0.18 kWh m−3
for fouling mitigation, comprising approximately 6% of the
total energy demand for a standard seawater RO desalination
process, or less than 20% of the energy consumption in
wastewater reclamation with RO. Typically, large doses of
chemicals, including oxidants, reductants, antiscalants, and
nonoxidizing biocides, are added in RO processes for water
flux maintenance via membrane chemical cleaning.309 In
contrast, EMs are expected to minimize the need for chemical
dosages, ultimately reducing operating costs.
Our analysis reveals that the SECs for membrane antifouling
and self-cleaning processes are similar (Figure 9B1): antifouling
modes can be operated under low cell potential, and self-
cleaning processes require only intermittent voltage applica-
tion. However, these results are based on lab-scale studies that
employ much higher foulant concentrations than those found
in real source waters. The SEC for membrane self-cleaning
processes depends on the energy consumption per area, ECA,
which can be calculated using18
UcellIt
ECA =
A (13)
where A is the effective membrane area. High foulant
concentrations lead to increased cleaning frequency, which
results in higher SEC for lab-scale membrane self-cleaning
processes. As shown in Figure 9B2, membrane self-cleaning can
achieve water flux recovery in ∼10 min with a low ECA of 0.04
kWh m−2. The in situ generation of radical species and the
modification of local pH in the porous structure enable facile
removal of foulants adhered to the membrane with high
current efficiency. Further, the combination of membrane self-
cleaning with physical cleaning, such as backwashing, can
balance the limitations of individual methods, thereby
maximizing the overall cleaning efficiency and lowering
operating costs.10,18 Therefore, it is expected that membrane
R https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
self-cleaning would be more energy-efficient than antifouling in
real applications because of the intermittent operation.
■ PERSPECTIVES AND OUTLOOK
EMs may be suitable for advancing fit-for-purpose water and
wastewater treatment, where pollutant removal and organic
fouling control represent the most viable applications.
Electrified transformation of contaminants such as nitrate
and organic micropollutants can effectively remove these
contaminants while eliminating the production of concentrated
waste streams and minimizing the addition of chemicals. Flow-
through EMs provide a scalable platform for these electro-
chemical processes due to enhancements in mass transfer,
conversion efficiency, and stability. In addition to contaminant
removal, EMs are promising for organic fouling control,
improving membrane longevity while minimizing pretreatment
steps and the addition of chemicals. Our discussion suggests
that EMs are most suitable for UF and MF applications due to
the feasibility of membrane surface modification and flow-
through filtration operation. Employing EMs as salt rejecting
membranes (i.e., RO and NF) would be very challenging as it
requires a paradigm shift in module design, which would
adversely impact membrane performance (i.e., water perme-
ability and salt rejection) and substantially increase the cost of
desalination.
EMs for contaminant degradation and fouling control could
provide multifunctional, modular treatment systems. These
technologies could be deployed for distributed treatment
applications to promote water security. For example, EMs may
be used where utility-scale treatment is not available.
Furthermore, electrification of water treatment enables
adaptability to bolster water resilience while also facilitating
decarbonization of water treatment.
EMs extend membrane functionalities beyond pure separa-
tion, enabling efficient removal of diverse contaminants
through various electrophenomena, including direct and free
radical-mediated electrooxidation, electroreduction, electro-
static repulsion, and electroporation. The electroactive layer,
characterized by high specific surface area and small pores,
enables EMs to achieve effective removal of contaminants in a
single-pass flow-through filtration due to convection-enhanced
mass transport, nanoconfinement, and electroassisted adsorp-
tion. Thus, the flow-through filtration mode of EMs can
achieve much higher current efficiencies and lower retention
times than the conventional flow-by operation mode using flat
plate electrodes. Additionally, the electroactive layer introduces
in situ fouling control on the membrane surface, improving
membrane performance and lifespan. Notably, the energy
consumption of EMs is comparable to that of mature water/
wastewater treatment and reclamation technologies. Further-
more, EM processes are sustainable due to their modular
design and avoidance of chemicals or auxiliary activation (e.g.,
UV irradiation). Given these advantages, EMs could be viable
for various water treatment applications.
Despite the potentially promising EM applications,
innovations in electroactive membrane materials are necessary
to advance the development of sustainable and low-cost EMs.
Materials commonly used for EM fabrication, such as CNTs
and Magnéli phase Ti4O7, suffer from drawbacks such as
corrosion, passivation, induction of membrane fouling, harsh
materials synthesis conditions, and high cost. Further efforts
are needed to develop EMs with superior porosity,
conductivity, reactivity, and stability during long-term
pubs.acs.org/estengg Review
operation. Moreover, EM fabrication methods should be
simple, cost-effective, and environmentally friendly. Thinking
beyond the development of suitable EM materials, tailored
catalysts or nanomaterials could be incorporated into the
conductive layer in order to attain rapid and selective removal
of target contaminants in complex water matrices.
Although EMs have demonstrated significant advantages for
a variety of applications, several hurdles remain for realizing
their implementation. Overall, practical applications require
the development of solutions for operating EMs under real
water/wastewater conditions. In order to achieve sustainable
and energy-efficient EM processes, further work should focus
on minimizing the occurrence of competing reactions and
enhancing the stability of EMs during long-term operation,
especially in complex water matrices. Further, the formation of
toxic DBPs, such as chlorinated organic compounds and
oxyhalides (e.g., ClO4−), needs to be controlled. When the
treatment of water for potable use or municipal wastewaters is
considered, the applicability of EMs to such waters that have
relatively low salt contents should be assessed. EMs for
contaminant removal should achieve ∼100% removal
efficiency with high current efficiency and low energy
consumption during single-pass flow-through filtration to
eliminate disposal hazards. The development of EMs for
fouling control applications should focus more on intermittent
self-cleaning processes than on continuous antifouling
processes in order to minimize energy consumption. Finally,
the design of EM modules needs to be improved to facilitate
integration with traditional membrane processes or applica-
tions for decentralized water treatment. When these challenges
are addressed, the advanced functionality of EMs should make
them viable for practical water treatment applications.
In addition to water decontamination and fouling control,
EMs are also promising for environmental sensing and
resource recovery. For example, EMs could provide superior
sensitivity, flexibility, robustness, and selectivity as membrane-
based electrochemical sensors. A variety of stimuli, including
organic molecules, inorganic ions, and bacteria, could interact
with the responsive sites on EMs to enable on-site, real-time
monitoring of pollutant removal, byproduct generation, fouling
formation, and membrane wetting during filtration processes.
Additionally, EMs also provide opportunities to reclaim
multiple valuable resources from wastewaters by integrating
electrochemical resource recovery methods into membrane
processes. By transforming aqueous contaminants into
nutrients or other useful materials, rather than removing
them and creating additional waste streams, EMs for resource
recovery could add economic value to the water treatment
process.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsestengg.1c00015.
Summary of conductive materials for EM preparation
(Table S1); summary of target contaminants and applied
voltages in different EM processes for organics oxidation
(Table S2); summary of foulants and applied voltages in
different EM processes for membrane fouling control
(Table S3) (PDF)
S https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
■
pubs.acs.org/estengg
AUTHOR INFORMATION
Corresponding Author
Menachem Elimelech − Department of Chemical and
Environmental Engineering, Yale University, New Haven,
Connecticut 06520-8286, United States; orcid.org/0000-
0003-4186-1563; Email: menachem.elimelech@yale.edu
Authors
Meng Sun − Department of Chemical and Environmental
Engineering, Yale University, New Haven, Connecticut
06520-8286, United States; orcid.org/0000-0002-8188-
9264
Xiaoxiong Wang − Department of Chemical and
Environmental Engineering, Yale University, New Haven,
Connecticut 06520-8286, United States
Lea R. Winter − Department of Chemical and Environmental
Engineering, Yale University, New Haven, Connecticut
06520-8286, United States
Yumeng Zhao − Department of Chemical and Environmental
Engineering, Yale University, New Haven, Connecticut
06520-8286, United States; State Key Laboratory of Urban
Water Resource and Environment, Harbin Institute of
Technology, Harbin 150090, China
Wen Ma − Department of Chemical and Environmental
Engineering, Yale University, New Haven, Connecticut
06520-8286, United States
Tayler Hedtke − Department of Chemical and Environmental
Engineering, Yale University, New Haven, Connecticut
06520-8286, United States
Jae-Hong Kim − Department of Chemical and Environmental
Engineering, Yale University, New Haven, Connecticut
06520-8286, United States; orcid.org/0000-0003-2224-
3516
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsestengg.1c00015
Author Contributions
# (16) Mao, R.; Li, N.; Lan, H.; Zhao, X.; Liu, H.; Qu, J.; Sun, M.
M.S. and X.W. contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the NSF Nanosystems Engineer-
ing Research Center for Nanotechnology-Enabled Water
Treatment (EEC-1449500).
■
REFERENCES
(1) Logan, B. E.; Elimelech, M. Membrane-based processes for
sustainable power generation using water. Nature 2012, 488, 313.
(2) Park, H. B.; Kamcev, J.; Robeson, L. M.; Elimelech, M.;
Freeman, B. D. Maximizing the right stuff: The trade-off between
membrane permeability and selectivity. Science 2017, 356 (6343),
eaab0530.
(3) Godri Pollitt, K. J.; Kim, J. H.; Peccia, J.; Elimelech, M.; Zhang,
Y.; Charkoftaki, G.; Hodges, B.; Zucker, I.; Huang, H.; Deziel, N. C.;
Murphy, K.; Ishii, M.; Johnson, C. H.; Boissevain, A.; O’Keefe, E.;
Anastas, P. T.; Orlicky, D.; Thompson, D. C.; Vasiliou, V. 1,4-
Dioxane as an emerging water contaminant: State of the science and
evaluation of research needs. Sci. Total Environ. 2019, 690, 853−866.
(4) Mauter, M. S.; Zucker, I.; Perreault, F.; Werber, J. R.; Kim, J.-H.;
Elimelech, M. The role of nanotechnology in tackling global water
challenges. Nature Sustainability 2018, 1 (4), 166−175.
T https://dx.doi.org/10.1021/acsestengg.1c00015
Review
(5) Miller, D. J.; Dreyer, D. R.; Bielawski, C. W.; Paul, D. R.;
Freeman, B. D. Surface modification of water purification membranes.
Angew. Chem., Int. Ed. 2017, 56 (17), 4662−4711.
(6) Wang, Y. H.; Wu, Y. H.; Tong, X.; Yu, T.; Peng, L.; Bai, Y.;
Zhao, X. H.; Huo, Z. Y.; Ikuno, N.; Hu, H. Y. Chlorine disinfection
significantly aggravated the biofouling of reverse osmosis membrane
used for municipal wastewater reclamation. Water Res. 2019, 154,
246−257.
(7) Liu, Y.; Gao, G.; Vecitis, C. D. Prospects of an Electroactive
Carbon Nanotube Membrane toward Environmental Applications.
Acc. Chem. Res. 2020, 53 (12), 2892−2902.
(8) Henry, J. D., Jr.; Lawler, L. F.; Kuo, C. H. A. A solid/liquid
separation process based on cross flow and electrofiltration. AIChE J.
1977, 23 (6), 851−859.
(9) Tang, L.; Iddya, A.; Zhu, X.; Dudchenko, A. V.; Duan, W.;
Turchi, C.; Vanneste, J.; Cath, T. Y.; Jassby, D. Enhanced Flux and
Electrochemical Cleaning of Silicate Scaling on Carbon Nanotube-
Coated Membrane Distillation Membranes Treating Geothermal
Brines. ACS Appl. Mater. Interfaces 2017, 9 (44), 38594−38605.
(10) Duan, W.; Ronen, A.; Walker, S.; Jassby, D. Polyaniline-Coated
Carbon Nanotube Ultrafiltration Membranes: Enhanced Anodic
Stability for In Situ Cleaning and Electro-Oxidation Processes. ACS
Appl. Mater. Interfaces 2016, 8 (34), 22574−22584.
(11) Zaky, A. M.; Chaplin, B. P. Mechanism of p-Substituted Phenol
Oxidation at a Ti4O7 Reactive Electrochemical Membrane. Environ.
Sci. Technol. 2014, 48 (10), 5857−5867.
(12) Zhu, X.; Jassby, D. Electroactive Membranes for Water
Treatment: Enhanced Treatment Functionalities, Energy Consid-
erations, and Future Challenges. Acc. Chem. Res. 2019, 52 (5), 1177−
1186.
(13) Feng, Y.; Yang, L.; Liu, J.; Logan, B. E. Electrochemical
technologies for wastewater treatment and resource reclamation.
Environ. Sci.: Water Res. & Technol. 2016, 2 (5), 800−831.
(14) Liao, P.; Yuan, S.; Chen, M.; Tong, M.; Xie, W.; Zhang, P.
Regulation of Electrochemically Generated Ferrous Ions from an Iron
Cathode for Pd-Catalytic Transformation of MTBE in Groundwater.
Environ. Sci. Technol. 2013, 47 (14), 7918−7926.
(15) Qin, Y.; Sun, M.; Liu, H.; Qu, J. AuPd/Fe3O4-based three-
dimensional electrochemical system for efficiently catalytic degrada-
tion of 1-butyl-3-methylimidazolium hexafluorophosphate. Electro-
chim. Acta 2015, 186, 328−336.
Dechlorination of Trichloroacetic Acid Using a Noble Metal-Free
Graphene-Cu Foam Electrode via Direct Cathodic Reduction and
Atomic H. Environ. Sci. Technol. 2016, 50 (7), 3829−37.
(17) Gayen, P.; Spataro, J.; Avasarala, S.; Ali, A.-M.; Cerrato, J. M.;
Chaplin, B. P. Electrocatalytic reduction of nitrate using magnéli
phase TiO2 reactive electrochemical membranes doped with Pd-
based catalysts. Environ. Sci. Technol. 2018, 52 (16), 9370−9379.
(18) Wang, X.; Sun, M.; Zhao, Y.; Wang, C.; Ma, W.; Wong, M. S.;
Elimelech, M. In Situ Electrochemical Generation of Reactive
Chlorine Species for Efficient Ultrafiltration Membrane Self-Cleaning.
Environ. Sci. Technol. 2020, 54 (11), 6997−7007.
(19) Ji, Q.; Yu, D.; Zhang, G.; Lan, H.; Liu, H.; Qu, J. Microfluidic
flow through polyaniline supported by lamellar-structured graphene
for mass-transfer-enhanced electrocatalytic reduction of hexavalent
chromium. Environ. Sci. Technol. 2015, 49 (22), 13534−13541.
(20) Gao, G.; Vecitis, C. D. Reactive Depth and Performance of an
Electrochemical Carbon Nanotube Network as a Function of Mass
Transport. ACS Appl. Mater. Interfaces 2012, 4 (11), 6096−6103.
(21) Ji, Q.; Zhang, G.; Liu, H.; Liu, R.; Qu, J. Field-Enhanced
Nanoconvection Accelerated Electrocatalytic Conversion of Water
Contaminants and Electricity Generation. Environ. Sci. Technol. 2019,
53 (5), 2713−2719.
(22) Yang, Z.; Qian, J.; Yu, A.; Pan, B. Singlet oxygen mediated iron-
based Fenton-like catalysis under nanoconfinement. Proc. Natl. Acad.
Sci. U. S. A. 2019, 116 (14), 6659−6664.
(23) Zhang, S.; Sun, M.; Hedtke, T.; Deshmukh, A.; Zhou, X.;
Weon, S.; Elimelech, M.; Kim, J.-H. Mechanism of Heterogeneous
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
Fenton Reaction Kinetics Enhancement under Nanoscale Spatial
Confinement. Environ. Sci. Technol. 2020, 54 (17), 10868−10875.
(24) Wang, X.; Wang, Z.; Chen, H.; Wu, Z. Removal of Cu (II) ions
from contaminated waters using a conducting microfiltration
membrane. J. Hazard. Mater. 2017, 339, 182−190.
(25) Zheng, J.; Wang, Z.; Ma, J.; Xu, S.; Wu, Z. Development of an
Electrochemical Ceramic Membrane Filtration System for Efficient
Contaminant Removal from Waters. Environ. Sci. Technol. 2018, 52
(7), 4117−4126.
(26) Yanez H, J. E.; Wang, Z.; Lege, S.; Obst, M.; Roehler, S.;
Burkhardt, C. J.; Zwiener, C. Application and characterization of
electroactive membranes based on carbon nanotubes and zerovalent
iron nanoparticles. Water Res. 2017, 108, 78−85.
(27) Guo, L.; Ding, K.; Rockne, K.; Duran, M.; Chaplin, B. P.
Bacteria inactivation at a sub-stoichiometric titanium dioxide reactive
electrochemical membrane. J. Hazard. Mater. 2016, 319, 137−146.
(28) Ronen, A.; Duan, W.; Wheeldon, I.; Walker, S.; Jassby, D.
Microbial Attachment Inhibition through Low-Voltage Electro-
chemical Reactions on Electrically Conducting Membranes. Environ.
Sci. Technol. 2015, 49 (21), 12741−12750.
(29) Almassi, S.; Li, Z.; Xu, W.; Pu, C.; Zeng, T.; Chaplin, B. P.
Simultaneous Adsorption and Electrochemical Reduction of N-
Nitrosodimethylamine Using Carbon-Ti4O7 Composite Reactive
Electrochemical Membranes. Environ. Sci. Technol. 2019, 53 (2),
928−937.
(30) Fan, X.; Zhao, H.; Quan, X.; Liu, Y.; Chen, S. Nanocarbon-
based membrane filtration integrated with electric field driving for
effective membrane fouling mitigation. Water Res. 2016, 88, 285−292.
(31) Gao, F.; Nebel, C. E. Electrically Conductive Diamond
Membrane for Electrochemical Separation Processes. ACS Appl.
Mater. Interfaces 2016, 8 (28), 18640−18646.
(32) Abid, H. S.; Lalia, B. S.; Bertoncello, P.; Hashaikeh, R.; Clifford,
B.; Gethin, D. T.; Hilal, N. Electrically conductive spacers for self-
cleaning membrane surfaces via periodic electrolysis. Desalination
2017, 416, 16−23.
(33) Trellu, C.; Coetsier, C.; Rouch, J.-C.; Esmilaire, R.; Rivallin, M.;
Cretin, M.; Causserand, C. Mineralization of organic pollutants by
anodic oxidation using reactive electrochemical membrane synthe-
sized from carbothermal reduction of TiO2. Water Res. 2018, 131,
310−319.
(34) Duan, W.; Dudchenko, A.; Mende, E.; Flyer, C.; Zhu, X.;
Jassby, D. Electrochemical mineral scale prevention and removal on
electrically conducting carbon nanotube–polyamide reverse osmosis
membranes. Environ. Sci. Process Impacts 2014, 16 (6), 1300−8.
(35) Tan, X.; Hu, C.; Zhu, Z.; Liu, H.; Qu, J. Electrically Pore-Size-
Tunable Polypyrrole Membrane for Antifouling and Selective
Separation. Adv. Funct. Mater. 2019, 29 (35), 1903081.
(36) Wang, H.; Dai, H. Strongly coupled inorganic-nano-carbon
hybrid materials for energy storage. Chem. Soc. Rev. 2013, 42 (7),
3088−3113.
(37) Martinez-Huitle, C. A.; Rodrigo, M. A.; Sires, I.; Scialdone, O.
Single and coupled electrochemical processes and reactors for the
abatement of organic water pollutants: A critical review. Chem. Rev.
2015, 115 (24), 13362−407.
(38) Gao, G.; Zhang, Q.; Vecitis, C. D. CNT-PVDF composite flow-
through electrode for single-pass sequential reduction-oxidation. J.
Mater. Chem. A 2014, 2 (17), 6185.
(39) Zhu, X.; Dudchenko, A. V.; Khor, C. M.; He, X.; Ramon, G. Z.;
Jassby, D. Field-Induced Redistribution of Surfactants at the Oil/
Water Interface Reduces Membrane Fouling on Electrically
Conducting Carbon Nanotube UF Membranes. Environ. Sci. Technol.
2018, 52 (20), 11591−11600.
(40) Rao, U.; Iddya, A.; Jung, B.; Khor, C. M.; Hendren, Z.; Turchi,
C.; Cath, T.; Hoek, E. M.; Ramon, G. Z.; Jassby, D. Mineral Scale
Prevention on Electrically Conducting Membrane Distillation
Membranes Using Induced Electrophoretic Mixing. Environ. Sci.
Technol. 2020, 54 (6), 3678−3690.
pubs.acs.org/estengg Review
(41) Vecitis, C. D.; Gao, G.; Liu, H. Electrochemical carbon
nanotube filter for adsorption, desorption, and oxidation of aqueous
dyes and anions. J. Phys. Chem. C 2011, 115 (9), 3621−3629.
(42) Wei, G.; Chen, S.; Fan, X.; Quan, X.; Yu, H. Carbon nanotube
hollow fiber membranes: High-throughput fabrication, structural
control and electrochemically improved selectivity. J. Membr. Sci.
2015, 493, 97−105.
(43) Huong Le, T. X.; Dumée, L. F.; Lacour, S.; Rivallin, M.; Yi, Z.;
Kong, L.; Bechelany, M.; Cretin, M. Hybrid graphene-decorated metal
hollow fibre membrane reactors for efficient electro-Fenton -
Filtration co-processes. J. Membr. Sci. 2019, 587, 117182.
(44) Jiang, W.-L.; Xia, X.; Han, J.-L.; Ding, Y.-C.; Haider, M. R.;
Wang, A.-J. Graphene modified electro-Fenton catalytic membrane
for in situ degradation of antibiotic florfenicol. Environ. Sci. Technol.
2018, 52 (17), 9972−9982.
(45) Gao, G.; Zhang, Q.; Hao, Z.; Vecitis, C. D. Carbon Nanotube
Membrane Stack for Flow-through Sequential Regenerative Electro-
Fenton. Environ. Sci. Technol. 2015, 49 (4), 2375−2383.
(46) Li, Y.; Cheng, C.; Bai, S.; Jing, L.; Zhao, Z.; Liu, L. The
performance of Pd-rGO electro-deposited PVDF/carbon fiber cloth
composite membrane in MBR/MFC coupled system. Chem. Eng. J.
2019, 365, 317−324.
(47) Radjenovic, J.; Sedlak, D. L. Challenges and Opportunities for
Electrochemical Processes as Next-Generation Technologies for the
Treatment of Contaminated Water. Environ. Sci. Technol. 2015, 49
(19), 11292−11302.
(48) Chaplin, B. P. The Prospect of Electrochemical Technologies
Advancing Worldwide Water Treatment. Acc. Chem. Res. 2019, 52
(3), 596−604.
(49) Liu, Q.; Qiu, G.; Zhou, Z.; Li, J.; Amy, G. L.; Xie, J.; Lee, J. Y.
An Effective Design of Electrically Conducting Thin-Film Composite
(TFC) Membranes for Bio and Organic Fouling Control in Forward
Osmosis (FO). Environ. Sci. Technol. 2016, 50 (19), 10596−10605.
(50) Wen, J.; Tan, X.; Hu, Y.; Guo, Q.; Hong, X. Filtration and
Electrochemical Disinfection Performance of PAN/PANI/AgNWs-
CC Composite Nanofiber Membrane. Environ. Sci. Technol. 2017, 51
(11), 6395−6403.
(51) Liu, R.; Sui, Y.; Wang, X. Metal-organic framework-based
ultrafiltration membrane separation with capacitive-type for enhanced
phosphate removal. Chem. Eng. J. 2019, 371, 903−913.
(52) Pan, Z.; Yu, F.; Li, L.; Liu, M.; Song, C.; Yang, J.; Li, H.; Wang,
C.; Pan, Y.; Wang, T. Low-cost electrochemical filtration carbon
membrane prepared from coal via self-bonding. Chem. Eng. J. 2020,
385, 123928.
(53) Liang, P.; Rivallin, M.; Cerneaux, S.; Lacour, S.; Petit, E.;
Cretin, M. Coupling cathodic Electro-Fenton reaction to membrane
filtration for AO7 dye degradation: A successful feasibility study. J.
Membr. Sci. 2016, 510, 182−190.
(54) Sun, M.; Feng, G.; Zhang, M.; Song, C.; Tao, P.; Wang, T.;
Shao, M. Enhanced removal ability of phenol from aqueous solution
using coal-based carbon membrane coupled with electrochemical
oxidation process. Colloids Surf., A 2018, 540, 186−193.
(55) Shi, H.; Wang, Y.; Li, C.; Pierce, R.; Gao, S.; Huang, Q.
Degradation of Perfluorooctanesulfonate by Reactive Electrochemical
Membrane Composed of Magnéli Phase Titanium Suboxide. Environ.
Sci. Technol. 2019, 53 (24), 14528−14537.
(56) Almassi, S.; Samonte, P. R. V.; Li, Z.; Xu, W.; Chaplin, B. P.
Mechanistic Investigation of Haloacetic Acid Reduction Using
Carbon-Ti4O7 Composite Reactive Electrochemical Membranes.
Environ. Sci. Technol. 2020, 54 (3), 1982−1991.
(57) Geng, P.; Chen, G. Magnéli Ti4O7 modified ceramic
membrane for electrically-assisted filtration with antifouling property.
J. Membr. Sci. 2016, 498, 302−314.
(58) Smith, J. R.; Walsh, F. C.; Clarke, R. L. Electrodes based on
Magnéli phase titanium oxides: the properties and applications of
Ebonex® materials. J. Appl. Electrochem. 1998, 28 (10), 1021−1033.
(59) Trellu, C.; Chaplin, B. P.; Coetsier, C.; Esmilaire, R.; Cerneaux,
S.; Causserand, C.; Cretin, M. Electro-oxidation of organic pollutants
U https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
by reactive electrochemical membranes. Chemosphere 2018, 208,
159−175.
(60) Nayak, S.; Chaplin, B. P. Fabrication and characterization of
porous, conductive, monolithic Ti4O7 electrodes. Electrochim. Acta
2018, 263, 299−310.
(61) Zhang, Y.; Wei, K.; Han, W.; Sun, X.; Li, J.; Shen, J.; Wang, L.
Improved electrochemical oxidation of tricyclazole from aqueous
solution by enhancing mass transfer in a tubular porous electrode
electrocatalytic reactor. Electrochim. Acta 2016, 189, 1−8.
(62) Zhou, C.; Wang, Y.; Chen, J.; Niu, J. Porous Ti/SnO2-Sb
anode as reactive electrochemical membrane for removing trace
antiretroviral drug stavudine from wastewater. Environ. Int. 2019, 133,
105157.
(63) Mameda, N.; Park, H.-J.; Choo, K.-H. Membrane electro-
oxidizer: a new hybrid membrane system with electrochemical
oxidation for enhanced organics and fouling control. Water Res.
2017, 126, 40−49.
(64) Liu, L.; Xu, Y.; Wang, K.; Li, K.; Xu, L.; Wang, J.; Wang, J.
Fabrication of a novel conductive ultrafiltration membrane and its
application for electrochemical removal of hexavalent chromium. J.
Membr. Sci. 2019, 584, 191−201.
(65) Sun, J.; Wang, Q.; Zhang, J.; Wang, Z.; Wu, Z. Degradation of
sulfadiazine in drinking water by a cathodic electrochemical
membrane filtration process. Electrochim. Acta 2018, 277, 77−87.
(66) Wallace, G.; Spinks, G. Conducting polymers - bridging the
bionic interface. Soft Matter 2007, 3 (6), 665−671.
(67) Ahmed, F.; Lalia, B. S.; Kochkodan, V.; Hilal, N.; Hashaikeh, R.
Electrically conductive polymeric membranes for fouling prevention
and detection: A review. Desalination 2016, 391, 1−15.
(68) Ronen, A.; Walker, S. L.; Jassby, D. Electroconductive and
electroresponsive membranes for water treatment. Rev. Chem. Eng.
2016, 32 (5), 533.
(69) Loh, I.-H.; Moody, R. A.; Huang, J. C. Electrically conductive
membranes: Synthesis and applications. J. Membr. Sci. 1990, 50 (1),
31−49.
(70) Li, B.; Sun, D.; Li, B.; Tang, W.; Ren, P.; Yu, J.; Zhang, J. One-
Step Electrochemically Prepared Graphene/Polyaniline Conductive
Filter Membrane for Permeation Enhancement by Fouling Mitigation.
Langmuir 2020, 36 (9), 2209−2222.
(71) Yuan, X.-S.; Guo, Z.-Y.; Geng, H.-Z.; Rhen, D. S.; Wang, L.;
Yuan, X.-T.; Li, J. Enhanced performance of conductive polysulfone/
MWCNT/PANI ultrafiltration membrane in an online fouling
monitoring application. J. Membr. Sci. 2019, 575, 160−169.
(72) Guo, L.; Jing, Y.; Chaplin, B. P. Development and
Characterization of Ultrafiltration TiO2Magnéli Phase Reactive
Electrochemical Membranes. Environ. Sci. Technol. 2016, 50 (3),
1428−1436.
(73) Wei, G.; Yu, H.; Quan, X.; Chen, S.; Zhao, H.; Fan, X.
Constructing All Carbon Nanotube Hollow Fiber Membranes with
Improved Performance in Separation and Antifouling for Water
Treatment. Environ. Sci. Technol. 2014, 48 (14), 8062−8068.
(74) Thamaraiselvan, C.; Ronen, A.; Lerman, S.; Balaish, M.; Ein-Eli,
Y.; Dosoretz, C. G. Low voltage electric potential as a driving force to
hinder biofouling in self-supporting carbon nanotube membranes.
Water Res. 2018, 129, 143−153.
(75) Liang, S.; Lin, H.; Habteselassie, M.; Huang, Q. Electro-
chemical inactivation of bacteria with a titanium sub-oxide reactive
membrane. Water Res. 2018, 145, 172−180.
(76) Fan, X.; Liu, Y.; Quan, X.; Zhao, H.; Chen, S.; Yi, G.; Du, L.
High desalination permeability, wetting and fouling resistance on
superhydrophobic carbon nanotube hollow fiber membrane under
self-powered electrochemical assistance. J. Membr. Sci. 2016, 514,
501−509.
(77) Li, Y.; Liu, L.; Yang, F.; Ren, N. Performance of carbon fiber
cathode membrane with C-Mn-Fe-O catalyst in MBR-MFC for
wastewater treatment. J. Membr. Sci. 2015, 484, 27−34.
(78) Li, X.; Shao, S.; Yang, Y.; Mei, Y.; Qing, W.; Guo, H.; Peng, L.
E.; Wang, P.; Tang, C. Y. Engineering Interface with a One-
Dimensional RuO2/TiO2 Heteronanostructure in an Electrocatalytic
pubs.acs.org/estengg Review
Membrane Electrode: Toward Highly Efficient Micropollutant
Decomposition. ACS Appl. Mater. Interfaces 2020, 12 (19), 21596−
21604.
(79) Xu, L.; Ma, X.; Niu, J.; Chen, J.; Zhou, C. Removal of trace
naproxen from aqueous solution using a laboratory-scale reactive
flow-through membrane electrode. J. Hazard. Mater. 2019, 379,
120692.
(80) Hui, H.; Wang, H.; Mo, Y.; Yin, Z.; Li, J. Optimal design and
evaluation of electrocatalytic reactors with nano-MnOx/Ti membrane
electrode for wastewater treatment. Chem. Eng. J. 2019, 376, 120190.
(81) Wang, X.; Wang, Z.; Chen, H.; Wu, Z. Removal of Cu(II) ions
from contaminated waters using a conducting microfiltration
membrane. J. Hazard. Mater. 2017, 339, 182−190.
(82) Li, X.; Liu, L.; Liu, T.; Zhang, D.; An, C.; Yang, F. An active
electro-Fenton PVDF/SS/PPy cathode membrane can remove
contaminant by filtration and mitigate fouling by pairing with
sacrificial iron anode. J. Membr. Sci. 2020, 605, 118100.
(83) Xie, L.; Shu, Y.; Hu, Y.; Cheng, J.; Chen, Y. SWNTs-PAN/
TPU/PANI composite electrospun nanofiber membrane for point-of-
use efficient electrochemical disinfection: New strategy of CNT
disinfection. Chemosphere 2020, 251, 126286.
(84) Liu, H.; Zuo, K.; Vecitis, C. D. Titanium Dioxide-Coated
Carbon Nanotube Network Filter for Rapid and Effective Arsenic
Sorption. Environ. Sci. Technol. 2014, 48 (23), 13871−13879.
(85) Zhang, Q.; Arribas, P.; Remillard, E. M.; García-Payo, M. C.;
Khayet, M.; Vecitis, C. D. Interlaced CNT Electrodes for Bacterial
Fouling Reduction of Microfiltration Membranes. Environ. Sci.
Technol. 2017, 51 (16), 9176−9183.
(86) Bakr, A. R.; Rahaman, M. S. Crossflow electrochemical
filtration for elimination of ibuprofen and bisphenol a from pure
and competing electrolytic solution conditions. J. Hazard. Mater.
2019, 365, 615−621.
(87) Liu, Y.; Dustin Lee, J. H.; Xia, Q.; Ma, Y.; Yu, Y.; Lanry Yung,
L. Y.; Xie, J.; Ong, C. N.; Vecitis, C. D.; Zhou, Z. A graphene-based
electrochemical filter for water purification. J. Mater. Chem. A 2014, 2
(39), 16554−16562.
(88) Werner, C. M.; Katuri, K. P.; Hari, A. R.; Chen, W.; Lai, Z.;
Logan, B. E.; Amy, G. L.; Saikaly, P. E. Graphene-Coated Hollow
Fiber Membrane as the Cathode in Anaerobic Electrochemical
Membrane Bioreactors - Effect of Configuration and Applied Voltage
on Performance and Membrane Fouling. Environ. Sci. Technol. 2016,
50 (8), 4439−4447.
(89) Liu, L.; Zhao, F.; Liu, J.; Yang, F. Preparation of highly
conductive cathodic membrane with graphene (oxide)/PPy and the
membrane antifouling property in filtrating yeast suspensions in
EMBR. J. Membr. Sci. 2013, 437, 99−107.
(90) Liu, H.; Vajpayee, A.; Vecitis, C. D. Bismuth-Doped Tin Oxide-
Coated Carbon Nanotube Network: Improved Anode Stability and
Efficiency for Flow-Through Organic Electrooxidation. ACS Appl.
Mater. Interfaces 2013, 5 (20), 10054−10066.
(91) Gayen, P.; Chen, C.; Abiade, J. T.; Chaplin, B. P.
Electrochemical Oxidation of Atrazine and Clothianidin on Bi-
doped SnO2-TinO2n-1 Electrocatalytic Reactive Electrochemical
Membranes. Environ. Sci. Technol. 2018, 52 (21), 12675−12684.
(92) Jung, B.; Kim, C. Y.; Jiao, S.; Rao, U.; Dudchenko, A. V.;
Tester, J.; Jassby, D. Enhancing boron rejection on electrically
conducting reverse osmosis membranes through local electrochemical
pH modification. Desalination 2020, 476, 114212.
(93) Duan, W.; Chen, G.; Chen, C.; Sanghvi, R.; Iddya, A.; Walker,
S.; Liu, H.; Ronen, A.; Jassby, D. Electrochemical removal of
hexavalent chromium using electrically conducting carbon nanotube/
polymer composite ultrafiltration membranes. J. Membr. Sci. 2017,
531, 160−171.
(94) Chen, S.; Wang, G.; Li, S.; Li, X.; Yu, H.; Quan, X. Porous
carbon membrane with enhanced selectivity and antifouling capability
for water treatment under electrochemical assistance. J. Colloid
Interface Sci. 2020, 560, 59−68.
V https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
(95) Geng, P.; Chen, G. Antifouling ceramic membrane electrode
modified by Magnéli Ti4O7 for electro-microfiltration of humic acid.
Sep. Purif. Technol. 2017, 185, 61−71.
(96) Liu, J.; Tian, C.; Xiong, J.; Wang, L. Polypyrrole blending
modification for PVDF conductive membrane preparing and fouling
mitigation. J. Colloid Interface Sci. 2017, 494, 124−129.
(97) Yanez H, J. E.; Wang, Z.; Lege, S.; Obst, M.; Roehler, S.;
Burkhardt, C. J.; Zwiener, C. Application and characterization of
electroactive membranes based on carbon nanotubes and zerovalent
iron nanoparticles. Water Res. 2017, 108, 78−85.
(98) Liu, Y.; Liu, H.; Zhou, Z.; Wang, T.; Ong, C. N.; Vecitis, C. D.
Degradation of the Common Aqueous Antibiotic Tetracycline using a
Carbon Nanotube Electrochemical Filter. Environ. Sci. Technol. 2015,
49 (13), 7974−7980.
(99) Sun, X.; Wu, J.; Chen, Z.; Su, X.; Hinds, B. J. Fouling
Characteristics and Electrochemical Recovery of Carbon Nanotube
Membranes. Adv. Funct. Mater. 2013, 23 (12), 1500−1506.
(100) Abid, H. S.; Johnson, D. J.; Clifford, B.; Gethin, D. T.;
Bertoncello, P.; Hashaikeh, R.; Hilal, N. Periodic electrolysis
technique for in situ fouling control and removal with low-pressure
membrane filtration. Desalination 2018, 433, 10−24.
(101) Liu, Z. W.; Peng, F.; Wang, H. J.; Yu, H.; Zheng, W. X.; Yang,
J. Phosphorus-doped graphite layers with high electrocatalytic activity
for the O2 reduction in an alkaline medium. Angew. Chem., Int. Ed.
2011, 50 (14), 3257−61.
(102) Yang, Y.; Qiao, S.; Zhou, J.; Quan, X. A novel porous-carbon-
based hollow fiber membrane with electrochemical reduction
mediated by in-situ hydroxyl radical generation for fouling control
and water treatment. Appl. Catal., B 2019, 255, 117772.
(103) Zhang, Q.; Vecitis, C. D. Conductive CNT-PVDF membrane
for capacitive organic fouling reduction. J. Membr. Sci. 2014, 459,
143−156.
(104) Liu, H.; Vecitis, C. D. Reactive Transport Mechanism for
Organic Oxidation during Electrochemical Filtration: Mass-Transfer,
Physical Adsorption, and Electron-Transfer. J. Phys. Chem. C 2012,
116 (1), 374−383.
(105) Zaky, A. M.; Chaplin, B. P. Porous Substoichiometric TiO2
Anodes as Reactive Electrochemical Membranes for Water Treat-
ment. Environ. Sci. Technol. 2013, 47 (12), 6554−6563.
(106) Donaghue, A.; Chaplin, B. P. Effect of Select Organic
Compounds on Perchlorate Formation at Boron-doped Diamond
Film Anodes. Environ. Sci. Technol. 2013, 47 (21), 12391−12399.
(107) Qian, J.; Gao, X.; Pan, B. Nanoconfinement-Mediated Water
Treatment: From Fundamental to Application. Environ. Sci. Technol.
2020, 54 (14), 8509−8526.
(108) Koblenz, T. S.; Wassenaar, J.; Reek, J. N. H. Reactivity within
a confined self-assembled nanospace. Chem. Soc. Rev. 2008, 37 (2),
247−262.
(109) Li, X.; Chen, S.; Quan, X.; Zhang, Y. Enhanced Adsorption of
PFOA and PFOS on Multiwalled Carbon Nanotubes under
Electrochemical Assistance. Environ. Sci. Technol. 2011, 45 (19),
8498−8505.
(110) Fan, X.; Zhao, H.; Liu, Y.; Quan, X.; Yu, H.; Chen, S.
Enhanced Permeability, Selectivity, and Antifouling Ability of CNTs/
Al2O3Membrane under Electrochemical Assistance. Environ. Sci.
Technol. 2015, 49 (4), 2293−2300.
(111) Xiao, J.; Pan, X.; Guo, S.; Ren, P.; Bao, X. Toward
Fundamentals of Confined Catalysis in Carbon Nanotubes. J. Am.
Chem. Soc. 2015, 137 (1), 477−482.
(112) Le, T. X. H.; Haflich, H.; Shah, A. D.; Chaplin, B. P. Energy-
Efficient Electrochemical Oxidation of Perfluoroalkyl Substances
Using a Ti4O7 Reactive Electrochemical Membrane Anode. Environ.
Sci. Technol. Lett. 2019, 6 (8), 504−510.
(113) Pan, Z.; Yu, F.; Li, L.; Song, C.; Yang, J.; Wang, C.; Pan, Y.;
Wang, T. Electrochemical microfiltration treatment of bisphenol A
wastewater using coal-based carbon membrane. Sep. Purif. Technol.
2019, 227, 115695.
(114) Luo, Y.; Guo, W.; Ngo, H. H.; Nghiem, L. D.; Hai, F. I.;
Zhang, J.; Liang, S.; Wang, X. C. A review on the occurrence of
W https://dx.doi.org/10.1021/acsestengg.1c00015
pubs.acs.org/estengg Review
micropollutants in the aquatic environment and their fate and removal
during wastewater treatment. Sci. Total Environ. 2014, 473, 619−641.
(115) Zhao, Y.; Sun, M.; Wang, X.; Wang, C.; Lu, D.; Ma, W.; Kube,
S. A.; Ma, J.; Elimelech, M. Janus electrocatalytic flow-through
membrane enables highly selective singlet oxygen production. Nat.
Commun. 2020, 11, 6228.
(116) Guo, D.; Liu, Y. Singlet Oxygen-Mediated Electrochemical
Filter for Selective and Rapid Degradation of Organic Compounds.
Ind. Eng. Chem. Res. 2020, 59 (31), 14180−14187.
(117) Gligorovski, S.; Strekowski, R.; Barbati, S.; Vione, D.
Environmental Implications of Hydroxyl Radicals ((*)OH). Chem.
Rev. 2015, 115 (24), 13051−92.
(118) Panizza, M.; Cerisola, G. Direct and mediated anodic
oxidation of organic pollutants. Chem. Rev. 2009, 109 (12), 6541−
6569.
(119) Fernandes, A.; Santos, D.; Pacheco, M. J.; Ciriaco, L.; Simoes,
R.; Gomes, A. C.; Lopes, A. Electrochemical treatment of cork boiling
wastewater with a boron-doped diamond anode. Environ. Technol.
2015, 36 (1), 26−35.
(120) Trellu, C.; Pechaud, Y.; Oturan, N.; Mousset, E.; Huguenot,
D.; van Hullebusch, E. D.; Esposito, G.; Oturan, M. A. Comparative
study on the removal of humic acids from drinking water by anodic
oxidation and electro-Fenton processes: Mineralization efficiency and
modelling. Appl. Catal., B 2016, 194, 32−41.
(121) Rajkumar, D.; Kim, J. G. Oxidation of various reactive dyes
with in situ electro-generated active chlorine for textile dyeing
industry wastewater treatment. J. Hazard. Mater. 2006, 136 (2), 203−
212.
(122) Ganiyu, S. O.; Van Hullebusch, E. D.; Cretin, M.; Esposito,
G.; Oturan, M. A. Coupling of membrane filtration and advanced
oxidation processes for removal of pharmaceutical residues: a critical
review. Sep. Purif. Technol. 2015, 156, 891−914.
(123) Sirés, I.; Brillas, E.; Oturan, M. A.; Rodrigo, M. A.; Panizza, M.
Electrochemical advanced oxidation processes: today and tomorrow.
A review. Environ. Sci. Pollut. Res. 2014, 21 (14), 8336−8367.
(124) Kraft, A. Electrochemical water disinfection: a short review.
Platinum Met. Rev. 2008, 52 (3), 177−185.
(125) Neodo, S.; Rosestolato, D.; Ferro, S.; De Battisti, A. On the
electrolysis of dilute chloride solutions: Influence of the electrode
material on Faradaic efficiency for active chlorine, chlorate and
perchlorate. Electrochim. Acta 2012, 80, 282−291.
(126) Dodgen, H.; Taube, H. The exchange of chlorine dioxide with
chlorite ion and with chlorine in other oxidation states. J. Am. Chem.
Soc. 1949, 71 (7), 2501−2504.
(127) Suen, N.-T.; Hung, S.-F.; Quan, Q.; Zhang, N.; Xu, Y.-J.;
Chen, H. M. Electrocatalysis for the oxygen evolution reaction: recent
development and future perspectives. Chem. Soc. Rev. 2017, 46 (2),
337−365.
(128) McCrory, C. C.; Jung, S.; Peters, J. C.; Jaramillo, T. F.
Benchmarking heterogeneous electrocatalysts for the oxygen
evolution reaction. J. Am. Chem. Soc. 2013, 135 (45), 16977−16987.
(129) Bonfatti, F.; Ferro, S.; Lavezzo, F.; Malacarne, M.; Lodi, G.;
De Battisti, A. Electrochemical incineration of glucose as a model
organic substrate. II. Role of active chlorine mediation. J. Electrochem.
Soc. 2000, 147 (2), 592.
(130) Scialdone, O.; Randazzo, S.; Galia, A.; Silvestri, G.
Electrochemical oxidation of organics in water: Role of operative
parameters in the absence and in the presence of NaCl. Water Res.
2009, 43 (8), 2260−2272.
(131) Grgur, B. N.; Mijin, D. Ž . A kinetics study of the methomyl
electrochemical degradation in the chloride containing solutions.
Appl. Catal., B 2014, 147, 429−438.
(132) Deborde, M.; Von Gunten, U. Reactions of chlorine with
inorganic and organic compounds during water treatmentkinetics
and mechanisms: a critical review. Water Res. 2008, 42 (1−2), 13−51.
(133) Sharma, V. K. Oxidation of inorganic contaminants by ferrates
(VI, V, and IV)–kinetics and mechanisms: a review. J. Environ.
Manage. 2011, 92 (4), 1051−73.
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
(134) Perry, S. C.; Pangotra, D.; Vieira, L.; Csepei, L.-I.; Sieber, V.;
Wang, L.; de León, C. P.; Walsh, F. C. Electrochemical synthesis of
hydrogen peroxide from water and oxygen. Nature Reviews Chemistry
2019, 3 (7), 442−458.
(135) Olvera-Vargas, H.; Rouch, J.-C.; Coetsier, C.; Cretin, M.;
Causserand, C. Dynamic cross-flow electro-Fenton process coupled to
anodic oxidation for wastewater treatment: Application to the
degradation of acetaminophen. Sep. Purif. Technol. 2018, 203, 143−
151.
(136) Li, X.; Liu, L.; Yang, F. CFC/PVDF/GO-Fe3+ membrane
electrode and flow-through system improved E-Fenton performance
with a low dosage of aqueous iron. Sep. Purif. Technol. 2018, 193,
220−231.
(137) Zhu, Q.; Hinkle, M.; Kim, D. J.; Kim, J.-H. Modular Hydrogen
Peroxide Electrosynthesis Cell with Anthraquinone-Modified Polyani-
line Electrocatalyst. ACS ES&T Engineering 2020, DOI: 10.1021/
acsestengg.0c00173.
(138) Zheng, J.; Xu, S.; Wu, Z.; Wang, Z. Removal of p-chloroaniline
from polluted waters using a cathodic electrochemical ceramic
membrane reactor. Sep. Purif. Technol. 2019, 211, 753−763.
(139) Zheng, J.; Ma, J.; Wang, Z.; Xu, S.; Waite, T. D.; Wu, Z.
Contaminant Removal from Source Waters Using Cathodic Electro-
chemical Membrane Filtration: Mechanisms and Implications.
Environ. Sci. Technol. 2017, 51 (5), 2757−2765.
(140) Lee, Y.; Von Gunten, U. Oxidative transformation of
micropollutants during municipal wastewater treatment: Comparison
of kinetic aspects of selective (chlorine, chlorine dioxide, ferrateVI,
and ozone) and non-selective oxidants (hydroxyl radical). Water Res.
2010, 44 (2), 555−566.
(141) Jayson, G.; Parsons, B.; Swallow, A. J. Some simple, highly
reactive, inorganic chlorine derivatives in aqueous solution. Their
formation using pulses of radiation and their role in the mechanism of
the Fricke dosimeter. J. Chem. Soc., Faraday Trans. 1 1973, 69, 1597−
1607.
(142) Yang, Y.; Pignatello, J. J.; Ma, J.; Mitch, W. A. Comparison of
Halide Impacts on the Efficiency of Contaminant Degradation by
Sulfate and Hydroxyl Radical-Based Advanced Oxidation Processes
(AOPs). Environ. Sci. Technol. 2014, 48 (4), 2344−2351.
(143) Brillas, E.; Martínez-Huitle, C. A. Decontamination of
wastewaters containing synthetic organic dyes by electrochemical
methods. An updated review. Appl. Catal., B 2015, 166−167, 603−
643.
(144) Panizza, M.; Kapalka, A.; Comninellis, C. Oxidation of organic
pollutants on BDD anodes using modulated current electrolysis.
Electrochim. Acta 2008, 53 (5), 2289−2295.
(145) Garcia-Segura, S.; Lanzarini-Lopes, M.; Hristovski, K.;
Westerhoff, P. Electrocatalytic reduction of nitrate: Fundamentals to
full-scale water treatment applications. Appl. Catal., B 2018, 236,
546−568.
(146) Mulholland, P. J.; Helton, A. M.; Poole, G. C.; Hall, R. O.;
Hamilton, S. K.; Peterson, B. J.; Tank, J. L.; Ashkenas, L. R.; Cooper,
L. W.; Dahm, C. N.; Dodds, W. K.; Findlay, S. E. G.; Gregory, S. V.;
Grimm, N. B.; Johnson, S. L.; McDowell, W. H.; Meyer, J. L.; Valett,
H. M.; Webster, J. R.; Arango, C. P.; Beaulieu, J. J.; Bernot, M. J.;
Burgin, A. J.; Crenshaw, C. L.; Johnson, L. T.; Niederlehner, B. R.;
O’Brien, J. M.; Potter, J. D.; Sheibley, R. W.; Sobota, D. J.; Thomas, S.
M. Stream denitrification across biomes and its response to
anthropogenic nitrate loading. Nature 2008, 452, 202−206.
(147) Steffen, W.; Richardson, K.; Rockström, J.; Cornell, S. E.;
Fetzer, I.; Bennett, E. M.; Biggs, R.; Carpenter, S. R.; De Vries, W.; De
Wit, C. A.; Folke, C.; Gerten, D.; Heinke, J.; Mace, G. M.; Persson, L.
M.; Ramanathan, V.; Reyers, B.; Sörlin, S. Planetary boundaries:
Guiding human development on a changing planet. Science 2015, 347
(6223), 1259855.
(148) Pennino, M. J.; Compton, J. E.; Leibowitz, S. G. Trends in
drinking water nitrate violations across the United States. Environ. Sci.
Technol. 2017, 51, 13450−13460.
(149) Kapoor, A.; Viraraghavan, T. Nitrate removal from drinking
water - Review. J. Environ. Eng. 1997, 123 (4), 371−380.
pubs.acs.org/estengg Review
(150) Garcia, F.; Ciceron, D.; Saboni, A.; Alexandrova, S. Nitrate
ions elimination from drinking water by nanofiltration: Membrane
choice. Sep. Purif. Technol. 2006, 52 (1), 196−200.
(151) Rezvani, F.; Sarrafzadeh, M. H.; Ebrahimi, S.; Oh, H. M.
Nitrate removal from drinking water with a focus on biological
methods: a review. Environ. Sci. Pollut. Res. 2019, 26 (2), 1124−1141.
(152) Guo, S.; Heck, K.; Kasiraju, S.; Qian, H.; Zhao, Z.; Grabow, L.
C.; Miller, J. T.; Wong, M. S. Insights into Nitrate Reduction over
Indium-Decorated Palladium Nanoparticle Catalysts. ACS Catal.
2018, 8, 503−515.
(153) Tugaoen, H. O. N.; Garcia-Segura, S.; Hristovski, K.;
Westerhoff, P. Challenges in photocatalytic reduction of nitrate as a
water treatment technology. Sci. Total Environ. 2017, 599−600,
1524−1551.
(154) Alvarez, P. J. J.; Chan, C. K.; Elimelech, M.; Halas, N. J.;
Villagrán, D. Emerging opportunities for nanotechnology to enhance
water security. Nat. Nanotechnol. 2018, 13 (8), 634−641.
(155) Loeb, S. K.; Alvarez, P. J. J.; Brame, J. A.; Cates, E. L.; Choi,
W.; Crittenden, J.; Dionysiou, D. D.; Li, Q.; Li-Puma, G.; Quan, X.;
Sedlak, D. L.; David Waite, T.; Westerhoff, P.; Kim, J.-H. The
Technology Horizon for Photocatalytic Water Treatment: Sunrise or
Sunset? Environ. Sci. Technol. 2019, 53 (6), 2937−2947.
(156) Jin, R.; Gao, W.; Chen, J.; Zeng, H.; Zhang, F.; Liu, Z.; Guan,
N. Photocatalytic reduction of nitrate ion drinking water by using
metal-loaded MgTiO3-TiO2 composite semiconductor catalyst. J.
Photochem. Photobiol., A 2004, 162 (2−3), 585−590.
(157) Dash, B. P.; Chaudhari, S. Electrochemical denitrificaton of
simulated ground water. Water Res. 2005, 39, 4065−4072.
(158) Bosko, M. L.; Rodrigues, M. A. S.; Ferreira, J. Z.; Miró, E. E.;
Bernardes, A. M. Nitrate reduction of brines from water desalination
plants by membrane electrolysis. J. Membr. Sci. 2014, 451, 276−284.
(159) Xu, D.; Li, Y.; Yin, L.; Ji, Y.; Niu, J.; Yu, Y. Electrochemical
removal of nitrate in industrial wastewater. Front. Environ. Sci. Eng.
2018, 12, 9.
(160) Dima, G. E.; Beltramo, G. L.; Koper, M. T. M. Nitrate
reduction on single-crystal platinum electrodes. Electrochim. Acta
2005, 50, 4318−4326.
(161) Martínez, J.; Ortiz, A.; Ortiz, I. State-of-the-art and
perspectives of the catalytic and electrocatalytic reduction of aqueous
nitrates. Appl. Catal., B 2017, 207, 42−59.
(162) Duca, M.; Koper, M. T. M. Powering denitrification: The
perspectives of electrocatalytic nitrate reduction. Energy Environ. Sci.
2012, 5 (12), 9726−9742.
(163) Barrabés, N.; Sá, J. Catalytic nitrate removal from water, past,
present and future perspectives. Appl. Catal., B 2011, 104 (1−2), 1−5.
(164) Reyter, D.; Bélanger, D.; Roué, L. Optimization of the cathode
material for nitrate removal by a paired electrolysis process. J. Hazard.
Mater. 2011, 192 (2), 507−513.
(165) Su, J. F.; Ruzybayev, I.; Shah, I.; Huang, C. P. The
electrochemical reduction of nitrate over micro-architectured metal
electrodes with stainless steel scaffold. Appl. Catal., B 2016, 180, 199−
209.
(166) Dima, G. E.; de Vooys, A. C. A.; Koper, M. T. M.
Electrocatalytic reduction of nitrate at low concentration on coinage
and transition-metal electrodes in acid solutions. J. Electroanal. Chem.
2003, 554 (555), 15−23.
(167) Paidar, M.; Bouzek, K.; Bergmann, H. Influence of cell
construction on the electrochemical reduction of nitrate. Chem. Eng. J.
2002, 85, 99−109.
(168) Simpson, B. K.; Johnson, D. C. Electrocatalysis of nitrate
reduction at copper-nickel alloy electrodes in acidic media. Electro-
analysis 2004, 16 (7), 532−538.
(169) Lee, J. K.; Kim, D.; Tak, Y. Transformation of Nitrogen in the
Form of Nitrate into Ammonia by Electrochemical Reaction. Korean
Chem. Eng. Res. 2008, 46 (5), 1013−1016.
(170) Rajmohan, K. S.; Chetty, R. Nitrate Reduction at Electro-
deposited Copper on Copper Cathode. ECS Trans. 2014, 59 (1),
397−407.
X https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
(171) Kuang, P.; Feng, C.; Li, M.; Chen, N.; Hu, Q.; Wang, G.; Li,
R. Improvement on electrochemical reduction of nitrate in synthetic
groundwater by reducing anode surface area. J. Electrochem. Soc. 2017,
164 (6), E103−E112.
(172) Ureta-Zañartu, S.; Yáñez, C. Electroreduction of nitrate ion on
Pt, Ir and on 70:30 Pt:Ir alloy. Electrochim. Acta 1997, 42 (11), 1725−
1731.
(173) da Cunha, M. C. P. M.; De Souza, J. P. I.; Nart, F. C. Reaction
Pathways for Reduction of Nitrate Ions on Platinum, Rhodium, and
Platinum-Rhodium Alloy Electrodes. Langmuir 2000, 16 (2), 771−
777.
(174) Strukul, G.; Gavagnin, R.; Pinna, F.; Modaferri, E.;
Perathoner, S.; Centi, G.; Marella, M.; Tomaselli, M. Use of
palladium based catalysts in the hydrogenation of nitrates in drinking
water: From powders to membranes. Catal. Today 2000, 55 (1−2),
139−149.
(175) De Vooys, A. C. A.; van Santen, R. A.; van Veen, J. A. R.
Electrocatalytic reduction of NO3- on palladium/copper electrodes. J.
Mol. Catal. A: Chem. 2000, 154 (1−2), 203−215.
(176) Mattarozzi, L.; Cattarin, S.; Comisso, N.; Guerriero, P.;
Musiani, M.; Vázquez-Gómez, L.; Verlato, E. Electrochemical
reduction of nitrate and nitrite in alkaline media at CuNi alloy
electrodes. Electrochim. Acta 2013, 89, 488−496.
(177) Amertharaj, S.; Hasnat, M. A.; Mohamed, N. Electroreduction
of nitrate ions at a platinum-copper electrode in an alkaline medium:
influence of sodium inositol phytate. Electrochim. Acta 2014, 136,
557−564.
(178) Durivault, L.; Brylev, O.; Reyter, D.; Sarrazin, M.; Bélanger,
D.; Roué, L. Cu-Ni materials prepared by mechanical milling: Their
properties and electrocatalytic activity towards nitrate reduction in
alkaline medium. J. Alloys Compd. 2007, 432 (1−2), 323−332.
(179) Liu, J. X.; Richards, D.; Singh, N.; Goldsmith, B. R. Activity
and Selectivity Trends in Electrocatalytic Nitrate Reduction on
Transition Metals. ACS Catal. 2019, 9 (8), 7052−7064.
(180) Lüdtke, K.; Peinemann, K. V.; Kasche, V.; Behling, R. D.
Nitrate removal of drinking water by means of catalytically active
membranes. J. Membr. Sci. 1998, 151 (1), 3−11.
(181) Zhao, Z.; Tong, G.; Tan, X. Nitrite removal from water by
catalytic hydrogenation in a Pd-CNTs/Al2O3 hollow fiber membrane
reactor. J. Chem. Technol. Biotechnol. 2016, 91 (8), 2298−2304.
(182) Chen, Y.-x.; Zhang, Y.; Liu, H.-y. Reduction of nitrate from
groundwater: powder catalysts and catalytic membranes. J. Environ.
Sci. 2003, 15 (5), 600−606.
(183) Ilinich, O. M.; Gribov, E. N.; Simonov, P. A. Water
denitrification over catalytic membranes: hydrogen spillover and
catalytic activity of macroporous membranes loaded with Pd and Cu.
Catal. Today 2003, 82, 49−56.
(184) Centi, G.; Perathoner, S. Remediation of water contamination
using catalytic technologies. Appl. Catal., B 2003, 41 (1−2), 15−29.
(185) Chen, Y. X.; Zhang, Y.; Liu, H. Y.; Sharma, K. R.; Chen, G. H.
Hydrogen-based tubular catalytic membrane for removing nitrate
from groundwater. Environ. Technol. 2004, 25 (2), 227−234.
(186) Wehbe, N.; Guilhaume, N.; Fiaty, K.; Miachon, S.; Dalmon, J.
A. Hydrogenation of nitrates in water using mesoporous membranes
operated in a flow-through catalytic contactor. Catal. Today 2010, 156
(3−4), 208−215.
(187) Pera-Titus, M.; Fridmann, M.; Guilhaume, N.; Fiaty, K.
Modelling nitrate reduction in a flow-through catalytic membrane
contactor: Role of pore confining effects on water viscosity. J. Membr.
Sci. 2012, 401−402, 204−216.
(188) Ilinitch, O. M.; Cuperus, F. P.; Nosova, L. V.; Gribov, E. N.
Catalytic membrane in reduction of aqueous nitrates: Operational
principles and catalytic performance. Catal. Today 2000, 56 (1−3),
137−145.
(189) Lange, C.; Storck, S.; Tesche, B.; Maier, W. F. Selective
hydrogenation reactions with a microporous membrane catalyst,
prepared by sol-gel dip coating. J. Catal. 1998, 175, 280−293.
(190) Reif, M.; Dittmeyer, R. Porous, catalytically active ceramic
membranes for gas-liquid reactions: a comparison between catalytic
pubs.acs.org/estengg Review
diffuser and forced through flow concept. Catal. Today 2003, 82, 3−
14.
(191) Hasnat, M. A.; Ben Aoun, S.; Rahman, M. M.; Asiri, A. M.;
Mohamed, N. Lean Cu-immobilized Pt and Pd films/-H+ Conducting
Membrane Assemblies: Relative Electrocatalytic Nitrate Reduction
Activities. J. Ind. Eng. Chem. 2015, 28, 131−137.
(192) Ghodbane, O.; Sarrazin, M.; Roué, L.; Bélanger, D.
Electrochemical Reduction of Nitrate on Pyrolytic Graphite-
Supported Cu and Pd-Cu Electrocatalysts. J. Electrochem. Soc. 2008,
155 (6), F117−F117.
(193) Lan, H.; Liu, X.; Liu, H.; Liu, R.; Hu, C.; Qu, J. Efficient
Nitrate Reduction in a Fluidized Electrochemical Reactor Promoted
by Pd-Sn/AC Particles. Catal. Lett. 2016, 146 (1), 91−99.
(194) Horányi, G.; Rizmayer, E. M. Role of adsorption phenomena
in the electrocatalytic reduction of nitric acid at a platinized platinum
electrode. J. Electroanal. Chem. Interfacial Electrochem. 1982, 140 (2),
347−366.
(195) Duan, W.; Li, G.; Lei, Z.; Zhu, T.; Xue, Y.; Wei, C.; Feng, C.
Highly active and durable carbon electrocatalyst for nitrate reduction
reaction. Water Res. 2019, 161, 126−135.
(196) Ding, J.; Li, W.; Zhao, Q.-L.; Wang, K.; Zheng, Z.; Gao, Y.-Z.
Electroreduction of nitrate in water: Role of cathode and cell
configuration. Chem. Eng. J. 2015, 271, 252−259.
(197) Teng, W.; Bai, N.; Liu, Y.; Liu, Y.; Fan, J.; Zhang, W.-x.
Selective Nitrate Reduction to Dinitrogen by Electrocatalysis on
Nanoscale Iron Encapsulated in Mesoporous Carbon. Environ. Sci.
Technol. 2018, 52 (1), 230−236.
(198) Peel, J. W.; Reddy, K. J.; Sullivan, B. P.; Bowen, J. M.
Electrocatalytic reduction of nitrate in water. Water Res. 2003, 37
(10), 2512−2519.
(199) Arsuaga, J. M.; Sotto, A.; del Rosario, G.; Martínez, A.;
Molina, S.; Teli, S. B.; de Abajo, J. Influence of the type, size, and
distribution of metal oxide particles on the properties of nano-
composite ultrafiltration membranes. J. Membr. Sci. 2013, 428, 131−
141.
(200) Hennepe, H. J. C. T.; Smolders, C. A.; Bargeman, D.; Mulder,
M. H. V. Exclusion and tortuosity effects for alcohol/water separation
by zeolite-filled PDMS membranes. Sep. Sci. Technol. 1991, 26 (4),
585−596.
(201) Werth, C. J.; Yan, C.; Troutman, J. P. Factors Impeding
Replacement of Ion Exchange with (Electro)Catalytic Treatment for
Nitrate Removal from Drinking Water. ACS ES&T Engineering 2021,
1 (1), 6−20.
(202) Liu, Y.; Zheng, Y.; Du, B.; Nasaruddin, R. R.; Chen, T.; Xie, J.
Golden Carbon Nanotube Membrane for Continuous Flow Catalysis.
Ind. Eng. Chem. Res. 2017, 56 (11), 2999−3007.
(203) Serrà, A.; Alcobé, X.; Sort, J.; Nogués, J.; Vallés, E. Highly
efficient electrochemical and chemical hydrogenation of 4-nitrophenol
using recyclable narrow mesoporous magnetic CoPt nanowires. J.
Mater. Chem. A 2016, 4 (40), 15676−15687.
(204) Das, R.; Sypu, V. S.; Paumo, H. K.; Bhaumik, M.; Maharaj, V.;
Maity, A. Silver decorated magnetic nanocomposite (Fe3O4@PPy-
MAA/Ag) as highly active catalyst towards reduction of 4-nitrophenol
and toxic organic dyes. Appl. Catal., B 2019, 244, 546−558.
(205) Rajkumar, C.; Veerakumar, P.; Chen, S.-M.; Thirumalraj, B.;
Lin, K.-C. Ultrathin Sulfur-Doped Graphitic Carbon Nitride Nano-
sheets As Metal-Free Catalyst for Electrochemical Sensing and
Catalytic Removal of 4-Nitrophenol. ACS Sustainable Chem. Eng.
2018, 6 (12), 16021−16031.
(206) Lv, Z.-S.; Zhu, X.-Y.; Meng, H.-B.; Feng, J.-J.; Wang, A.-J.
One-pot synthesis of highly branched Pt@Ag core-shell nanoparticles
as a recyclable catalyst with dramatically boosting the catalytic
performance for 4-nitrophenol reduction. J. Colloid Interface Sci. 2019,
538, 349−356.
(207) Huang, R.; Zhu, H.; Su, R.; Qi, W.; He, Z. Catalytic
Membrane Reactor Immobilized with Alloy Nanoparticle-Loaded
Protein Fibrils for Continuous Reduction of 4-Nitrophenol. Environ.
Sci. Technol. 2016, 50 (20), 11263−11273.
Y https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
(208) Liu, Y.; Zhang, K. H.; Li, W. Y.; Ma, J. H.; Vancso, G. J. Metal
nanoparticle loading of gel-brush grafted polymer fibers in membranes
for catalysis. J. Mater. Chem. A 2018, 6 (17), 7741−7748.
(209) Chaplin, B. P.; Schrader, G.; Farrell, J. Electrochemical
Destruction of N-Nitrosodimethylamine in Reverse Osmosis
Concentrates using Boron-doped Diamond Film Electrodes. Environ.
Sci. Technol. 2010, 44 (11), 4264−4269.
(210) Puyo, M.; Fau, P.; Kahn, M. L.; Mesguich, D.; Launay, J.;
Fajerwerg, K. Removable Composite Electrode Made of Silver
Nanoparticles on Pyrolyzed Photoresist Film for the Electroreduction
of 4-Nitrophenol. Langmuir 2019, 35 (44), 14194−14202.
(211) Bai, Y.; Mavrikakis, M. Mechanistic Study of Nitric Oxide
Reduction by Hydrogen on Pt(100) (I): A DFT Analysis of the
Reaction Network. J. Phys. Chem. B 2018, 122 (2), 432−443.
(212) Misal, S. N.; Lin, M.-H.; Mehraeen, S.; Chaplin, B. P.
Modeling electrochemical oxidation and reduction of sulfamethox-
azole using electrocatalytic reactive electrochemical membranes. J.
Hazard. Mater. 2020, 384, 121420.
(213) Stern, C. M.; Jegede, T. O.; Hulse, V. A.; Elgrishi, N.
Electrochemical reduction of Cr(vi) in water: lessons learned from
fundamental studies and applications. Chem. Soc. Rev. 2021, 50 (3),
1642−1667.
(214) Sun, M.; Zhang, G.; Qin, Y.; Cao, M.; Liu, Y.; Li, J.; Qu, J.;
Liu, H. Redox Conversion of Chromium(VI) and Arsenic(III) with
the Intermediates of Chromium(V) and Arsenic(IV) via AuPd/CNTs
Electrocatalysis in Acid Aqueous Solution. Environ. Sci. Technol. 2015,
49 (15), 9289−9297.
(215) Mousset, E.; Doudrick, K. A review of electrochemical
reduction processes to treat oxidized contaminants in water. Current
Opinion in Electrochemistry 2020, 22, 221−227.
(216) Matilainen, A.; Gjessing, E. T.; Lahtinen, T.; Hed, L.;
Bhatnagar, A.; Sillanpää, M. An overview of the methods used in the
characterisation of natural organic matter (NOM) in relation to
drinking water treatment. Chemosphere 2011, 83 (11), 1431−1442.
(217) Shon, H.; Vigneswaran, S.; Snyder, S. A. Effluent organic
matter (EfOM) in wastewater: constituents, effects, and treatment.
Crit. Rev. Environ. Sci. Technol. 2006, 36 (4), 327−374.
(218) Zhao, Y.; Lu, D.; Cao, Y.; Luo, S.; Zhao, Q.; Yang, M.; Xu, C.;
Ma, J. Interaction Analysis between Gravity-Driven Ceramic
Membrane and Smaller Organic Matter: Implications for Retention
and Fouling Mechanism in Ultralow Pressure-Driven Filtration
System. Environ. Sci. Technol. 2018, 52 (23), 13718−13727.
(219) Ma, H.; Bowman, C. N.; Davis, R. H. Membrane fouling
reduction by backpulsing and surface modification. J. Membr. Sci.
2000, 173 (2), 191−200.
(220) Dudchenko, A. V.; Rolf, J.; Russell, K.; Duan, W.; Jassby, D.
Organic fouling inhibition on electrically conducting carbon nano-
tube-polyvinyl alcohol composite ultrafiltration membranes. J. Membr.
Sci. 2014, 468, 1−10.
(221) Hua, L.; Cao, H.; Ma, Q.; Shi, X.; Zhang, X.; Zhang, W.
Microalgae Filtration Using an Electrochemically Reactive Ceramic
Membrane: Filtration Performances, Fouling Kinetics, and Foulant
Layer Characteristics. Environ. Sci. Technol. 2020, 54 (3), 2012−2021.
(222) Fan, X. F.; Liu, Y. M.; Wang, X. C.; Quan, X.; Chen, S.
Improvement of Antifouling and Antimicrobial Abilities on Silver-
Carbon Nanotube Based Membranes under Electrochemical
Assistance. Environ. Sci. Technol. 2019, 53 (9), 5292−5300.
(223) Alam, I.; Guiney, L. M.; Hersam, M. C.; Chowdhury, I.
Application of external voltage for fouling mitigation from graphene
oxide, reduced graphene oxide and molybdenum disulfide function-
alized surfaces. Environ. Sci.: Nano 2019, 6 (3), 925−936.
(224) Moritz, T.; Benfer, S.; Arki, P.; Tomandl, G. Influence of the
surface charge on the permeate flux in the dead-end filtration with
ceramic membranes. Sep. Purif. Technol. 2001, 25 (1−3), 501−508.
(225) Chuo, T.-W.; Wei, T.-C.; Chang, Y.; Liu, Y.-L. Electrically
Driven Biofouling Release of a Poly(tetrafluoroethylene) Membrane
Modified with an Electrically Induced Reversibly Cross-Linked
Polymer. ACS Appl. Mater. Interfaces 2013, 5 (20), 9918−9925.
pubs.acs.org/estengg Review
(226) Fu, W. C.; Wang, X. Y.; Zheng, J. J.; Liu, M. X.; Wang, Z. W.
Antifouling performance and mechanisms in an electrochemical
ceramic membrane reactor for wastewater treatment. J. Membr. Sci.
2019, 570, 355−361.
(227) Yang, Y.; Qiao, S.; Zhou, J.; Quan, X. A novel porous-carbon-
based hollow fiber membrane with electrochemical reduction
mediated by in-situ hydroxyl radical generation for fouling control
and water treatment. Appl. Catal., B 2019, 255, 117772.
(228) Fu, W.; Wang, X.; Zheng, J.; Liu, M.; Wang, Z. Antifouling
performance and mechanisms in an electrochemical ceramic
membrane reactor for wastewater treatment. J. Membr. Sci. 2019,
570−571, 355−361.
(229) Webster, R. D.; Chilukuri, S. V. V.; Levesley, J. A.; Webster, B.
J. Electrochemical cleaning of microporous metallic filters fouled with
bovine serum albumin and phosphate under low cross-flow velocities.
J. Appl. Electrochem. 2000, 30 (8), 915−924.
(230) Sun, J.; Hu, C.; Wu, B.; Qu, J. Fouling mitigation of a
graphene hydrogel membrane electrode by electrical repulsion and in
situ self-cleaning in an electro-membrane reactor. Chem. Eng. J. 2020,
393, 124817.
(231) Matin, A.; Rahman, F.; Shafi, H. Z.; Zubair, S. M. Scaling of
reverse osmosis membranes used in water desalination: Phenomena,
impact, and control; future directions. Desalination 2019, 455, 135−
157.
(232) Bogler, A.; Lin, S.; Bar-Zeev, E. Biofouling of membrane
distillation, forward osmosis and pressure retarded osmosis:
Principles, impacts and future directions. J. Membr. Sci. 2017, 542,
378−398.
(233) Goh, P.; Zulhairun, A.; Ismail, A.; Hilal, N. Contemporary
antibiofouling modifications of reverse osmosis desalination mem-
brane: A review. Desalination 2019, 468, 114072.
(234) Vecitis, C. D.; Schnoor, M. H.; Rahaman, M. S.; Schiffman, J.
D.; Elimelech, M. Electrochemical multiwalled carbon nanotube filter
for viral and bacterial removal and inactivation. Environ. Sci. Technol.
2011, 45 (8), 3672−9.
(235) Liu, H.; Ni, X. Y.; Huo, Z. Y.; Peng, L.; Li, G. Q.; Wang, C.;
Wu, Y. H.; Hu, H. Y. Carbon Fiber-Based Flow-Through Electrode
System (FES) for Water Disinfection via Direct Oxidation
Mechanism with a Sequential Reduction-Oxidation Process. Environ.
Sci. Technol. 2019, 53 (6), 3238−3249.
(236) Rahaman, M. S.; Vecitis, C. D.; Elimelech, M. Electrochemical
carbon-nanotube filter performance toward virus removal and
inactivation in the presence of natural organic matter. Environ. Sci.
Technol. 2012, 46 (3), 1556−64.
(237) Lei, Q.; Zheng, J.; Ma, J.; Wang, X.; Wu, Z.; Wang, Z.
Simultaneous solid-liquid separation and wastewater disinfection
using an electrochemical dynamic membrane filtration system.
Environ. Res. 2020, 180, 108861.
(238) Sharma, P.; Jha, A. B.; Dubey, R. S.; Pessarakli, M. Reactive
oxygen species, oxidative damage, and antioxidative defense
mechanism in plants under stressful conditions. J. Bot. 2012, 2012, 1.
(239) Kim, S. Y.; Park, C.; Jang, H.-J.; Kim, B.-o.; Bae, H.-W.;
Chung, I.-Y.; Kim, E. S.; Cho, Y.-H. Antibacterial strategies inspired
by the oxidative stress and response networks. J. Microbiol. 2019, 57
(3), 203−212.
(240) Wang, X. X.; Zhang, T. Y.; Dao, G. H.; Hu, H. Y. Tolerance
and resistance characteristics of microalgae Scenedesmus sp. LX1 to
methylisothiazolinone. Environ. Pollut. 2018, 241, 200−211.
(241) Long, Y.; Ni, J.; Wang, Z. Subcellular mechanism of
Escherichia coli inactivation during electrochemical disinfection with
boron-doped diamond anode: a comparative study of three
electrolytes. Water Res. 2015, 84, 198−206.
(242) Huang, E.; White, T.; Wang, B.; Shi, H.; Liu, J. Disinfection of
Escherichia coli by a Reactive Electrochemical Membrane System
Involving Activated Carbon Fiber Cloth (ACFC). Water 2019, 11
(3), 430.
(243) Li, H.; Singh, A. K.; McIntyre, L. M.; Sherman, L. A.
Differential gene expression in response to hydrogen peroxide and the
Z https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering
putative PerR regulon of Synechocystis sp. strain PCC 6803. J.
Bacteriol. 2004, 186 (11), 3331−3345.
(244) Fan, X.; Liu, Y.; Wang, X.; Quan, X.; Chen, S. Improvement of
Antifouling and Antimicrobial Abilities on Silver-Carbon Nanotube
Based Membranes under Electrochemical Assistance. Environ. Sci.
Technol. 2019, 53 (9), 5292−5300.
(245) Ben-Sasson, M.; Zodrow, K. R.; Genggeng, Q.; Kang, Y.;
Giannelis, E. P.; Elimelech, M. Surface functionalization of thin-film
composite membranes with copper nanoparticles for antimicrobial
surface properties. Environ. Sci. Technol. 2014, 48 (1), 384−93.
(246) Zhang, N.; Qiu, H.; Liu, Y.; Wang, W.; Li, Y.; Wang, X.; Gao,
J. Fabrication of gold nanoparticle/graphene oxide nanocomposites
and their excellent catalytic performance. J. Mater. Chem. 2011, 21
(30), 11080−11083.
(247) Bei, F.; Hou, X.; Chang, S. L.; Simon, G. P.; Li, D. Interfacing
colloidal graphene oxide sheets with gold nanoparticles. Chem. - Eur. J.
2011, 17 (21), 5958−64.
(248) Valko, M.; Morris, H.; Cronin, M. T. D. Metals, toxicity and
oxidative stress. Curr. Med. Chem. 2005, 12, 1161−1208.
(249) Chatterjee, A. K.; Chakraborty, R.; Basu, T. Mechanism of
antibacterial activity of copper nanoparticles. Nanotechnology 2014, 25
(13), 135101.
(250) Raffi, M.; Mehrwan, S.; Bhatti, T. M.; Akhter, J. I.; Hameed,
A.; Yawar, W.; Ul Hasan, M. M. Investigations into the antibacterial
behavior of copper nanoparticles against Escherichia coli. Ann.
Microbiol. 2010, 60 (1), 75−80.
(251) Xiaochen, W.; Xinfei, F.; Xie, Q. Preparation of Cu-CNT/
ceramic Hollow Fiber Membranes and Investigation of their
Antibiofouling Performance under Electrochemical Assistance. Adv.
Eng. Res. 2018, 170, 499−502.
(252) Thamaraiselvan, C.; Ronen, A.; Lerman, S.; Balaish, M.; Ein-
Eli, Y.; Dosoretz, C. G. Low voltage electric potential as a driving
force to hinder biofouling in self-supporting carbon nanotube
membranes. Water Res. 2018, 129, 143−153.
(253) Jiang, L.; Chen, L.; Zhu, L. Electrically conductive membranes
for anti-biofouling in membrane distillation with two novel operation
modes: Capacitor mode and resistor mode. Water Res. 2019, 161,
297−307.
(254) Wang, X.; Zhou, L.; Lu, L.; Lobo, F. L.; Li, N.; Wang, H.;
Park, J.; Ren, Z. J. Alternating Current Influences Anaerobic
Electroactive Biofilm Activity. Environ. Sci. Technol. 2016, 50,
9169−9176.
(255) Stoner, G.; Cahen Jr, G.; Sachyani, M.; Gileadi, E. 457The
mechanism of low frequency ac electrochemical disinfection. J.
Electroanal. Chem. Interfacial Electrochem. 1982, 141 (3), 229−243.
(256) Baek, Y.; Yoon, H.; Shim, S.; Choi, J.; Yoon, J. Electro-
conductive feed spacer as a tool for biofouling control in a membrane
system for water treatment. Environ. Sci. Technol. Lett. 2014, 1 (2),
179−184.
(257) Bell, D.; Sengpiel, R.; Wessling, M. Metallized hollow fiber
membranes for electrochemical fouling control. J. Membr. Sci. 2020,
594, 117397.
(258) Liu, C.; Xie, X.; Zhao, W.; Liu, N.; Maraccini, P. A.;
Sassoubre, L. M.; Boehm, A. B.; Cui, Y. Conducting nanosponge
electroporation for affordable and high-efficiency disinfection of
bacteria and viruses in water. Nano Lett. 2013, 13 (9), 4288−93.
(259) Yao, Y.; Zhang, P.; Jiang, C.; DuChanois, R. M.; Zhang, X.;
Elimelech, M. High performance polyester reverse osmosis desalina-
tion membrane with chlorine resistance. Nat. Sustainability 2021, 4,
138−146.
(260) Drees, K. P.; Abbaszadegan, M.; Maier, R. M. Comparative
electrochemical inactivation of bacteria and bacteriophage. Water Res.
2003, 37 (10), 2291−2300.
(261) Hijnen, W.; Beerendonk, E.; Medema, G. J. Inactivation credit
of UV radiation for viruses, bacteria and protozoan (oo) cysts in
water: a review. Water Res. 2006, 40 (1), 3−22.
(262) Michen, B.; Graule, T. Isoelectric points of viruses. J. Appl.
microbiol. 2010, 109 (2), 388−397.
AA
pubs.acs.org/estengg Review
(263) Huo, Z.-Y.; Du, Y.; Chen, Z.; Wu, Y.-H.; Hu, H.-Y. Evaluation
and prospects of nanomaterial-enabled innovative processes and
devices for water disinfection: A state-of-the-art review. Water Res.
2020, 173, 115581.
(264) Brady-Estévez, A. S.; Schnoor, M. H.; Vecitis, C. D.; Saleh, N.
B.; Elimelech, M. Multiwalled carbon nanotube filter: improving viral
removal at low pressure. Langmuir 2010, 26 (18), 14975−14982.
(265) Kim, J. P.; Kim, J. H.; Kim, J.; Lee, S. N.; Park, H.-O. A
nanofilter composed of carbon nanotube-silver composites for virus
removal and antibacterial activity improvement. J. Environ. Sci. 2016,
42, 275−283.
(266) Hallum, J.; Youngner, J. The effect of oxidative controlled
potential electrolysis on viruses. Virology 1960, 12 (2), 283−308.
(267) Chu, C.; Ryberg, E. C.; Loeb, S. K.; Suh, M.-J.; Kim, J.-H.
Water disinfection in rural areas demands unconventional solar
technologies. Acc. Chem. Res. 2019, 52 (5), 1187−1195.
(268) Monteiro, G. S.; Staggemeier, R.; Klauck, C. R.; Bernardes, A.
M.; Rodrigues, M. A. S.; Spilki, F. R. Degradation and inactivation of
adenovirus in water by photo-electro-oxidation. Brazilian Journal of
Biology 2015, 75 (4), 37−42.
(269) Horovitz, I.; Avisar, D.; Luster, E.; Lozzi, L.; Luxbacher, T.;
Mamane, H. MS2 bacteriophage inactivation using a N-doped TiO2-
coated photocatalytic membrane reactor: Influence of water-quality
parameters. Chem. Eng. J. 2018, 354, 995−1006.
(270) Rao, G.; Brastad, K. S.; Zhang, Q.; Robinson, R.; He, Z.; Li, Y.
Enhanced disinfection of Escherichia coli and bacteriophage MS2 in
water using a copper and silver loaded titanium dioxide nanowire
membrane. Front. Environ. Sci. Eng. 2016, 10 (4), 11.
(271) Liu, L.; Liu, Z.; Bai, H.; Sun, D. D. Concurrent filtration and
solar photocatalytic disinfection/degradation using high-performance
Ag/TiO2 nanofiber membrane. Water Res. 2012, 46 (4), 1101−12.
(272) Zodrow, K.; Brunet, L.; Mahendra, S.; Li, D.; Zhang, A.; Li,
Q.; Alvarez, P. J. Polysulfone ultrafiltration membranes impregnated
with silver nanoparticles show improved biofouling resistance and
virus removal. Water Res. 2009, 43 (3), 715−23.
(273) De Gusseme, B.; Hennebel, T.; Christiaens, E.; Saveyn, H.;
Verbeken, K.; Fitts, J. P.; Boon, N.; Verstraete, W. Virus disinfection
in water by biogenic silver immobilized in polyvinylidene fluoride
membranes. Water Res. 2011, 45 (4), 1856−64.
(274) Nemeth, Z.; Szekeres, G. P.; Schabikowski, M.; Schrantz, K.;
Traber, J.; Pronk, W.; Hernadi, K.; Graule, T. Enhanced virus
filtration in hybrid membranes with MWCNT nanocomposite. R. Soc.
Open Sci. 2019, 6 (1), 181294.
(275) Huo, Z.-Y.; Zhou, J.-F.; Wu, Y.; Wu, Y.-H.; Liu, H.; Liu, N.;
Hu, H.-Y.; Xie, X. A Cu3P nanowire enabling high-efficiency, reliable,
and energy-efficient low-voltage electroporation-inactivation of
pathogens in water. J. Mater. Chem. A 2018, 6 (39), 18813−18820.
(276) Huo, Z.-Y.; Liu, H.; Wang, W.-L.; Wang, Y.-H.; Wu, Y.-H.;
Xie, X.; Hu, H.-Y. Low-voltage alternating current powered
polydopamine-protected copper phosphide nanowire for electro-
poration-disinfection in water. J. Mater. Chem. A 2019, 7 (13), 7347−
7354.
(277) Zhou, J.; Wang, T.; Chen, W.; Lin, B.; Xie, X. Emerging
investigator series: locally enhanced electric field treatment (LEEFT)
with nanowire-modified electrodes for water disinfection in pipes.
Environ. Sci.: Nano 2020, 7 (2), 397−403.
(278) Liu, C.; Xie, X.; Zhao, W.; Yao, J.; Kong, D.; Boehm, A. B.;
Cui, Y. Static electricity powered copper oxide nanowire microbicidal
electroporation for water disinfection. Nano Lett. 2014, 14 (10),
5603−8.
(279) Brady-Estevez, A. S.; Nguyen, T. H.; Gutierrez, L.; Elimelech,
M. Impact of solution chemistry on viral removal by a single-walled
carbon nanotube filter. Water Res. 2010, 44 (13), 3773−80.
(280) Kotnik, T.; Rems, L.; Tarek, M.; Miklavčič, D. Membrane
electroporation and electropermeabilization: mechanisms and models.
Annu. Rev. Biophys. 2019, 48, 63−91.
(281) Zhou, J.; Wang, T.; Yu, C.; Xie, X. Locally enhanced electric
field treatment (LEEFT) for water disinfection. Front. Environ. Sci.
Eng. 2020, 14 (5), 78.
https://dx.doi.org/10.1021/acsestengg.1c00015
ACS EST Engg. XXXX, XXX, XXX−XXX
ACS ES&T Engineering pubs.acs.org/estengg Review

(282) Huo, Z. Y.; Xie, X.; Yu, T.; Lu, Y.; Feng, C.; Hu, H. Y. Treatment: Validation in Wastewater at Mild pH. Environ. Sci.
Nanowire-Modified Three-Dimensional Electrode Enabling Low- Technol. 2020, 54 (7), 4664−4674.
Voltage Electroporation for Water Disinfection. Environ. Sci. Technol. (301) Jing, Y.; Guo, L.; Chaplin, B. P. Electrochemical impedance
2016, 50 (14), 7641−9. spectroscopy study of membrane fouling and electrochemical
(283) Yue, L.; Chen, S.; Wang, S.; Wang, C.; Hao, X.; Cheng, Y. F. regeneration at a sub-stoichiometric TiO2 reactive electrochemical
Water disinfection using Ag nanoparticle-CuO nanowire co-modified membrane. J. Membr. Sci. 2016, 510, 510−523.
3D copper foam nanocomposites in high flow under low voltages. (302) de Lannoy, C.-F.; Jassby, D.; Gloe, K.; Gordon, A. D.;
Environ. Sci.: Nano 2019, 6 (9), 2801−2809. Wiesner, M. R. Aquatic Biofouling Prevention by Electrically Charged
(284) Gao, G.; Vecitis, C. D. Electrocatalysis aqueous phenol with Nanocomposite Polymer Thin Film Membranes. Environ. Sci. Technol.
carbon nanotubes networks as anodes: Electrodes passivation and 2013, 47 (6), 2760−2768.
regeneration and prevention. Electrochim. Acta 2013, 98, 131−138. (303) Pandit, S.; Shanbhag, S.; Mauter, M.; Oren, Y.; Herzberg, M.
(285) Ohmori, S.; Saito, T. Electrochemical durability of single-wall Influence of Electric Fields on Biofouling of Carbonaceous Electrodes.
carbon nanotube electrode against anodic oxidation in water. Carbon Environ. Sci. Technol. 2017, 51 (17), 10022−10030.
2012, 50 (13), 4932−4938. (304) Azizi, O.; Hubler, D.; Schrader, G.; Farrell, J.; Chaplin, B. P.
(286) Belhadj Tahar, N.; Savall, A. Electropolymerization of phenol Mechanism of Perchlorate Formation on Boron-Doped Diamond
on a vitreous carbon electrode in alkaline aqueous solution at different Film Anodes. Environ. Sci. Technol. 2011, 45 (24), 10582−10590.
temperatures. Electrochim. Acta 2009, 55 (2), 465−469. (305) Skoumal, M.; Arias, C.; Cabot, P. L.; Centellas, F.; Garrido, J.
(287) Yi, Y.; Tornow, J.; Willinger, E.; Willinger, M. G.; Ranjan, C.; A.; Rodríguez, R. M.; Brillas, E. Mineralization of the biocide
Schlögl, R. Electrochemical Degradation of Multiwall Carbon chloroxylenol by electrochemical advanced oxidation processes.
Chemosphere 2008, 71 (9), 1718−1729.
Nanotubes at High Anodic Potential for Oxygen Evolution in Acidic
(306) McCarty, P. L.; Bae, J.; Kim, J. Domestic Wastewater
Media. ChemElectroChem 2015, 2 (12), 1929−1937.
Treatment as a Net Energy Producer-Can This be Achieved? Environ.
(288) Gao, G.; Vecitis, C. D. Doped Carbon Nanotube Networks for
Sci. Technol. 2011, 45 (17), 7100−7106.
Electrochemical Filtration of Aqueous Phenol: Electrolyte Precip-
(307) Lee, Y.; Gerrity, D.; Lee, M.; Gamage, S.; Pisarenko, A.;
itation and Phenol Polymerization. ACS Appl. Mater. Interfaces 2012, Trenholm, R. A.; Canonica, S.; Snyder, S. A.; von Gunten, U. Organic
4 (3), 1478−1489. Contaminant Abatement in Reclaimed Water by UV/H2O2 and a
(289) Moreira, F. C.; Boaventura, R. A. R.; Brillas, E.; Vilar, V. J. P. Combined Process Consisting of O3/H2O2 Followed by UV/H2O2:
Electrochemical advanced oxidation processes: A review on their Prediction of Abatement Efficiency, Energy Consumption, and
application to synthetic and real wastewaters. Appl. Catal., B 2017, Byproduct Formation. Environ. Sci. Technol. 2016, 50 (7), 3809−
202, 217−261. 3819.
(290) Chaplin, B. P. Critical review of electrochemical advanced (308) Katsoyiannis, I. A.; Canonica, S.; von Gunten, U. Efficiency
oxidation processes for water treatment applications. Environ. Sci.: and energy requirements for the transformation of organic micro-
Processes & Impacts 2014, 16 (6), 1182−1203. pollutants by ozone, O3/H2O2 and UV/H2O2. Water Res. 2011, 45
(291) Pouilleau, J.; Devilliers, D.; Groult, H.; Marcus, P. Surface (13), 3811−3822.
study of a titanium-based ceramic electrode material by X-ray (309) Tang, F.; Hu, H.-Y.; Sun, L.-J.; Wu, Q.-Y.; Jiang, Y.-M.; Guan,
photoelectron spectroscopy. J. Mater. Sci. 1997, 32 (21), 5645−5651. Y.-T.; Huang, J.-J. Fouling of reverse osmosis membrane for municipal
(292) Khan, I.; Saeed, K.; Khan, I. Nanoparticles: Properties, wastewater reclamation: Autopsy results from a full-scale plant.
applications and toxicities. Arabian J. Chem. 2019, 12 (7), 908−931. Desalination 2014, 349, 73−79.
(293) Weon, S.; Huang, D.; Rigby, K.; Chu, C.; Wu, X.; Kim, J.-H.
Environmental Materials beyond and below the Nanoscale: Single-
Atom Catalysts. ACS ES&T Engineering 2021, 1 (2), 157−172.
(294) Farhat, A.; Keller, J.; Tait, S.; Radjenovic, J. Removal of
Persistent Organic Contaminants by Electrochemically Activated
Sulfate. Environ. Sci. Technol. 2015, 49 (24), 14326−14333.
(295) Barazesh, J. M.; Prasse, C.; Sedlak, D. L. Electrochemical
Transformation of Trace Organic Contaminants in the Presence of
Halide and Carbonate Ions. Environ. Sci. Technol. 2016, 50 (18),
10143−10152.
(296) Buxton, G. V.; Greenstock, C. L.; Helman, W. P.; Ross, A. B.
Critical Review of rate constants for reactions of hydrated electrons,
hydrogen atoms and hydroxyl radicals (·OH/·O- in Aqueous
Solution. J. Phys. Chem. Ref. Data 1988, 17 (2), 513−886.
(297) Khan, S.; He, X.; Khan, J. A.; Khan, H. M.; Boccelli, D. L.;
Dionysiou, D. D. Kinetics and mechanism of sulfate radical- and
hydroxyl radical-induced degradation of highly chlorinated pesticide
lindane in UV/peroxymonosulfate system. Chem. Eng. J. 2017, 318,
135−142.
(298) Westerhoff, P.; Mezyk, S. P.; Cooper, W. J.; Minakata, D.
Electron Pulse Radiolysis Determination of Hydroxyl Radical Rate
Constants with Suwannee River Fulvic Acid and Other Dissolved
Organic Matter Isolates. Environ. Sci. Technol. 2007, 41 (13), 4640−
4646.
(299) Zhang, Q.; Chen, S.; Quan, X.; Liu, Y.; Yu, H.; Wang, H.
Superpermeable nanoporous carbon-based catalytic membranes for
electro-Fenton driven high-efficiency water treatment. J. Mater. Chem.
A 2018, 6 (46), 23502−23512.
(300) Ye, Z.; Padilla, J. A.; Xuriguera, E.; Beltran, J. L.; Alcaide, F.;
Brillas, E.; Sirés, I. A Highly Stable Metal-Organic Framework-
Engineered FeS2/C Nanocatalyst for Heterogeneous Electro-Fenton

AB https://dx.doi.org/10.1021/acsestengg.1c00015
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